US3457079A - Photographic silver halide emulsions stabilized with gallic acid or an alkyl ester thereof - Google Patents
Photographic silver halide emulsions stabilized with gallic acid or an alkyl ester thereof Download PDFInfo
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- US3457079A US3457079A US515739A US3457079DA US3457079A US 3457079 A US3457079 A US 3457079A US 515739 A US515739 A US 515739A US 3457079D A US3457079D A US 3457079DA US 3457079 A US3457079 A US 3457079A
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- gallate
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- 239000000839 emulsion Substances 0.000 title claims description 27
- -1 silver halide Chemical class 0.000 title claims description 14
- 229910052709 silver Inorganic materials 0.000 title claims description 4
- 239000004332 silver Substances 0.000 title claims description 4
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 title description 14
- 229940074391 gallic acid Drugs 0.000 title description 5
- 235000004515 gallic acid Nutrition 0.000 title description 5
- 125000005907 alkyl ester group Chemical group 0.000 title description 2
- 150000001875 compounds Chemical class 0.000 claims description 28
- 230000000087 stabilizing effect Effects 0.000 claims description 4
- 229920000159 gelatin Polymers 0.000 claims description 3
- 235000019322 gelatine Nutrition 0.000 claims description 3
- 108010010803 Gelatin Proteins 0.000 claims 1
- 239000008273 gelatin Substances 0.000 claims 1
- 235000011852 gelatine desserts Nutrition 0.000 claims 1
- 239000010410 layer Substances 0.000 description 11
- 238000002360 preparation method Methods 0.000 description 11
- 239000003381 stabilizer Substances 0.000 description 9
- 230000005070 ripening Effects 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 5
- ZTHYODDOHIVTJV-UHFFFAOYSA-N Propyl gallate Chemical compound CCCOC(=O)C1=CC(O)=C(O)C(O)=C1 ZTHYODDOHIVTJV-UHFFFAOYSA-N 0.000 description 4
- 206010070834 Sensitisation Diseases 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 230000008313 sensitization Effects 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000002411 adverse Effects 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 239000001828 Gelatine Substances 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 230000029087 digestion Effects 0.000 description 2
- VFPFQHQNJCMNBZ-UHFFFAOYSA-N ethyl gallate Chemical compound CCOC(=O)C1=CC(O)=C(O)C(O)=C1 VFPFQHQNJCMNBZ-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- FBSFWRHWHYMIOG-UHFFFAOYSA-N methyl 3,4,5-trihydroxybenzoate Chemical compound COC(=O)C1=CC(O)=C(O)C(O)=C1 FBSFWRHWHYMIOG-UHFFFAOYSA-N 0.000 description 2
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N o-dicarboxybenzene Natural products OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- NRPKURNSADTHLJ-UHFFFAOYSA-N octyl gallate Chemical compound CCCCCCCCOC(=O)C1=CC(O)=C(O)C(O)=C1 NRPKURNSADTHLJ-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N perisophthalic acid Natural products OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 235000010388 propyl gallate Nutrition 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- CYXJEHCKVOQFOV-UHFFFAOYSA-N (4-amino-2-methylphenyl) hydrogen sulfate Chemical compound CC1=CC(N)=CC=C1OS(O)(=O)=O CYXJEHCKVOQFOV-UHFFFAOYSA-N 0.000 description 1
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 description 1
- YBMTWYWCLVMFFD-UHFFFAOYSA-N 3-methylbutyl 3,4,5-trihydroxybenzoate Chemical compound CC(C)CCOC(=O)C1=CC(O)=C(O)C(O)=C1 YBMTWYWCLVMFFD-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
- INVVMIXYILXINW-UHFFFAOYSA-N 5-methyl-1h-[1,2,4]triazolo[1,5-a]pyrimidin-7-one Chemical compound CC1=CC(=O)N2NC=NC2=N1 INVVMIXYILXINW-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 229920002284 Cellulose triacetate Polymers 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- RPWFJAMTCNSJKK-UHFFFAOYSA-N Dodecyl gallate Chemical compound CCCCCCCCCCCCOC(=O)C1=CC(O)=C(O)C(O)=C1 RPWFJAMTCNSJKK-UHFFFAOYSA-N 0.000 description 1
- 239000004262 Ethyl gallate Substances 0.000 description 1
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 1
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- 229910021612 Silver iodide Inorganic materials 0.000 description 1
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- XOPOEBVTQYAOSV-UHFFFAOYSA-N butyl 3,4,5-trihydroxybenzoate Chemical compound CCCCOC(=O)C1=CC(O)=C(O)C(O)=C1 XOPOEBVTQYAOSV-UHFFFAOYSA-N 0.000 description 1
- 239000000298 carbocyanine Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000586 desensitisation Methods 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
- 150000002148 esters Chemical class 0.000 description 1
- 235000019277 ethyl gallate Nutrition 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 238000009472 formulation Methods 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
- TYCUSKFOGZNIBO-UHFFFAOYSA-N hexadecyl 3,4,5-trihydroxybenzoate Chemical compound CCCCCCCCCCCCCCCCOC(=O)C1=CC(O)=C(O)C(O)=C1 TYCUSKFOGZNIBO-UHFFFAOYSA-N 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- IBKQQKPQRYUGBJ-UHFFFAOYSA-N methyl gallate Natural products CC(=O)C1=CC(O)=C(O)C(O)=C1 IBKQQKPQRYUGBJ-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- QWYZFXLSWMXLDM-UHFFFAOYSA-M pinacyanol iodide Chemical compound [I-].C1=CC2=CC=CC=C2N(CC)C1=CC=CC1=CC=C(C=CC=C2)C2=[N+]1CC QWYZFXLSWMXLDM-UHFFFAOYSA-M 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- TXGSOSAONMOPDL-UHFFFAOYSA-N propan-2-yl 3,4,5-trihydroxybenzoate Chemical compound CC(C)OC(=O)C1=CC(O)=C(O)C(O)=C1 TXGSOSAONMOPDL-UHFFFAOYSA-N 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 1
- 229940045105 silver iodide Drugs 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 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
- G03C1/34—Fog-inhibitors; Stabilisers; Agents inhibiting latent image regression
Definitions
- This invention relates to stabilized photographic compositions, and more particularly, it concerns with a photographic element, e.g., photographic film, paper or plate, bearing on a support a photosensitive layer containing gallic acid or its alkyl esters which may be generically referred to a gallic compound hereinafter.
- a photographic element e.g., photographic film, paper or plate
- a photosensitive layer containing gallic acid or its alkyl esters which may be generically referred to a gallic compound hereinafter.
- Another object of the present invention is to provide a photographic element which is entirely safe from formation of fog.
- the gallic compound may be incorporated into at least one of the gelatine-containing layers of a photographic element, such layers including emulsion layers, sublayers, internal layers, protective layers and backing layers.
- a photographic element such layers including emulsion layers, sublayers, internal layers, protective layers and backing layers.
- Suitable gallic compounds can be represented by the general formula HO- OH COOR wherein R represents hydrogen atom or a straight of branched alkyl radical containing 1 to 18 carbon atoms.
- Typical compounds are gallic acid (M.P. 235 C. (decomp.)), methyl gallate .(M.P. 200 C.), ethyl gallate (M.P. 155 C.), n-propyl galate (M.P. 148 C.), isopropyl gallate (M.P. 124 C.), n-butyl gallate (M.P. 134 C.) isoamyl gallate (M.P. 146 C.), n-amyl gallate (M.P. 109 C.), n-hexyl gallate (M.P. 93 C.), n-heptyl gallate (M.P.
- lower alkyl gallates can be readily prepared by the conventional techniques known by those skilled in the art, and higher alkyl gallates, for example, having more than ten carbon atoms can be prepared by the method described in Rec. Trav. Chim., 70, 277-284 (1951).
- Incorporation of the gallic compound into a layer or layers of the photographic element-of the present invention can be made in the manner heretofore known per se :in the art.
- the gallic compound is to be present in an emulsion layer of the said element, it is possible to add the said compound into the emulsion at any time just before, during or after the second ripening of the said emulsion. Addition of the gallic compound at the stage after the second ripening of the emulsion is most preferred.
- the gallic compound may be added to a starting material for preparation of the emulsion, for example, gelatine.
- the amount added will vary depending on the type of emulsions, the degree of stabilization desired and the type of a layer to which the gallic compound is added, but it usually is within the range of from 0.003 g. to 3.0 g. per liter of the emulsion or coating solution. It is desirable to add this compound in solution dissolved in a suitable solvent, e.g., Water, methanol, ethanol, etc., if the addition is made to an emulsion.
- a suitable solvent e.g., Water, methanol, ethanol, etc.
- gallic compound as a stabilizer does not adversely influence on sensitization of a photographic emulsion concerned.
- the photographic emulsion sensitized by way of gold-, sulfuror other chemical sensitization or optical sensitization can be successfully stabilized with the gallic compound.
- Any hardener, coating aid or other known photographic additives may be optionally used in combination with the gallic compound, without a significant loss of its stabilizing effect.
- Still another advantage of the present invention is that fog and desensitization both which frequently occur during the storage of a color photographic material containing color formers in the emulsion can be effectively prevented by using the gallic compound.
- Suitable supports include films, papers and glass plates.
- films of the types such as cellulose esters, e.g., cellulose triacetate; polyesters obtained by the polycondensati'on of phthalic, isophthalic or terephthalic acid with a dihydric alcohol, e.g., polyethylene terephthalate, poly [cyclohexane 1.4 dimethylol]terephthalate, etc.; and polycarbonates including those obtained by the polycondensation of bis-phenol A with carbonic acid, are suitable.
- tion is added with 5-methyl-7-hydroxy-1,3,4-triazaindolizine which is the known stabilizer.
- Each portions are prepared to form films.
- Each films are cut into three pieces, one of which is immediately subjected to the later specified sensitometric test, and the second and third pieces are stored at 55 C. for 2 days or at 50 C. under a relative humidity of 80% for 2 days before the same test. Samples of these film coatings were then exposed in an intensity-scale type sensitometer and developed for five minutes in a developer of the following formulation:
- R represents hydrogen atom or a straight or branched alkyl radical having 1 to 18 carbon atoms.
- n-Octyl gallate 220 98 0.11 92 0. 16 115 0. 11 n-Decyl gallate 250 100 0. 12 06 0. 17 0. 10 n-Tetradecyl gallate 290 100 0. 12 97 0. 16 115 0. l1 n-Oetadecyl gallate 330 98 0. 13 99 0. 18 112 0. 11 Known stabilizer- 80 0. 13 76 0. 12 61 0. 09
- EXAMPLE 2 The photographic emulsion used in Example 1 is sub- -jected to second ripening in the same manner as in Example l. Five minutes before completion of the second 5 having incorporated therein a stabilizing compound of the formula COOR to 3.0 g. per liter of the emulsion in the coating solution used in the preparation of the emulsion layer.
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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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
Description
United States Patent Office Patented July 22, 1969 3,457,079 PHOTOGRAPHIC SILVER HALIDE EMULSIONS STABILIZED WITH GALLIC ACID R AN ALKYL ESTER THEREOF Kenichi Koda, Shui Sato, Masayuki Shoono, and Haruo Hori, Tokyo, Japan, assignors to Konishiroku Photo gndustry C0,, Ltd., Tokyo, Japan, a corporation of apan No Drawing. Filed Dec. 22, 1965, Ser. No. 515,739 Claims priority, application Japan, Dec. 30, 1964, 39/74,371 Int. Cl. G03n 1/34 U.S. Cl. 96-109 5 Claims This invention relates to stabilized photographic compositions, and more particularly, it concerns with a photographic element, e.g., photographic film, paper or plate, bearing on a support a photosensitive layer containing gallic acid or its alkyl esters which may be generically referred to a gallic compound hereinafter.
In the art it is well known that photographic compositions, when stored for a long period after their preparation, sufiier from decrease in speed and formation of undesired fog. In order to prevent these adverse effects, a variety of stabilizers also have been proposed. Incorporation of the known stabilizers (e.g., azaindolizine), however, is disadvantageous because it often causes decrease in speed, and the demand in the art has been directed to develop a stabilizer which will permit to pervent fog without any adverse influence on photosensitivity.
It is accordingly one object of the present invention to provide a photographic composition which can resist to any undesired effect caused by storage over a long period of time.
Another object of the present invention is to provide a photographic element which is entirely safe from formation of fog.
Other objects, features, capabilities and advantages which are comprehended by the invention will be apparent from the specification and claims which follow.
The above-mentioned and other objects can be attained by incorporating a gallic compound as a stabilizer into a photographic composition.
We have now found that if the gallic compound is present in a photographic composition of the present invention, the said composition can be safely stored over a long period of time, without suffering from decrease in speed or formation of fog. In a typical embodiment of the present invention, the gallic compound may be incorporated into at least one of the gelatine-containing layers of a photographic element, such layers including emulsion layers, sublayers, internal layers, protective layers and backing layers. Another advantage of the present invention is that Where the gallic compound is added to a photographic emulsion during its digestion or ripening, it is possible to prevent fog formation and consequently to facilitate an increase of speed due to the digestion or ripening.
Suitable gallic compounds can be represented by the general formula HO- OH COOR wherein R represents hydrogen atom or a straight of branched alkyl radical containing 1 to 18 carbon atoms.
Typical compounds are gallic acid (M.P. 235 C. (decomp.)), methyl gallate .(M.P. 200 C.), ethyl gallate (M.P. 155 C.), n-propyl galate (M.P. 148 C.), isopropyl gallate (M.P. 124 C.), n-butyl gallate (M.P. 134 C.) isoamyl gallate (M.P. 146 C.), n-amyl gallate (M.P. 109 C.), n-hexyl gallate (M.P. 93 C.), n-heptyl gallate (M.P. 96 C.), n-octyl gallate (M.P. 96 C.), n-nonyl gallate (M.P. 97 C.), n-decyl gallate (M.P. C.), nhendecyl gallate (M.P. 97 C.), n-dodecyl gallate (M.P. 97 C.), n-tetradecyl gallate (M.P. 97 C.), n-hexadecyl gallate (M.P. 100 C.) and n-octadecyl gallate (M.P. 104 C.). Among these compounds, lower alkyl gallates can be readily prepared by the conventional techniques known by those skilled in the art, and higher alkyl gallates, for example, having more than ten carbon atoms can be prepared by the method described in Rec. Trav. Chim., 70, 277-284 (1951).
Incorporation of the gallic compound into a layer or layers of the photographic element-of the present invention can be made in the manner heretofore known per se :in the art. For example, if the gallic compound is to be present in an emulsion layer of the said element, it is possible to add the said compound into the emulsion at any time just before, during or after the second ripening of the said emulsion. Addition of the gallic compound at the stage after the second ripening of the emulsion is most preferred. Alternatively, the gallic compound may be added to a starting material for preparation of the emulsion, for example, gelatine. The amount added will vary depending on the type of emulsions, the degree of stabilization desired and the type of a layer to which the gallic compound is added, but it usually is within the range of from 0.003 g. to 3.0 g. per liter of the emulsion or coating solution. It is desirable to add this compound in solution dissolved in a suitable solvent, e.g., Water, methanol, ethanol, etc., if the addition is made to an emulsion.
Use of the gallic compound as a stabilizer does not adversely influence on sensitization of a photographic emulsion concerned. Thus, the photographic emulsion sensitized by way of gold-, sulfuror other chemical sensitization or optical sensitization can be successfully stabilized with the gallic compound. Any hardener, coating aid or other known photographic additives may be optionally used in combination with the gallic compound, without a significant loss of its stabilizing effect. Furthermore, it sometimes can provide desirable effect to facilitate an increase of speed because the said compound will prevent increased fog which frequently occurs accompanying to the sensitization. It is, of course, true that decrease of speed and increase of fog during storage of the emulsion also can be prevented by using the gallic compound.
Still another advantage of the present invention is that fog and desensitization both which frequently occur during the storage of a color photographic material containing color formers in the emulsion can be effectively prevented by using the gallic compound.
The emulsion to which the gallic compound has been added can be applied to a suitable support in the manner heretofore known per se in the art, e.g., coating or pouring. Suitable supports include films, papers and glass plates. For example, films of the types, such as cellulose esters, e.g., cellulose triacetate; polyesters obtained by the polycondensati'on of phthalic, isophthalic or terephthalic acid with a dihydric alcohol, e.g., polyethylene terephthalate, poly [cyclohexane 1.4 dimethylol]terephthalate, etc.; and polycarbonates including those obtained by the polycondensation of bis-phenol A with carbonic acid, are suitable.
The following examples describe certain ways in which the principle of the invention has been applied, but are not to be construed as limiting its scope.
3 EXAMPLE 1 A silver bromo-iodide emulsion useful for high speed negatives and containing 3 mol percent of silver iodide is prepared according to neutral process. This emulsion 4 ripening, the emulsion is optically sensitized by addition of 9-methyl-3,3'-diethyl seleno carbocyanine bromide in the amount of 50 mg. per liter of the emulsion. The emulsion is divided to nine portions, one of which is used for preparation of control film without any stabilizer and is added With a gold-sensitilef and then Subjected to 5 the other seven used after the addition of the gallic comond ripening at a temperature of 60 C. for 75 minutes. pounds specified in the respective columns of Table II. After the said ripening, the emulsion 18 divided to eleven Th remaining one portion i dd d ith the same known portions, one of which is used for preparation of control stabilizer as in Example 1. Each portions are prepared film without any stabilizer and the other nine used after to fo film T t pieces ut f om the films are then the addition of the gallic Compounds spficlfied 1n e subjected to a comparative test in the same manner as in respective columns of Table I. The remaining one por- Example 1. The results obtained are set forth in Table II.
TABLE II Incubated at 50 C. Just aiter Iueubated at 55 C. and 80% RH for 2 preparation for 2 days after days after oi the film preparation preparation Amount used Relative Fog Relative Fog Relative Fog Compound (mg/1.) speed speed spee Control 0 100 0. 09 67 0. 34 90 0. 12 Gallic acid 135 101 0. 10 93 0. 12 90 0. 10 Ethyl gallatenn 160 96 0. 09 90 0. 12 100 0. 00 n-Propyl gallate 170 100 0. 09 90 0. 0B 101 0. 10 n-Butyl gal1ate. 180 100 0. 09 9e 0. 11 100 o. 10 n-Heptyl gallate. 210 100 0. 09 89 0. 10 110 0. 11 n-Dodeeyl gallate. 270 102 0. 10 98 0. 11 100 0. 11 n-Hexadecylgallat 310 103 0. 10 99 0. 12 103 0. 11 Known stabilizer- 150 96 0. 09 84 0.08 73 0. 08
tion is added with 5-methyl-7-hydroxy-1,3,4-triazaindolizine which is the known stabilizer. Each portions are prepared to form films. Each films are cut into three pieces, one of which is immediately subjected to the later specified sensitometric test, and the second and third pieces are stored at 55 C. for 2 days or at 50 C. under a relative humidity of 80% for 2 days before the same test. Samples of these film coatings were then exposed in an intensity-scale type sensitometer and developed for five minutes in a developer of the following formulation:
Grams Metol (monomethyl-p-aminophenol sulfate 1.5 Sodium sulfite (anhydrous) 25.0 Hydroquinon 3.0 Sodium carbonate (monohydrate) 15.0 Potassium bromide 0.5
Water to make 1.0 liter.
The developed samples were stopped with dilute acetic acid and then fixed, washed and dried. The results are set forth in Table I.
COOR
wherein R represents hydrogen atom or a straight or branched alkyl radical having 1 to 18 carbon atoms.
TABLE I Incubated at C. Just aiter Incubated at 55 C. and RH for 2 preparation for 2 days after days after of the film preparation preparation Amount used Relative Fog Relative Fog Relative Fog Compound (mg/l.) speed speed speed Control. 0 0. 14 74 0. 43 142 0. 22 Gallic acid- 135 98 0. 12 98 0. 18 115 0. 11 Ethyl gallat 160 100 0. 10 100 0. 16 109 0. 10 n-Propyl gallate 170 95 0. 10 92 0. 15 107 0. 10 Isoamyl g 190 09 0. 12 95 0. 17 110 0. 10 n-Hoxyl gallate 200 100 0. 12 06 0. 16 0. 12 n-Octyl gallate 220 98 0.11 92 0. 16 115 0. 11 n-Decyl gallate 250 100 0. 12 06 0. 17 0. 10 n-Tetradecyl gallate 290 100 0. 12 97 0. 16 115 0. l1 n-Oetadecyl gallate 330 98 0. 13 99 0. 18 112 0. 11 Known stabilizer- 80 0. 13 76 0. 12 61 0. 09
In this test, photographic speed which is a reciprocal of 65 the exposure to give an optical density of 0.5 above fog density, is expressed as relative speed to that of unstored control film, which is rated as 100. The data of Table I clearly indicates that alkyl gallates are useful for prevention of undesired fog formation during incubation.
EXAMPLE 2 The photographic emulsion used in Example 1 is sub- -jected to second ripening in the same manner as in Example l. Five minutes before completion of the second 5 having incorporated therein a stabilizing compound of the formula COOR to 3.0 g. per liter of the emulsion in the coating solution used in the preparation of the emulsion layer.
References Cited UNITED STATES PATENTS wherein R represents hydrogen atom or a straight or 10 NORMAN GTORCHINPrimary Examiner branched alkyl radical having 1 to 18 carbon atoms, the amount of said stabilizing compound being equal to 0.0003
R. E. FICHTER, Assistant Examiner
Claims (1)
1. A LIGHT-SENSITIVE, PHOTOGRAPHIC SILVER HALIDE EMULSION COMPRISING GELATIN HAVING LIGHE-SENSITIVE SILVER HALIDE DISPERSED THEREIN AND CONTAINING A STABILIZING AMOUNT OF A COMPOUND OF THE GENERAL FORMULA
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7437164 | 1964-12-30 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3457079A true US3457079A (en) | 1969-07-22 |
Family
ID=13545220
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US515739A Expired - Lifetime US3457079A (en) | 1964-12-30 | 1965-12-22 | Photographic silver halide emulsions stabilized with gallic acid or an alkyl ester thereof |
Country Status (2)
| Country | Link |
|---|---|
| US (1) | US3457079A (en) |
| GB (1) | GB1096670A (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3775124A (en) * | 1971-06-14 | 1973-11-27 | Fuji Photo Film Co Ltd | Stabilizing method and composition for color photographic processing |
| US3929486A (en) * | 1973-05-12 | 1975-12-30 | Konishiroku Photo Ind | Silver halide photographic material containing a sensitizing and stabilizing combination of a polyalkylene oxide, a tetrazaindene and a resorcinol derivative |
| US4254217A (en) * | 1978-06-19 | 1981-03-03 | Mitsubishi Paper Mills, Ltd. | Hardener-incorporated gelatin composition |
| EP0147854A2 (en) | 1983-12-29 | 1985-07-10 | Fuji Photo Film Co., Ltd. | Silver halide photographic light-sensitive materials |
| EP0209118A2 (en) | 1985-07-17 | 1987-01-21 | Konica Corporation | Silver halide photographic material |
| US4741980A (en) * | 1985-09-19 | 1988-05-03 | Konishiroku Photo Industry Co., Ltd. | Method for increasing color-fastness of organic coloring matter |
| US4756997A (en) * | 1986-07-23 | 1988-07-12 | Minnesota Mining And Manufacturing Company | Photographic silver halide developer compositions and process for forming photographic silver images |
| US4789624A (en) * | 1983-01-20 | 1988-12-06 | Fuji Photo Film Co., Ltd. | Silver halide color photographic light-sensitive material |
| US5130226A (en) * | 1989-05-25 | 1992-07-14 | Konica Corporation | Silver halide photographic light-sensitive material |
| US5198517A (en) * | 1991-08-06 | 1993-03-30 | Eastman Kodak Company | Polymeric scavengers for oxidized developing agents and photographic elements containing the same |
| US5478702A (en) * | 1992-08-18 | 1995-12-26 | Fuji Photo Film Co., Ltd. | Method for forming a color image by scanning exposure using a photographic material containing a specific phenol derivative |
| EP0800113A2 (en) | 1996-04-05 | 1997-10-08 | Fuji Photo Film Co., Ltd. | Silver halide color photographic light-sensitive material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US853643A (en) * | 1906-05-15 | 1907-05-14 | Auguste Lumiere | Photographic paper. |
| GB812673A (en) * | 1956-07-25 | 1959-04-29 | Gevaert Photo Prod Nv | Improvements in or relating to photographic material |
-
1965
- 1965-12-22 US US515739A patent/US3457079A/en not_active Expired - Lifetime
- 1965-12-22 GB GB54412/65A patent/GB1096670A/en not_active Expired
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US853643A (en) * | 1906-05-15 | 1907-05-14 | Auguste Lumiere | Photographic paper. |
| GB812673A (en) * | 1956-07-25 | 1959-04-29 | Gevaert Photo Prod Nv | Improvements in or relating to photographic material |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3775124A (en) * | 1971-06-14 | 1973-11-27 | Fuji Photo Film Co Ltd | Stabilizing method and composition for color photographic processing |
| US3929486A (en) * | 1973-05-12 | 1975-12-30 | Konishiroku Photo Ind | Silver halide photographic material containing a sensitizing and stabilizing combination of a polyalkylene oxide, a tetrazaindene and a resorcinol derivative |
| US4254217A (en) * | 1978-06-19 | 1981-03-03 | Mitsubishi Paper Mills, Ltd. | Hardener-incorporated gelatin composition |
| US4789624A (en) * | 1983-01-20 | 1988-12-06 | Fuji Photo Film Co., Ltd. | Silver halide color photographic light-sensitive material |
| EP0147854A2 (en) | 1983-12-29 | 1985-07-10 | Fuji Photo Film Co., Ltd. | Silver halide photographic light-sensitive materials |
| EP0209118A2 (en) | 1985-07-17 | 1987-01-21 | Konica Corporation | Silver halide photographic material |
| US4741980A (en) * | 1985-09-19 | 1988-05-03 | Konishiroku Photo Industry Co., Ltd. | Method for increasing color-fastness of organic coloring matter |
| US4756997A (en) * | 1986-07-23 | 1988-07-12 | Minnesota Mining And Manufacturing Company | Photographic silver halide developer compositions and process for forming photographic silver images |
| US5130226A (en) * | 1989-05-25 | 1992-07-14 | Konica Corporation | Silver halide photographic light-sensitive material |
| US5198517A (en) * | 1991-08-06 | 1993-03-30 | Eastman Kodak Company | Polymeric scavengers for oxidized developing agents and photographic elements containing the same |
| US5478702A (en) * | 1992-08-18 | 1995-12-26 | Fuji Photo Film Co., Ltd. | Method for forming a color image by scanning exposure using a photographic material containing a specific phenol derivative |
| EP0800113A2 (en) | 1996-04-05 | 1997-10-08 | Fuji Photo Film Co., Ltd. | Silver halide color photographic light-sensitive material |
Also Published As
| Publication number | Publication date |
|---|---|
| GB1096670A (en) | 1967-12-29 |
| DE1572059A1 (en) | 1970-02-19 |
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