US3658547A - Silver halide photographic emulsions containing phenozine-n-oxides desensitizers - Google Patents
Silver halide photographic emulsions containing phenozine-n-oxides desensitizers Download PDFInfo
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- US3658547A US3658547A US17316A US3658547DA US3658547A US 3658547 A US3658547 A US 3658547A US 17316 A US17316 A US 17316A US 3658547D A US3658547D A US 3658547DA US 3658547 A US3658547 A US 3658547A
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- Prior art keywords
- silver halide
- halide photographic
- compound
- emulsion
- sensitivity
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- -1 Silver halide Chemical class 0.000 title claims abstract description 46
- 239000000839 emulsion Substances 0.000 title claims abstract description 44
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 43
- 239000004332 silver Substances 0.000 title claims abstract description 43
- 229940090898 Desensitizer Drugs 0.000 title description 3
- 150000001875 compounds Chemical class 0.000 claims description 33
- 230000035945 sensitivity Effects 0.000 claims description 19
- 239000000975 dye Substances 0.000 abstract description 8
- VEPOHXYIFQMVHW-XOZOLZJESA-N 2,3-dihydroxybutanedioic acid (2S,3S)-3,4-dimethyl-2-phenylmorpholine Chemical compound OC(C(O)C(O)=O)C(O)=O.C[C@H]1[C@@H](OCCN1C)c1ccccc1 VEPOHXYIFQMVHW-XOZOLZJESA-N 0.000 abstract description 2
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 abstract description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 5
- FFISWZPYNKWIRR-UHFFFAOYSA-N 5-oxidophenazin-5-ium Chemical class C1=CC=C2[N+]([O-])=C(C=CC=C3)C3=NC2=C1 FFISWZPYNKWIRR-UHFFFAOYSA-N 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 229920002284 Cellulose triacetate Polymers 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-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
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 2
- WOAHJDHKFWSLKE-UHFFFAOYSA-N 1,2-benzoquinone Chemical compound O=C1C=CC=CC1=O WOAHJDHKFWSLKE-UHFFFAOYSA-N 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- RUFPHBVGCFYCNW-UHFFFAOYSA-N 1-naphthylamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1 RUFPHBVGCFYCNW-UHFFFAOYSA-N 0.000 description 1
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 1
- ZVNPWFOVUDMGRP-UHFFFAOYSA-N 4-methylaminophenol sulfate Chemical compound OS(O)(=O)=O.CNC1=CC=C(O)C=C1.CNC1=CC=C(O)C=C1 ZVNPWFOVUDMGRP-UHFFFAOYSA-N 0.000 description 1
- ZXQHSPWBYMLHLB-BXTVWIJMSA-M 6-ethoxy-1-methyl-2-[(e)-2-(3-nitrophenyl)ethenyl]quinolin-1-ium;methyl sulfate Chemical compound COS([O-])(=O)=O.C1=CC2=CC(OCC)=CC=C2[N+](C)=C1\C=C\C1=CC=CC([N+]([O-])=O)=C1 ZXQHSPWBYMLHLB-BXTVWIJMSA-M 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 240000007673 Origanum vulgare Species 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- 238000007361 Wohl-Aue reaction Methods 0.000 description 1
- XCFIVNQHHFZRNR-UHFFFAOYSA-N [Ag].Cl[IH]Br Chemical compound [Ag].Cl[IH]Br XCFIVNQHHFZRNR-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229940101006 anhydrous sodium sulfite Drugs 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
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000003975 dentin desensitizing agent Substances 0.000 description 1
- 125000004663 dialkyl amino group Chemical group 0.000 description 1
- MQRJBSHKWOFOGF-UHFFFAOYSA-L disodium;carbonate;hydrate Chemical compound O.[Na+].[Na+].[O-]C([O-])=O MQRJBSHKWOFOGF-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002988 phenazines Chemical class 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- SOUHUMACVWVDME-UHFFFAOYSA-N safranin O Chemical compound [Cl-].C12=CC(N)=CC=C2N=C2C=CC(N)=CC2=[N+]1C1=CC=CC=C1 SOUHUMACVWVDME-UHFFFAOYSA-N 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- 229940076133 sodium carbonate monohydrate Drugs 0.000 description 1
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
- G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
- G03C1/36—Desensitisers
-
- 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
- Y10S430/167—X-ray
Definitions
- ABSTRACT Foreign Application Priority Data Photographic silver halide emulsion and photographic elements containing same, said elements containing certain Mar. 7, Japan henazine desensitizing dyes
- the dyes of this invention elec. tively desensitize the silver halide emulsion to visible light, as [5 U.S. Cl ..96/10l contrasted i x ⁇ 51 ..G03c 1/36
- the present invention relates to a silver halide photographic emulsion having selectively reduced sensitivity to visible light and, more particularly, to a silver halide photographic emulsion of which the sensitivity to visible light has been reduced without reducing sensitivity to X-rays.
- the sensitivity thereof to X-rays is in direct proportion to sensitivity to visible light.
- An object of the present invention is to provide a specific silver halide photographic emulsion, the sensitivity of which to visible light has been selectively reduced without reducing the sensitivity thereof to X-rays, whereby it becomes possible to handle the light-sensitive element made from such a light-sensitive photographic emulsion under visible light after the lightsensitive element is exposed to X-rays.
- Another object of the present invention is to provide a desensitizing agent capable of reducing selectively the sensitivity of a silver halide photographic emulsion to visible light without reducing the sensitivity thereof to X-rays.
- an ordinary desensitizing dye such as pinakryptol yellow, phenosafranine, methylene blue and the like, the sensitivity of a silver halide photographic emulsion to X-rays may be reduced considerably, but these materials tend to remain after development as stains.
- R R R and R each represents a hydrogen atom, an alkyl group (e.g. lower alkyl), an aryl group (e.g. phenyl), a nitro group, a hydroxyl group, an alkoxy group eg lower alkoxy), a halogen atom, an amino group or a substituted amino group, or said R, and R or said R and R may be condensed with each other to form a benzene ring.
- R R R R and R each represents a hydrogen atom, an alkyl group (e.g. lower alkyl), an aryl group (e.g. phenyl), a nitro group, a hydroxyl group, an alkoxy group eg lower alkoxy), a halogen atom, an amino group or a substituted amino group, or said R, and R or said R and R may be condensed with each other to form a benzene ring.
- phenazine derivatives as desensitizing dyes is known but it has never been known that the phenazine oxide derivatives employed in the present invention selectively desensitize a silver halide photographic emulsion to visible light while having much less effect upon the sensitivity of the emulsion to X-rays.
- the aforesaid compound to be used in the present invention has the advantage that when the compound is incorporated into a silver halide photographic emulsion layer of a photographic light-sensitive element, less stain is left after the light-sensitive element is developed and, further, since the absorption wave length of the compound is in the short wave length region, any stain which may remain after development, is inconspicuous.
- the aforesaid phenazine oxide derivative used in the present invention may be incorporated into a silver halide photographic emulsion as a solution in a water-miscible organic solvent such as methanol, ethanol, acetone, pyridine and the like.
- the amount of the compound to be incorporated in the silver halide photographic emulsion is preferably 1.5 X 10 to l X 10' mole per mole of silver halide in the silver halide emulsion.
- the silver halide photographic emulsion there may be profitably used a silver iodobromide emulsion, a silver bromide emulsion, and a silver chloroiodo-bromide emulsion.
- the silver halide photographic emulsion containing the above-mentioned desensitizing dye may be applied to any suitable support, such as a cellulose triacetate film, a polyethylene terephthalate film, a baryta-coated paper, a resin-coated paper or other plastic film.
- phenazine oxide derivatives used in the present invention may be prepared by either of the following well known methods:
- a desired amount of a methanol solution of the compound of this invention in a desired concentration was added to the system followed by stirring.
- the resultant silver halide emulsion was applied to a cellulose triacetate film in a thickness of 7.5 microns i 0.5 micron and dried to provide a silver halide photographic light-sensitive film.
- the photographic light-sensitive film thus prepared was cut into two portions.
- One specimen was exposed to X-rays using an X-ray source of 75 k. V. and 6 amp. through an aluminum 3 ,6 5 8 ,5 47 5 6 wedge of a definte thickness.
- the other specimen was exposed N for 8 minutes to a daylight source through a yellow filter for safe light'(More Light; made by Eastman Kodak Co.) under definite conditions.
- the specimen films thus exposed were developed for 4 5 minutes at 20 C. in a developer having the following composition and then fixed Metol 4 g. Anhydrous sodium sulfite 60 g. 10 OH 10 g Hydroquinone ⁇ N/ Sodium carbonate mono-hydrate 53 g. 8 Potassium bromide 2.5 g. Water to make 1 liter N 0 0211
- the relative sensitivity to X-rays and the density of fog by yellow light of the various specimens were measured, the ⁇ N// results of which measurements are shown in the following ta- 1 ble. 0
- Amount Relative Fog den- Compound and cone. of the of solution sensitivity sity by yel No. solution of the compound (ml.) to X'-rays low light 1 None 325 3.
- C A silver halide photographic emulsion having a reduced sensitivity to visible light and a high sensitivity to x-rays con.-
- moo sisting essentially of a desensitizmg amount of a compound represented by the general formula selected from the group i consisting of CH a N l N R3 11 R4 0 and O T o N I RX Re I CH3 s J1 R4 ⁇ N/ wherein R R R and R each is selected from the group consisting of hydrogen, alkyl, aryl, nitro, hydroxyl, alkoxy,
- a silver halide photographic light-sensitive element for NHCOCH3 X-ray photography comprising a support having thereon a layer of silver halide photographic emulsion as set forth in claim 1.
- a silver halide photographic emulsion having a reduced sensitivity to visible light and a high sensitivity to X-rays consisting essentially of a compound selected from the group con- NHCOCH;
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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)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Photographic silver halide emulsion and photographic elements containing same, said elements containing certain phenazine desensitizing dyes. The dyes of this invention selectively desensitize the silver halide emulsion to visible light, as contrasted with X-rays.
Description
ilited States Patent Shiba et al. 51 Apr. 25, 1972 [541 SILVER HALIDE PHOTOGRAPHIC EMULSIONS CONTAINING References Cited PHENOZINE-N-OXIDES UNITED STATES PATENTS DESENSITIZERS 3,403,025 9/1968 Rees et al. ..96/10l [72] Inventors: Keisuke Shiba; Reiichi Ohi; Masatoshi Su- 3 250 3 5 19 Stewart et l 9 101 X giyama; All! Ohhashi; Momhiko Tsub- 3,340,063 9/1967 Kalenda ....96/10l x of Kanagawa, Japan 3,237,008 2/1966 Dostes et al ..96/10l x [73] Assignee: Fuji Photo Film Co., Ltd., Ashigara- Kamigum, Kanagawa, Japan Primary ExammerNorman G. Torchm Assistant Examiner-Won H. Louie, Jr. [22] Fled: Man 1970 Attorney-Sughrue, Rothwell, Mion, Zinn& Macpeak ["21] Appl. No.: 17,316
[57] ABSTRACT [30] Foreign Application Priority Data Photographic silver halide emulsion and photographic elements containing same, said elements containing certain Mar. 7, Japan henazine desensitizing dyes The dyes of this invention elec. tively desensitize the silver halide emulsion to visible light, as [5 U.S. Cl ..96/10l contrasted i x {51 ..G03c 1/36 [58 Field of Search ..96/ 101 5 Claims, No Drawings SILVER I'IALIDE PHOTOGRAPI'IIC EMULSIONS CONTAINING PI-IENOZINE-N-OXIDES DESENSITIZERS BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic emulsion having selectively reduced sensitivity to visible light and, more particularly, to a silver halide photographic emulsion of which the sensitivity to visible light has been reduced without reducing sensitivity to X-rays.
2. Description of the Prior Art Usually, photographic light-sensitive elements must be developed, after image exposure, in a dark room or under safe light and the development must also be conducted, in general, under controlled conditions of temperature, time, agitation and the like. Thus, as these developing operations must be conducted in a dark room or under safe light, various attempts have been made to allow the conducting of these operations under more convenient conditions.
In ordinary silver halide photographic emulsions, the sensitivity thereof to X-rays is in direct proportion to sensitivity to visible light.
An object of the present invention is to provide a specific silver halide photographic emulsion, the sensitivity of which to visible light has been selectively reduced without reducing the sensitivity thereof to X-rays, whereby it becomes possible to handle the light-sensitive element made from such a light-sensitive photographic emulsion under visible light after the lightsensitive element is exposed to X-rays.
Another object of the present invention is to provide a desensitizing agent capable of reducing selectively the sensitivity of a silver halide photographic emulsion to visible light without reducing the sensitivity thereof to X-rays.
Still another object of the present invention is to provide a silver halide photographic X ray-sensitive element having a silver halide emulsion layer containing the desensitizing dye as mentioned above.
In this respect, by using an ordinary desensitizing dye, such as pinakryptol yellow, phenosafranine, methylene blue and the like, the sensitivity of a silver halide photographic emulsion to X-rays may be reduced considerably, but these materials tend to remain after development as stains.
SUMMARY OF THE INVENTION The inventors have found that the above objects of the present invention can be attained by incorporating into a silver halide photographic emulsion a compound represented by the general formula wherein R R R and R each represents a hydrogen atom, an alkyl group (e.g. lower alkyl), an aryl group (e.g. phenyl), a nitro group, a hydroxyl group, an alkoxy group eg lower alkoxy), a halogen atom, an amino group or a substituted amino group, or said R, and R or said R and R may be condensed with each other to form a benzene ring.
DETAILED DESCRIPTION OF THE INVENTION Examples of alkyl substituting groups of the phenazine oxide derivatives represented by the above mentioned general formula are lower alkyl groups, such as methyl, ethyl, butyl and the like. Examples of halogen atoms are chlorine, bromine and the like and examples of substituted amino groups are lower alkyl-substituted amino groups, such as alkyl amino, dialkyl amino, and acylamido group, and the like.
The use of phenazine derivatives as desensitizing dyes is known but it has never been known that the phenazine oxide derivatives employed in the present invention selectively desensitize a silver halide photographic emulsion to visible light while having much less effect upon the sensitivity of the emulsion to X-rays.
Moreover, the aforesaid compound to be used in the present invention has the advantage that when the compound is incorporated into a silver halide photographic emulsion layer of a photographic light-sensitive element, less stain is left after the light-sensitive element is developed and, further, since the absorption wave length of the compound is in the short wave length region, any stain which may remain after development, is inconspicuous.
The aforesaid phenazine oxide derivative used in the present invention may be incorporated into a silver halide photographic emulsion as a solution in a water-miscible organic solvent such as methanol, ethanol, acetone, pyridine and the like. The amount of the compound to be incorporated in the silver halide photographic emulsion is preferably 1.5 X 10 to l X 10' mole per mole of silver halide in the silver halide emulsion. As the silver halide photographic emulsion, there may be profitably used a silver iodobromide emulsion, a silver bromide emulsion, and a silver chloroiodo-bromide emulsion.
The silver halide photographic emulsion containing the above-mentioned desensitizing dye may be applied to any suitable support, such as a cellulose triacetate film, a polyethylene terephthalate film, a baryta-coated paper, a resin-coated paper or other plastic film.
Typical examples of the aforesaid compounds represented by the above-mentioned general formula are shown below. It should, however, be understood that the invention shall not be limited to only these compounds. The temperatures shown with the compounds are the melting or decomposition points of the corresponding compounds;
Compound Structure C.
I Compound (a) N 222 258 Compound (b) N Com ound (c).. N 154-155 D o 02H;
Compound ((1) N C} 203 Hz 0 O- N Compound (e) C H;
IIIHCOCH;
Compound (1) Compound Compound (k) Compound (1) Com ound m) Compound (n) Compound (p) r 0 Compound (o).. 188490 Compound (q) Nn 161-162 B i N r Compound (1') N m 282 Compound (5) N 01 250 Com ound t N 198 p 0 mow 1;
Br N The aforesaid phenazine oxide derivatives used in the present invention may be prepared by either of the following well known methods:
1. A Wohl-Aue reaction, wherein an aniline or naphthylamine is reacted with a nitrobenzene in a nonpolar solvent, such as benzene or toluene, using potassium hydroxide as the condensing agent.
2. A method wherein a phenazine obtained by the condensation reaction of an o-quinone and and o-phenylenediamine is oxidized using hydrogen peroxide.
The invention will be further illustrated by the following example.
EXAMPLE One kilogram of a gelatino silver iodobromide emulsion (containing 1 mole% iodine) was melted at 40 C. in a beaker.
A desired amount of a methanol solution of the compound of this invention in a desired concentration was added to the system followed by stirring. The resultant silver halide emulsion was applied to a cellulose triacetate film in a thickness of 7.5 microns i 0.5 micron and dried to provide a silver halide photographic light-sensitive film.
The photographic light-sensitive film thus prepared was cut into two portions. One specimen was exposed to X-rays using an X-ray source of 75 k. V. and 6 amp. through an aluminum 3 ,6 5 8 ,5 47 5 6 wedge of a definte thickness. The other specimen was exposed N for 8 minutes to a daylight source through a yellow filter for safe light'(More Light; made by Eastman Kodak Co.) under definite conditions.
The specimen films thus exposed were developed for 4 5 minutes at 20 C. in a developer having the following composition and then fixed Metol 4 g. Anhydrous sodium sulfite 60 g. 10 OH 10 g Hydroquinone \N/ Sodium carbonate mono-hydrate 53 g. 8 Potassium bromide 2.5 g. Water to make 1 liter N 0 0211 The relative sensitivity to X-rays and the density of fog by yellow light of the various specimens were measured, the \N// results of which measurements are shown in the following ta- 1 ble. 0
Amount Relative Fog den- Compound and cone. of the of solution sensitivity sity by yel No. solution of the compound (ml.) to X'-rays low light 1 None 325 3. 2. Compound (:1), 1X10 mo1e.. 20 360 2. 70 40 200 0. 40 80 100 0. 30 20 480 0. 57 40 430 0. 32 80 150 0.20 80 325 0. 200 250 0.20 400 145 0.10 20 360 0. 52 40 350 0. 22 80 200 0.10 80 200 0. 200 200 0.12 400 200 0.10
What is claimed is: C 1. A silver halide photographic emulsion having a reduced sensitivity to visible light and a high sensitivity to x-rays con.-
. moo sisting essentially of a desensitizmg amount of a compound represented by the general formula selected from the group i consisting of CH a N l N R3 11 R4 0 and O T o N I RX Re I CH3 s J1 R4 \N/ wherein R R R and R each is selected from the group consisting of hydrogen, alkyl, aryl, nitro, hydroxyl, alkoxy,
Br halo, amino and substituted amino, and wherein said R and N I R and said R and R together may be condensed with each CH other to form a benzene ring.
2. The silver halide photographic emulsion of claim 1 wherein said compound is incorporated into the silver halide d3 emulsion in an amount offrom 1.5 X 10 to l X 10' mole per mole of silver halide in said emulsion.
3. A silver halide photographic light-sensitive element for NHCOCH3 X-ray photography comprising a support having thereon a layer of silver halide photographic emulsion as set forth in claim 1.
4. The silver halide photographic emulsion of claim 1, wherein said compound is a member selected from the group consisting of \Ny Br and N N Br 5. A silver halide photographic emulsion having a reduced sensitivity to visible light and a high sensitivity to X-rays consisting essentially ofa compound selected from the group con- NHCOCH;
l z v 3) Q U N Br O: n H0 (31 5 and N H 00 N a N Br said compound being incorporated into the silver halide emulsion in an amount of from 1.5 X 10 to l X 10 mol per mol of silver halide in said emulsion.
Claims (4)
- 2. The silver halide photographic emulsion of claim 1 wherein said compound is incorporated into the silver halide emulsion in an amount of from 1.5 X 10 4 to 1 X 10 2 mole per mole of silver halide in said emulsion.
- 3. A silver halide photographic light-sensitive element for X-ray photography comprising a support having thereon a layer of silver halide photographic emulsion as set forth in claim 1.
- 4. The silver halide photographic emulsion of claim 1, wherein said compound is a member selected from the group consisting of
- 5. A silver halide photographic emulsion having a reduced sensitivity to visible light and a high sensitivity to X-rays consisting essentially of a compound selected from the group consisting of
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP44017259A JPS4832366B1 (en) | 1969-03-07 | 1969-03-07 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3658547A true US3658547A (en) | 1972-04-25 |
Family
ID=11938949
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US17316A Expired - Lifetime US3658547A (en) | 1969-03-07 | 1970-03-06 | Silver halide photographic emulsions containing phenozine-n-oxides desensitizers |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US3658547A (en) |
| JP (1) | JPS4832366B1 (en) |
| BE (1) | BE746882A (en) |
| DE (1) | DE2010765A1 (en) |
| FR (1) | FR2037800A5 (en) |
| GB (1) | GB1263868A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4472497A (en) * | 1983-02-18 | 1984-09-18 | Minnesota Mining And Manufacturing Company | White light handleable photographic materials |
| US4539291A (en) * | 1982-12-24 | 1985-09-03 | Fuji Photo Film Co., Ltd. | Direct positive silver halide photographic materials |
| DE4119505A1 (en) * | 1991-06-13 | 1992-12-17 | Du Pont Deutschland | METHOD FOR PRODUCING A RADIOGRAPHIC RECORDING MATERIAL WITH LOW LIGHT SENSITIVITY |
| US5783379A (en) * | 1995-07-18 | 1998-07-21 | Agfa-Gevaert, N.V. | X-ray silver halide photographic material suitable for maintenance in bright darkroom lighting conditions |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3237008A (en) * | 1961-01-19 | 1966-02-22 | Eastman Kodak Co | Roomlight handling radiographic element including an x-ray sensitive layer overcoated with a dye desensitized silver halide emulsion |
| US3250618A (en) * | 1959-05-13 | 1966-05-10 | Eastman Kodak Co | Thermal resensitization of desensitized silver halide photographic emulsions |
| US3340063A (en) * | 1963-09-04 | 1967-09-05 | Eastman Kodak Co | Photographic colloid transfer system |
| US3403025A (en) * | 1965-08-25 | 1968-09-24 | Eastman Kodak Co | Desensitization of silver halides to visible radiation with thiuram disulfides |
-
1969
- 1969-03-07 JP JP44017259A patent/JPS4832366B1/ja active Pending
-
1970
- 1970-03-05 BE BE746882D patent/BE746882A/en unknown
- 1970-03-05 GB GB00640/70A patent/GB1263868A/en not_active Expired
- 1970-03-06 US US17316A patent/US3658547A/en not_active Expired - Lifetime
- 1970-03-06 DE DE19702010765 patent/DE2010765A1/en active Pending
- 1970-03-09 FR FR7008277A patent/FR2037800A5/fr not_active Expired
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3250618A (en) * | 1959-05-13 | 1966-05-10 | Eastman Kodak Co | Thermal resensitization of desensitized silver halide photographic emulsions |
| US3237008A (en) * | 1961-01-19 | 1966-02-22 | Eastman Kodak Co | Roomlight handling radiographic element including an x-ray sensitive layer overcoated with a dye desensitized silver halide emulsion |
| US3340063A (en) * | 1963-09-04 | 1967-09-05 | Eastman Kodak Co | Photographic colloid transfer system |
| US3403025A (en) * | 1965-08-25 | 1968-09-24 | Eastman Kodak Co | Desensitization of silver halides to visible radiation with thiuram disulfides |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4539291A (en) * | 1982-12-24 | 1985-09-03 | Fuji Photo Film Co., Ltd. | Direct positive silver halide photographic materials |
| US4472497A (en) * | 1983-02-18 | 1984-09-18 | Minnesota Mining And Manufacturing Company | White light handleable photographic materials |
| DE4119505A1 (en) * | 1991-06-13 | 1992-12-17 | Du Pont Deutschland | METHOD FOR PRODUCING A RADIOGRAPHIC RECORDING MATERIAL WITH LOW LIGHT SENSITIVITY |
| US5783379A (en) * | 1995-07-18 | 1998-07-21 | Agfa-Gevaert, N.V. | X-ray silver halide photographic material suitable for maintenance in bright darkroom lighting conditions |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS4832366B1 (en) | 1973-10-05 |
| BE746882A (en) | 1970-08-17 |
| FR2037800A5 (en) | 1970-12-31 |
| GB1263868A (en) | 1972-02-16 |
| DE2010765A1 (en) | 1970-09-24 |
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