US3533794A - Color photographic light-sensitive material containing ultraviolet absorbing agents - Google Patents
Color photographic light-sensitive material containing ultraviolet absorbing agents Download PDFInfo
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- US3533794A US3533794A US810343A US3533794DA US3533794A US 3533794 A US3533794 A US 3533794A US 810343 A US810343 A US 810343A US 3533794D A US3533794D A US 3533794DA US 3533794 A US3533794 A US 3533794A
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- United States
- Prior art keywords
- ultraviolet absorbing
- photographic light
- sensitive material
- color photographic
- phosphate
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- Expired - Lifetime
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- 239000000463 material Substances 0.000 title description 39
- 239000006096 absorbing agent Substances 0.000 title description 28
- 150000001875 compounds Chemical class 0.000 description 44
- 239000010410 layer Substances 0.000 description 43
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 26
- 108010010803 Gelatin Proteins 0.000 description 25
- 239000008273 gelatin Substances 0.000 description 25
- 229920000159 gelatin Polymers 0.000 description 25
- 235000019322 gelatine Nutrition 0.000 description 25
- 235000011852 gelatine desserts Nutrition 0.000 description 25
- 229910019142 PO4 Inorganic materials 0.000 description 22
- 239000010452 phosphate Substances 0.000 description 22
- 239000006185 dispersion Substances 0.000 description 20
- 238000009835 boiling Methods 0.000 description 18
- 239000003960 organic solvent Substances 0.000 description 16
- 239000000839 emulsion Substances 0.000 description 15
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- -1 isooctyl group Chemical group 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 239000002904 solvent Substances 0.000 description 10
- 229940125904 compound 1 Drugs 0.000 description 9
- 229960002380 dibutyl phthalate Drugs 0.000 description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 125000000217 alkyl group Chemical group 0.000 description 8
- 239000013078 crystal Substances 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 239000000084 colloidal system Substances 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 6
- 229910052709 silver Inorganic materials 0.000 description 6
- 239000004332 silver Substances 0.000 description 6
- 229940125782 compound 2 Drugs 0.000 description 5
- 229940126214 compound 3 Drugs 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 5
- NMPAICLYKOKXAP-UHFFFAOYSA-N (2-chlorophenyl) diphenyl phosphate Chemical compound ClC1=CC=CC=C1OP(=O)(OC=1C=CC=CC=1)OC1=CC=CC=C1 NMPAICLYKOKXAP-UHFFFAOYSA-N 0.000 description 4
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 4
- UCVPKAZCQPRWAY-UHFFFAOYSA-N dibenzyl benzene-1,2-dicarboxylate Chemical compound C=1C=CC=C(C(=O)OCC=2C=CC=CC=2)C=1C(=O)OCC1=CC=CC=C1 UCVPKAZCQPRWAY-UHFFFAOYSA-N 0.000 description 4
- 125000005843 halogen group Chemical group 0.000 description 4
- 230000009931 harmful effect Effects 0.000 description 4
- 239000011241 protective layer Substances 0.000 description 4
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- SJOOOZPMQAWAOP-UHFFFAOYSA-N [Ag].BrCl Chemical compound [Ag].BrCl SJOOOZPMQAWAOP-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 3
- LHPPDQUVECZQSW-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4,6-ditert-butylphenol Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC(N2N=C3C=CC=CC3=N2)=C1O LHPPDQUVECZQSW-UHFFFAOYSA-N 0.000 description 2
- WXHVQMGINBSVAY-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 WXHVQMGINBSVAY-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- 229920002284 Cellulose triacetate Polymers 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-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
- 238000000576 coating method Methods 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000007429 general method Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 239000007970 homogeneous dispersion Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- JQDJSFVRBAXBCM-UHFFFAOYSA-N 2-tert-butyl-6-(5-chloro-2H-benzotriazol-4-yl)-4-methylphenol Chemical compound CC(C)(C)C1=CC(C)=CC(C=2C=3N=NNC=3C=CC=2Cl)=C1O JQDJSFVRBAXBCM-UHFFFAOYSA-N 0.000 description 1
- XBTWVJKPQPQTDW-UHFFFAOYSA-N 4-n,4-n-diethyl-2-methylbenzene-1,4-diamine Chemical compound CCN(CC)C1=CC=C(N)C(C)=C1 XBTWVJKPQPQTDW-UHFFFAOYSA-N 0.000 description 1
- QNGVNLMMEQUVQK-UHFFFAOYSA-N 4-n,4-n-diethylbenzene-1,4-diamine Chemical compound CCN(CC)C1=CC=C(N)C=C1 QNGVNLMMEQUVQK-UHFFFAOYSA-N 0.000 description 1
- BVNWQSXXRMNYKH-UHFFFAOYSA-N 4-phenyl-2h-benzotriazole Chemical compound C1=CC=CC=C1C1=CC=CC2=C1NN=N2 BVNWQSXXRMNYKH-UHFFFAOYSA-N 0.000 description 1
- UWSMKYBKUPAEJQ-UHFFFAOYSA-N 5-Chloro-2-(3,5-di-tert-butyl-2-hydroxyphenyl)-2H-benzotriazole Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC(N2N=C3C=C(Cl)C=CC3=N2)=C1O UWSMKYBKUPAEJQ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241001674048 Phthiraptera Species 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- 150000003931 anilides Chemical class 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
- BJFLSHMHTPAZHO-UHFFFAOYSA-N benzotriazole Chemical compound [CH]1C=CC=C2N=NN=C21 BJFLSHMHTPAZHO-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- OCWYEMOEOGEQAN-UHFFFAOYSA-N bumetrizole Chemical compound CC(C)(C)C1=CC(C)=CC(N2N=C3C=C(Cl)C=CC3=N2)=C1O OCWYEMOEOGEQAN-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 229940125773 compound 10 Drugs 0.000 description 1
- 229940125758 compound 15 Drugs 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229960004132 diethyl ether Drugs 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-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
- G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
- G03C1/815—Photosensitive materials characterised by the base or auxiliary layers characterised by means for filtering or absorbing ultraviolet light, e.g. optical bleaching
- G03C1/8155—Organic compounds therefor
Definitions
- R; and R can be hydrogen or up to a four carbon atom alkyl group.
- R can be hydrogen or a halogen.
- An organic solvent having a high boiling point is also present.
- This invention relates to a color photographic lightsensitive material containing ultraviolet absorbing agents, and particularly to a color photographic light-sensitive material containing at least two ultraviolet absorbing compounds selected from Z-aryl benzotriazole derivatives.
- Ultraviolet absorbing agents incorporated into photographic light-sensitive materials must have the following properties.
- Ultraviolet absorbing agents must not color themselves, and their ultraviolet absorptivity should not lower under exposure to light.
- Z-aryl benzotriazole derivatives are excellent ultraviolet absorbing agents. Further, it is known (see U.S. Pat. 3,253,921) that oilsoluble derivatives of said compounds having a long chain alkyl group can be added to the photographic lightsensitive material in the form of a dispersion.
- the compounds having a comparatively low molecular weight which are described in U.S. Pat. 3,004,896 do not have sufficient solubilities in the desired organic solvents having a high boiling point (for example, dibutyl phthalate, tricresyl phosphate, etc.). Accordingly, a large amount of the solvent is required in order to dissolve these compounds, therefore, the amount of gelatin needed for dispersion increases, and consequently, the thickness of the layer of the photographic sensitive materials increases.
- organic solvents having a lower boiling point for example, ethyl acetate
- the solvent mixture is dispersed in an equeous gelating solution and the dispersion is coated as a supersaturated solution (the solution including the ultraviolet absorbing agent in an over-saturated state in the organic solvent having a high boiling point), there is apt to occur crystallization, and consequently the capacity of the gelatin layer is harmed by separation of crystals in the gelatin layer.
- the present invention comprises a color photographic light-sensitive material containing a dispersion of at least two ultraviolet absorbing compounds selected from those represented by the formula:
- N OH R3 l K/ N Br R and R can represent a member selected from the group consisting of a hydrogen atom and an alkyl group having up to four carbon atoms, and R represents a member selected from the group consisting of a hydrogen atom and a halogen atom.
- An organic solvent having a high boiling point is also present.
- the material comprises at least one photographic silver halide emulsion layer and at least one hydrophilic colloid layer, at least one of these should contain a dispersion of the ultraviolet absorbing compounds.
- the gelatin layer may contain a dispersion of at least two of the ultraviolet absorbing compounds.
- the gelatin layer can contain a dispersion of at least two ultraviolet absorbing compounds.
- One object of this invention is to provide a color photographic light-sensitive material containing a dispersion of ultraviolet absorbing agents having a comparatively low molecular weight.
- Another object of this invention is to provide a color photographic light-sensitive material containing ultraviolet absorbing agents which absorb ultraviolet rays of 300- 400 m but which do not absorb visible rays of over 420 Ill 1..
- a further object of this invention is to provide a color photographic light-sensitive material containing ultraviolet absorbing agents which do not flow out or discolor during processing, which do not color or deteriorate with respect to ultraviolet absorptivity by exposure, and which do not have any harmful influence upon the photographic light-sensitive material during preparation, storage or processing.
- the objects can be accomplished by the use of a color photographic light-sensitive material containing a dispersion of at least two ultraviolet absorbing compounds selected from those represented by the following formula, and an organic solvent having a high boiling point:
- the organic solvent having a high boiling point used in this invention are such as those described in 11.8. Pat. 2,322,027.
- the preferred solvents include di-n-butylphthalate, benzylphthalate, triphenyl phosphate, tri-ocresyl phosphate, diphenyl mono-p-tert-butyl phenyl phosphate, monophenyl di-p-tert butyl phenyl phosphate, diphenyl mono-o-chlorophenyl phosphate, monophenyl di-o-chlorophenyl phosphate, tri-p-tert-butylphenyl phosphate, tri-o-phenylphenyl phosphate, di-p-tert-butylphenyl mono (5-tert-butyI-Z-phenylphenyl)phosphate, etc.
- the low boiling organic solvents such as methanol, ethanol, ethyl acetate, butyl acetate, diethylether, dioxane, tetrahydrofuran, acetone, methylethyl ketone, ethylene glycol, diethylene glycol, dipropylene glycol, ethylene glycol monoethyl ether and diethylene glycol monoethyl ether may be used as the solvent assistant.
- the material was then rapidly cooled by immersion in ice-water, and was then allowed to stand at 5 C. in a refrigerator. The separation of crystals was thus observed.
- 2-aryl benzotriazole derivatives represented by Formula 1 used as ultraviolet absorbing agents for color photographic lightsensitive material do not crystallize if two or more of said compounds are used together. It is not as effective to use two or more of the Z-aryl bezotriazole derivatives when the mixing ratio of a compound which is the minimum component is less than 5%, or the mixing ratio of the compound which is the maximum component is over Accordingly, when two or more 2-aryl benzotriazole derivatives are used as ultraviolet absorbing agents for photographic light-sensitive materials, the mixing ratio of these compounds is preferably in the range of from 5% to 90%.
- the 2-aryl benzotriazole derivatives may be used in the range of 1-100 mg./ cm. preferably 5-50 mg./ 100 cm. in forming the film.
- EXAMPLE 1 To a baryta-coated paper, a blue-sensitive silver bromide gelatin emulsion layer containing a yellow coupler: 5-(p-octadecycloyl-aminobenzoyl acetamino) isophthalic acid, a gelatin intermediate layer, a green-sensitive silver bromoiodide gelatin emulsion layer containing a magenta coupler: 1-(3-sulfo-4-phenoxyphenyl)-3-heptadecyI-S-pyrazolone, a gelatin intermediate layer, and a redsensitive silver chlorobromide gelatin emulsion layer containing a cyan coupler: N-octadecyl-1-hydroxy-4- sulfo-Z-naphtamide were applied, in the order recited.
- the obtained coating was divided into two samples, to one of which there was applied a dispersion containing ultraviolet absorbing agents produced by the following procedure so as to contain 20 rug/100 cm. of the ultraviolet absorbing agent. To the other there was applied only a gelatin solution for use as a protective layer.
- the dispersion containing ultraviolet absorbing agents was prepared as follows: 30 g. of Compound 1 and 15 g. each of Compounds 2 and 3 were dissolved in a mixture of 80 g. of dibutyl phthalate and 200 g. of butyl acetate by heating. This solution was added to a mixture of 1 kg. of a 10% aqueous solution of gelatin and 100 g. of a 5% aqueous solution of sodium dodecylbenzene sulfonate. The mixture was dispersed using a colloid mill to produce a homogeneous dispersion.
- Sample coatings thus obtained were given exposure to light through blue, green and red step wedges.
- the samples were then developed with a color developer containing N,N diethyl p phenylene-diamine, and then washed with water, fixed, washed with water, bleached, washed with water, hardened, washed with water and dried by state of the art methods.
- the reflection density thereof was measured at three points (0.5, 1.0 and 1.5 reflection density) for each sample before re-exposing to light.
- a decreasing density ratio was calculated by dividing the balance of the density before exposure and the density after exposure by the density before exposure.
- the calculated decrease of density ratio is shown in the following table.
- EXAMPLE 2 Into the color printing paper described in Example 1, a dispersion containing ultraviolet absorbing agents prepared by the following procedure was added (in the amount of 10 mg./100 cm. of the ultraviolet absorbing agents to the uppermost light-sensitive emulsion layer containing a cyan coupler). The uppermost protective layer was formed of gelatin alone. The same examination was carried out as in Example 1.
- the dispersion described above was prepared" as follows: 30 g. of Compound 1, 10 g. of Compound 2, 10 g. of Compound 3 and 10 g. of Compound 4 were dis-solved (by heating) in a mixture of 60 g. of dibutyl phthalate and 100 g. of ethyl acetate. This solution was added to a mixture of 1 kg. of a 10% aqueous solution of gelatin and 100 g. of a 5% aqueous solution of sodium dodecylbenzene sulfonate. The mixture was dispersed with a colloid mill to obtain a homogeneous dispersion.
- the photographic properties of the red-sensitive emulsion layer were not influenced by the addition of Compounds 1, 2, 3 and 4.
- the couplers were used as a solution of dibutyl phthalate.
- a dispersion containing the ultraviolet absorbing agents used in Example 1 was applied in an amount of 30 mg./100 cm. of the ultraviolet absorbing agent. The film was then dried.
- the color film thus obtained was exposed to light through blue, green and red step wedges.
- the exposed film was then developed with a developer containing 4- amino-3-methyl-N,N-diethylaniline, washed with Water, fixed, washed with water, bleached, washed with water, and dried by conventional state of the art methods.
- the sample thus obtained was exposed for 50 hours to a xenon are by facing the second surface of the sample to the source of light.
- a decrease in the ratio of the color density of this sample was compared with that of the sample which did not have the ultraviolet absorbing layer on the second surface.
- the decrease in the ratio of the color density which was calculated by the same method as in Example 1, is shown in the following table.
- the boiling point for the solvent in the most preferred form of the invention should be a minimum of C., under normal atmospheric pressure.
- the solvent is generally present in an amount less than three times the amount of coupler.
- the amount of solvent can vary from this range, and that amounts greater than three times the amount of coupler are operable.
- a color photographic light-Sensitive material which comprises a support, at least one photographic silver halide emulsion layer and at least one hydrophilic colloid layer, at least one of either the emulsion layers or the colloid layer containing a dispersion of at least two ultraviolet absorbing compounds selected from those represented by the formula:
- R and R each represents a member selected from the group consisting of a hydrogen atom and an alkyl group having up to 4 carbon atoms, and R represents a member selected from the group consisting of a hydrogen atom and a halogen atom, and an organic solvent having a high boiling point.
- a color photographic light-sensitive material which comprises an opaque film support, at least one photographic silver halide emulsion layer superposed on said support, and an outer gelatin layer containing a dispersion of at least two ultraviolet absorbing compounds selected from those represented by the formula:
- R and R each represents a member selected from the group consisting of a hydrogen atom and an alkyl group having up to 4 carbon atoms, and R represents a member selected from the group consisting of a hydrogen atom and a halogen atom, and an organic solvent having a high boiling point.
- a color photographic light-sensitive material which comprises a transparent film support, at least one photographic silver halide emulsion layer superposed on said support, and a gelatin layer superposed on the other surface of said support, said gelatin layer containing a dispersion of at least two ultraviolet absorbing compounds selected from those represented by the formula:
- R and R each represents a member selected from the group consisting of a hydrogen atom and an alkyl group having up to 4 carbon atoms, and R represents a member selected from the group consisting of a hydrogen atom and a halogen atom, and an organic solvent having a high boiling point.
- said ultraviolet absorbing compounds are members selected from the group consisting of 2-(2'-hydroXy-5-tert-butyl phenyl)benzotri azole, 2-(2'-hydroxy-3,5'-di-tert butyl phenyl)benzotriazole, 2-(2'-hydroXy-3-tert-butyl-5'-methyl
- said organic solvent having a high boiling point is a member selected from the group consisting of di-n-butylphthalate, benzylphthalate, triphenyl phosphate, tri-o-cresyl phosphate, diphenyl monop-tert-butyl phenyl phosphate, monophenyl di-p-tert-butyl phenyl phosphate, diphenyl mono-o-chlorophenyl phosphate, monophenyl di-o-chlorophenyl phosphate, tri-p-tertbutylphenyl phosphate, tri-o-phenylphenyl phosphate and di-p-tert-butylphenyl mono(5-tert-butyl-2-phenylphenyl) phosphate.
- said ultraviolet absorbing compounds are members selected from the group consisting of 2-(2'-hydroxy,5-tert-butyl phenyl)benzotriazole, 2 (2'- hydroxy-B,5-di-tert-butyl phenyl)benzotriazole, 2 (2- hydroXy-3-tert-butyl-5'-methyl phenyl) 5 chlorobenzotriazole and
- a color photographic light-sensitive material as claimed in claim 2 wherein said organic solvent having a high boiling point is a member selected from the group consisting of di-n-butylphthalate, benzylphthalate, triphenyl phosphate, tri-o-cresyl phosphate, diphenyl monop-tert-butyl phenyl phosphate, monophenyl di-p-tert-butyl phenyl phosphate, diphenyl mono-o-chlorophenyl phosphate, monophenyl di-o-chlorophenyl phosphate, tri-p-tertbutylphenyl phosphate, tri-o-phenyl-phenyl phosphate and di-p-tert-butylphenyl mono(S-tert-butyI-Z-phenyI-phenyl) phosphate.
- said organic solvent having a high boiling point is a member selected from the group consisting of di-n-butylphthalate, benzy
- a color photographic light-sensitivematerial as claimed in claim 3 wherein said ultraviolet absorbing compounds are members selected from the group consisting of 2- (2-hydroxy-5 -tert-buty1 phenyl benzotriazole, 2- (2'- hydroxy-3',5-di-tert-butyl phenyl) benzotriazole, 2-(2'- hydroxy-3'-tert butyl-5-methyl phenyD-S-chlorobenzotriazole and 2-(2'-hydroxy-3,5-di-tert-butyl phenyl)-5- chlorobenzotriazole.
- a color photographic light-sensitive material as claimed in claim 3 wherein said organic solvent having a high boiling point is a member selected from the group consisting of di-n-butylphthalate, benzylphthalate, triphenyl phosphate, tri-o-cresyl phosphate, diphenyl monop-tert-butyl phenyl phosphate, monophenyl di-ptert-butyl phenyl phosphate, diphenyl mono-o-chlorophenyl phosphate, monophenyl di-o-chlorophenyl phosphate, tri-p-tertbutylphenyl phosphate, tri-o-phenyl-phenyl phosphate and di-p-tert-butyl-phenyl mono(S tert-butyI-Z-phenyl-phenyl)-phosphate.
- said organic solvent having a high boiling point is a member selected from the group consisting of di-n-butylphthalate, benzy
- the color photographic light-sensitive material of claim 1 wherein the mixing ratio of said ultraviolet absorbing compounds is in the range of from 5% to 90%.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP1929968 | 1968-03-25 |
Publications (1)
Publication Number | Publication Date |
---|---|
US3533794A true US3533794A (en) | 1970-10-13 |
Family
ID=11995530
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US810343A Expired - Lifetime US3533794A (en) | 1968-03-25 | 1969-03-25 | Color photographic light-sensitive material containing ultraviolet absorbing agents |
Country Status (5)
Country | Link |
---|---|
US (1) | US3533794A (en, 2012) |
BE (1) | BE730255A (en, 2012) |
DE (1) | DE1915118A1 (en, 2012) |
FR (1) | FR2004675B1 (en, 2012) |
GB (1) | GB1220425A (en, 2012) |
Cited By (25)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3923519A (en) * | 1972-01-03 | 1975-12-02 | Polaroid Corp | U.V. light absorbers in supports of integral diffusion transfer film units |
US4009038A (en) * | 1974-05-23 | 1977-02-22 | Fuji Photo Film Co., Ltd. | Silver halide color photographic materials |
US4220711A (en) * | 1978-03-09 | 1980-09-02 | Fuji Photo Film Co., Ltd. | Silver halide color photographic light-sensitive element |
US4330608A (en) * | 1979-08-24 | 1982-05-18 | Xerox Corporation | Benzotriazole stabilized photosensitive device |
JPS58211147A (ja) * | 1982-06-02 | 1983-12-08 | Konishiroku Photo Ind Co Ltd | カラ−写真感光材料 |
US4456681A (en) * | 1982-05-28 | 1984-06-26 | Konishiroku Photo Industry Co., Ltd. | Color photographic materials |
EP0147854A2 (en) | 1983-12-29 | 1985-07-10 | Fuji Photo Film Co., Ltd. | Silver halide photographic light-sensitive materials |
US4587208A (en) * | 1982-06-02 | 1986-05-06 | Konishiroku Photo Industry Co., Ltd. | Color photographic light-sensitive material |
EP0209118A2 (en) | 1985-07-17 | 1987-01-21 | Konica Corporation | Silver halide photographic material |
EP0239363A2 (en) | 1986-03-25 | 1987-09-30 | Konica Corporation | Light-sensitive silver halide photographic material feasible for high speed processing |
US4790959A (en) * | 1983-05-21 | 1988-12-13 | Konishiroku Photo Industry Co., Ltd. | Dispersion |
US4803149A (en) * | 1985-10-04 | 1989-02-07 | Fuji Photo Film Co., Ltd. | Silver halide photographic materials |
US4931382A (en) * | 1984-06-08 | 1990-06-05 | Fuji Photo Film Co., Ltd. | Silver halide color photographic light-sensitive material |
US4933271A (en) * | 1987-09-30 | 1990-06-12 | Ciba-Geigy Ag | Stabilizers for color photography recording materials |
US4975360A (en) * | 1986-04-24 | 1990-12-04 | Konica Corporation | Silver halide photographic light sensitive material |
US5149828A (en) * | 1987-09-30 | 1992-09-22 | Ciba-Geigy Ag | Stabilizers for color photography recording materials |
EP0698817A1 (en) | 1994-08-22 | 1996-02-28 | Agfa-Gevaert N.V. | Assortment of silver halide photographic industrial X-ray films and method of processing said assortment |
US5561028A (en) * | 1994-06-24 | 1996-10-01 | Mitsubishi Paper Mills Limited | Silver halide photographic photosensitive material |
EP0772088A1 (en) | 1991-03-05 | 1997-05-07 | Fuji Photo Film Co., Ltd. | Heat-developable diffusion transfer color photographic material |
EP0800113A2 (en) | 1996-04-05 | 1997-10-08 | Fuji Photo Film Co., Ltd. | Silver halide color photographic light-sensitive material |
US5814438A (en) * | 1996-03-29 | 1998-09-29 | Eastman Kodak Company | Benzotriazole-based novel UV absorbers and photographic elements containing them |
EP1016537A2 (en) | 1998-12-28 | 2000-07-05 | Fuji Photo Film Co., Ltd. | Method and apparatus for forming image with plural coating liquids |
US20040228986A1 (en) * | 2003-03-26 | 2004-11-18 | Tetsuto Miyanishi | Interior ornament and indicator panel for vehicle |
WO2013103139A1 (ja) | 2012-01-06 | 2013-07-11 | コニカミノルタアドバンストレイヤー株式会社 | フィルムミラー、フィルムミラーの製造方法、太陽熱発電用フィルムミラー及び太陽熱発電用反射装置 |
US9329281B2 (en) | 2013-02-28 | 2016-05-03 | Konica Minolta, Inc. | Deposition substrate and scintillator panel |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS59139031A (ja) * | 1983-01-29 | 1984-08-09 | Konishiroku Photo Ind Co Ltd | ハロゲン化銀写真感光材料 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3004896A (en) * | 1956-12-14 | 1961-10-17 | Geigy Ag J R | Ultra-violet light-absorbing composition of matter |
US3244524A (en) * | 1960-03-01 | 1966-04-05 | Gen Aniline & Film Corp | U. v. absorbing composition |
US3253921A (en) * | 1961-10-10 | 1966-05-31 | Eastman Kodak Co | Novel photographic elements protected against ultraviolet radiation |
-
1969
- 1969-03-21 BE BE730255D patent/BE730255A/xx unknown
- 1969-03-25 FR FR696908660A patent/FR2004675B1/fr not_active Expired
- 1969-03-25 DE DE19691915118 patent/DE1915118A1/de active Pending
- 1969-03-25 GB GB05626/69A patent/GB1220425A/en not_active Expired
- 1969-03-25 US US810343A patent/US3533794A/en not_active Expired - Lifetime
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3004896A (en) * | 1956-12-14 | 1961-10-17 | Geigy Ag J R | Ultra-violet light-absorbing composition of matter |
US3244524A (en) * | 1960-03-01 | 1966-04-05 | Gen Aniline & Film Corp | U. v. absorbing composition |
US3253921A (en) * | 1961-10-10 | 1966-05-31 | Eastman Kodak Co | Novel photographic elements protected against ultraviolet radiation |
Cited By (26)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3923519A (en) * | 1972-01-03 | 1975-12-02 | Polaroid Corp | U.V. light absorbers in supports of integral diffusion transfer film units |
US4009038A (en) * | 1974-05-23 | 1977-02-22 | Fuji Photo Film Co., Ltd. | Silver halide color photographic materials |
US4220711A (en) * | 1978-03-09 | 1980-09-02 | Fuji Photo Film Co., Ltd. | Silver halide color photographic light-sensitive element |
US4330608A (en) * | 1979-08-24 | 1982-05-18 | Xerox Corporation | Benzotriazole stabilized photosensitive device |
US4456681A (en) * | 1982-05-28 | 1984-06-26 | Konishiroku Photo Industry Co., Ltd. | Color photographic materials |
JPS58211147A (ja) * | 1982-06-02 | 1983-12-08 | Konishiroku Photo Ind Co Ltd | カラ−写真感光材料 |
US4587208A (en) * | 1982-06-02 | 1986-05-06 | Konishiroku Photo Industry Co., Ltd. | Color photographic light-sensitive material |
US4790959A (en) * | 1983-05-21 | 1988-12-13 | Konishiroku Photo Industry Co., Ltd. | Dispersion |
EP0147854A2 (en) | 1983-12-29 | 1985-07-10 | Fuji Photo Film Co., Ltd. | Silver halide photographic light-sensitive materials |
US4931382A (en) * | 1984-06-08 | 1990-06-05 | Fuji Photo Film Co., Ltd. | Silver halide color photographic light-sensitive material |
EP0209118A2 (en) | 1985-07-17 | 1987-01-21 | Konica Corporation | Silver halide photographic material |
US4803149A (en) * | 1985-10-04 | 1989-02-07 | Fuji Photo Film Co., Ltd. | Silver halide photographic materials |
EP0239363A2 (en) | 1986-03-25 | 1987-09-30 | Konica Corporation | Light-sensitive silver halide photographic material feasible for high speed processing |
US4975360A (en) * | 1986-04-24 | 1990-12-04 | Konica Corporation | Silver halide photographic light sensitive material |
US4933271A (en) * | 1987-09-30 | 1990-06-12 | Ciba-Geigy Ag | Stabilizers for color photography recording materials |
US5149828A (en) * | 1987-09-30 | 1992-09-22 | Ciba-Geigy Ag | Stabilizers for color photography recording materials |
EP0772088A1 (en) | 1991-03-05 | 1997-05-07 | Fuji Photo Film Co., Ltd. | Heat-developable diffusion transfer color photographic material |
US5561028A (en) * | 1994-06-24 | 1996-10-01 | Mitsubishi Paper Mills Limited | Silver halide photographic photosensitive material |
EP0698817A1 (en) | 1994-08-22 | 1996-02-28 | Agfa-Gevaert N.V. | Assortment of silver halide photographic industrial X-ray films and method of processing said assortment |
US5814438A (en) * | 1996-03-29 | 1998-09-29 | Eastman Kodak Company | Benzotriazole-based novel UV absorbers and photographic elements containing them |
EP0800113A2 (en) | 1996-04-05 | 1997-10-08 | Fuji Photo Film Co., Ltd. | Silver halide color photographic light-sensitive material |
EP1016537A2 (en) | 1998-12-28 | 2000-07-05 | Fuji Photo Film Co., Ltd. | Method and apparatus for forming image with plural coating liquids |
US20040228986A1 (en) * | 2003-03-26 | 2004-11-18 | Tetsuto Miyanishi | Interior ornament and indicator panel for vehicle |
WO2013103139A1 (ja) | 2012-01-06 | 2013-07-11 | コニカミノルタアドバンストレイヤー株式会社 | フィルムミラー、フィルムミラーの製造方法、太陽熱発電用フィルムミラー及び太陽熱発電用反射装置 |
US9329281B2 (en) | 2013-02-28 | 2016-05-03 | Konica Minolta, Inc. | Deposition substrate and scintillator panel |
US9739895B2 (en) | 2013-02-28 | 2017-08-22 | Konica Minolta, Inc. | Deposition substrate and scintillator panel |
Also Published As
Publication number | Publication date |
---|---|
GB1220425A (en) | 1971-01-27 |
BE730255A (en, 2012) | 1969-09-01 |
DE1915118A1 (de) | 1969-10-02 |
FR2004675A1 (en, 2012) | 1969-11-28 |
FR2004675B1 (en, 2012) | 1974-06-14 |
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