US3822135A - Process for producing photographic emulsions - Google Patents
Process for producing photographic emulsions Download PDFInfo
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- US3822135A US3822135A US00206878A US20687871A US3822135A US 3822135 A US3822135 A US 3822135A US 00206878 A US00206878 A US 00206878A US 20687871 A US20687871 A US 20687871A US 3822135 A US3822135 A US 3822135A
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- 239000000839 emulsion Substances 0.000 title abstract description 34
- 238000000034 method Methods 0.000 title abstract description 26
- 230000008569 process Effects 0.000 title abstract description 22
- 239000000243 solution Substances 0.000 abstract description 27
- 239000004094 surface-active agent Substances 0.000 abstract description 26
- -1 SILVER HALIDE Chemical class 0.000 abstract description 25
- 229910052709 silver Inorganic materials 0.000 abstract description 21
- 239000004332 silver Substances 0.000 abstract description 21
- 239000007864 aqueous solution Substances 0.000 abstract description 18
- 230000001235 sensitizing effect Effects 0.000 abstract description 16
- 239000000975 dye Substances 0.000 description 72
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 33
- 239000003960 organic solvent Substances 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- 230000003595 spectral effect Effects 0.000 description 7
- 239000001397 quillaja saponaria molina bark Substances 0.000 description 6
- 229930182490 saponin Natural products 0.000 description 6
- 150000007949 saponins Chemical class 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 5
- 238000011978 dissolution method Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 4
- 125000000623 heterocyclic group Chemical group 0.000 description 4
- 229940083575 sodium dodecyl sulfate Drugs 0.000 description 4
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- QGKMIGUHVLGJBR-UHFFFAOYSA-M (4z)-1-(3-methylbutyl)-4-[[1-(3-methylbutyl)quinolin-1-ium-4-yl]methylidene]quinoline;iodide Chemical compound [I-].C12=CC=CC=C2N(CCC(C)C)C=CC1=CC1=CC=[N+](CCC(C)C)C2=CC=CC=C12 QGKMIGUHVLGJBR-UHFFFAOYSA-M 0.000 description 3
- 125000004070 6 membered heterocyclic group Chemical group 0.000 description 3
- 229920002284 Cellulose triacetate Polymers 0.000 description 3
- 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 3
- 125000004429 atom Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 125000001165 hydrophobic group Chemical group 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 150000000183 1,3-benzoxazoles Chemical class 0.000 description 2
- NOLHRFLIXVQPSZ-UHFFFAOYSA-N 1,3-thiazolidin-4-one Chemical class O=C1CSCN1 NOLHRFLIXVQPSZ-UHFFFAOYSA-N 0.000 description 2
- 125000002373 5 membered heterocyclic group Chemical group 0.000 description 2
- 108010010803 Gelatin Proteins 0.000 description 2
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 2
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 2
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 229940111121 antirheumatic drug quinolines Drugs 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 125000003785 benzimidazolyl group Chemical class N1=C(NC2=C1C=CC=C2)* 0.000 description 2
- KXNQKOAQSGJCQU-UHFFFAOYSA-N benzo[e][1,3]benzothiazole Chemical class C1=CC=C2C(N=CS3)=C3C=CC2=C1 KXNQKOAQSGJCQU-UHFFFAOYSA-N 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical class C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- ZEUDGVUWMXAXEF-UHFFFAOYSA-L bromo(chloro)silver Chemical compound Cl[Ag]Br ZEUDGVUWMXAXEF-UHFFFAOYSA-L 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229960002380 dibutyl phthalate Drugs 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 2
- 230000001804 emulsifying effect Effects 0.000 description 2
- 239000008273 gelatin Substances 0.000 description 2
- 229920000159 gelatin Polymers 0.000 description 2
- 235000019322 gelatine Nutrition 0.000 description 2
- 235000011852 gelatine desserts Nutrition 0.000 description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 description 2
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 2
- 229940071826 hydroxyethyl cellulose Drugs 0.000 description 2
- 239000000693 micelle Substances 0.000 description 2
- 150000002916 oxazoles Chemical class 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 229930195734 saturated hydrocarbon Natural products 0.000 description 2
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 2
- SDKPSXWGRWWLKR-UHFFFAOYSA-M sodium;9,10-dioxoanthracene-1-sulfonate Chemical compound [Na+].O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2S(=O)(=O)[O-] SDKPSXWGRWWLKR-UHFFFAOYSA-M 0.000 description 2
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 150000003557 thiazoles Chemical class 0.000 description 2
- 150000003549 thiazolines Chemical class 0.000 description 2
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 2
- FUOSTELFLYZQCW-UHFFFAOYSA-N 1,2-oxazol-3-one Chemical class OC=1C=CON=1 FUOSTELFLYZQCW-UHFFFAOYSA-N 0.000 description 1
- AIGNCQCMONAWOL-UHFFFAOYSA-N 1,3-benzoselenazole Chemical class C1=CC=C2[se]C=NC2=C1 AIGNCQCMONAWOL-UHFFFAOYSA-N 0.000 description 1
- PXHFLWCSJYTAFU-UHFFFAOYSA-N 1,3-oxazolidin-4-one Chemical compound O=C1COCN1 PXHFLWCSJYTAFU-UHFFFAOYSA-N 0.000 description 1
- GCSBYWTVHSKTNC-UHFFFAOYSA-N 1,3-oxazolidin-5-one Chemical compound O=C1CNCO1 GCSBYWTVHSKTNC-UHFFFAOYSA-N 0.000 description 1
- KZPUZEPLLNUDDZ-UHFFFAOYSA-N 1,3-thiazolidine 1-oxide Chemical compound O=S1CCNC1 KZPUZEPLLNUDDZ-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- CZWWCTHQXBMHDA-UHFFFAOYSA-N 3h-1,3-thiazol-2-one Chemical class OC1=NC=CS1 CZWWCTHQXBMHDA-UHFFFAOYSA-N 0.000 description 1
- 229920001817 Agar Polymers 0.000 description 1
- 102000009027 Albumins Human genes 0.000 description 1
- 108010088751 Albumins Proteins 0.000 description 1
- 101100422644 Caenorhabditis elegans syx-5 gene Proteins 0.000 description 1
- 241000206672 Gelidium Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- PCKPVGOLPKLUHR-UHFFFAOYSA-N OH-Indolxyl Natural products C1=CC=C2C(O)=CNC2=C1 PCKPVGOLPKLUHR-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 229940123464 Thiazolidinedione Drugs 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 1
- 241000933336 Ziziphus rignonii Species 0.000 description 1
- SJOOOZPMQAWAOP-UHFFFAOYSA-N [Ag].BrCl Chemical compound [Ag].BrCl SJOOOZPMQAWAOP-UHFFFAOYSA-N 0.000 description 1
- XCFIVNQHHFZRNR-UHFFFAOYSA-N [Ag].Cl[IH]Br Chemical compound [Ag].Cl[IH]Br XCFIVNQHHFZRNR-UHFFFAOYSA-N 0.000 description 1
- HOLVRJRSWZOAJU-UHFFFAOYSA-N [Ag].ICl Chemical compound [Ag].ICl HOLVRJRSWZOAJU-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- 239000001785 acacia senegal l. willd gum Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000002015 acyclic group Chemical group 0.000 description 1
- 235000010419 agar Nutrition 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 125000005526 alkyl sulfate group Chemical group 0.000 description 1
- 229940051880 analgesics and antipyretics pyrazolones Drugs 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- HNYOPLTXPVRDBG-UHFFFAOYSA-N barbituric acid Chemical class O=C1CC(=O)NC(=O)N1 HNYOPLTXPVRDBG-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005354 coacervation Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 150000001469 hydantoins Chemical class 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- GVONPBONFIJAHJ-UHFFFAOYSA-N imidazolidin-4-one Chemical compound O=C1CNCN1 GVONPBONFIJAHJ-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- JYGFTBXVXVMTGB-UHFFFAOYSA-N indolin-2-one Chemical compound C1=CC=C2NC(=O)CC2=C1 JYGFTBXVXVMTGB-UHFFFAOYSA-N 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- DZVCFNFOPIZQKX-LTHRDKTGSA-M merocyanine Chemical class [Na+].O=C1N(CCCC)C(=O)N(CCCC)C(=O)C1=C\C=C\C=C/1N(CCCS([O-])(=O)=O)C2=CC=CC=C2O\1 DZVCFNFOPIZQKX-LTHRDKTGSA-M 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000004682 monohydrates Chemical class 0.000 description 1
- 239000000025 natural resin Substances 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 150000002918 oxazolines Chemical class 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920006316 polyvinylpyrrolidine Polymers 0.000 description 1
- JEXVQSWXXUJEMA-UHFFFAOYSA-N pyrazol-3-one Chemical class O=C1C=CN=N1 JEXVQSWXXUJEMA-UHFFFAOYSA-N 0.000 description 1
- 150000003248 quinolines Chemical class 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000006798 ring closing metathesis reaction Methods 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 239000000984 vat dye Substances 0.000 description 1
- 239000000080 wetting agent Substances 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
Definitions
- the present invention relates to a process for producing new photographic sensitive elements and particularly to an improved process for spectrally sensitizing photo'- graphic emulsions.
- spectral sensitizing dyes used for the spectral sensitization of silver halide photographic emulsions are insoluble in water.
- an organic solvent miscible with water such as methanol, ethanol, propanol, acetone, etc.
- a dye such as 3,3-diethyl-5,5- diphenyl-9-ethyl-oxacarbocyanine thiocyanate. can barely be dissolved in methanol when 1 part by weight thereof is added to 10,000 parts by weight of methanol.
- photographic sensitizing or desensitizing cyanine dyes incorporated silver halide photographic emulsions are soluble in an aqueous solution of certain kinds of surface active agents, and that when such aqueous dye-surface active agent solutions are added to silver halide photographic emulsions, the photographic speed obtained is equal to or more than that obtained from silver halide emulsions in which the dye is added as a solution dissolved in organic solvents.
- spectral sensitizing dyes which are poorly soluble in organic solvents such as alcohols (methanol, ethanol and propanol, etc.) and acetone can easily be dissolved in an aqueous solution of such surface active agents.
- the present invention should also be distinguished from French Pat. 1,482,774 and British Pat. 1,154,781.
- surface active agents such as sodium alkylnaphthalene sulfonates are required, these surface active agents are used as an emulsifier for emulsifying the organic solvent in which the spectral sensitizing dyes are dissolved. Accordingly, these patents are clearly different from the present invention, and also require an emulsifying step.
- the solvent used in examples of the present invention is solely water, it may contain, if desired, a small amount of organic solvents (for example, up to about 30% by weight).
- uniformity of coating can be kept upon coating'the photographic emulsions to a support, particularly at high coating speeds (for example, 30 m./min. m./min.) when organic solvents are not added, or even if added in the small amount recited into the aqueous solvent for the photographic sensitizing or desensitizing dyes.
- the present invention it is possible not only to greatly increase the concentration of the dye solutions as compared with the prior art processes for dissolving using organic solvents, since the solubility of the dyes becomes higher, but to vary, if desired, the concentration of the dye solutions in a wide range.
- a hydrophilic colloid such as gelatin and derivatives thereof, albumin, arabic gum, agar-agar, syn- 3 thetic resin (such as polyvinyl alcohol, polyvinyl pyrrolidine), water soluble cellulose derivatives (such as alkyl ester of carboxy cellulose, hydroxy ethyl cellulose, carb
- antifogging agents In the production of the photographic sensitive elements spectrally sensitized in accordance with the present invention, antifogging agents, stabilizers, toning agents, hardening agents, wetting agents, plasticizers, development accelerators, surface active agents for coating dyes for inhibiting irradiation effects, fluorescent agents, ultraviolet absorbers, filter dyes and color formers may be added for their art-recognized function.
- a surface active agent suitable for coating for example, saponin
- a part or whole of the surface active agent for coating can be eliminated.
- the surface active agents used in the present invention are those comprising a combination of a hydrophobic group and a hydrophilic group such that the amount of surface active agents relevant to the present invention may be varied according to the dyes employed in combinaton with the surface active agents.
- the amount greater than the critical concentration for the formation of micelle for the surface active agents (hereinafter referred to as C.M.C.) is preferred in the present inven tion.
- the C.M.C. is described in Ichiro Nishi et al. Kaimen Kasseyai Binran as SO OSO and --COO.
- Preferred hydrophobic groups are aromatic groups substituted by saturated or unsaturated hydrocarbon groups having up to 18 carbon atoms, or aliphatic hydrocarbon groups having up to 20 carbon atoms.
- the following compounds are examples of such surface active agents.
- N-CH N-CH:
- Typical examples of photographic sensitizing or desensitizing cyanine dyes used in the present invention are cyanines (in a narrow sense), mercocyanine dyes, hemicyanine dyesllhe preferred. compounds are repreful because of having excellent solubility and good sensititizing action.
- Example 1 This example illustrates that the dissolution method of the present invention is excellent.
- Dye (I) One part by weight of Dye (I) was dissolved in 4,000 parts by weight of a 1% aqueous solution of sodium dodecylsulfate, 4,000 parts by weight of a 1% aqueous solution of oleyl-N-methyl sodium tauride, 4,000 parts by weight of a 1% aqueous solution of p-nonylphenoxyethoxy-ethoxyethylsulfonic acid or 4,000 parts by weight of a 2% aqueous solution of saponin.
- the dye easily dissolved, and precipitation of crystals was not observed even upon standing for two weeks at room temperature.
- 1 part by weight of the same dye was added to 4,000 parts by weight of methanol, the dye was poorly soluble and crystals precipitated after standing for 3 days at room temperature. This dye was substantially insoluble in distilled water.
- Dye (II) One part by weight of Dye (III) was dissolved in 4,000 parts by weight of a 1% aqueous solution of sodium dodecylsulfate, 4,000 parts by weight of a 1% aqueous solution of sodium dodecylbenzenesulfonate, 4,000 parts by weight of a 1% aqueous solution of sodium oleate or 4,000 parts by weight of a 2% aqueous solution of saponin.
- the dye dissolved very easily and precipitation of crystals was not observed even upon standing for 2 weeks at room temperature. This dye was substantially insoluble in distilled water.
- Example 4 This example illustrates that aqueous dye solutions prepared by the dye dissolution method of the present invention have excellent stability.
- Dyes II (Example 2), III (Example 3) and IV (Example 4) were dissolved, respectively, in 1% aqueous solutions of the above described surface active agents 5, 7, 10, 11, 12, 16,21, 22, 28 and 30. After standing for 14 days at room temperature, the spectral density of the solutions was determined by diluting with an aqueous solution of the same surface active agent. The ratio of the dye remaining in the solution was determined from the density values of the absorption maximum before and after standing. The results are shown in Table 1.
- Example 5 This example illustrates dye solutions prepared according to the dye dissolution method of the present invention exhibits an excellent sensitizing action.
- a dye solution was prepared by dissolving 1 part by weight of Dye (II) in 4,000 parts by weight of methanol (control).
- a further dye solution was prepared by dissolving 1 part by weight of Dye (II) in 2,000 parts by weight of a. 1% aqueous solution of sodium dodecylsulfate.
- These dye solutions were added to a silver chloride bromide (Br: 60% mol, Cl: 40% mol) emulsion containing a sulfur sensitizer and a gold salt sensitizer, prepared by known methods to provide 0.045 g. of the dye per mol of silver halide. After standing for 10 minutes at 40 C., stabilizers and a hardening agent were added to the emulsions.
- the resulting emulsions were then applied to a cellulose triacetate film support.
- the samples were subjected to sensitometric exposure through a green filter through which rays having a wavelength range of 500 mp.- 600 mu passed, and then developed using a known black the developing agents.
- Example 6 This example also illustrates dye solutions prepared according to the dye dissolution method of the present invention exhibits an excellent sensitizing action.
- a dye solution was prepared by dissolving 1 part by weight of Dye (I) in 4,000 parts by weight of. methanol (control).
- a further dye solution was prepared by dissolving 1 part by weight of Dye (I) in 4,000 parts by weight of a 1% aqueous solution of oleyl-N-methyl sodium tauride.
- These dye solutions were added to a silver chloride bromide (Br: 30% mol,,Cl: 70% mol) emulsion to provide 0.065 g. of the dye per mol of silver halide. After adding stabilizers and hardening agents, 150 g.
- Dye -(III)'in 4,000 parts by weight of a 21% aqueous saponin solution.
- dyes solutions were added to a silver iodobromide (I: 6%mol, Br: 94% mol) emulsion containing a sulfur sensitizer and a gold salt sensitizer, prepared by known methods to provide 0.050 g. of th e dyeper mol of silver halide.
- a hydrophobic group of the surface active agent is selected from aromatic groups substituted by saturated or unsaturated hydrocarbon groups having up to 18 carbon atoms and aliphatic hydrocarbon groups having up to 20 carbon atoms.
- n 1, 2 or 3; H
- d represents 1, 2 or 3;
- X- represents an acid group
- Z and Z each represent the group of atoms necessary to complete a or 6-membered heterocyclic ring customarily employed as the cyanine nucleus;
- P and Q each represent CN and COOR (R represents an alkyl group) or P and Q may form a heterocyclic ring by ring closure;
- Y and Y each represent an atom or group of atoms necessary to complete a S-membered heterocyclic ring customarily employed as the merocyanine nucleus.
- a process as claimed in Claim 3 which in the photographic dyes are those having a SO; or COO- group.
- a process for producing a photographic light-sensitive material which comprises applying the silver halide photographic emulsion as claimed in Claim 1 to a support at a rate of 30 m./minute-160 m./minute.
- the 5- or 6-membered heterocyclic ring completed by Z is selected from the group consisting of thiazoles, benzothiazoles, naphthothiazoles, oxazoles, benzoxazoles, selenazoles, benzoselenazoles, naphthoselen'azoles, nap'thoxazoles, thiazolines, oxazolines, selenazolines, 2-qu'inolines, 4 quinolines, 3,3 dialkylindolenines and benzimidazoles; wherein the 5- or 6-membered heterocyclic ring completed by Z is selected from the group consisting of thiazoles, benzothiazoles, naphthothiazoles, oxazoles, benzoxazoles, selenazoles, napthoxazoles, thiazolines, 2-quinolines and benzimidazoles, wherein the heterocyclic ring formed by P and Q is selected from the group consisting of pyrazolones,
- alkyl group containing a sulfo group or a carboxy group is selected from the group consisting of a fl-sulfoethyl group, a 'y-sulfopropyl group, a a-sulfobutyl group, a p-sulfoethoxyethyl group and a carboxyethyl group.
- the surface active material is selected from the group consisting of sodium dodecylsulfate, oleyl-N-methyl sodium tauride, p-nonylphenoxy-e'thoxyethoxyethylsulfonic acid, saponin, sodium dodecylbenzenesulfonate, sodium oleate,
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP45109870A JPS4944895B1 (enrdf_load_stackoverflow) | 1970-12-10 | 1970-12-10 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3822135A true US3822135A (en) | 1974-07-02 |
Family
ID=14521268
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US00206878A Expired - Lifetime US3822135A (en) | 1970-12-10 | 1971-12-10 | Process for producing photographic emulsions |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US3822135A (enrdf_load_stackoverflow) |
| JP (1) | JPS4944895B1 (enrdf_load_stackoverflow) |
| DE (1) | DE2161184A1 (enrdf_load_stackoverflow) |
| GB (1) | GB1373223A (enrdf_load_stackoverflow) |
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3955996A (en) * | 1973-11-15 | 1976-05-11 | Fuji Photo Film Co., Ltd. | Method for spectrally sensitizing photographic light-sensitive emulsion |
| US3963499A (en) * | 1973-10-12 | 1976-06-15 | Fuji Photo Film Co., Ltd. | Photographic light-sensitive material |
| US4006025A (en) * | 1975-06-06 | 1977-02-01 | Polaroid Corporation | Process for dispersing sensitizing dyes |
| US4021247A (en) * | 1973-11-13 | 1977-05-03 | Fuji Photo Film Co., Ltd. | Method of dispersing organic compounds useful in photography |
| US4134767A (en) * | 1973-10-22 | 1979-01-16 | Konishiroku Photo Industry Co., Ltd. | Silver halide photosensitive material for color photography |
| US4138266A (en) * | 1974-12-24 | 1979-02-06 | Fuji Photo Film Co., Ltd. | Method for spectrally sensitizing photographic light-sensitive emulsions |
| US4199360A (en) * | 1974-12-24 | 1980-04-22 | Fuji Photo Film Co., Ltd. | Method for spectrally sensitizing photographic light-sensitive emulsions |
| EP0124795A2 (en) | 1983-04-11 | 1984-11-14 | Fuji Photo Film Co., Ltd. | Silver halide photographic emulsion |
| US4965183A (en) * | 1988-10-05 | 1990-10-23 | Eastman Kodak Company | Tri-nuclear dyes for photographic compositions and method of prepartion |
| US4987062A (en) * | 1988-07-04 | 1991-01-22 | Fuji Photo Film Co., Ltd. | Process for preparing a silver halide emulsion |
| US5015561A (en) * | 1988-03-04 | 1991-05-14 | Fuji Photo Film Co., Ltd. | Method for forming a direct positive image |
| US5079139A (en) * | 1988-10-05 | 1992-01-07 | Eastman Kodak Company | Silver halide photographic material |
| US5151346A (en) * | 1988-07-04 | 1992-09-29 | Fuji Photo Film Co. Ltd. | Process for preparing a silver halide emulsion |
| US5238797A (en) * | 1991-08-26 | 1993-08-24 | Konica Corporation | Silver halide color photographic light-sensitive material containing a 1-pentahalogenophenyl-substituted 5-pyrazolone colored magenta coupler |
| EP0562476A1 (en) | 1992-03-19 | 1993-09-29 | Fuji Photo Film Co., Ltd. | A silver halide photographic emulsion and a photographic light-sensitive material |
| EP0578173A1 (en) | 1992-07-06 | 1994-01-12 | Fuji Photo Film Co., Ltd. | Silver halide color photographic material and method for forming a color image |
| US5302506A (en) * | 1991-06-26 | 1994-04-12 | Konica Corporation | Silver halide photographic materials |
| US5580711A (en) * | 1993-03-02 | 1996-12-03 | Konica Corporation | Silver halide photographic light-sensitive material |
| EP1251395A1 (en) | 2001-04-17 | 2002-10-23 | Fuji Photo Film Co., Ltd. | Silver halide photographic material and methine dye |
| EP1914594A2 (en) | 2004-01-30 | 2008-04-23 | FUJIFILM Corporation | Silver halide color photographic light-sensitive material and color image-forming method |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2965772D1 (en) * | 1978-12-22 | 1983-07-28 | Ciba Geigy Ag | Process for increase of light-fastness, fluorescence polarisation and fluorescence quantum efficiency of cyanine dyestuffs, stabilized cyanine dyestuff preparation, process for its preparation and its use |
| JP2652202B2 (ja) * | 1988-07-12 | 1997-09-10 | 富士写真フイルム株式会社 | ハロゲン化銀乳剤の製造方法 |
-
1970
- 1970-12-10 JP JP45109870A patent/JPS4944895B1/ja active Pending
-
1971
- 1971-12-09 GB GB5734971A patent/GB1373223A/en not_active Expired
- 1971-12-09 DE DE19712161184 patent/DE2161184A1/de active Pending
- 1971-12-10 US US00206878A patent/US3822135A/en not_active Expired - Lifetime
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3963499A (en) * | 1973-10-12 | 1976-06-15 | Fuji Photo Film Co., Ltd. | Photographic light-sensitive material |
| US4134767A (en) * | 1973-10-22 | 1979-01-16 | Konishiroku Photo Industry Co., Ltd. | Silver halide photosensitive material for color photography |
| US4021247A (en) * | 1973-11-13 | 1977-05-03 | Fuji Photo Film Co., Ltd. | Method of dispersing organic compounds useful in photography |
| US3955996A (en) * | 1973-11-15 | 1976-05-11 | Fuji Photo Film Co., Ltd. | Method for spectrally sensitizing photographic light-sensitive emulsion |
| US4138266A (en) * | 1974-12-24 | 1979-02-06 | Fuji Photo Film Co., Ltd. | Method for spectrally sensitizing photographic light-sensitive emulsions |
| US4199360A (en) * | 1974-12-24 | 1980-04-22 | Fuji Photo Film Co., Ltd. | Method for spectrally sensitizing photographic light-sensitive emulsions |
| US4006025A (en) * | 1975-06-06 | 1977-02-01 | Polaroid Corporation | Process for dispersing sensitizing dyes |
| EP0124795A2 (en) | 1983-04-11 | 1984-11-14 | Fuji Photo Film Co., Ltd. | Silver halide photographic emulsion |
| US5015561A (en) * | 1988-03-04 | 1991-05-14 | Fuji Photo Film Co., Ltd. | Method for forming a direct positive image |
| US4987062A (en) * | 1988-07-04 | 1991-01-22 | Fuji Photo Film Co., Ltd. | Process for preparing a silver halide emulsion |
| US5151346A (en) * | 1988-07-04 | 1992-09-29 | Fuji Photo Film Co. Ltd. | Process for preparing a silver halide emulsion |
| US4965183A (en) * | 1988-10-05 | 1990-10-23 | Eastman Kodak Company | Tri-nuclear dyes for photographic compositions and method of prepartion |
| US5079139A (en) * | 1988-10-05 | 1992-01-07 | Eastman Kodak Company | Silver halide photographic material |
| US5302506A (en) * | 1991-06-26 | 1994-04-12 | Konica Corporation | Silver halide photographic materials |
| US5238797A (en) * | 1991-08-26 | 1993-08-24 | Konica Corporation | Silver halide color photographic light-sensitive material containing a 1-pentahalogenophenyl-substituted 5-pyrazolone colored magenta coupler |
| EP0562476A1 (en) | 1992-03-19 | 1993-09-29 | Fuji Photo Film Co., Ltd. | A silver halide photographic emulsion and a photographic light-sensitive material |
| EP0578173A1 (en) | 1992-07-06 | 1994-01-12 | Fuji Photo Film Co., Ltd. | Silver halide color photographic material and method for forming a color image |
| US5580711A (en) * | 1993-03-02 | 1996-12-03 | Konica Corporation | Silver halide photographic light-sensitive material |
| EP1251395A1 (en) | 2001-04-17 | 2002-10-23 | Fuji Photo Film Co., Ltd. | Silver halide photographic material and methine dye |
| EP1914594A2 (en) | 2004-01-30 | 2008-04-23 | FUJIFILM Corporation | Silver halide color photographic light-sensitive material and color image-forming method |
Also Published As
| Publication number | Publication date |
|---|---|
| GB1373223A (en) | 1974-11-06 |
| DE2161184A1 (de) | 1972-07-20 |
| JPS4944895B1 (enrdf_load_stackoverflow) | 1974-11-30 |
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