US3808009A - Light-sensitive super-sensitized silver halide photographic emulsions - Google Patents
Light-sensitive super-sensitized silver halide photographic emulsions Download PDFInfo
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- US3808009A US3808009A US00280715A US28071572A US3808009A US 3808009 A US3808009 A US 3808009A US 00280715 A US00280715 A US 00280715A US 28071572 A US28071572 A US 28071572A US 3808009 A US3808009 A US 3808009A
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- 239000000839 emulsion Substances 0.000 title claims abstract description 58
- -1 silver halide Chemical class 0.000 title claims abstract description 31
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 29
- 239000004332 silver Substances 0.000 title claims abstract description 29
- 150000001875 compounds Chemical class 0.000 claims abstract description 41
- 239000000975 dye Substances 0.000 abstract description 21
- 125000000217 alkyl group Chemical group 0.000 abstract description 18
- 206010070834 Sensitisation Diseases 0.000 abstract description 11
- 230000008313 sensitization Effects 0.000 abstract description 11
- 125000004429 atom Chemical group 0.000 abstract description 8
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 abstract description 8
- 125000002768 hydroxyalkyl group Chemical group 0.000 abstract description 8
- 125000000623 heterocyclic group Chemical group 0.000 abstract description 7
- 125000004964 sulfoalkyl group Chemical group 0.000 abstract description 7
- 125000003545 alkoxy group Chemical group 0.000 abstract description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 5
- 125000004181 carboxyalkyl group Chemical group 0.000 abstract description 5
- 229910052717 sulfur Inorganic materials 0.000 abstract description 5
- 239000011593 sulfur Substances 0.000 abstract description 5
- AIGNCQCMONAWOL-UHFFFAOYSA-N 1,3-benzoselenazole Chemical compound C1=CC=C2[se]C=NC2=C1 AIGNCQCMONAWOL-UHFFFAOYSA-N 0.000 abstract description 4
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical compound C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 abstract description 4
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical group [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 abstract description 4
- 150000001450 anions Chemical group 0.000 abstract description 4
- 125000003118 aryl group Chemical group 0.000 abstract description 4
- 125000005843 halogen group Chemical group 0.000 abstract description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 4
- 125000001422 pyrrolinyl group Chemical group 0.000 abstract description 4
- KIWUVOGUEXMXSV-UHFFFAOYSA-N rhodanine Chemical compound O=C1CSC(=S)N1 KIWUVOGUEXMXSV-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052711 selenium Inorganic materials 0.000 abstract description 4
- CBDKQYKMCICBOF-UHFFFAOYSA-N thiazoline Chemical compound C1CN=CS1 CBDKQYKMCICBOF-UHFFFAOYSA-N 0.000 abstract description 4
- UGWULZWUXSCWPX-UHFFFAOYSA-N 2-sulfanylideneimidazolidin-4-one Chemical compound O=C1CNC(=S)N1 UGWULZWUXSCWPX-UHFFFAOYSA-N 0.000 abstract description 3
- 238000000034 method Methods 0.000 description 12
- 230000035945 sensitivity Effects 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 230000001235 sensitizing effect Effects 0.000 description 8
- 230000003595 spectral effect Effects 0.000 description 8
- 239000000523 sample Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 229910052727 yttrium Inorganic materials 0.000 description 6
- SJOOOZPMQAWAOP-UHFFFAOYSA-N [Ag].BrCl Chemical compound [Ag].BrCl SJOOOZPMQAWAOP-UHFFFAOYSA-N 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 125000000547 substituted alkyl group Chemical group 0.000 description 3
- QGKMIGUHVLGJBR-UHFFFAOYSA-M (4z)-1-(3-methylbutyl)-4-[[1-(3-methylbutyl)quinolin-1-ium-4-yl]methylidene]quinoline;iodide Chemical class [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 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000013068 control sample Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 2
- 239000004848 polyfunctional curative Substances 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 230000005070 ripening Effects 0.000 description 2
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 2
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 description 1
- 229920002284 Cellulose triacetate Polymers 0.000 description 1
- 101150065749 Churc1 gene Proteins 0.000 description 1
- 101100289061 Drosophila melanogaster lili gene Proteins 0.000 description 1
- 239000004129 EU approved improving agent Substances 0.000 description 1
- 206010034960 Photophobia Diseases 0.000 description 1
- 102100038239 Protein Churchill Human genes 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
- XCFIVNQHHFZRNR-UHFFFAOYSA-N [Ag].Cl[IH]Br Chemical compound [Ag].Cl[IH]Br XCFIVNQHHFZRNR-UHFFFAOYSA-N 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000000298 carbocyanine 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
- 230000001627 detrimental effect Effects 0.000 description 1
- XLNOKJLJDWVOQP-UHFFFAOYSA-L disodium;formaldehyde;sulfite Chemical compound [Na+].[Na+].O=C.[O-]S([O-])=O XLNOKJLJDWVOQP-UHFFFAOYSA-L 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 208000015181 infectious disease Diseases 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 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 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000000007 visual effect Effects 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
- Y10S430/15—Lithographic emulsion
Definitions
- ABSTRACT A light-sensitive silver-halide photographic emulsion having a combination of two types of dyes to enable superior additivity sensitization of the emulsion, said [451 Apr. 30, 1971 emulsion comprising at least one compound of the general formula (I),
- R and R are individually an alkyl, hydroxyalkyl, carboxalkyl or sulfoalkyl group;
- R is an alkyl group;
- Y, and Y are individually a sulfur or selenium atom;
- V V V and V are individually a hydrogen atom, an alkyl group, an alkoxyl group or a halogen atom, or V and V, or V and V may bond to each other to form a benzene ring;
- X is an anion; and m is 0 or 1, and at least one compound of the general formula (ll),
- R and R are individually an alkyl, hydroxyalkyl, carboxyalkyl or sulfoalkyl group or an aryl group;
- Z is a non-metallic atom grouping necessary to complete a heterocyclic ring, which is a benzoxazole, benzothiazole, benzoselenazole, thiazoline or pyrroline ring;
- Q is a non-metallic atom grouping necessary to complete the heterocyclic ring, which is a rhodanine, 2-thiohydant0in or 2-thiooxazolidinedione ring.
- FIGI %M m/q LIGHT-SENSITIVE SUPER-SENSITIZED SILVER HALIDE PHOTOGRAPHIC EMULSIONS This invention relates to a light-sensitive silver halide photographic emulsion.
- the sensitive wave length area of a silver halide photographic emulsion is ordinarily an extremely limited short wave length region of ultraviolet rays or blue light. It is well known that the use of a certain class of cyanine dye compound is markedly effective for spectral sensitization of such silver halide emulsion. It is also well known that a combination of the said dye with a certain other sensitizing dye or an organic compound is added to a silver halide emulsion, whereby a sensitivity greater than the total sum of sensitivities of the individual compounds can be imparted to the emulsion. Such effect is called super additivity sensitization, and combinations of many compounds have already been reported.
- the method should not deteriorate the characteristics of the lithtype emulsion which shows extremely high contrast.
- the method should contribute to the improvement in quality of fine dots withoutdegrading the sharpness of the half tone image.
- the method should not give dye stains and fog to the photographicfilm after development.
- the method is desired to give such effects to a panchromatic lith-type emulsion, which requires a sensitivity extending to a visible wave length region, particularly a red light-sensitive region, that both the green and blue light-sensitive regions are not desensitized, and a sharp and good dot quality can be displayed by development carried out for a relatively short period of time (2 to 3 minutes).
- An object of the present invention is to provide a light-sensitive silver halide photographic material which has been subjected to super additivity sensitization satisfying the aforesaid requirements.
- Another object of the invention is to provide a lightsensitive silver halide photographic material which has no detrimental interactions with co-existing photographic additives, and has stable photographic properties even when the emulsion is allowed to stand or a coating of said emulsion on a support'is stored over a long periodof time.
- R and R are individually an alkyl group or a substituted alkyl group such as hydroxyalkyl, carboxyalkyl, sulfoalkyl, etc.;
- R is an alkyl group;
- Y and Y are individually a sulfur or selenium atom;
- V V V and V are individually a hydrogen atom, an alkyl group, an alkoxyl group or a halogen atom, provided that V, and V or V and V may bond to each other to form a benzene ring;
- X is an anion; and m is 0 or 1.
- R and R are individually an alkyl group, a substituted alkyl group such as hydroxyalkyl, carboxalkyl, sulfoalkyl, etc., or an aryl group
- Z is a nonmetallic atom grouping necessary to complete the heterocyclic ring, which is a benzoxazole, benzothiazole, benzoselenazole, thiazoline or pyrroline ring
- Q is a non-metallic atom grouping necessary to complete the heterocyclic ring, which is a rhodanine, 2- thiohydantoin or Z-thiooxazolidinedione ring.
- the alkyl group and the alkoxy group indicate a lower alkyl group and a lower alkoxyl group both having one to two carbon atoms, and preferable as the substituted alkyl group is, for example, a B-hydroxyethyl, carboxymethyl, B-carboxyethyl, fi-sulfoethyl, 'y-sulfopropyl or fi-sulfobutyl group.
- the compound of the aforesaid general formula (I) is a thiaor selena-carbocyanine dye
- the compound of the aforesaid general formula (ll) is a dimethine-merocyanine dye.
- the dye of the general formula (I) can be easily synthesized according to any of the processes disclosed in U.S. Pat. Nos. 2,450,400 and 2,213,238, and British Patent Specification No.*-742,l l2, and the dye Examples of typical compounds of the general formula (ll) are as follows:
- HzlaCOOH A light-sensitive photographic material, which has been subjected according to the present invention to super additivity sensitization by use of the combination of the above-mentioned specific compounds, has such excellent characteristics as mentioned previously and is ideal in sensitivity.
- the combination of said compounds can impart excellent properties not only to lithtype light-sensitive materials but also to light-sensitive photographic materials containing silver chloride or silver chlorobromide emulsions.
- the sensitizing dyes according to the present invention may be added, to a silver halide emulsion, either in the form of a solution, or individual solutions, in methanol, ethanol or the like organic solvent. These sensitizing dyes may be added to a silver halide emulsion at any time during the step of preparation of the emulsion, but is preferably added after completion of second ripening of the emulsion.
- the amounts of the dyes to be added vary depending on the kind of silver halide emulsion. Ordinarily, however, the total amount of the dyes of the formulas (I) and (ll) is within a wide r e.
- Qff Qm, 1 as to 0 ms, d h m xins retiq 0f the dye of the formula (I) to the dye of the formula (II) is preferably from 1:10 to 10:1 by weight.
- the silver halide emulsion used in the present invention may be any of silver chloride, silver chlorobromide, silver bromide, silver iodobromide and silver chloroiodobromide emulsions. These emulsions may have been incorporated with noble metal sensitizers, sulfur sensitizers and the like sensitizers, or with polyalkylene oxide type compounds as contrast-improving agents. Further, the sensitizing dyes according to the present invention may be used in combination with other sensitizing dyes, e.g. cyanine dyes or merocyanine dyes, and may have been incorporated with stabilizers, hardeners, coating aids and the like photographic additives which are used in general.
- sensitizing dyes e.g. cyanine dyes or merocyanine dyes
- the above-mentioned silver halide photographic emulsion containing the compounds used in the present invention is coated according to an ordinary procedure on a suitable support such as glass, cellulose triacetate base, polyester base or paper, and then dried to obtain a light-sensitive silver halide photographic material of the present invention.
- EXAMPLE 1 A lith-type silver chlorobromide emulsion containing 20 mole percent of silver bromide was subjected to second ripening according to gold sensitization method, and was equally divided into several portions. To each emulsion were added, either independently or in combination, methanol solutions of the exemplified compounds shown in Table 1. This emulsion was sufficiently stabilized by stirring at about 40C. for 20 minutes, and then incorporated with a suitable amount of a polyalkylene oxide derivative as a contrast-imparting agent, and with a hardener, a stabilizer and a coating aid. Thereafter, the emulsion was coated on a film base, and then dried to obtain a panchromatic lith-type lightsensitive material.
- Hot water 500 ml. Formaldehyde-sodium sulfite addition product 50 g. Hydroqumonel9 g. Sodium carbonate 80 g. Boric acid l g. Potassium bromide 2.2 g. Water to make l,000 ml.
- the relative speed is a value measured by assuming as 100 the red light speed of the exemplified dye (l set forth in Table 2, in which the relative speed is a value measured in the same manner as in Example 1; the contrast is represented by an average gradient between the densities 0.5 and 2.0; and the evaluation of dot image is represented by a grade ranging from 1 to 5, assuming as the grade the dot image which is free from fringes and is most sharp in dot.
- the dot image was evaluated according to a visual evaluation method in which the sample was brought into close contact and the residual color is a value of density measured by with a commit Screen, exposed to light, and develmeans of a color densitometer.
- tions of the compounds according to the present invention are more excellent in photographic speeds (for green light and red light) and have been more improved in residual color than the samples containing each of the said compounds.
- FIG. 1 shows the spectral sensitivity curve of the silver chlorobromide emulsion
- FIG. 2 shows the spectral sensitivity curves of Sample No. 2 (dotted line) and Sample No. 3 (solid line);
- HO. 3 shows the spectral sensitivity curve of Sample No. 7 according to the present invention in which the compounds (4) and (10) have been used in combination with each other.
- EXAMPLE 2 According to the procedures of Example 1, the'combinations of exemplified compounds shown in Table 2 were individually added to the same emulsion as in Example l. A For comparison, control compounds (A) and (S) of the formulas shown below were individually added to the emulsion.
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- 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)
Abstract
A light-sensitive silver halide photographic emulsion having a combination of two types of dyes to enable superior additivity sensitization of the emulsion, said emulsion comprising at least one compound of the general formula (I),
where R1 and R2 are individually an alkyl, hydroxyalkyl, carboxalkyl or sulfoalkyl group; R3 is an alkyl group; Y1 and Y2 are individually a sulfur or selenium atom; V1, V2, V3 and V4 are individually a hydrogen atom, an alkyl group, an alkoxyl group or a halogen atom, or V1 and V2 or V3 and V4 may bond to each other to form a benzene ring; X is an anion; and m is 0 or 1, and at least one compound of the general formula (II),
wherein R4 and R5 are individually an alkyl, hydroxyalkyl, carboxyalkyl or sulfoalkyl group or an aryl group; Z is a nonmetallic atom grouping necessary to complete a heterocyclic ring, which is a benzoxazole, benzothiazole, benzoselenazole, thiazoline or pyrroline ring; and Q is a non-metallic atom grouping necessary to complete the heterocyclic ring, which is a rhodanine, 2-thiohydantoin or 2-thiooxazolidinedione ring.
where R1 and R2 are individually an alkyl, hydroxyalkyl, carboxalkyl or sulfoalkyl group; R3 is an alkyl group; Y1 and Y2 are individually a sulfur or selenium atom; V1, V2, V3 and V4 are individually a hydrogen atom, an alkyl group, an alkoxyl group or a halogen atom, or V1 and V2 or V3 and V4 may bond to each other to form a benzene ring; X is an anion; and m is 0 or 1, and at least one compound of the general formula (II),
wherein R4 and R5 are individually an alkyl, hydroxyalkyl, carboxyalkyl or sulfoalkyl group or an aryl group; Z is a nonmetallic atom grouping necessary to complete a heterocyclic ring, which is a benzoxazole, benzothiazole, benzoselenazole, thiazoline or pyrroline ring; and Q is a non-metallic atom grouping necessary to complete the heterocyclic ring, which is a rhodanine, 2-thiohydantoin or 2-thiooxazolidinedione ring.
Description
United States Patent [191 Sakazume et al.
[ LIGHT-SENSITIVE SUPER-SENSITIZED SILVER HALIDE PHOTOGRAPHIC EMULSIONS [75] Inventors: Kaiichiro Sakazume; Shui Sato, both of Tokyo; Eiichi Sakamoto, l-lanno; Noboru Fujimori, Tokyo; Shigemasa Itoh, Tokyo; Kiyornitsu Mine, Tokyo, all of Japan [73] Assignee: Konishiroku Photo Industry Co.,
Ltd
22 Filed: Aug. 14, 1972 21 Appl. No.: 280,715
[30] Foreign Application Priority Data Primary Examiner-J. Travis Brown [57] ABSTRACT A light-sensitive silver-halide photographic emulsion having a combination of two types of dyes to enable superior additivity sensitization of the emulsion, said [451 Apr. 30, 1971 emulsion comprising at least one compound of the general formula (I),
where R and R are individually an alkyl, hydroxyalkyl, carboxalkyl or sulfoalkyl group; R is an alkyl group; Y, and Y are individually a sulfur or selenium atom; V V V and V, are individually a hydrogen atom, an alkyl group, an alkoxyl group or a halogen atom, or V and V, or V and V may bond to each other to form a benzene ring; X is an anion; and m is 0 or 1, and at least one compound of the general formula (ll),
wherein R and R are individually an alkyl, hydroxyalkyl, carboxyalkyl or sulfoalkyl group or an aryl group; Z is a non-metallic atom grouping necessary to complete a heterocyclic ring, which is a benzoxazole, benzothiazole, benzoselenazole, thiazoline or pyrroline ring; and Q is a non-metallic atom grouping necessary to complete the heterocyclic ring, which is a rhodanine, 2-thiohydant0in or 2-thiooxazolidinedione ring.
6 Claims, 3 Drawing Figures PATENTEDAPR 30 1914 FIGI %M (m/q LIGHT-SENSITIVE SUPER-SENSITIZED SILVER HALIDE PHOTOGRAPHIC EMULSIONS This invention relates to a light-sensitive silver halide photographic emulsion.
The sensitive wave length area of a silver halide photographic emulsion is ordinarily an extremely limited short wave length region of ultraviolet rays or blue light. It is well known that the use of a certain class of cyanine dye compound is markedly effective for spectral sensitization of such silver halide emulsion. It is also well known that a combination of the said dye with a certain other sensitizing dye or an organic compound is added to a silver halide emulsion, whereby a sensitivity greater than the total sum of sensitivities of the individual compounds can be imparted to the emulsion. Such effect is called super additivity sensitization, and combinations of many compounds have already been reported. ln case such super additivity sensitization method is intended to be applied to a silver halide emulsion, particularly the lith-type emulsion, it is desirable that not only the increase in spectral sensitizing effect but also such requirements as mentioned below are satisfied.
l. The method should not deteriorate the characteristics of the lithtype emulsion which shows extremely high contrast.
2. The method should contribute to the improvement in quality of fine dots withoutdegrading the sharpness of the half tone image.
3. The method should not give dye stains and fog to the photographicfilm after development.
Further, the method is desired to give such effects to a panchromatic lith-type emulsion, which requires a sensitivity extending to a visible wave length region, particularly a red light-sensitive region, that both the green and blue light-sensitive regions are not desensitized, and a sharp and good dot quality can be displayed by development carried out for a relatively short period of time (2 to 3 minutes).
However, most of the conventional super additivity sensitization methods are directed to usual silver iodobromide emulsions for negative,'and a method applicable to high contrast lith-type silver chlorobromide emulsions is substantially nil. There is no method satisfying the aforesaid requirements as far as spectral sensitization extending particularly to the red light-sensitive region is intended. I
An object of the present invention is to provide a light-sensitive silver halide photographic material which has been subjected to super additivity sensitization satisfying the aforesaid requirements.
Another object of the invention is to provide a lightsensitive silver halide photographic material which has no detrimental interactions with co-existing photographic additives, and has stable photographic properties even when the emulsion is allowed to stand or a coating of said emulsion on a support'is stored over a long periodof time.
As the result of extensive studies, we havefound that when at least one compound of the belowmentioned general formula (I) is added to a silver halide emulsion in combination with at least one compound of the below-mentioned general formula (ll), not only the spectral sensitizing effect is greatly increased but also the aforesaid requirements are satisfied.
General Formula (I):
wherein R and R are individually an alkyl group or a substituted alkyl group such as hydroxyalkyl, carboxyalkyl, sulfoalkyl, etc.; R is an alkyl group; Y and Y are individually a sulfur or selenium atom; V V V and V, are individually a hydrogen atom, an alkyl group, an alkoxyl group or a halogen atom, provided that V, and V or V and V may bond to each other to form a benzene ring; X is an anion; and m is 0 or 1.
General Formula (II):
wherein R and R are individually an alkyl group, a substituted alkyl group such as hydroxyalkyl, carboxalkyl, sulfoalkyl, etc., or an aryl group; Z is a nonmetallic atom grouping necessary to complete the heterocyclic ring, which is a benzoxazole, benzothiazole, benzoselenazole, thiazoline or pyrroline ring; and Q is a non-metallic atom grouping necessary to complete the heterocyclic ring, which is a rhodanine, 2- thiohydantoin or Z-thiooxazolidinedione ring.
In the above formulas, the alkyl group and the alkoxy group indicate a lower alkyl group and a lower alkoxyl group both having one to two carbon atoms, and preferable as the substituted alkyl group is, for example, a B-hydroxyethyl, carboxymethyl, B-carboxyethyl, fi-sulfoethyl, 'y-sulfopropyl or fi-sulfobutyl group.
The compound of the aforesaid general formula (I) is a thiaor selena-carbocyanine dye, and the compound of the aforesaid general formula (ll) is a dimethine-merocyanine dye. When these sensitizing dyes according to the present invention are used in combination with each other, there is obtained a mixed maximum sensitivity value which is different from maximum sensitivity values attained when the individual dyes are used singly, whereby optimum red and green sensitivities can be imparted to silver halide emulsions. That is, due to synergistic effect derived from specific combination of said compounds, the spectral sensitization is markedly enhanced over the red and green light region. Particularly when the combination is applied to a lithtype emulsion, which is used in a photographic material to be developed with an aldehyde-containing lithdeveloper (infections developer) containing hydroquinone as developing agent, there is attained such characteristic that a sharp dot image which is extremely high in contrast can be formed.
Concrete examples of the compounds represented by the aforesaid general formulas (l) and (II) are enumerated below, but compounds usable in the present invention are not limited to these.
By the way, the dye of the general formula (I) can be easily synthesized according to any of the processes disclosed in U.S. Pat. Nos. 2,450,400 and 2,213,238, and British Patent Specification No.*-742,l l2, and the dye Examples of typical compounds of the general formula (ll) are as follows:
( HzlaCOOH A light-sensitive photographic material, which has been subjected according to the present invention to super additivity sensitization by use of the combination of the above-mentioned specific compounds, has such excellent characteristics as mentioned previously and is ideal in sensitivity. Thus, the combination of said compounds can impart excellent properties not only to lithtype light-sensitive materials but also to light-sensitive photographic materials containing silver chloride or silver chlorobromide emulsions.
The sensitizing dyes according to the present invention may be added, to a silver halide emulsion, either in the form of a solution, or individual solutions, in methanol, ethanol or the like organic solvent. These sensitizing dyes may be added to a silver halide emulsion at any time during the step of preparation of the emulsion, but is preferably added after completion of second ripening of the emulsion. The amounts of the dyes to be added vary depending on the kind of silver halide emulsion. Ordinarily, however, the total amount of the dyes of the formulas (I) and (ll) is within a wide r e. Qff Qm, 1 as to 0 ms, d h m xins retiq 0f the dye of the formula (I) to the dye of the formula (II) is preferably from 1:10 to 10:1 by weight.
The silver halide emulsion used in the present invention may be any of silver chloride, silver chlorobromide, silver bromide, silver iodobromide and silver chloroiodobromide emulsions. These emulsions may have been incorporated with noble metal sensitizers, sulfur sensitizers and the like sensitizers, or with polyalkylene oxide type compounds as contrast-improving agents. Further, the sensitizing dyes according to the present invention may be used in combination with other sensitizing dyes, e.g. cyanine dyes or merocyanine dyes, and may have been incorporated with stabilizers, hardeners, coating aids and the like photographic additives which are used in general.
The above-mentioned silver halide photographic emulsion containing the compounds used in the present invention is coated according to an ordinary procedure on a suitable support such as glass, cellulose triacetate base, polyester base or paper, and then dried to obtain a light-sensitive silver halide photographic material of the present invention.
The present invention is illustrated below with reference to example, but the examples are illustrative and do, of course, not limit the scope of the invention.
EXAMPLE 1 A lith-type silver chlorobromide emulsion containing 20 mole percent of silver bromide was subjected to second ripening according to gold sensitization method, and was equally divided into several portions. To each emulsion were added, either independently or in combination, methanol solutions of the exemplified compounds shown in Table 1. This emulsion was sufficiently stabilized by stirring at about 40C. for 20 minutes, and then incorporated with a suitable amount of a polyalkylene oxide derivative as a contrast-imparting agent, and with a hardener, a stabilizer and a coating aid. Thereafter, the emulsion was coated on a film base, and then dried to obtain a panchromatic lith-type lightsensitive material.
Samples obtained in the above manner were individually exposed to light of lux (2,660l() by means of Sensitometer Model KS-Vll (manufactured by Konishiroku Photo Industry Co., Ltd.), using Wratten No. 25A as a red filter and Wratten No. 58 as a green filter, and then developed at 20C. for 3 minutes with a developer of the following composition:
The results obtained were as set forth in Table l, in which the relative speed is a value measured by assuming as 100 the red light speed of the exemplified dye (l set forth in Table 2, in which the relative speed is a value measured in the same manner as in Example 1; the contrast is represented by an average gradient between the densities 0.5 and 2.0; and the evaluation of dot image is represented by a grade ranging from 1 to 5, assuming as the grade the dot image which is free from fringes and is most sharp in dot. The dot image was evaluated according to a visual evaluation method in which the sample was brought into close contact and the residual color is a value of density measured by with a commit Screen, exposed to light, and develmeans of a color densitometer.
Table l oped in the same manner as in Example 1, and the re- From Table l and from the drawings shown later, it is d r e atthszsam s s m n ns thesa flfin sulting dot image was observed by means of a microscope.
Table 2 Sample Amount of exemplified Relative Relative Contrast Evaluation No. compound added green red of dot (mg/kg emulsion) light light image speed speed 9 (A) mg. (S) 30 mg. 100 6.0 23
(Control) 10 (2)do. +(l2) do. 70 l05 I40 4 ll (3) do. +(l5) do. 60 I10 l3.5 5 l2 (4) do. +(ll)do. 75 115 I20 5 l3 +(l7)do. 70 110 11.5 4
tions of the compounds according to the present invention are more excellent in photographic speeds (for green light and red light) and have been more improved in residual color than the samples containing each of the said compounds.
In the accompanying drawings,
FIG. 1 shows the spectral sensitivity curve of the silver chlorobromide emulsion;
FIG. 2 shows the spectral sensitivity curves of Sample No. 2 (dotted line) and Sample No. 3 (solid line); and
HO. 3 shows the spectral sensitivity curve of Sample No. 7 according to the present invention in which the compounds (4) and (10) have been used in combination with each other.
EXAMPLE 2 According to the procedures of Example 1, the'combinations of exemplified compounds shown in Table 2 were individually added to the same emulsion as in Example l. A For comparison, control compounds (A) and (S) of the formulas shown below were individually added to the emulsion.
Control compound (A):
l,l '-Diethyl-2,2'-cyanine iodide Control compound (S):
3 ,3 '-Diethyl-9-methyl-4,5 ,4,5 -dibenzothiacarbocyanine iodide These emulsions were individually coated on a polyester film base to prepare panchromatic lith-type light-- sensitive materials, which were then treated in the same manner as in Example 1. The results obtained were as As is clear from Table 2, the samples 10) to 13) are quite excellent in every one of speed, contrast and dot property as compared with the control sample. EXAM- PLE 3 Sample films prepared in the above manner were measured, in photographic properties in the cases where they were stored under high temperature and humidity conditions and in the cases were they were incubated spontaneously. The results obtained were as set forth in Table 3, in which the relative speeds are values of green and red light sensitivities in the cases where the samples were developed at 20C. for 3 minutes by means of a D-ll Developer (Eastman Kodak Go).
From Table 3, it is understood that the samples according to the present invention are more excellent in both speed and fog than the control sample (A+S), and are not deteriorated in photographic properties even when stored under high temperature and humidity conditions.
Table 3 Sample Exemplified Spontaneously incubated for incubated for No, compound incubated for 3 days at 55C. 3 days at 50C.
(mg/kg emulsion) 3 qgys. and 80%RH Relative Relative Relative Relative Relative Relative Fog red green Fog red green Fog red green light light light light light light speed spced speed speed speed speed l4 (s) 40 mg (A) 20 mg. 0.04 I 40 0.05 90 30 0.05 90 35 I5 (3) do. (13) do. 0.03 no 60 0.04 no 55 0.04 los 60 I6 4 do. (10) do. 0.03 115 70 0.03 no 65 0.03 11s 65 I7 (5) do. (16) do. 0.03 mo 60 0.03 ms 30 0.03 mo 60 What we claim is: l. A light-sensitive silver halide photographic emulsion characterized by containing in combination at least one compound of the general formula (l),
\ 2H 63/ Y Yl Y: N N
/ (r snl soan =CHC=CH- v V4 (x 20 Ba 9 I (CH2)3S086 I .3? vs S wherein R and R are individually selected from the I I =CH $=CH group consisting of alkyl, hydroxyalkyl, carboxyalkyl, N C2116 g and sulkoalkyl; R is an alkyl group; Y and Y are indil (I: 9 vidually a sulfur or selenium atom; V V V and V (CHmSOaNa are individually a hydrogen atom, an alkyl group, an alkoxyl group or a halogen atom, or V and V or V and V may bond to each other to form a benzene ring; X is an anion; and m is 0 or 1, and at least one com- Cl pound of the general formula (11), C2H5 g/ G1 I {ZR 02H! lHflasQ-g IIII-I-('I=CHCH=(IJ o 56 Se R4 0: -I IR5 =CHC=CH- wherein R and R are individually selected from the 0H; group consisting of alkyl, hydroxyalkyl, carboxyalkyl, 40 E sulfoalkyl, and aryl; Z is a non-metallic atom grouping HmSOaH (01194803 necessary to complete a heterocyclic ring, which is a s s benzoxazole, benzothiazole, benzoselenazole, thiazoline or pyrroline ring; and Q is a non-metallic atom =CHC=CH- l h h l' C1 CH: grouping necessary to comp ete t e eterocyc ic ring, 0 H, 9/ which is a rhodanine, '2-thiohydantoin or 2-thiooxazoli- N dinedione ring. 0 1,115 (OH2)3SOa 2. A light-sensitive silver halide photographic emuland sion as claimed in claim 1, where the compound of the s s said general formula (l) is a compound selected from es llp wa n =CH =CH 11,0 can 01 N N s s 5 JD m 1120112011 momcoomsr =CH-C=CH C1 g; l 3. A light-sensitive silver halide photographic emulsion as claimed in claim 1, wherein the compound of 0H, son (43H) so a a the said general formula (II) is a-compound selected a S from the group consisting of =orr-c=cn- I i OH H o hHr g} pmomon (cm soln ormlsol Se Se\ \N O=(L N/ I =CH-Z=CH fim oaNe c1 OCH:
H e N a a N/ 1 fi9l. a smhsqr w (JJHmS OsNa lili J;
5. A light-sensitive silver halide photographic emulsion as claimed in claim 1, wherein the total amounts of the compounds of the general formulas (l) and (II) is 1 mg. to 200 mg. per kilogram of the emulsion.
6. A light-sensitive silver halide photographic emulsion as claimed in claim 1, wherein the emulsion is of 91i :t .P-,. a
Claims (5)
- 2. A light-sensitive silver halide photographic emulsion as claimed in claim 1, where the compound of the said general formula (I) is a compound selected from the group consisting of
- 3. A light-sensitive silver halide photographic emulsion as claimed in claim 1, wherein the compound of the said general formula (II) is a compound selected from the group consisting of
- 4. A light-sensitive silver halide photographic emulsion as claimed in claim 1, wherein the compound of the said general formula (I) and the compound of the said general formula (II) are combined at the weight ratio of from 1:10 to 10:1.
- 5. A light-sensitive silver halide photographic emulsion as claimed in claim 1, wherein the total amounts of the compounds of the general formulas (I) and (II) is 1 mg. to 200 mg. per kilogram of the emulsion.
- 6. A light-sensitive silver halide photographic emulsion as claimed in claim 1, wherein the emulsion is of the lith-type.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP46061411A JPS516536B2 (en) | 1971-08-14 | 1971-08-14 |
Publications (1)
Publication Number | Publication Date |
---|---|
US3808009A true US3808009A (en) | 1974-04-30 |
Family
ID=13170341
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US00280715A Expired - Lifetime US3808009A (en) | 1971-08-14 | 1972-08-14 | Light-sensitive super-sensitized silver halide photographic emulsions |
Country Status (4)
Country | Link |
---|---|
US (1) | US3808009A (en) |
JP (1) | JPS516536B2 (en) |
DE (1) | DE2239711A1 (en) |
GB (1) | GB1401859A (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4040841A (en) * | 1974-08-09 | 1977-08-09 | Fuji Photo Film Co., Ltd. | Silver halide photographic emulsion |
US4057430A (en) * | 1973-04-25 | 1977-11-08 | Fuji Photo Film Co., Ltd. | Silver halide photographic emulsion |
JPS62276539A (en) * | 1986-05-23 | 1987-12-01 | Fuji Photo Film Co Ltd | Silver halide photographic sensitive material |
US5126237A (en) * | 1989-08-18 | 1992-06-30 | Konica Corporation | Silver halide light-sensitive photographic material |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5033846B2 (en) * | 1971-09-02 | 1975-11-04 | ||
JPS5228659B2 (en) * | 1973-04-23 | 1977-07-28 | ||
IT988270B (en) * | 1973-06-18 | 1975-04-10 | Minnesota Mining & Mfg | CYANININE DYES AND THEIR USE WITH ME SPECTRAL SENSITIZERS IN DIRECT POSITIVE PHOTOGRAPHIC MATERIALS OF THE SPECTRALLY SENSITIZED HERSCHEL EFFECT TYPE |
US4273862A (en) * | 1977-06-11 | 1981-06-16 | Mitsubishi Paper Mills, Ltd. | Direct-positive silver halide photographic sensitive materials |
JPS589044Y2 (en) * | 1977-11-16 | 1983-02-18 | 松下電器産業株式会社 | liquid fuel combustion equipment |
WO2018104777A1 (en) * | 2016-12-05 | 2018-06-14 | Arne Holmgren | Antibiotic compositions comprising silver and selenium |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2411507A (en) * | 1943-12-20 | 1946-11-26 | Ilford Ltd | Photographic material |
US3522052A (en) * | 1965-11-06 | 1970-07-28 | Fuji Photo Film Co Ltd | Photographic supersensitized silver halide emulsions |
US3527641A (en) * | 1965-10-22 | 1970-09-08 | Fuji Photo Film Co Ltd | Supersensitized photographic silver halide emulsion |
US3537858A (en) * | 1966-03-11 | 1970-11-03 | Eastman Kodak Co | Reversal silver halide emulsions |
US3698910A (en) * | 1969-06-23 | 1972-10-17 | Konishiroku Photo Ind | Light-sensitive silver halide photographic material |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
BE471518A (en) * | 1945-10-26 | |||
BE520133A (en) * | 1952-05-23 | |||
DE1929037A1 (en) * | 1968-06-10 | 1970-05-21 | Konishiroku Photo Ind | Photosensitive silver halide photographic emulsion |
JPS4838408B1 (en) * | 1970-01-16 | 1973-11-17 |
-
1971
- 1971-08-14 JP JP46061411A patent/JPS516536B2/ja not_active Expired
-
1972
- 1972-08-11 DE DE2239711A patent/DE2239711A1/en not_active Withdrawn
- 1972-08-14 US US00280715A patent/US3808009A/en not_active Expired - Lifetime
- 1972-08-14 GB GB3784072A patent/GB1401859A/en not_active Expired
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2411507A (en) * | 1943-12-20 | 1946-11-26 | Ilford Ltd | Photographic material |
US3527641A (en) * | 1965-10-22 | 1970-09-08 | Fuji Photo Film Co Ltd | Supersensitized photographic silver halide emulsion |
US3522052A (en) * | 1965-11-06 | 1970-07-28 | Fuji Photo Film Co Ltd | Photographic supersensitized silver halide emulsions |
US3537858A (en) * | 1966-03-11 | 1970-11-03 | Eastman Kodak Co | Reversal silver halide emulsions |
US3698910A (en) * | 1969-06-23 | 1972-10-17 | Konishiroku Photo Ind | Light-sensitive silver halide photographic material |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4057430A (en) * | 1973-04-25 | 1977-11-08 | Fuji Photo Film Co., Ltd. | Silver halide photographic emulsion |
US4040841A (en) * | 1974-08-09 | 1977-08-09 | Fuji Photo Film Co., Ltd. | Silver halide photographic emulsion |
JPS62276539A (en) * | 1986-05-23 | 1987-12-01 | Fuji Photo Film Co Ltd | Silver halide photographic sensitive material |
US5126237A (en) * | 1989-08-18 | 1992-06-30 | Konica Corporation | Silver halide light-sensitive photographic material |
Also Published As
Publication number | Publication date |
---|---|
GB1401859A (en) | 1975-07-30 |
DE2239711A1 (en) | 1973-03-08 |
JPS4828224A (en) | 1973-04-14 |
JPS516536B2 (en) | 1976-02-28 |
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Legal Events
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AS | Assignment |
Owner name: KONICA CORPORATION, JAPAN Free format text: RELEASED BY SECURED PARTY;ASSIGNOR:KONISAIROKU PHOTO INDUSTRY CO., LTD.;REEL/FRAME:005159/0302 Effective date: 19871021 |