US3615637A - Spectrally sensitized photographic silver halide emulsions - Google Patents
Spectrally sensitized photographic silver halide emulsions Download PDFInfo
- Publication number
- US3615637A US3615637A US882271A US3615637DA US3615637A US 3615637 A US3615637 A US 3615637A US 882271 A US882271 A US 882271A US 3615637D A US3615637D A US 3615637DA US 3615637 A US3615637 A US 3615637A
- Authority
- US
- United States
- Prior art keywords
- silver halide
- halide emulsion
- group
- sensitizing dye
- emulsion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000000839 emulsion Substances 0.000 title claims abstract description 66
- -1 silver halide Chemical class 0.000 title claims abstract description 60
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 54
- 239000004332 silver Substances 0.000 title claims abstract description 54
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 123
- 230000001235 sensitizing effect Effects 0.000 claims abstract description 37
- 125000002943 quinolinyl group Chemical class N1=C(C=CC2=CC=CC=C12)* 0.000 claims abstract 2
- 125000000217 alkyl group Chemical group 0.000 claims description 15
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 125000005843 halogen group Chemical group 0.000 claims description 7
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- SJOOOZPMQAWAOP-UHFFFAOYSA-N [Ag].BrCl Chemical compound [Ag].BrCl SJOOOZPMQAWAOP-UHFFFAOYSA-N 0.000 claims description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 claims description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 3
- 239000012141 concentrate Substances 0.000 claims description 2
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 claims description 2
- 239000000975 dye Substances 0.000 description 33
- 239000007859 condensation product Substances 0.000 description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 239000002253 acid Substances 0.000 description 9
- 125000004429 atom Chemical group 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 6
- 230000035945 sensitivity Effects 0.000 description 6
- 238000003756 stirring Methods 0.000 description 5
- DNUYOWCKBJFOGS-UHFFFAOYSA-N 2-[[10-(2,2-dicarboxyethyl)anthracen-9-yl]methyl]propanedioic acid Chemical compound C1=CC=C2C(CC(C(=O)O)C(O)=O)=C(C=CC=C3)C3=C(CC(C(O)=O)C(O)=O)C2=C1 DNUYOWCKBJFOGS-UHFFFAOYSA-N 0.000 description 4
- UYEMGAFJOZZIFP-UHFFFAOYSA-N 3,5-dihydroxybenzoic acid Chemical compound OC(=O)C1=CC(O)=CC(O)=C1 UYEMGAFJOZZIFP-UHFFFAOYSA-N 0.000 description 4
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 4
- 150000001450 anions Chemical class 0.000 description 4
- 125000003710 aryl alkyl group Chemical group 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- IJFXRHURBJZNAO-UHFFFAOYSA-N meta--hydroxybenzoic acid Natural products OC(=O)C1=CC=CC(O)=C1 IJFXRHURBJZNAO-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 4
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 4
- 125000006569 (C5-C6) heterocyclic group Chemical group 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- 235000010724 Wisteria floribunda Nutrition 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 150000001342 alkaline earth metals Chemical class 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 150000003248 quinolines Chemical class 0.000 description 3
- RPAJSBKBKSSMLJ-DFWYDOINSA-N (2s)-2-aminopentanedioic acid;hydrochloride Chemical class Cl.OC(=O)[C@@H](N)CCC(O)=O RPAJSBKBKSSMLJ-DFWYDOINSA-N 0.000 description 2
- WXTMDXOMEHJXQO-UHFFFAOYSA-N 2,5-dihydroxybenzoic acid Chemical compound OC(=O)C1=CC(O)=CC=C1O WXTMDXOMEHJXQO-UHFFFAOYSA-N 0.000 description 2
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229940079877 pyrogallol Drugs 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000003460 sulfonic acids Chemical class 0.000 description 2
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical class C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical class C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- BRRSNXCXLSVPFC-UHFFFAOYSA-N 2,3,4-Trihydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C(O)=C1O BRRSNXCXLSVPFC-UHFFFAOYSA-N 0.000 description 1
- GPULXEIKKFAUAW-UHFFFAOYSA-N 2,4-dihydroxybenzenesulfonic acid Chemical compound OC1=CC=C(S(O)(=O)=O)C(O)=C1 GPULXEIKKFAUAW-UHFFFAOYSA-N 0.000 description 1
- ZZJVDYQPZOHNIK-UHFFFAOYSA-N 2,6-dihydroxybenzenesulfonic acid Chemical compound OC1=CC=CC(O)=C1S(O)(=O)=O ZZJVDYQPZOHNIK-UHFFFAOYSA-N 0.000 description 1
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 description 1
- USUZYWKJOZPTMO-UHFFFAOYSA-N 2-hydroxybenzenesulfonic acid;sodium Chemical compound [Na].OC1=CC=CC=C1S(O)(=O)=O USUZYWKJOZPTMO-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- ZCLXQTGLKVQKFD-UHFFFAOYSA-N 3-hydroxybenzenesulfonic acid Chemical compound OC1=CC=CC(S(O)(=O)=O)=C1 ZCLXQTGLKVQKFD-UHFFFAOYSA-N 0.000 description 1
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 1
- FEPBITJSIHRMRT-UHFFFAOYSA-N 4-hydroxybenzenesulfonic acid Chemical compound OC1=CC=C(S(O)(=O)=O)C=C1 FEPBITJSIHRMRT-UHFFFAOYSA-N 0.000 description 1
- ZMZGIVVRBMFZSG-UHFFFAOYSA-N 4-hydroxybenzohydrazide Chemical compound NNC(=O)C1=CC=C(O)C=C1 ZMZGIVVRBMFZSG-UHFFFAOYSA-N 0.000 description 1
- 150000005168 4-hydroxybenzoic acids Chemical class 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
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical group C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 101150065749 Churc1 gene Proteins 0.000 description 1
- KIWBPDUYBMNFTB-UHFFFAOYSA-N Ethyl hydrogen sulfate Chemical group CCOS(O)(=O)=O KIWBPDUYBMNFTB-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 102100038239 Protein Churchill Human genes 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001408 amides 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
- 239000002585 base Substances 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- AMTXUWGBSGZXCJ-UHFFFAOYSA-N benzo[e][1,3]benzoselenazole Chemical class C1=CC=C2C(N=C[se]3)=C3C=CC2=C1 AMTXUWGBSGZXCJ-UHFFFAOYSA-N 0.000 description 1
- KXNQKOAQSGJCQU-UHFFFAOYSA-N benzo[e][1,3]benzothiazole Chemical class C1=CC=C2C(N=CS3)=C3C=CC2=C1 KXNQKOAQSGJCQU-UHFFFAOYSA-N 0.000 description 1
- WMUIZUWOEIQJEH-UHFFFAOYSA-N benzo[e][1,3]benzoxazole Chemical class C1=CC=C2C(N=CO3)=C3C=CC2=C1 WMUIZUWOEIQJEH-UHFFFAOYSA-N 0.000 description 1
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical class C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 1
- 229960003328 benzoyl peroxide Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000006081 fluorescent whitening agent Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 description 1
- 150000005204 hydroxybenzenes Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002916 oxazoles Chemical class 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 150000003557 thiazoles Chemical class 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 238000005406 washing Methods 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
- G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
- G03C1/08—Sensitivity-increasing substances
- G03C1/28—Sensitivity-increasing substances together with supersensitising substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
- C08G8/20—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with polyhydric phenols
- C08G8/22—Resorcinol
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/28—Chemically modified polycondensates
- C08G8/30—Chemically modified polycondensates by unsaturated compounds, e.g. terpenes
-
- 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
- G03C1/04—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with macromolecular additives; with layer-forming substances
Definitions
- the emulsion is supersensitized.
- the sensitizing dye must contain at least one quinoline nucleus.
- This invention relates to photographic silver halide emulsions, and more particularly, to supersensitized silver halide emulsions.
- the present invention essentially, involves the discovery that a supersensitized photographic silver halide emulsion may be formed by a combination of certain sensitizing dyes and a condensate of formaldehyde and a polyhydroxybenzene, which may be substituted or unsubstituted.
- the photographic silver halide emulsion must contain at least one sensitizing dye represented by the following general formula I:
- R and R are each a member selected from the class consisting of an alkyl group having one to five carbon atoms and an alkyl group substituted by a member selected from the class consisting of hydroxyl, acetoxy, sulfate, carboxyl carboxyalkoxyl, sulpho, hydroxysulpho, alkoxy-sulphoalkoxy, m represents 1 or 2
- X represents an anion
- p represents 1 or 2 and at least one condensate of formaldehyde and a member selected from the group consisting of a substituted polyhydroxybenzene and an unsubstituted polyhydroxybenzene represented by the following general formulas,
- Z represents a nonmetallic atom group necessary to complete the 4-quinoline nucleus
- l represents a nonmetallic atom necessary to complete a 5-6membered heterocyclic ring
- R and R represent a substituted or an unsubstituted alkyl group
- in represents 1 or 2
- X represents an anion
- p represents 1 or 2 p being 1 when the dye forms an internal salt.
- the 4-quinoline nucleus containing Z may also contain such substituted groups as halogen atom, an alkyl group, an alkoxyl group, a hydroxyl group, etc.
- 2 represents nonmetallic groups necessary for completing heterocyclic rings such as e.g., 4-quinoline nucleus, 2-quinoline nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzosele'nazole nucleus, naphthoselenazole nucleus, benzoxazole nucleus, naphthoxazole nucleus, thiazole nucleus, oxazole nucleus, benzoimidazole nucleus, 3,3-dialkylindolenine nucleus, etc.
- R and R each represents a lower alkyl group' (e.g., methyl group, ethyl group, propyl group, etc.) or substituted alkyl group such as a B-hydroxyethyl group, B-ace
- the substituted or unsubstituted polyhydroxybenzene used in the present invention is shown by the following general formulas:
- R and R each represents OH, OM OR NH N(R NI'INH NHR or NHNHRAwhere R represents an alkyl group having one to eight carbon atoms, an aryl group,
- R represents a hydroxyl group or halogen group
- n and n each represents 1, 2, or 3.
- Typical examples of compounds shown by the above general formulas are P-dihydroxybenzene, o-dihydroxybenzene, p-hydroxybenzoic acid, p-hydroxybenzenesulphonic acid, m-hydroxybenzoic acid, m-hydroxybenzenesulphonic acid, a-resorcinic acid, B-resorcinic acid, -resorcinic acid, 3,S-dihydroxybenzenesulphonic acid, 2,4- dihydroxybenzenesulphonic acid, 2,6-dihydroxybenzenesulphonic acid, 2,5-dihydroxybenzoic acid, 3,5- dihydroxybenzoic acid, 2,5-hydroxybenzenesulphonic acid, pyr'ogallol carboxylic acid, (5), pyrogallol carboxylic acid (4), pyrogallol sulfonic acid (5), pyrogallol sulfonic acid (4) and their alkali metal salts (Li, Na, K, etc.), and their al
- materials efiectively used in the present invention are the amides or hydrazides of the above-mentioned carboxylic acids or sulfonic acids, and amide compounds or hydrazide compounds of these N-alkyl (one to eight carbon atoms) or N-aralkyl or N- allyl derivatives.
- the esters of the above-mentioned carboxylic acids or sulfonic acids can also be effectively employed in this invitation.
- the condensate of the above-mentioned substituted or unsubstituted polyhydroxybenzene and formaldehyde may be prepared by any conventional method for forming a novolaktype phenol-formaldehyde resin. While the preparation thereof is not particularly critical, such a material is generally prepared as follows. The polysubstituted hydroxybenzene is dispersed in water, and after adding concentrated hydrochloric acid and 37 percent formalin, the dispersion is stirred for 30 to 60 minutes at 100 C. Thereafter, if necessary, hydrochloric acid is added, followed by the continuation of heating and stirring. After the reaction is finished, the product is poured into cold water and the precipitate is collected and purified to provide the condensate.
- the above-mentioned method or a slightly modified method can be applied to easily obtain the condensate.
- the condensate obtained by the above-mentioned method has, like the common novolak-resin, about 2-10 units in a condensation unit (degree of polymerization).
- a condensate having 2-10 units in its degree of polymerization is effective in the present invention, but a condensate having 2-5 units in its degree of polymerization and having a molecular weight of 300-800 is particularly desirable.
- a formalin condensate of the present invention When a formalin condensate of the present invention is added to a silver halide emulsion containing the sensitizing dye of formula (1), excellent supersensitization can be obtained and, moreover, the formation of fog can be remarkably reduced compared with the case where the sensitizing dye alone is added to the emulsion.
- Some of the sensitizing dyes of formula (1) when incorporated in photographic light-sensitive materials, have the drawback that their sensitivity is lowered during storage, but such a lowering storage can be remarkably prevented by incorporating the dye in the emulsion together with the formalin condensate in accordance with the present invention.
- the concentration of the sensitizing dye of the present invention in the silver halide emulsion is preferably 0.002-0.2 g./mol. silver halide, and the concentration of the formalin condensate in the said emulsion is preferably 0.1-5.0 g./mol. silver halide.
- the most effective concentration ratio of the sensitizing dye to the formalin condensate is preferably from 1:5 to 1:500.
- the sensitizing dye may be added into the emulsion by any suitable method known in this field.
- the formalin condensate may be incorporated in the silver halide emulsion as a solution thereof in water or in an organic solvent such as methanol or ethanol. It is convenient to incorporate the sensitizing dye and the formalin condensate into the emulsion before coating.
- the sensitizing dye may be added into the emulsion either before or after the addition of the formalin condensate, or a mixture of the sensitizing dye and the formalin condensate may be added into the emulsion. Further, they may be added into the emulsion not only before coating but also during ripening of the emulsion after washing.
- gelatin in the present emulsion, gelatin is generally used as a binder for the silver halide emulsion, but other binders such as resinuous material or cellulose derivatives which do not have a bad influence on the photographic light sensitive materials may be used.
- the photographic emulsion used in this invention may be a gelatino-silver halide such' as gelatino silver-chloride, -br0- mide,-bromoiodide, -bromochloride or -bromochloroiodide.
- the silver halide emulsion used in this invention may further contain the normal state of the art additives such as a chemical sensitizer, an antifoggant, a stabilizer, a hardening agent, a wetting agent, a plasticizer, a developing accelerator, a toner, a fluorescent whitening agent, an antiairfoggant, a coupler, etc.
- the silver halide emulsion may be applied by any conventional method to a suitable support such as a glass plate, a cellulose derivative film, a synthetic film or a baryta paper.
- sensitizing dyes of the formula (1) employed in the present invention are should below but it showul be understood that they are not limited to the the following examples.
- the sensitivity of the film is shown by the reciprocal of the exposure necessary to give fog +0.1 in optical density.
- the sensitivity in the case of incorporating only the sensitizing dye in the emulsion is defined to be 100, and the sensitivity in the case of incorporating the formalin condensate together with the sensitizing dye in the emulsion is shown by a comparison with the defined sensitivity.
- lower alkyl in this specification means methyl group, ethyl group, propyl group, and butyl group.
- R an aralkyl group can have l-8 carbon atoms.
- the condensation reaction is further described in Preparative Methods of Polymer Chemesitry” published by John Wiley and Sons, Inc. in 1961, W. R. Sorenson and P. W. Campbell. Finally, the condensate reaction of the substituted or unsubstituted polyhydroxybenzene and formaldehyde is always carried out in acidic range.
- R and R are each a member selected from the class consisting of an alkyl group having one to five carbon atoms and an alkyl group substituted by a member selected from the class consisting of hydroxyl, acetoxy, sulfate carboxyl, carboxyalkoxyl, sulpho, hydroxysulpho, alkyoxy-sulphoalkoxy, m represents 1 or 2, 1: represents an anion, and p represents 1 or 2, and at least one condensate of formaldehyde and a member (I18) 3013 (IIb) S 11;, (He) R wherein R and R represents a member selected from the group consisting of OH, OM, 0R NHR NH N(R NH)
- sensitizing dye contains at least one quinoline nucleus, which may also have substituted thereon groups selected from the class consisting of halogen atoms, and alkyl group having one to eight carbon atoms, and alkoxyl group and a hydroxyl group, and said fonnalin condensate has 2-10 units as a degree of polymerization and a molecular weight of 300-800.
- a photographic silver halide element comprising a support and a photographic silver halide emulsion layer thereon containing at least one sensitizing dye represented by the following general formula:
- R, and R are each a member selected from the class consisting an alkyl group having one to five carbon atoms and an alkyl group substituted by a member selected from the group consisting of hydroxyl, acetoxyl, sulfate carboxyl, carboxyalkoxyl, sulpho, hydroxysulpho, alkyoxy-sulphoalkoxy, m represents 1 or 2, X represents an anion, and p represents 1 or 2, and at least one condensate of formaldehyde and a member selected from the group consisting of a substituted polyhydroxybenzene and an unsubstituted polyhydroxybenzene represented by the following general formula (0H)n1 (OHhZ OH I (Ila) COR; (IIb) S 0 R; (IIc) R5 wherein R and R each represents a
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- Spectroscopy & Molecular Physics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Physics & Mathematics (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Plural Heterocyclic Compounds (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 |
|---|---|---|---|
| JP43088768A JPS4949504B1 (enrdf_load_stackoverflow) | 1968-12-04 | 1968-12-04 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3615637A true US3615637A (en) | 1971-10-26 |
Family
ID=13952024
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US882271A Expired - Lifetime US3615637A (en) | 1968-12-04 | 1969-12-04 | Spectrally sensitized photographic silver halide emulsions |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US3615637A (enrdf_load_stackoverflow) |
| JP (1) | JPS4949504B1 (enrdf_load_stackoverflow) |
| BE (1) | BE742588A (enrdf_load_stackoverflow) |
| DE (1) | DE1960730B2 (enrdf_load_stackoverflow) |
| FR (1) | FR2025194A1 (enrdf_load_stackoverflow) |
| GB (1) | GB1283595A (enrdf_load_stackoverflow) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4883867A (en) * | 1985-11-01 | 1989-11-28 | Becton, Dickinson And Company | Detection of reticulocytes, RNA or DNA |
| US20040230057A1 (en) * | 2003-05-14 | 2004-11-18 | Chao-Nan Kuo | Dye for optical recording medium |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55110239U (enrdf_load_stackoverflow) * | 1979-01-29 | 1980-08-02 | ||
| US6495692B1 (en) * | 1996-12-10 | 2002-12-17 | Abbott Laboratories | Helium-neon excitable reticulocyte dyes derivable from halolepidines |
-
1968
- 1968-12-04 JP JP43088768A patent/JPS4949504B1/ja active Pending
-
1969
- 1969-12-03 BE BE742588D patent/BE742588A/xx unknown
- 1969-12-03 GB GB59025/69A patent/GB1283595A/en not_active Expired
- 1969-12-03 DE DE19691960730 patent/DE1960730B2/de active Granted
- 1969-12-03 FR FR6941642A patent/FR2025194A1/fr not_active Withdrawn
- 1969-12-04 US US882271A patent/US3615637A/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4883867A (en) * | 1985-11-01 | 1989-11-28 | Becton, Dickinson And Company | Detection of reticulocytes, RNA or DNA |
| US20040230057A1 (en) * | 2003-05-14 | 2004-11-18 | Chao-Nan Kuo | Dye for optical recording medium |
Also Published As
| Publication number | Publication date |
|---|---|
| DE1960730B2 (de) | 1973-02-08 |
| GB1283595A (en) | 1972-07-26 |
| JPS4949504B1 (enrdf_load_stackoverflow) | 1974-12-27 |
| DE1960730A1 (de) | 1970-07-02 |
| FR2025194A1 (enrdf_load_stackoverflow) | 1970-09-04 |
| BE742588A (enrdf_load_stackoverflow) | 1970-05-14 |
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