US3667960A - Spectrally supersensitized silver halide photographic emulsion - Google Patents
Spectrally supersensitized silver halide photographic emulsion Download PDFInfo
- Publication number
- US3667960A US3667960A US23122A US2312270A US3667960A US 3667960 A US3667960 A US 3667960A US 23122 A US23122 A US 23122A US 2312270 A US2312270 A US 2312270A US 3667960 A US3667960 A US 3667960A
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- silver halide
- formula
- dye
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- halide photographic
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- Expired - Lifetime
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- -1 silver halide Chemical class 0.000 title abstract description 52
- 239000000839 emulsion Substances 0.000 title abstract description 38
- 229910052709 silver Inorganic materials 0.000 title abstract description 35
- 239000004332 silver Substances 0.000 title abstract description 35
- 239000000975 dye Substances 0.000 abstract description 102
- 230000001235 sensitizing effect Effects 0.000 abstract description 66
- 230000003595 spectral effect Effects 0.000 abstract description 15
- AMTXUWGBSGZXCJ-UHFFFAOYSA-N benzo[e][1,3]benzoselenazole Chemical compound C1=CC=C2C(N=C[se]3)=C3C=CC2=C1 AMTXUWGBSGZXCJ-UHFFFAOYSA-N 0.000 abstract description 7
- WMUIZUWOEIQJEH-UHFFFAOYSA-N benzo[e][1,3]benzoxazole Chemical compound C1=CC=C2C(N=CO3)=C3C=CC2=C1 WMUIZUWOEIQJEH-UHFFFAOYSA-N 0.000 abstract description 7
- 230000035945 sensitivity Effects 0.000 description 27
- 125000000217 alkyl group Chemical group 0.000 description 21
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 206010070834 Sensitisation Diseases 0.000 description 9
- 230000008313 sensitization Effects 0.000 description 9
- AIGNCQCMONAWOL-UHFFFAOYSA-N 1,3-benzoselenazole Chemical compound C1=CC=C2[se]C=NC2=C1 AIGNCQCMONAWOL-UHFFFAOYSA-N 0.000 description 8
- 125000003545 alkoxy group Chemical group 0.000 description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 7
- 125000003118 aryl group Chemical group 0.000 description 6
- 125000005843 halogen group Chemical group 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- KXNQKOAQSGJCQU-UHFFFAOYSA-N benzo[e][1,3]benzothiazole Chemical compound C1=CC=C2C(N=CS3)=C3C=CC2=C1 KXNQKOAQSGJCQU-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 150000001450 anions Chemical group 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 125000000623 heterocyclic group Chemical group 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 235000010724 Wisteria floribunda Nutrition 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KIWBPDUYBMNFTB-UHFFFAOYSA-N Ethyl hydrogen sulfate Chemical compound CCOS(O)(=O)=O KIWBPDUYBMNFTB-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 241000981595 Zoysia japonica Species 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-M benzenesulfonate Chemical compound [O-]S(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-M 0.000 description 2
- 229940077388 benzenesulfonate Drugs 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000004438 eyesight Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 239000004848 polyfunctional curative Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 125000000547 substituted alkyl group Chemical group 0.000 description 2
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 2
- 125000001544 thienyl group Chemical group 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
- QGKMIGUHVLGJBR-UHFFFAOYSA-M (4z)-1-(3-methylbutyl)-4-[[1-(3-methylbutyl)quinolin-1-ium-4-yl]methylidene]quinoline;iodide Chemical compound [I-].C12=CC=CC=C2N(CCC(C)C)C=CC1=CC1=CC=[N+](CCC(C)C)C2=CC=CC=C12 QGKMIGUHVLGJBR-UHFFFAOYSA-M 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- SJOOOZPMQAWAOP-UHFFFAOYSA-N [Ag].BrCl Chemical compound [Ag].BrCl SJOOOZPMQAWAOP-UHFFFAOYSA-N 0.000 description 1
- XCFIVNQHHFZRNR-UHFFFAOYSA-N [Ag].Cl[IH]Br Chemical compound [Ag].Cl[IH]Br XCFIVNQHHFZRNR-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000013019 agitation Methods 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
- 239000011230 binding agent Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000000586 desensitisation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- ORTFAQDWJHRMNX-UHFFFAOYSA-N hydroxidooxidocarbon(.) Chemical compound O[C]=O ORTFAQDWJHRMNX-UHFFFAOYSA-N 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920006289 polycarbonate film Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 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
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004094 surface-active agent 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
Definitions
- the spectral sensitizing action is affected by the chemical structure of the sensitizing dye and the properties of the silver halide emulsion used, for example, the hydrogen ion concentration, silver ion concentration, crystal habit of the silver halide fine crystals, grain diameter and halogen composition. It is also markedly afi'ected by the particular fog inhibitor, stabilizer, sensitizer, hardener, binder, precipitant, plasticizer, color former and photographic dye employed in the emulsion. Many of such materials act so as to weaken the spectral sensitization obtained.
- the spectral sensitization obtained with a given sensitizing dye is synergistically strengthened by using it in combination with another selected sensitizing dye or organic compound preferably an aromatic organic compound.
- Such action is known as supersensitization.
- sensitizing dyes used for super-panchromatic spectral sensitization have the ability to absorb long wave length light and generally result in a large desensitizing action.
- the spectral sensitization efiiciency obtained by using such dyes is therefore often low. This is a disadvantage in the obtaining of a silver halide photographic emulsion having high spectral sensitivity.
- the above object can be accomplished by employing, in a silver halide photographic emulsion, a combination of at least (a) one of a sensitizing dye represented by the formula in which R is hydrogen or a lower alkyl group, such as a methyl or ethyl group; R and R are each a lower alkyl group, such as methyl, ethyl and propyl groups, an aryl group or a substituted lower alkyl group, such as Y- lower alkyl, wherein Y is hydroxy, lower alkoxy, carboxy, sulto, sulfo-lower alkoxy (as examples of such groups may be mentioned 2 hydroxyethyl, 2 methoxyethyl, carboxymethyl, 3 carboxypropyl, 4 carboxybutyl, 3- sulfobutyl, 3 sulfopropyl, 4 sulfobutyl, 2 (3 sulfopropoxy)ethyl, and 2-hydroxy propy
- the essential feature of the sensitizing dye represented by Formula I is that at least one of the two heterocyclic nuclei is a heterocyclic nucleus selected from the group consisting of naphthothiazole, naphthoselenazole and naphthoxazole nuclei.
- This sensitizing dye is capable of providing spectral sensitivity at sulficiently long wave lengths.
- the sensitivity obtained using either dye alone is not always sufiicient.
- both of R and R in Formula I are alkyl or aryl groups, in particular, desensitization is severe and contrast is sharply reduced.
- R of Formula I is an aryl group, such as phenyl or substituted phenyl, thenyl, thienyl, substituted thienyl or furyl.
- the use of the two dyes in combination provides marked sensitization in the red range as well as high contrast. If both R and R of Formula I are unsubstituted alkyl or aryl groups, there is also a tendency towards supersensitization, but less than that of the present invention.
- R and R is a substituted alkyl group
- a hydrophilic substituent such as hydroxyl, carboxyl or sulfo
- the supersensitizin-g action is obtained to a remarkable degree.
- an alkyl group substituted by a sulfo group is desirable.
- the well-known dyes belonging to the group represented by Formula I such as those disclosed in British Patent 1,137,084 and US.
- Patent 3,177,210 provide a marked supersensitizing action when incorporated into a silver halide photographic emulsion in combination with the sensitizing dye represented by Formula II .
- Wheu R of Formula I is an aryl group, there is a slight tendency towards supersensitization but not nearly to the extent obtained in the case of employing those compounds represented by Formula II of the present invention.
- a feature of the chemical structure of the sensitizing dye represented by Formula II is the presence of at least one Z-quinoline nucleus. Another feature consists in that Z, represents an atomic group necessary to complete either a Z-quinoline nucleus or an unsubstituted or lower alkyl group-, phenyl groupor halogen atom-substituted benzothiazole nucleus or benzoselenazole nucleus. Not only does the sensitizing dye represented by Formula II provide high red sensitivity through its remarkable supersensitization to the sensitizing dye represented by Formula I, but, also, sensitivity in the green region of the former is itself raised.
- the green sensitivity is lowered to some extent when used in combination with the sensitizing dye of Formula I.
- This is an undesirable tendency with regard to attaining the object of the present invention.
- Some sensitizing benzimidazolocarbocyanine and oxacarbocyanine dyes also have a similar tendency when used in combination with the sensitizing dyes of Formula I. That is to say, red sensitivity is increased by the combined use over that obtained by using the dye of Formula I alone, but green sensitivity is somewhat lowered by the use of the combination.
- the important characteristic of the present invention is to obtain high sensitivity and contrast, not only in the red range but also the green range by using, in combination, at least one of the sensitizing dyes represented by Formula I and at least one of the sensitizing dyes represented by Formula II.
- the sensitizing dyes used in the present invention may be dissolved in water or a water-soluble organic solvent such as methanol, ethanol, acetone, methyl Cellosolve or pyridine and added to a silver halide emulsion in admixture or individually. Ultrasonic wave agitation or stirring may be applied in the solubilization of the sensitizing dyes.
- the method of addition, amounts added and order of addition may be varied as desired. The amounts added may range preferably from 1X10 mol to 5 X 10" mol per 1 mol of silver halide, the ratio of the sensitizing dye represented by Formula II to that of Formula I being :1 to 1:10, in particular, 10:1 to 1:2.
- Illustrative of the conventional silver halide emulsions which may be used in the present invention are silver iodobro'mide, silver bromide, silver chlorobromide, silver chloride and silver chloroiodobromide emulsions and the like.
- To these emulsions may be applied conventional chemical sensitization as well as the usual additives such as fog inhibitors, stabilizers, sensitizers, surfactants, hardeners, plasticizers and photographic dyes and the like.
- the emulsions may be coated onto any suitable support, such as a cellulose derivative film, polyethylene terephthalate film, polycarbonate film, plastic film, baryta paper, resin coated paper, synthetic paper, resin laminated paper, glass sheets and the like.
- sensitizing dyes which may be used in the present invention are set forth below Without intending to limit the invention to those materials specifi cally exemplified. Other such dyes which would be suitable for use in accordance with the present invention will readily occur to those skilled in this art.
- Sensitizing dyes represented by general formula I Sensitizing dye for comparison sensitizing dyes represented by general formula II Sensitizing dyes for comparison
- the sensitizing dyes represented by Formulas I and II can readily be synthesized by well-known methods, for example, as disclosed in US. Pat. No. 2,504,776, British Pat. No. 742,112, German Pat. No. 1,072,765 and Japanese patent publication Nos. 23,467/65, 1,412/65, 27,- 166/ 67 and 27,167/ 67.
- the sensitizing dyes represented by Formulas I and II were respectively dissolved in methanol in given concentrations. Certain amounts of the sensitizing dye solutions as shown in Tables 1 and 2 were respectively dissolved in methanol in given concentrations. Certain amounts of the sensitizing dye solutions as shown in Tables 1 and 2 were respectively taken in test tubes, added to the emulsion, mixed and stirred. After 10 minutes, 7 ml. of each emulsion was taken, coated onto a glass sheet of cabinet size, set and dried to provide a test sample.
- the resulting sample was cut into two pieces, one of which was then subjected to light wedge exposure through a yellow filter (K-12 (trademark), made by Fuji Photo Film Co.) and a red filter (K7 (trademark)) using an actinometer, the color temperature of which had been converted into 5400 K. by applying a Davis-Gibson converting filter to a light source of color temperature 2666 K., and another of which was subjected to light wedge exposure for ,6 second using as a light source a monochromatic light near the maximum absorption Wave length in the green range obtained by the use of the sensitized dye represented by the general Formula II (mainly corresponding to the I -hand).
- the maximum absorption wave length (A m used is shown in the table.
- the exposed sample was developed at 20 C. for 10 minutes with a developer having the following composition, passed through a stopping solution and fixing solution and washed with water to obtain a strip, the density of which was measured by the use of an S-type densitometer made by Fuji Photo Film Co.
- the yellow filter sensitivity S red filter sensitivity (S and sensitivity to a Composition of the developer employed:
- the relative sensitivity in Table l is a value determined by taking the sensitivity of S S and S, to be 100 in the case of adding 20 m1. of the dye (I A) in No. 1.
- the experiment as shown in Table 2 was carried out in order to further clarify the characteristics of the sensitizing dyes used in the present invention.
- the "relative sensitivity in Table 2 is determined by setting of for a value S S and S in the case of adding 20 ml. of the dye (IF) in No. 1 of Table 2.
- the non-exposed sample was subjected to light wedge exposure using a reflection type refractive lattice spectrograph (GR-2 (trademark), made by Nar-umi Co.) and then to development in the same manner as above to obtain a wedge spectrogram.
- GR-2 reflection type refractive lattice spectrograph
- Curve 1 of FIG. 1 is a spectrogram obtained by adding 20 ml. of the sensitizing dye (IF) in Table 2
- Curve 2 is that obtained by adding 40 ml. of the sensitizing dye (HA)
- Curve 3 is that obtained by using 20 ml. of the dye (IF) and 40 ml. of the dye (IIA) in combination.
- Curve 1 of FIG. 2 is a spectrogram obtained by using 10 ml. of the sensitizing dye (A) for comparison
- Curve 2 is that obtained by using 40 ml. of the dye (HA)
- Curve 3 is that obtained by using 10 ml. of the dye (A) and 40 ml. of the dye (IIA) in combination.
- Curves 1- 2 and 3 of FIG. 3 are spectrograms obtained by using 20 ml. of the dye (IF), 20 ml. of the sensitizing dye (C) for comparison and 20 ml. of the dye (C) and 20 ml. of the dye (IF) in combination, respectively and Curves 1, 2 and 3 of FIG. 3 are spectrograms obtained by using 20 ml. of the dye (IF), 40 ml. of the dye (B) and 20 ml. of the dye (IF) and 40 ml. of the dye (B) in combination, respectively. It can be readily seen that, in the case of FIG.
- the sensitivity obtained by using the dyes (IF) and (HA) in combination is supersensitization over the entire sensitive wave length region as compared with that obtained by using the dye (IF) 01' (HA) along. Similar results may be observed with regard to the other figures.
- a silver halide photographic emulsion containing a supersensitizing combination comprising at least one sensitizing dye represented by the formula:
- R represents a member selected from the group consisting of an alkyl group of from 1 to 4 carbon atoms and a hydrogen atom;
- R and R each represent a member selected from the group consisting of a lower alkyl group and a substituted lower alkyl group having at least one substituent selected from the group consisting of a sulfo radical and a carboxy radical, at least one of R and R being a substituted lower alkyl group;
- Z represents an atomic group necessary to complete a nucleus selected from the group consisting of a naphthothiazole, a naphthoselenazole and a naphthoxazole;
- Z represents an atomic group necessary to complete a nucleus selected from the group consisting of a naphthothiazole, a benzothiazole, a naphthoselenazole, a benzoselenazole, a naphthoxazole,
- X represents an acid anion group
- n is an integer of 1 or 2, the dye being an intramolecular salt when n is 1, and at least one sensitizing dye of the formula (II) wherein R and R each represent a member selected from the group consisting of an alkyl group and a substituted lower alkyl group having at least one substituent selected from the group consisting of hydroxy, lower alkoxy, carboxy, sulfo, and sulfo-lower alkoxy; Z represents an atomic group necessary to complete a 2-quinoline nucleus, which may be further substituted with a member selected from the group consisting of a lower alkyl group, an alkoxy group, a hydroxyl group, and a halogen atom; Z representing an atomic group necessary to complete a nucleus selected from the group consisting of a Z-quinoline nucleus, a benzothiazole nucleus, which may be further substituted with a member selected from the group consist
- a silver halide photographic emulsion as claimed in claim 1, where a sensitizing dye of formula and a sensitizing dye of formula se ⁇ i, CH C ⁇ N OH:
- a photographic light-sensitive element comprising a support having thereon at least one layer containing a silver halide photographic emulsion as recited in claim 1.
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- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Physics & Mathematics (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
- Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2332069 | 1969-03-27 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3667960A true US3667960A (en) | 1972-06-06 |
Family
ID=12107278
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US23122A Expired - Lifetime US3667960A (en) | 1969-03-27 | 1970-03-27 | Spectrally supersensitized silver halide photographic emulsion |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US3667960A (de) |
| BE (1) | BE748021A (de) |
| DE (1) | DE2014896A1 (de) |
| FR (1) | FR2037271B1 (de) |
| GB (1) | GB1307904A (de) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3769024A (en) * | 1970-07-16 | 1973-10-30 | Konishiroku Photo Ind | Light-sensitive silver halide photographic material with sensitizing dye combination |
| US3808008A (en) * | 1970-09-10 | 1974-04-30 | Fuji Photo Film Co Ltd | Spectrally sensitized silver halide photographic emulsion |
| US3953215A (en) * | 1973-07-16 | 1976-04-27 | Fuji Photo Film Co., Ltd. | Silver halide photographic emulsions |
| US3955979A (en) * | 1970-10-16 | 1976-05-11 | Fuji Photo Film Co., Ltd. | Flash exposure of supersensitized silver halide photographic light-sensitive material |
| US3977883A (en) * | 1973-12-06 | 1976-08-31 | Fuji Photo Film Co., Ltd. | Spectrally sensitized silver halide photographic emulsion |
| US4018610A (en) * | 1974-07-26 | 1977-04-19 | Fuji Photo Film Co., Ltd. | Supersensitized silver halide photographic emulsion |
| EP0467370A1 (de) * | 1990-07-19 | 1992-01-22 | Eastman Kodak Company | Sensibilisierungsfarbstoffe für photographische Materialien |
| EP0472004A1 (de) * | 1990-08-16 | 1992-02-26 | Eastman Kodak Company | Sensibilisatorfarbstoffkombination für photographische Materialien |
| EP1750173A1 (de) | 2005-08-04 | 2007-02-07 | Fuji Photo Film Co., Ltd. | Lichtempfindliches Silberhalogenidmaterial und dieses enthaltender verpackter Gegenstand |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5121340B1 (de) * | 1971-03-23 | 1976-07-01 |
-
1970
- 1970-03-26 DE DE19702014896 patent/DE2014896A1/de active Pending
- 1970-03-26 GB GB1495570A patent/GB1307904A/en not_active Expired
- 1970-03-26 BE BE748021A patent/BE748021A/xx unknown
- 1970-03-27 US US23122A patent/US3667960A/en not_active Expired - Lifetime
- 1970-03-27 FR FR7011294A patent/FR2037271B1/fr not_active Expired
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3769024A (en) * | 1970-07-16 | 1973-10-30 | Konishiroku Photo Ind | Light-sensitive silver halide photographic material with sensitizing dye combination |
| US3808008A (en) * | 1970-09-10 | 1974-04-30 | Fuji Photo Film Co Ltd | Spectrally sensitized silver halide photographic emulsion |
| US3955979A (en) * | 1970-10-16 | 1976-05-11 | Fuji Photo Film Co., Ltd. | Flash exposure of supersensitized silver halide photographic light-sensitive material |
| US3953215A (en) * | 1973-07-16 | 1976-04-27 | Fuji Photo Film Co., Ltd. | Silver halide photographic emulsions |
| US3977883A (en) * | 1973-12-06 | 1976-08-31 | Fuji Photo Film Co., Ltd. | Spectrally sensitized silver halide photographic emulsion |
| US4018610A (en) * | 1974-07-26 | 1977-04-19 | Fuji Photo Film Co., Ltd. | Supersensitized silver halide photographic emulsion |
| EP0467370A1 (de) * | 1990-07-19 | 1992-01-22 | Eastman Kodak Company | Sensibilisierungsfarbstoffe für photographische Materialien |
| US5091298A (en) * | 1990-07-19 | 1992-02-25 | Eastman Kodak Company | Sensitizing dyes for photographic materials |
| JP3122169B2 (ja) | 1990-07-19 | 2001-01-09 | イーストマン コダック カンパニー | 写真材料用増感色素 |
| EP0472004A1 (de) * | 1990-08-16 | 1992-02-26 | Eastman Kodak Company | Sensibilisatorfarbstoffkombination für photographische Materialien |
| US5597687A (en) * | 1990-08-16 | 1997-01-28 | Eastman Kodak Company | Sensitizing dye combination for photographic materials |
| EP1750173A1 (de) | 2005-08-04 | 2007-02-07 | Fuji Photo Film Co., Ltd. | Lichtempfindliches Silberhalogenidmaterial und dieses enthaltender verpackter Gegenstand |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2037271B1 (de) | 1976-02-06 |
| DE2014896A1 (de) | 1970-11-05 |
| FR2037271A1 (de) | 1970-12-31 |
| GB1307904A (en) | 1973-02-21 |
| BE748021A (fr) | 1970-08-31 |
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