US3770449A - Spectrally sensitized silver halide photographic emulsion - Google Patents
Spectrally sensitized silver halide photographic emulsion Download PDFInfo
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- US3770449A US3770449A US00183492A US3770449DA US3770449A US 3770449 A US3770449 A US 3770449A US 00183492 A US00183492 A US 00183492A US 3770449D A US3770449D A US 3770449DA US 3770449 A US3770449 A US 3770449A
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- silver halide
- halide photographic
- photographic emulsion
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- 239000000839 emulsion Substances 0.000 title claims abstract description 39
- -1 silver halide Chemical class 0.000 title claims abstract description 32
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 22
- 239000004332 silver Substances 0.000 title claims abstract description 22
- 230000001235 sensitizing effect Effects 0.000 claims abstract description 38
- 239000000298 carbocyanine Substances 0.000 claims abstract 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 3
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 abstract description 18
- 125000000217 alkyl group Chemical group 0.000 abstract description 14
- AIGNCQCMONAWOL-UHFFFAOYSA-N 1,3-benzoselenazole Chemical class C1=CC=C2[se]C=NC2=C1 AIGNCQCMONAWOL-UHFFFAOYSA-N 0.000 abstract description 9
- 150000001450 anions Chemical class 0.000 abstract description 6
- 125000000623 heterocyclic group Chemical group 0.000 abstract description 5
- 150000003839 salts Chemical class 0.000 abstract description 5
- 125000003118 aryl group Chemical group 0.000 abstract description 4
- 125000000738 acetamido group Chemical group [H]C([H])([H])C(=O)N([H])[*] 0.000 abstract description 3
- 239000000975 dye Substances 0.000 description 47
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 36
- 230000035945 sensitivity Effects 0.000 description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 238000000586 desensitisation Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 230000003595 spectral effect Effects 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-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
- 206010070834 Sensitisation Diseases 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 229940077388 benzenesulfonate Drugs 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 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
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 229920002284 Cellulose triacetate Polymers 0.000 description 1
- NIPMJVLJVGQZRB-UHFFFAOYSA-N Cl[IH]Br Chemical compound Cl[IH]Br NIPMJVLJVGQZRB-UHFFFAOYSA-N 0.000 description 1
- KIWBPDUYBMNFTB-UHFFFAOYSA-N Ethyl hydrogen sulfate Chemical compound CCOS(O)(=O)=O KIWBPDUYBMNFTB-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical group [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 241000534944 Thia Species 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 1
- 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 1
- 239000000654 additive Substances 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-M benzenesulfonate Chemical compound [O-]S(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-M 0.000 description 1
- 229910021538 borax Inorganic materials 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
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- VUQUOGPMUUJORT-UHFFFAOYSA-N methyl 4-methylbenzenesulfonate Chemical compound COS(=O)(=O)C1=CC=C(C)C=C1 VUQUOGPMUUJORT-UHFFFAOYSA-N 0.000 description 1
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 230000008313 sensitization Effects 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
- 239000000126 substance Substances 0.000 description 1
Images
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
- 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
-
- 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
Definitions
- ABSTRACT A silver halide photographic emulsion containing a supersensitizing combination of at least one carbocyanine dye having a heterocyclic necleus comprising a benzothiazole or benzoselenazole nucleus, at least one of the heterocyclic nuclei having an acetylamino group at the 5-position thereof, and having a sensitized maximum portion within the range of from 600 to 660 nm, and at least one sensitizing dye of the following general formula (ll)' wherein R and R each represents a lower alkyl group; A represents a lower alkyl group or an aryl group; Z and Z each represents an atomic group necessary to complete a benzothiazole, benzoselenazole or B-naphthothiazole nucleus; X represents an anion; and m is 0 or 1, m being 0 when an intermolecular salt is formed.
- This invention relates to a spectrally sensitized silver halide photographic emulsion and more especially to a silver halide photographic emulsion which is supersensitized by the combined use of at least two sensitizing dyes resulting in a high red sensitivity.
- sensitizing dyes which are in supersensitization relation to each other and have a small inherent desensitization, Le, a less desensitization, in the wavelength region inherent to silver halide grains.
- the object of this invention is to provide a silver halide photographic emulsion having a panchromatically sensitized region, particularly a high red sensitivity within the spectrosensitized wavelength region of 640-685 nm and a small inherent desensitization by the combined use of two different types of sensitizing dyes.
- a panchromatically sensitized region is used generally for black and white photographic sensitive materials.
- the object of this invention has been accomplished by the combined use of a carbocyanine dye comprising heretocyclic nuclei selected from benzothiazole and benzoselenazole nuclei, at least one of the heterocyclic nuclei having an acetylamino group at the 5-position thereof, and having a sensitized maximum portion within the range of from 600 to 660 nm., preferably of the following general formula (I), and a sensitizing dye of the general formula (II) in a silver halide photographic emulsion:
- R l and R each represents a lower alkyl group, e.g., methyl, ethyl, 'y-sulfopropyl, 'y-sulfobutyl, 6-sulfobutyl, allyl etc.;
- A represents a lower alkyl group, e.g., methyl, ethyl etc.;
- 2 represents an atomic group necessary to complete a benzothiazole or benzoselenazole nucleus, which may be substituted by a halogen atom, e.g., chlorine, etc., a lower alkyl group, e.g., methyl, ethyl, etc.; an alkoxyl group, e.g., methoxy, ethoxy, etc.; or a phenyl group;
- Z represents a sulfur or selenium atom;
- X represents an anion, e.g., a chloride, bromide, io
- R and R each represents lower alkyl, e.g. methyl, ethyl, 'y-sulfopropyl, 'y-sulfobutyl, 8-sulfobutyl, B-hydroxyalkyl, B-carboxyalkyl, etc.;
- A represents lower alkyl, e.g. methyl, ethyl, etc., or an aryl group, e.g. phenyl;
- Z and Z each represents an atomic group necessary to complete a benzothiazole, benzoselenazole or B-naphthothiazole nucleus, which maybe sub-- stituted by a halogen, e.g.
- a lower alkyl group e.g. methyl, ethyl, etc.; alkoxy, e.g. m'ethoxy, ethoxy etc.; a hydroxyl group or a phenyl group;
- X represents an anion, e.g., a chloride, bromide. iodide, p-toluene sulfonate or benzenesulfonate ion, etc. and those used generally in the art;
- FIGS. 1-4 are spectograms illustrating the supersensitization effects of the combination of dyes according to the present invention.
- the combined use of the sensitizing dyes according to this invention provides a silver halide emulsion having a higher red sensitivity compared to the use of each sensitizing dye alone and, at the same time, a very small inherent desensitization.
- Another sensitizing dye for improving the .green sensitivity e.g., 2,2-cyanine, thia* 2 -cyani ne etc.
- another sensitizing dye for improving the .green sensitivity e.g., 2,2-cyanine, thia* 2 -cyani ne etc.
- those having other s jE ctral sensitizing wavelength regions e.g., 2,2-cyanine, thia* 2 -cyani ne etc.
- sensitizing dyes used in this invention are mentioned as follows, but the sensitizing dyes used in this invention are not to be restricted only to those examples.
- the carbocyanine dyes and sensitizing dyes of the general formula (II) which are used in this invention can be synthesized by a known method.
- a known method for example, with reference to US. Pat. No. 2,503,776 and German Pat. Nos. 929,080 and 1,072,765, those skilled in the art can readily synthesize them.
- the solvent is distilled off and treated with ethyl ether and then with acetone to yield coarse crystals of Dye C.
- the coarse crystals are recrystallized from a mixed solvent of chloroform/ methanol to yield 550 mg of Dye C having a meltingpoint above 310 C and a k of 559 nm.
- Other sensitizing dyes can be obtained by a similar method to the process as mentioned above.
- the sensitizing dyes of the general formula (I) are used, in general.
- tion is effective for the spectral sensitization of any silver halide photographic emulsions. And, it can sensitize sufiiciently an emulsion containing a hydrophilic colloid other than gelatin, for example, agar collodion, water soluble cellulose derivatives, polyvinyl alcohol and other synthetic or natural hydrophilic polymers.
- a mixed silver halide emulsion such as silver iodobromide, chloroiodobromide, and the like is suitable.
- sensitizing dyes For the preparation of spectrally sensitized photographic emulsions according to this invention, it is enough to add the sensitizing dyes to a photographic emulsion in a common manner. In practice, it is convenient to add the dyes as a solution thereof in a suitable solvent such as methanol, ethanol, cellosolve etc., to the emulsion.
- a suitable solvent such as methanol, ethanol, cellosolve etc.
- the photographic emulsion according to this invention may be treated by a known method for hyperand The spectral sensitizing process according to this invenother super-sensitization.
- additives ' which are generally used in the art of photographic EXAMPLES
- silver halide photographic emulsions containing a combination of the sensitizing dyes of this invention were also prepared.
- emulsions were coated onto a cellulose triacetate film base, dried, exposed through a red filter (transmitting rays of a wavelength longer than 580 nm) and a blue filter (transmitting rays of a wavelength of 400 490 nm and having a maximum transmission at,
- Amount of Amount of sensitizing Senfiilizing Sensitized myse s l added' mu EX erimental Dyg (10' mol/kg Dye (10 mol/kg wave length Relative red Inherent Referred to 1&6.
- Example No. Flo. emuLsi n No. emulsion) Emulsion (nm) sensitivity sensitivityv in drawings A 4 AgBr/l 656 12s 94 Fig.3(8).
- AgBr/l 648 I00 AgBr/l 648 I25 I87 AgBr/I 648 I40 87 AgBr/l 662 50 93 3 AgBr/l 662 I00 90 3 C 4 2 1 AgBr/I 654 94 C 4 2 ,535. 3!!! .9, 199, 94
- AgBr/l 666 10 90 AgBr/l 634 13 87 AgBr/l 634 26 87 4 1 AgBr/I 652 120 96 AgBr/I 660 135 96 AgBr/l 600 16 1 93 Fi .,2(41. AgBr/l 600 313 93 5 AgBr/l 632 60 85 Fig. 2(5).
- the addition of a single sensitizing dye according to this invention reduces inherent sensitivity together with an increase of red sensitivity as the amount of dye added is increased.
- the combined use of the sensitizing dyes provides a higher red sensitivity than in the single use of the corresponding sensitizing dye alone.
- the effect of the combination of said sensitizing dyes is not injured by the further addition of a green sensitizing l0 dye thereto, e.g. the combined use of green sensitizing dye (i) or (ii) with the combination of the sensitizing dyes according to this invention.
- the said green sensitizing dyes have the following chemical structures, but they are not restricted only to these sensitizing dyes.
- Dye ll wherein R and R each represents a lower alkyl group; A, represents a lower alkyl group or an aryl group; 2;, and Z each represents an atomic group necessary to complete a benzothiazole, benzoselenazole or B naph-. thothiazole nucleus; X, represents an anion; and m is Qorbmkei wh an szrmv ssql saltisf tmcd- 2.
- R and R each represents a lower alkyl group
- A represents a lower alkyl group
- z rep res ents an atomic group necessary to complete a benzothiazole or benzoselenazole nucleus
- Z represents a sulfur or a selemum atom
- X 1- represents an anion, and n is 0 or 1
- the silver halide photographic emulsion of claim 1 further containing at least one green sensitizing cyanine dye selected from the group consisting of 2,2- yan1ne and thia-2 -c yanine 4.
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- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Physics & Mathematics (AREA)
- Organic Chemistry (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
- Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
Abstract
A silver halide photographic emulsion containing a supersensitizing combination of at least one carbocyanine dye having a heterocyclic necleus comprising a benzothiazole or benzoselenazole nucleus, at least one of the heterocyclic nuclei having an acetylamino group at the 5-position thereof, and having a sensitized maximum portion within the range of from 600 to 660 nm, and at least one sensitizing dye of the following general formula (II)
wherein R3 and R4 each represents a lower alkyl group; A2 represents a lower alkyl group or an aryl group; Z3 and Z4 each represents an atomic group necessary to complete a benzothiazole, benzoselenazole or Beta -naphthothiazole nucleus; X2 represents an anion; and m is 0 or 1, m being 0 when an intermolecular salt is formed.
wherein R3 and R4 each represents a lower alkyl group; A2 represents a lower alkyl group or an aryl group; Z3 and Z4 each represents an atomic group necessary to complete a benzothiazole, benzoselenazole or Beta -naphthothiazole nucleus; X2 represents an anion; and m is 0 or 1, m being 0 when an intermolecular salt is formed.
Description
United States Patent [1 1 Shiba et al.
[ 1 Nov. 6, 1973 SPECTRALLY SENSITIZED SILVER HALIDE PHOTOGRAPHIC EMULSION [75] Inventors: Keisuke Shiba; l-laruo Takei; Akira Sato; Tadashi lkeda, all of Kanagawa, Japan [73] Assignee: Fuji Photo Film Co., Ltd.,
Kanagawa, Japan [22] Filed: Sept. 24, 1971 [2]] Appl. No.: 183,492
[30] Foreign Application Priority Data Primary ExaminerJ. Travis Brown Attorney-Richard C. Sughrue et al.
[57] ABSTRACT A silver halide photographic emulsion containing a supersensitizing combination of at least one carbocyanine dye having a heterocyclic necleus comprising a benzothiazole or benzoselenazole nucleus, at least one of the heterocyclic nuclei having an acetylamino group at the 5-position thereof, and having a sensitized maximum portion within the range of from 600 to 660 nm, and at least one sensitizing dye of the following general formula (ll)' wherein R and R each represents a lower alkyl group; A represents a lower alkyl group or an aryl group; Z and Z each represents an atomic group necessary to complete a benzothiazole, benzoselenazole or B-naphthothiazole nucleus; X represents an anion; and m is 0 or 1, m being 0 when an intermolecular salt is formed.
5 Claims, 4 Drawing Figures PMENIEmwv 6 ma 3,770,4 9
2. Description of the Prior art Photographic light sensitive materials which are used conventionallyare required to have spectral sensitivity distributions corresponding to the photographing purpose.
In the manufacture of the sensitive material, it is an important technique to develop the combination of sensitizing dyes which are in supersensitization relation to each other and have a small inherent desensitization, Le, a less desensitization, in the wavelength region inherent to silver halide grains.
The object of this invention is to provide a silver halide photographic emulsion having a panchromatically sensitized region, particularly a high red sensitivity within the spectrosensitized wavelength region of 640-685 nm and a small inherent desensitization by the combined use of two different types of sensitizing dyes.
A panchromatically sensitized region is used generally for black and white photographic sensitive materials.
SUMMARY OF THE INVENTION The object of this invention has been accomplished by the combined use of a carbocyanine dye comprising heretocyclic nuclei selected from benzothiazole and benzoselenazole nuclei, at least one of the heterocyclic nuclei having an acetylamino group at the 5-position thereof, and having a sensitized maximum portion within the range of from 600 to 660 nm., preferably of the following general formula (I), and a sensitizing dye of the general formula (II) in a silver halide photographic emulsion:
wherein R l and R, each represents a lower alkyl group, e.g., methyl, ethyl, 'y-sulfopropyl, 'y-sulfobutyl, 6-sulfobutyl, allyl etc.; A represents a lower alkyl group, e.g., methyl, ethyl etc.; 2 represents an atomic group necessary to complete a benzothiazole or benzoselenazole nucleus, which may be substituted by a halogen atom, e.g., chlorine, etc., a lower alkyl group, e.g., methyl, ethyl, etc.; an alkoxyl group, e.g., methoxy, ethoxy, etc.; or a phenyl group; Z represents a sulfur or selenium atom; X; represents an anion, e.g., a chloride, bromide, iodide, perchlorate, p-toluene sulfonate, benzene sulfonate, thiocyanate, methyl sulfate or ethyl sulfate ion, etc.; n is 0 or I and n 0 for the intermolecular salt;
wherein R and R each represents lower alkyl, e.g. methyl, ethyl, 'y-sulfopropyl, 'y-sulfobutyl, 8-sulfobutyl, B-hydroxyalkyl, B-carboxyalkyl, etc.; A represents lower alkyl, e.g. methyl, ethyl, etc., or an aryl group, e.g. phenyl; Z and Z each represents an atomic group necessary to complete a benzothiazole, benzoselenazole or B-naphthothiazole nucleus, which maybe sub-- stituted by a halogen, e.g. chlorine or bromine, etc., a lower alkyl group, e.g. methyl, ethyl, etc.; alkoxy, e.g. m'ethoxy, ethoxy etc.; a hydroxyl group or a phenyl group; X represents an anion, e.g., a chloride, bromide. iodide, p-toluene sulfonate or benzenesulfonate ion, etc. and those used generally in the art; m is 0 or 1 and m=0 for the intermolecular salt.
BRIEF DESCRIPTION OF THE DRAWINGS FIGS. 1-4 are spectograms illustrating the supersensitization effects of the combination of dyes according to the present invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS Many cyanine dyes of the general formula (II) have a sharp sensitized maximum portion and a high red sensitivity.
The combined use of the sensitizing dyes according to this invention provides a silver halide emulsion having a higher red sensitivity compared to the use of each sensitizing dye alone and, at the same time, a very small inherent desensitization.
It is also possible to use at the same time another sensitizing dye for improving the .green sensitivity (e.g., 2,2-cyanine, thia* 2 -cyani ne etc.) or those having other s jE ctral sensitizing wavelength regions.
The embodiments of sensitizing dyes used in this invention are mentioned as follows, but the sensitizing dyes used in this invention are not to be restricted only to those examples.
The carbocyanine dyes and sensitizing dyes of the general formula (II) which are used in this invention can be synthesized by a known method. For example, with reference to US. Pat. No. 2,503,776 and German Pat. Nos. 929,080 and 1,072,765, those skilled in the art can readily synthesize them. I
The synthesis of a typical sensitiiin'g' dye of the general formula (I) is described as follows:
Synthesis Dye C One grom of 5-chlor0-3-(y-sulf0propyl)-2- thioFr-opionyl-methylenebenzothiazoline is reacted with 1 g of methyl p-toluene sulfonate at 65 C for 2 hrs and then treated with ethyl ether to yield a methyl thiocarbinol compound. 1.1 g of S-acetylamino- 3-ethyl-2-methylbenzothiazolium p-toluene sulfonate salt are added thereto, and dissolved in ml of ethanol, 2 ml of further triethylamine are added and the whole is heated for 3 hrs under reflux. After the completion of reaction, the solvent is distilled off and treated with ethyl ether and then with acetone to yield coarse crystals of Dye C. The coarse crystals are recrystallized from a mixed solvent of chloroform/ methanol to yield 550 mg of Dye C having a meltingpoint above 310 C and a k of 559 nm. Other sensitizing dyes can be obtained by a similar method to the process as mentioned above.
The physical values of typical embodiments of said carbocyanine dyes according to this invention are as follows:
M1. (C) A I A 300 566 l B 300 554 l C 300 559 l D 276 565 l E 300 560.5 I F 282 562 l G 296.5 562 l H 231 567 l l 300 558.5
The sensitizing dyes of the general formula (I) are used, in general.
tion is effective for the spectral sensitization of any silver halide photographic emulsions. And, it can sensitize sufiiciently an emulsion containing a hydrophilic colloid other than gelatin, for example, agar collodion, water soluble cellulose derivatives, polyvinyl alcohol and other synthetic or natural hydrophilic polymers. For the photographic emulsion used in this invention, a mixed silver halide emulsion such as silver iodobromide, chloroiodobromide, and the like is suitable.
For the preparation of spectrally sensitized photographic emulsions according to this invention, it is enough to add the sensitizing dyes to a photographic emulsion in a common manner. In practice, it is convenient to add the dyes as a solution thereof in a suitable solvent such as methanol, ethanol, cellosolve etc., to the emulsion. The mol ratio of the sensitizing dyes according to this invention to be contained in the emulsion may be varied within a wide range of from 9:1 to 1:9 corresponding to the effect desired.
The photographic emulsion according to this invention may be treated by a known method for hyperand The spectral sensitizing process according to this invenother super-sensitization. In the preparation of photographic emulsions according to this invention, additives 'which are generally used in the art of photographic EXAMPLES Sensitizing dyes used in this invention as mentioned above were added individually to a silver iodobromide emulsion (Agl AgBr =7:93 in mol percent to prepare silver halide photographic emulsions. On the other hand, silver halide photographic emulsions containing a combination of the sensitizing dyes of this invention were also prepared.
These emulsions were coated onto a cellulose triacetate film base, dried, exposed through a red filter (transmitting rays of a wavelength longer than 580 nm) and a blue filter (transmitting rays of a wavelength of 400 490 nm and having a maximum transmission at,
450 nm) to a daylight of 64 Luxes (corresponding to 5,400 K) and developed.
As the developer, one having the following composition was used.
TABLE 1 Metol 2 g sodium sulfite 100 g Hydroquinone 5 g Borax 2 g Water to make 1000 ml.
The relative red .sensitivity and inherent desensitization to the original emulsion for the single use of the sensiziting dyes as well as in the combined use of said sensitizing dyes according to this invention are shown in the following Table 2.
.TABkEZ.
Amount of Amount of sensitizing Senfiilizing Sensitized myse s l added' mu EX erimental Dyg (10' mol/kg Dye (10 mol/kg wave length Relative red Inherent Referred to 1&6. Example No. Flo. emuLsi n No. emulsion) Emulsion (nm) sensitivity sensitivityv in drawings A 4 AgBr/l 656 12s 94 Fig.3(8). A 8 AgBr/l 656 I30 85 AgBr/l 648 9O AgBr/l 650 78 90 AgBr/l 654 l 00 90 l AgBr/l 660 I20 AgBr/l 656 170 94 AgBr/l 656 l85 94 4 AgBr/l 656 I85 94 AgBr/I 600 5 87 Fig. 347 2 AgBr/l 600 6 80 AgBr/l 654 135 90 Fig. 3(9).
AgBr/l 648 I00 AgBr/l 648 I25 I87 AgBr/I 648 I40 87 AgBr/l 662 50 93 3 AgBr/l 662 I00 90 3 C 4 2 1 AgBr/I 654 94 C 4 2 ,535. 3!!! .9, 199, 94
TABLE 2. -Continued Amount of Amount of sensitizing sensitizing Sensitized dye added dye added maximum Experimental Dye mol/kg Dye (10 mol/kg wave length Relative red Inherent Referred to No. emulsion) Emulsion (nm) sensitivity sensitivity in drawings Example No. No. emulsion) No.
. AgBr/l 666 10 90 AgBr/l 634 13 87 AgBr/l 634 26 87 4 1 AgBr/I 652 120 96 AgBr/I 660 135 96 AgBr/l 600 16 1 93 Fi .,2(41. AgBr/l 600 313 93 5 AgBr/l 632 60 85 Fig. 2(5).
AgBr/l 632 110 93 Fig. 2(6).
AgBr/l 640 96 AgBr/l 640 36 90 AgBr/I 640 36 s0 6 AgBr/l 660 1 I0 62 AgBr/l 648 145 90 AgBr/l 648 145 90 A ar/1 642 145 90 AgBr/l 648 36 94 7 AgBr/l 650 62 94 AgBr/l 650 100 94 AgBr/l 648 170 94 AgBr/l 650 I80 94 AgBr/l 600 92 AgBr/l 630 90 11 AgBr/l 630 115 AgBr/l 650 175 94 AgBr/I 650 I80 94 AgBr/l 630 100 Fig. 1 1). AgBr/l 640 150 so AgBr/l 685 73 96 Fig. 1(2). 9 AgBr/l 686 146 96 AgBr/l 686 1511 117 9 11 4 0.5 AgBr/l 680 120 96 Fig. 1(3) H 4 7 1 AgBr/l 682 170 96 AgBr/l 665 50 AgBr/I 665 100 10 AgBr/l 665 95 AgBr/l 665 86 AgBr/l 660 l 96 AgBr/l 646 85 95 Fig. 41101. AgBr/I 664 105 95 11 2 AgBr/l 638 75 110 4 AgBr/l 640 85 70 Fig. 411111 8 AgBr/l 640 85 60 4 B 642 130 100 Fi .4 12 4 451 94. .1
1 AgBr/l 680 35 90 12 2 AgBr/l 680 70 11s 4 AgBr/l 680 120 70 1 AgB'r/I 670 150 90 2 AgBr/l 676 170 90 13 4 AgBr/l 640 I80 106 14 1 AgBr/I 652 195 100 2 AgBr/l 650 50 94 4 AgBr/l 654 90 92 15 6 AgBr/l 658 .130 92 2 AgBr/l 652 .94 4 AgBr/l 658 175 94 2 AgBr/l 1 600 I 20 92 4 AgBr/l 626 48 90 8 AgBr/I 626 75 x5 16 c 4 12 2 AgBr/l 646 150 94 16 c 4 12 4 AgBr/l 646 165 92 The red sensitivity is shown as a relative sensitivity tivity is shown as a relative sensitivity assuming that the assuming that the red sensitivity of sensitizing dye l,exsensitivity of the original emulsion which is exposed posed through a red filter (a filter transmitting rays of 65 through a blue filter (a filter transmitting rays of from a wavelength longer than 580 nm) in an amount of 4 400 to 490 nm and having a maximum transmission at X 10- mol/kg emulsion is 100; and the inherent sensi- 450 nm) is 100.
As is obvious from Table 2, the addition of a single sensitizing dye according to this invention reduces inherent sensitivity together with an increase of red sensitivity as the amount of dye added is increased. However, it is seen that the combined use of the sensitizing dyes provides a higher red sensitivity than in the single use of the corresponding sensitizing dye alone. As is also obvious from examples 13 and l4 in Table 2, the effect of the combination of said sensitizing dyes is not injured by the further addition of a green sensitizing l0 dye thereto, e.g. the combined use of green sensitizing dye (i) or (ii) with the combination of the sensitizing dyes according to this invention.
The said green sensitizing dyes have the following chemical structures, but they are not restricted only to these sensitizing dyes.
CH N
Dye ll wherein R and R each represents a lower alkyl group; A, represents a lower alkyl group or an aryl group; 2;, and Z each represents an atomic group necessary to complete a benzothiazole, benzoselenazole or B naph-. thothiazole nucleus; X, represents an anion; and m is Qorbmkei wh an szrmv ssql saltisf tmcd- 2. The silver halide photographic emulsion of claim 1 wherein the carbocyanine dye is represented by the following generalformula (I) Zi -Zi A! f -cu=l:-cn= 3 NHCOCH;
I N R H R I (lit) n wherein R and R, each represents a lower alkyl group;
A represents a lower alkyl group; z rep res ents an atomic group necessary to complete a benzothiazole or benzoselenazole nucleus; Z represents a sulfur or a selemum atom; X 1- represents an anion, and n is 0 or 1,
n, b e i r g 0 when an intermolecular salt is formed.
3. The silver halide photographic emulsion of claim 1 further containing at least one green sensitizing cyanine dye selected from the group consisting of 2,2- yan1ne and thia-2 -c yanine 4. The silver halide photographic emulsion of claim 1 wherein said carbocyanine dye is selected from the group consisting of Dye 11 s s can -on=h-c1r= emo zmcocm I|-I N and Dye 1.
Dyu 1 s s S C s c 11 -u o01[= CH=JJCH= NIIC0CH 5 N N N N ((inmsoa (L211, i i (HmSoa y S. The silver halide photographic emulsion of claim 2)a aH z s)s 1, wherein said sensitizing dye is selected from the D 8 group consisting of ye 03 S (Hah s zh l Dye 10.
Claims (4)
- 2. The silver halide photographic emulsion of claim 1 wherein the carbocyanine dye is represented by the following general formula (I) :
- 3. The silver halide photographic emulsion of claim 1 further containing at least one green sensitizing cyanine dye selected from the group consisting of 2,2''-cyanine and thia-2''-cyanine.
- 4. The silver halide photographic emulsion of claim 1 wherein said carbocyanine dye is selected from the group consisting of
- 5. The silver halide photographic emulsion of claim 1, wherein said sensitizing dye is selected from the group consisting of
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP45083653A JPS4842498B1 (en) | 1970-09-24 | 1970-09-24 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3770449A true US3770449A (en) | 1973-11-06 |
Family
ID=13808395
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US00183492A Expired - Lifetime US3770449A (en) | 1970-09-24 | 1971-09-24 | Spectrally sensitized silver halide photographic emulsion |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US3770449A (en) |
| JP (1) | JPS4842498B1 (en) |
| DE (1) | DE2147893C3 (en) |
| FR (1) | FR2108455A5 (en) |
| GB (1) | GB1355853A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3918979A (en) * | 1970-09-21 | 1975-11-11 | Fuji Photo Film Co Ltd | Spectrally sensitized silver halide photographic emulsion |
| US5316904A (en) * | 1992-11-19 | 1994-05-31 | Eastman Kodak Company | Amide substituted dye compounds and silver halide photographic elements containing such dyes |
| US5354651A (en) * | 1992-11-19 | 1994-10-11 | Eastman Kodak Company | Hydroxyarylacyl dye compounds and silver halide photographic elements containing such dyes |
| US5492802A (en) * | 1992-11-19 | 1996-02-20 | Eastman Kodak Company | Dye compounds and photographic elements containing such dyes |
| 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 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2066966A (en) * | 1931-02-07 | 1937-01-05 | Agfa Ansco Corp | Manufacture of light sensitive materials |
| US2066967A (en) * | 1931-02-07 | 1937-01-05 | Agfa Ansco Corp | Dyes of the cyanine series |
| US3679428A (en) * | 1969-07-23 | 1972-07-25 | Fuji Photo Film Co Ltd | Spectrally sensitized photographic emulsions |
-
1970
- 1970-09-24 JP JP45083653A patent/JPS4842498B1/ja active Pending
-
1971
- 1971-09-23 GB GB4452071A patent/GB1355853A/en not_active Expired
- 1971-09-23 FR FR7134240A patent/FR2108455A5/fr not_active Expired
- 1971-09-24 DE DE2147893A patent/DE2147893C3/en not_active Expired
- 1971-09-24 US US00183492A patent/US3770449A/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2066966A (en) * | 1931-02-07 | 1937-01-05 | Agfa Ansco Corp | Manufacture of light sensitive materials |
| US2066967A (en) * | 1931-02-07 | 1937-01-05 | Agfa Ansco Corp | Dyes of the cyanine series |
| US3679428A (en) * | 1969-07-23 | 1972-07-25 | Fuji Photo Film Co Ltd | Spectrally sensitized photographic emulsions |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3918979A (en) * | 1970-09-21 | 1975-11-11 | Fuji Photo Film Co Ltd | Spectrally sensitized silver halide photographic emulsion |
| US5316904A (en) * | 1992-11-19 | 1994-05-31 | Eastman Kodak Company | Amide substituted dye compounds and silver halide photographic elements containing such dyes |
| US5354651A (en) * | 1992-11-19 | 1994-10-11 | Eastman Kodak Company | Hydroxyarylacyl dye compounds and silver halide photographic elements containing such dyes |
| US5492802A (en) * | 1992-11-19 | 1996-02-20 | Eastman Kodak Company | Dye compounds and photographic elements containing such dyes |
| 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 |
|---|---|
| JPS4842498B1 (en) | 1973-12-13 |
| DE2147893B2 (en) | 1974-05-16 |
| DE2147893A1 (en) | 1972-05-25 |
| FR2108455A5 (en) | 1972-05-19 |
| DE2147893C3 (en) | 1974-12-12 |
| GB1355853A (en) | 1974-06-05 |
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