JPH0132974B2 - - Google Patents
Info
- Publication number
- JPH0132974B2 JPH0132974B2 JP18366580A JP18366580A JPH0132974B2 JP H0132974 B2 JPH0132974 B2 JP H0132974B2 JP 18366580 A JP18366580 A JP 18366580A JP 18366580 A JP18366580 A JP 18366580A JP H0132974 B2 JPH0132974 B2 JP H0132974B2
- Authority
- JP
- Japan
- Prior art keywords
- layer
- compound
- formula
- silver halide
- photographic product
- 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
Links
- 239000010410 layer Substances 0.000 claims description 206
- 150000001875 compounds Chemical class 0.000 claims description 141
- 239000000975 dye Substances 0.000 claims description 126
- 239000000203 mixture Substances 0.000 claims description 99
- 239000000047 product Substances 0.000 claims description 87
- -1 silver halide Chemical class 0.000 claims description 70
- 239000004332 silver Substances 0.000 claims description 63
- 229910052709 silver Inorganic materials 0.000 claims description 63
- 239000000839 emulsion Substances 0.000 claims description 48
- 238000012545 processing Methods 0.000 claims description 46
- 238000012546 transfer Methods 0.000 claims description 38
- 239000000463 material Substances 0.000 claims description 30
- 238000009792 diffusion process Methods 0.000 claims description 28
- 239000002904 solvent Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 13
- 150000001450 anions Chemical class 0.000 claims description 10
- 239000002244 precipitate Substances 0.000 claims description 9
- 238000012216 screening Methods 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 125000006575 electron-withdrawing group Chemical group 0.000 claims description 7
- 239000002356 single layer Substances 0.000 claims description 7
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 6
- QDLAGTHXVHQKRE-UHFFFAOYSA-N lichenxanthone Natural products COC1=CC(O)=C2C(=O)C3=C(C)C=C(OC)C=C3OC2=C1 QDLAGTHXVHQKRE-UHFFFAOYSA-N 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 4
- FECNOIODIVNEKI-UHFFFAOYSA-N 2-[(2-aminobenzoyl)amino]benzoic acid Chemical class NC1=CC=CC=C1C(=O)NC1=CC=CC=C1C(O)=O FECNOIODIVNEKI-UHFFFAOYSA-N 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims description 3
- 238000003384 imaging method Methods 0.000 claims description 3
- 239000012463 white pigment Substances 0.000 claims 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 90
- 239000000243 solution Substances 0.000 description 52
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 40
- 238000003756 stirring Methods 0.000 description 32
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 26
- 230000002829 reductive effect Effects 0.000 description 22
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 18
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 18
- 238000000354 decomposition reaction Methods 0.000 description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 15
- 230000003287 optical effect Effects 0.000 description 15
- 238000004809 thin layer chromatography Methods 0.000 description 15
- 239000001018 xanthene dye Substances 0.000 description 15
- 238000012937 correction Methods 0.000 description 14
- 239000007858 starting material Substances 0.000 description 14
- 239000007788 liquid Substances 0.000 description 13
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000012299 nitrogen atmosphere Substances 0.000 description 12
- 239000002253 acid Substances 0.000 description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 9
- 108010010803 Gelatin Proteins 0.000 description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 9
- 229920000159 gelatin Polymers 0.000 description 9
- 239000008273 gelatin Substances 0.000 description 9
- 235000019322 gelatine Nutrition 0.000 description 9
- 235000011852 gelatine desserts Nutrition 0.000 description 9
- 239000011541 reaction mixture Substances 0.000 description 9
- 150000003732 xanthenes Chemical class 0.000 description 9
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- 230000002427 irreversible effect Effects 0.000 description 8
- 229910052938 sodium sulfate Inorganic materials 0.000 description 8
- 235000011152 sodium sulphate Nutrition 0.000 description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 7
- 239000002585 base Substances 0.000 description 7
- 239000007795 chemical reaction product Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 6
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 239000011780 sodium chloride Substances 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 229960000583 acetic acid Drugs 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- 239000012043 crude product Substances 0.000 description 5
- 238000004042 decolorization Methods 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000012362 glacial acetic acid Substances 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 229910000104 sodium hydride Inorganic materials 0.000 description 5
- 125000001424 substituent group Chemical group 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 238000003820 Medium-pressure liquid chromatography Methods 0.000 description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- OKJPEAGHQZHRQV-UHFFFAOYSA-N Triiodomethane Natural products IC(I)I OKJPEAGHQZHRQV-UHFFFAOYSA-N 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 239000002168 alkylating agent Substances 0.000 description 4
- 229940100198 alkylating agent Drugs 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000004061 bleaching Methods 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 230000002939 deleterious effect Effects 0.000 description 4
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229920000578 graft copolymer Polymers 0.000 description 4
- 239000000543 intermediate Substances 0.000 description 4
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 4
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 4
- 235000019341 magnesium sulphate Nutrition 0.000 description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 125000006850 spacer group Chemical group 0.000 description 4
- 230000003595 spectral effect Effects 0.000 description 4
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 4
- 229940124530 sulfonamide Drugs 0.000 description 4
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical class ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 4
- VJYGFSGAAOVTLC-UHFFFAOYSA-N 1,1-dioxospiro[2,1$l^{6}-benzoxathiole-3,9'-xanthene]-3',6'-diol Chemical compound O1S(=O)(=O)C2=CC=CC=C2C21C1=CC=C(O)C=C1OC1=CC(O)=CC=C21 VJYGFSGAAOVTLC-UHFFFAOYSA-N 0.000 description 3
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 3
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 3
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000007853 buffer solution Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- DDKMFOUTRRODRE-UHFFFAOYSA-N chloromethanone Chemical compound Cl[C]=O DDKMFOUTRRODRE-UHFFFAOYSA-N 0.000 description 3
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 3
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 3
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 3
- 230000011987 methylation Effects 0.000 description 3
- 238000007069 methylation reaction Methods 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 238000006798 ring closing metathesis reaction Methods 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- WBRPQQSADOCKCH-UHFFFAOYSA-N 2-methylsulfanylaniline Chemical compound CSC1=CC=CC=C1N WBRPQQSADOCKCH-UHFFFAOYSA-N 0.000 description 2
- LULAYUGMBFYYEX-UHFFFAOYSA-N 3-chlorobenzoic acid Chemical compound OC(=O)C1=CC=CC(Cl)=C1 LULAYUGMBFYYEX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 2
- 239000005041 Mylar⢠Substances 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000001448 anilines Chemical group 0.000 description 2
- XFOZBWSTIQRFQW-UHFFFAOYSA-M benzyl-dimethyl-prop-2-enylazanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC1=CC=CC=C1 XFOZBWSTIQRFQW-UHFFFAOYSA-M 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000007844 bleaching agent Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 230000000670 limiting effect Effects 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000020477 pH reduction Effects 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 239000012312 sodium hydride Substances 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 1
- APORIKJNLVVUNX-UHFFFAOYSA-N 2-amino-1-(2-diphenoxyphosphorylpyrrolidin-1-yl)ethanone Chemical compound NCC(=O)N1CCCC1P(=O)(OC=1C=CC=CC=1)OC1=CC=CC=C1 APORIKJNLVVUNX-UHFFFAOYSA-N 0.000 description 1
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- WAVOOWVINKGEHS-UHFFFAOYSA-N 3-(diethylamino)phenol Chemical compound CCN(CC)C1=CC=CC(O)=C1 WAVOOWVINKGEHS-UHFFFAOYSA-N 0.000 description 1
- MPNBBQFKLWQJIP-UHFFFAOYSA-N 4-benzhydrylidenecyclohexa-2,5-dien-1-one Chemical compound C1=CC(=O)C=CC1=C(C=1C=CC=CC=1)C1=CC=CC=C1 MPNBBQFKLWQJIP-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 125000003047 N-acetyl group Chemical group 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000004414 alkyl thio group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000008064 anhydrides Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- WRUAHXANJKHFIL-UHFFFAOYSA-N benzene-1,3-disulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC(S(O)(=O)=O)=C1 WRUAHXANJKHFIL-UHFFFAOYSA-N 0.000 description 1
- 239000001045 blue dye Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 230000002925 chemical effect Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000002026 chloroform extract Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000001046 green dye Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004464 hydroxyphenyl group Chemical group 0.000 description 1
- 208000013403 hyperactivity Diseases 0.000 description 1
- 230000003100 immobilizing effect Effects 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 150000002596 lactones Chemical group 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- OPUAWDUYWRUIIL-UHFFFAOYSA-N methanedisulfonic acid Chemical compound OS(=O)(=O)CS(O)(=O)=O OPUAWDUYWRUIIL-UHFFFAOYSA-N 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 description 1
- AJDUTMFFZHIJEM-UHFFFAOYSA-N n-(9,10-dioxoanthracen-1-yl)-4-[4-[[4-[4-[(9,10-dioxoanthracen-1-yl)carbamoyl]phenyl]phenyl]diazenyl]phenyl]benzamide Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2NC(=O)C(C=C1)=CC=C1C(C=C1)=CC=C1N=NC(C=C1)=CC=C1C(C=C1)=CC=C1C(=O)NC1=CC=CC2=C1C(=O)C1=CC=CC=C1C2=O AJDUTMFFZHIJEM-UHFFFAOYSA-N 0.000 description 1
- KEBXGLIHHLGNJH-UHFFFAOYSA-N n-methylsulfanylaniline Chemical compound CSNC1=CC=CC=C1 KEBXGLIHHLGNJH-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012746 preparative thin layer chromatography Methods 0.000 description 1
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 1
- 239000013014 purified material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000001044 red dye Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 239000001022 rhodamine dye Substances 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 239000001003 triarylmethane dye Substances 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 239000001043 yellow dye Substances 0.000 description 1
Description
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The present invention relates to the use of new xanthene compounds in photographic products, for example as optical screening dyes. Photographic film, particularly multicolor film, can and generally does vary from lot to lot, despite efforts to "recreate" previous films. Manufacturers of multicolor photographic film have developed a number of methods to minimize the effect of unavoidable variations during manufacturing operations on the final multicolor image. These changes primarily reflect shifts in color balance, which is reflected in the mismatch of the D log E curves for red, green, and blue exposures. Although the equipment used to apply multicolor films is highly sophisticated, silver halide and/or
Variations occur between the intended coverage of the dye-imaging material. Batches of silver halide can, and generally do, vary in their photographic response from batch to batch. Each individual layer may be dried to a slightly different extent. The film has the opportunity to be stored for a period of time after application to "age" to stabilize the sensitometric changes after application prior to sale. If the film is designed to be developed in a photofinishing machine or in a darkroom, the processing of exposed multicolor film can be carried out within very narrow limits to minimize sensitometric changes from film to film. Generally, the temperature is controlled within ±0.5 degrees of the specified temperature. If the multicolor film is a negative-working film, the opportunity to adjust the sensitometry occurs during printing of the final positive image, and print exposure during this operation can be carried out using suitable color filters. The basic factors that cause sensitometric changes as described above also exist in multicolor diffusion transfer films, and once the film is shipped, complexity is added and sensitometric properties are fixed.
Practically speaking, the adjustment opportunities provided during darkroom processing are not available to users of self-developing films. While professional and advanced amateur photographers can at least partially "rebalance" the color balance using color correction filters, these additional operations can be complicated for the average film user. Only. The use of optical screening dyes in photographic elements is well known. Such dyes may be applied in a light-sensitive emulsion layer (single or multilayer), or in a layer coated on top of one or more light-sensitive emulsion layers or between two different color sensitized emulsion layers. They can be incorporated as filter dyes into the emulsion layer to modify the optical recording properties in the emulsion layer or to modify the spectral composition of light incident on the underlying photosensitive layer. Alternatively, such dyes can be incorporated as antihalation dyes into non-photosensitive layers disposed on either side of a support carrying a photosensitive layer (single or multilayer). In addition to having the spectral absorption properties required for their intended use, the dyes used for these purposes must be photochemically inert, i.e. they must be present in the light-sensitive emulsion layer (monolayer). or multilayers) should not have any deleterious effect on the properties. Additionally, these dyes must be able to be bleached or removed during photographic processing and not remain behind to contaminate the processed photographic element. When the dye is removed by dissolving it in the processing solution, the dye is Decolorization is also usually preferred. Although various groups of dyes have been proposed for use in antihalation layers and color correction filter layers, all of the previously used dyes have not been satisfactory. Some dyes tend to reduce sensitivity, cause fog, or have other deleterious effects on photosensitive materials. However, the main drawback of conventionally used dyes is that they either produce stains due to incomplete bleaching or
or that some of the bleached form has a tendency to return to its original colored form. For example, a group of dyes "bleachs", that is, relies on the presence of auxiliary agents such as sulfides for decolorization, and unless the dye is removed from the photosensitive material during or after processing, it will lose its color. After all, it can be reproduced. Among the types of photoscreening dyes previously used are triarylmethanes and xanthenes. For example, U.S. Patent No. 1879537;
No. 1994876; No. 2350090; and No. 3005711 use fuchsone in the antihalation layer.
discloses the use of dyes, and U.S. Patent No.
Nos. 3406069 and 3615548 relate to metal chelates of fuxon dyes as antihalation dyes. These and other types of triarylmethane dyes exhibit one or more of the drawbacks mentioned above, especially when conventional dyes of this type are decolorized during the "bleaching" following processing and at the PH normally encountered in the final product. It was difficult to continue. Xanthenes are used in antihalation layers, and these are removed during photographic processing. For example, U.S. Pat. Nos. 2,182,794; 2,203,767 and 2,203,768 disclose the use of rhodamine dyes in certain antihalation layers; It is therefore removed during processing in an acid bath or a simple water rinse bath. James W., filed December 26, 1979.
Foley, co-pending U.S. patent application Ser. It relates to colored triarylmethane compounds having a group that provides a group to be added to the central carbon atom to undergo an irreversible decomposition reaction to form a new closed ring compound that is colorless. As described and filed in this patent application, these compounds are superior to conventional optical screening dyes because of their complete and virtually irreversible decolorizing ability to an inert, colorless product. It is useful as a photographic light screening dye offering advantages. The present invention has been found to be useful as a photographic optical screening dye, and does not have the disadvantages associated with dyes previously used for this purpose.
It concerns photographic products using another group of compounds, namely xanthene compounds. The xanthene dyes used in the present invention, described in particular detail below, effectively absorb radiation within a predetermined range of the visible range from 400 to 700 nm and are transparent to gelatin or other processing compositions. It can be incorporated into a binder and decolorized with alkaline PH to produce a colorless product. Because these compounds can be completely and irreversibly decolorized in base without the need for additional auxiliaries such as sulfides for the "bleaching" reaction, and the new colorless product produced by irreversible decomposition. Because the product remains colorless in aqueous solution over a PH range of about 4.5 to 14, this decomposition product can typically be retained in photographic light-sensitive elements without the ability to reproduce color at any given time. In addition to being non-staining, the compounds of the present invention are substantially inert to photosensitive materials and therefore can be placed in layers adjacent to silver halide emulsion layers or free of any deleterious effects on the emulsion. It can be directly incorporated into the emulsion layer without having any effect. Structural formula (wherein R is H or -COCH3 )
Chemic, Vol. 27, p. 534. These compounds are prepared by condensing m-diethylaminophenol with sacculin at a temperature of 165°C to produce a compound in which R is H, which is then boiled with acetic anhydride to produce the N-acylated derivative. It is synthesized by As described in the above literature, solutions of N-acetyl compounds, unlike solutions of N-unsubstituted compounds (R=H), were not decolorized by boiling, but were boiled with alcoholic sodium hydroxide for a long time. Only later will the acetyl group be separated.
Furthermore, compared to the N-unsubstituted compound, this compound is colorless at alkaline PH, brightly colored at neutral, and becomes more intensely colored as the PH decreases. It is therefore an object of the present invention to provide photographic products using new xanthene compounds. Other objects of the invention will be partly obvious and partly obvious from the description that follows. According to the invention, with certain substituted phenyl groups in the 3 and 6 positions; in the 9 position with the formula
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ãããã·ã¢ããâSO2CH3ïŒ[Formula] is an electron-withdrawing group selected from the group consisting of -COCH 3 , -SO 2 N (CH 2 Ph) 2 (where Ph is phenyl) and -SO 2 N (CH 3 ) 2 ) and optionally a sulfo group in the 2-position or a sulfo group in the 2- and 7-positions. When the compounds used in this invention come into contact with alkaline photographic processing compositions, they irreversibly decolorize by forming new ring-closure compounds. For a fuller understanding of the nature and objects of the invention, the following detailed description should be considered in conjunction with the accompanying drawings. FIG. 1 is a diagrammatically enlarged cross-sectional view of a diffusion transfer film unit incorporating the xanthene dye of the present invention as a bleachable antihalation dye layer; and FIG. 2 as a color correcting filter dye in the image receiving layer. FIG. 2 is a diagrammatically enlarged cross-sectional view of another diffusion transfer film unit incorporating the xanthene dyes of the present invention. In particular, the compounds used according to the invention have the formula and (In the formula, each R 1 is lower alkyl, and each R 2 is nitro, cyano, -SO 2 CH 3 ;
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[Formula] COCH 3 is an electron-withdrawing group selected from the group consisting of -SO 2 N (CH 2 Ph) 2 (where Ph is phenyl); and -SO 2 N (CH 3 ) 2 , and teeth
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where Y is an electron-withdrawing group as defined for R 2 , n is 0 or 1, and A is an anion)
It can be shown as Typical R 1 groups are alkyl containing 1 to 3 carbon atoms, such as methyl,
ethyl, n-propyl and the R 3 group is lower alkyl having 1 to 3 carbon atoms. The anion associated with the xanthene compound used in the present invention, that is, the compound of the above formula, may be any simple anion, such as tosylate, sulfate, nitrate, perchlorate, methanesulfonate, methanehydrogendisulfonate, m - halides such as benzene hydrogen disulfonate, acetate, oxalate or chloride or bromide. The compound of formula is substituted with one, preferably two, sulfo groups and thus has a "floating group".
(floating), that is, the external A is erased. Furthermore, the presence of two such groups increases the dispersibility of the dye applied from an aqueous dispersion into the binder material, and the second sulfo group also increases the medial properties with certain polymeric binders. Can be used as a base to prevent dye migration in photographic products. It is to be understood that other resonance forms of the xanthene compounds used in the present invention are also encompassed by formulas and. As mentioned above, the xanthene compounds used in the present invention are initially colored, ie, capable of absorbing visible radiation, and are transformed into colorless compounds by undergoing an irreversible decomposition reaction with a base at alkaline PH. The colorless compound formed is reversible to the colored compound by changing the pH, and is a new compound different from the colored compound. In particular, the X group substituted on the phenyl group undergoes an irreversible decomposition reaction that is completed in an alkaline solution at a predetermined alkaline pH within a predetermined time to yield a new colorless compound, i.e.
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(b) reacting this sulfonyl chloride with ammonia to form the sulfonyl chloride corresponding to the formula (In the formula, R 1 and R 2 have the same meanings as above)
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[Formula] (wherein R 2 is an electron-withdrawing group as previously defined),
Substituting another chloro group, the formula (3) reacting the compound of step ( 2 ) with an alkylating agent;
One of the N atoms is replaced by an alkyl group and the compound thus obtained is then reacted with a second alkylating agent to replace the other N atom with another alkyl group, or in step (2) The compound is reacted with an alkylating agent to replace both N atoms with the same alkyl group. When the R 2 substituent (one or two) of the N,N-dialkylated compound is alkylthio, converting the compound of step (3) to the corresponding alkylsulfonyl-substituted compound,
It is then converted to the sulfonyl chloride as in step (a) above. If the R 2 groups are the same, both chloro groups of the sulfonefluorescene dichloride starting compound can be replaced in a single step, but it is preferred to replace them in a stepwise manner as described above. The acylating agent is selected in a conventional manner, e.g.
The equivalent is obtained by reacting HO(CH 2 ) 2 Y with phosgene.
It can be produced by producing ClCO 2 (CH 2 ) 2 Y. The following examples further illustrate the preparation of compounds used in the invention and the invention. These examples are not intended to limit the scope of the invention. Example 1 (reference example) Formula Manufacture of a compound having (a) Sulfonefluorescene dichloride A mixture of 10.0 g (0.05 M) and p-(N,N-dimethylsulfonamido)aniline 20.26 (0.05 M) in 160 ml of 2-methoxyethyl was stirred together for 24 hours, filtered, and a small amount of 2 -Methoxy-ethyl ether, then ether, then dried under vacuum to remove the compound. Obtain 18.53g. (b) 20.0g (35.1mM) of the above compound, p-(N,N
-dimethylsulfonamide)aniline 14.1g
(70.3 mM) and 20 ml of 1-methyl-2-pyrrolizidone are heated in an oil bath at 170° C. under nitrogen atmosphere for 4 hours. The deep magenta mixture was treated with 100 ml of 1-methyl-2-pyrrolizidone,
Allow to cool to room temperature, then add 200ml of concentrated HCl and water
Pour into 1400 ml of solution. The mixture is centrifuged and the residue is washed with saturated sodium chloride solution and air-dried on a crystallization dish over the weekend. The residue containing significant amounts of sodium chloride was then dried at 70°C under reduced pressure for 4 hours to remove the compound 25.4 g of crude product are obtained. (c) 25.4g (34.7mM) of the compound produced in step (b)
Dissolve in 300 ml of dry dimethyl sulfoxide.
(Some solid material is seen floating in the solution, this is probably sodium chloride). Add 6.72 g of 50% sodium hydride dispersion to this solution.
in one portion and then stirred at room temperature for 1.5 hours.
The green solution is cooled in an ice bath and iodomethane (300 g) is added dropwise over about 1 hour.
The mixture is allowed to warm to room temperature overnight with stirring. The mixture is poured into 3 portions of water containing 200 ml of concentrated HCl and extracted with methylene chloride (6 x 200 ml). The combined methylene chloride extracts are washed with 2N HCl solution (5 x 1000 ml) and dried over sodium sulfate. Removal of the solvent under reduced pressure yields the compound 10.41g is obtained. (d) 10.4g (approximately 13.7mM) of the compound produced in step (c)
Dissolve in 150 ml of chloroform and add phosphorus pentachloride.
Treat with 6.25g (30mM). The resulting mixture is heated to reflux for 5 hours, then stirred at room temperature overnight. Transfer the purple solution to a separate funnel and add water (2 x 75
ml) and then dried over magnesium sulfate. The mixture is filtered to remove the magnesium sulfate and the liquid is then cooled in an ice bath. liquid is formula Contains sulfonyl chloride. (e) Blow ammonia gas into the liquid obtained in step (d) until it is saturated. Then let it come to room temperature and stir overnight. (The purple color of the solution will gradually become lighter). The mixture is filtered to remove the salts and the solvent is removed under reduced pressure, leaving 10.67 g of residue. The residue is taken up in 25 ml of chloroform:methanol (100:1) and placed in a medium pressure liquid chromatography column, eluting with chloroform:methanol (100:1) and then with chloroform:methanol (50:1). Fractions 2-7 were collected and eluted again with chloroform:methanol (100:1) to remove the compound. Obtain 5.0 g (90-95% purity). (f) Dissolve 4.85 g of the compound prepared in step (e) in 60 ml of dry 2-methoxyethyl ether. Add 0.88 g of potassium orbutoxide to this solution.
(7.9mM) all at once and stir the resulting solution for 1 hour at room temperature. Cool the dark mixture in an ice bath and add 0.75 ml (1.0 g) of dimethyl sulfate;
7.9mM) all at once. Mixture overnight
Leave to come to room temperature, then add sodium chloride 30
Pour into 600 ml of water containing g. The mixture is stirred for about 15 minutes, filtered, and the product is then washed with water. Take the product in about 100 ml of methylene chloride,
Wash with saturated sodium chloride solution (2 x 75 ml);
Then dry over sodium sulfate. If the methylation was not complete, the dried product was dissolved in 60 ml of dry 2-methoxyethyl ether and then 0.95 g of potassium tert-butoxide was added.
(8.47mM) and repeat the methylation.
The mixture is heated at 50° C. for 1 hour and cooled in an ice bath. Mixture then dimethyl sulfate 0.80ml
(1.068g; 8.47mM). The resulting reaction mixture is left to reach room temperature and stirred for 5 days. Mix 600 g of water containing 30 g of sodium chloride
ml and stir for 15 minutes. The reaction product is taken and then dissolved in about 100 ml of methylene chloride. The methylene chloride solution is washed with saturated sodium chloride solution and then dried over sodium sulfate. Remove the solvent and remove the compound Obtain 3.7g. (g) Suspend 774 mg (1.0 mM) of the compound prepared in step (f) in 20 ml of glacial acetic acid. Zinc powder is added to this suspension.
261 g (4.0 mg-atoms) are added and the mixture is heated at about 50° C. in a water bath under nitrogen atmosphere. (After 3 hours, TLC shows the presence of some starting compound). Add another 261 mg of zinc dust and bring the mixture to 60 mg.
â for 2 hours, then under nitrogen atmosphere overnight.
Let cool to room temperature. (TLC does not show the presence of starting compounds). The mixture is poured into 100 ml with stirring for 15 minutes, filtered, washed with water and then dried under reduced pressure. The residue was dissolved in methylene chloride and filtered to remove unreacted zinc dust and salts, then the solvent was removed under reduced pressure and the compound Get 0.8. (h) 0.80 g (1.0 mM) of the compound prepared in step (g) was placed in 10 ml of dry pyridine and dissolved in ClCO 2
Treat with 746 mg (4.0 mM) of (CH 2 ) 2 SO 2 CH 3 overnight under nitrogen atmosphere. Pour the mixture into 100 ml of water with stirring, then add chloroform (3 x 25
ml). The collected chloroform extract
Wash with 1NHCl solution (3 x 25 ml) and saturated sodium chloride (1 x 25 ml) and then dry over sodium sulfate. The solvent was stripped off under reduced pressure and the formula 0.92 g of leuco dye precursor is obtained. (i) Leuco dye precursor 2.9 in 150 ml of methylene chloride
g (3.13mM) is treated with 1.15g (4.7mM) of O-chloranil with stirring overnight. 50 mixture
ml, cooled in an ice bath, and then bubbled hydrogen bromide gas through the cold solution to saturation. Then leave the solution to come to room temperature and add 650 ml of ether.
Pour into the mixture while stirring for 15 minutes. Take the product and wash with ether to obtain 1.8g of the title compound.
is purified by medium pressure liquid chromatography using 8.5% methanol/methylene chloride solvent. Enter
max568, Epsilon 76000 (in ethanol). Example 2 (reference example) Formula Manufacture of a compound having (a) 68.9 g (0.17 M) of sulfonefluorescene dichloride in 135 ml of dimethyl sulfoxide, 2
- a mixture of 50 g (0.36 M) of methylthio-aniline and 7.26 g (0.18 M) of magnesium oxide.
2.5 with stirring under nitrogen atmosphere at 140-145 °C
Heat for an hour and then pour into 2N hydrochloric acid with vigorous stirring. The mixture was stirred for about 1 hour, the crude reaction product was taken, washed with plenty of water, then dried under vacuum overnight, and the formula 94.9 g of a solid consisting of the compound is obtained. (b) 50% to a mixture of 50 g (0.082 M) of the compound prepared in step (a) in 500 ml of dimethyl sulfoxide.
19.65 g (â¡9.82 g, 0.41 M) of sodium hydride (prewashed with hexane) are added under nitrogen atmosphere. The resulting mixture was allowed to stir at room temperature for 2 hours, then 100 g of iodomethane
(0.70M) dropwise to this green solution.
The mixture turns magenta within minutes. The mixture was allowed to stir at room temperature over the weekend, then
Pour into 6000 ml of 2N hydrochloric acid, stir for about 0.5 hour, then filter. The percake is treated with approximately 1200 ml of methylene chloride, washed with 1N hydrochloric acid (4 x 500 ml) and 1/2 saturated sodium chloride (1 x 500 ml), then dried over magnesium sulfate. Evaporation of the solvent under reduced pressure yields the crude reaction product
57.67g remains. When this crude product was subjected to high pressure liquid chromatography, the formula 20.47 g of a compound with . The overall yield from sulfonefluorescein is 35% by weight. Dissolve 1.0g of sample in a small amount of methylene chloride,
Precipitate in about 100 ml of ether, remove the precipitate,
Dry under reduced pressure. (ethanol:
λmax543nm - Epsilon 98000). (c) 10.0 g of the compound of step (b) in 75 ml of methylene chloride.
(15.7mM) in 400ml of methylene chloride.
~90% m-cloperoxybenzoic acid 20.2g
(corresponding to 16.2-18.2 g) dropwise. The temperature rises from 18°C to 32°C. The mixture is left stirring at room temperature overnight. The mixture is then filtered to remove a small amount of m-chlorobenzoic acid. The solution was diluted with 10% aqueous sodium hydrogen sulfide (3 x 250 ml), 5% aqueous sodium bicarbonate (3 x 250 ml), 1/2 saturated sodium chloride solution (2
x 250 ml) and then dried over sodium sulfate. The solvent was evaporated under reduced pressure and the residue was dried under high vacuum for about 1 hour, giving the formula 9.7 g of the compound is obtained. (ethanol:
λmax534nm-Epsilon105000). (d) Add phosphorus pentachloride to a solution of 17.89 g (24.45 mM) of the compound of step (c) dissolved in 400 ml of chloroform.
Add 10.6g (50.9mM). The resulting mixture is heated to reflux for 6 hours and then left to reach room temperature overnight. formula The reaction product containing the compound is used directly in the next step without isolation from the reaction mixture. (e) Cool the reaction mixture of step (d) to about 5°C in an ice bath. The mixture is then saturated with anhydrous NH 3 gas. The temperature increases from 5°C to 22°C. Remove the ice bath and allow the reaction mixture to warm to room temperature. After stirring for 6 hours, the mixture is filtered to remove the salts. The liquor is washed with water (3 x 200 ml) containing a small amount of sodium chloride and then dried over anhydrous sodium sulfate. The solvent is evaporated under reduced pressure to obtain 18.58 g of crude product.
This product was further purified by high pressure liquid chromatography and the formula This yields 15.27 g of the compound as a light pink solid. A 1.0 g sample of this compound is crystallized from ethanol containing a small amount of NH 3 gas to give 0.45 g of a light pink solid. When this solid is dissolved in methanol and added to buffer solutions having PH 4, 5, 6 and 7 respectively, the compound is colored at PH 4 and 5, but colorless at PH 6 and PH 7. (f) Step (e) in 0.75 ml of 1.0N sodium hydroxide (0.75 mM) in 10 ml of methylene chloride and 10 ml of water.
to a mixture of 0.50g (0.71mM) of the compound, 85%
Tetra-n-butylammonium chloride 232
mg (â¡197.3mg; 0.71mM) and iodomethane
Add 0.25ml (â¡568; 4.0mM). After about 45 minutes, the reaction appears to be substantially complete.
(TLC shows absence of starting compound).
The reaction mixture is left stirring overnight.
TLC looks the same. The methylene chloride layer was separated, washed with water (5 x 25 ml), dried over sodium sulfate, and the solvent was then evaporated, leaving 0.57 g of the reaction product, which was crystallized from approximately 5 ml of ethanol. let, expression The compound is obtained. When a methanol solution of this compound is added to buffer solutions having PH 4, 5, 6 and 7 respectively, the compound is colored at PH 4, but colorless at PH 5, 6 and 7. (g) 11.71 g of the compound of step (f) in 150 ml of glacial acetic acid.
(16.35mM) solution with 3.2g (49mg-atom) of zinc powder at about 50°C in an ice bath under nitrogen atmosphere.
Process for an hour and then at room temperature over the weekend.
(Suitable amounts were taken periodically for TLC, which showed the presence of varying amounts of starting compound even after 8 hours.)
Pour the mixture into 1500 ml of water with stirring. The precipitate is collected, washed with water and then treated with methylene chloride (approximately 300 ml). The methylene chloride solution is filtered, washed with water (approximately 100 ml) and then dried over sodium sulfate. The solvent was evaporated under reduced pressure and the formula yielding 11.35 g (97%) of the compound. (h) Compound 10.4 of step (g) in 125 ml of dry pyridine.
g (14.mM) mixture of ClCO2
Treat with 10.8g ( 58mM ) of ( CH2 ) 2SO2CH3 .
The mixture is stirred at room temperature under nitrogen atmosphere overnight. (A moderate amount of TLC shows no presence of the starting compound, only a single spot corresponding to the leuco dye). The mixture was poured into 1400 ml of water, the precipitated reaction product was collected, washed with water, dried under reduced pressure, and the formula 10.74 g of the compound are obtained as a light pink solid. (i) 721 mg of the compound of step (h) in 15 ml of methylene chloride
(0.83mM) solution to 393mg of 0-chloranil
(1.6mM). The mixture is stirred at room temperature until TLC shows no starting compound. The mixture is cooled in an ice bath and then saturated with HBr gas. The mixture is allowed to warm to room temperature and then poured into 250 ml of ether. The crude product is taken, washed thoroughly with ether and then dried under reduced pressure to obtain 0.86 g of solid. This solid is purified by medium pressure liquid chromatography techniques using 12% methanol in chloroform. The fractions corresponding to the main components are collected, the solvent is evaporated under reduced pressure, and the residue is dissolved in a small amount of methylene chloride. Add methylene chloride solution to 100 ml of ethyl ether, take the precipitated product, wash with ether and dry under reduced pressure to yield 392 mg of the title compound (ethanol: λmax 550 nm-) Epsilon
96000). Repeat step (i) as follows: Compound of step (h) dissolved in 100 ml of methylene chloride.
0-chloranil 2.26 in a solution of 4.0g (4.6mM)
(9.2mM) all at once. The resulting mixture is stirred at room temperature until TLC shows the absence of starting compound (approximately 1 hour). The mixture is cooled in an ice bath and then saturated with anhydrous HBr gas. 1 of the mixture
Leave to warm up for an hour, then ether
Pour into 1000ml. The precipitated product is collected, washed with ether and then dried under reduced pressure to yield 4.69 g of the title compound. (ethanol:
λmax548nm - Epsilon 99800). Calculated value as N 3 O 11 S 4 C 40 H 40 Br: C: 50.73; H: 4.26; N: 4.44; S:
13.55; Br: 8.44 N 3 O 11 S 4 C 40 H 40 Calculated value as Brã»2HBr: C: 43.33; H: 3.82; N: 3.79; S:
11.57; Br: 21.62 Actual value: C: 43.67; H: 3.56; N: 3.60; S:
11.31;Br:19.09. 0.50 of this dry product to liberate the dry product of 2HBr shown to be present by elemental analysis.
Dissolve the g sample in 20 ml of methylene chloride and then wash with 5% sodium bicarbonate solution (3 x 20 ml). Dry the methylene chloride solution over sodium sulfate to form a solid
Obtain 0.49g. This is purified by medium pressure liquid chromatography. The purified material was measured in ethanol with λmax = 550 nm and epsilon = 101000
has. The elemental analysis values for N 3 O 11 S 4 C 40 H 40 Br of the purified dye are as follows: Calculated: C: 50.73; H: 4.26; N: 4.44; S:
13.55; Br: 8.44 Actual value: C: 49.65; H: 4.35; N: 4.29; S:
11.76;Br:8.59. Steps (a) and (b) are carried out using ethylene glycol instead of dimethyl sulfoxide/magnesium oxide for the condensation of 2-methylthioaniline and sulfonefluorescene dichloride. (a) 10.0 g of sulfofluorescene dichloride (24.6 mM) and 2-methylthioaniline in 100 ml of ethylene glycol.
12.4 ml (d1.111; 13.8 g, 99 mM) of the mixture is heated at 160° C. for 7 hours under nitrogen atmosphere. Pour the mixture into 1000 ml of 1N hydrochloric acid with stirring. After stirring for about 30 minutes, the precipitated product is taken and washed with water and a little acetone, then the product is air dried. This dry substance (15.2
g) was continuously extracted with acetone for 24 hours, then dried under reduced pressure and the corresponding 3,6-bis-
13.4 g of (2'-methylthioanilino)-sulfonefluorescein are obtained. (b) A 1000 ml three-necked flask equipped with an overhead stirrer, nitrogen inlet-outlet tube and dropping funnel is charged with 12.0 g (19.65 mM) of the compound of step (a) and 400 ml of dry dimethyl sulfoxide under a nitrogen atmosphere. To this solution, add 50% pre-washed with hexane.
Add NH3.78g (â¡1.89g; 78.6mM) all at once. The mixture gradually turns dark green. After 2 hours, add 5.9 ml (13.5 ml) of iodomethane to the above solution.
g; 95mM) dropwise. (The mixture gradually turns magenta in color). Leave the mixture stirring over the weekend. The mixture is then poured into 4000 ml of 2N hydrochloric acid solution and left stirring for about 0.5 hour. The precipitated product is filtered, washed with water and then dissolved in methylene chloride (approximately 500 ml). The methylene chloride solution is washed with 2N hydrochloric acid solution (2 x 250 ml), dried over magnesium sulfate and the solvent is evaporated under reduced pressure to obtain 19.5 g of crude reaction product.
The crude product (18.0 g) was purified by high pressure liquid chromatography and N-methylated 3,6-bis-
11.06 g of (2'-methylthioanilino)-sulfonefluorescein are obtained. (ethanol:
λmax543nmâEpsilon=105000). The overall yield from sulfonefluorescein is 78% by weight. The methylation of step (b) is also carried out in KOH/dimethyl sulfoxide and in NaH/dimethyl sulfate as follows: (b) 11.77 g of the compound of step (e) in 150 ml of dry 2-methoxyethyl ether. (16.77mM) solution
Treat with 0.85 g of 50% NaH (â¡0.425 g; 17.6 mM) under nitrogen atmosphere. The mixture was left stirring at room temperature for 1 hour and then 1.75 ml of dimethyl sulfate (â¡
2.333; 18.5mM). A TLC sample taken after 3 hours shows the presence of some starting compound. Another 0.21 g of 50% NaH is added and the mixture is left stirring for 1 hour. Then dimethyl sulfate
Also add 0.40ml. A suitable TLC taken after an additional hour shows no presence of starting compound, only product. Mixture with 75g of sodium chloride
Pour into 1500 ml of water in 15 minutes. The precipitated product is taken, washed with plenty of water, and air dried to obtain 1171 g of product. Examples 3 to 6 (Reference Examples) Same compound as the compound of Example 2 except for different relative ions, i.e. formula [In the formula Z=HSO 4 Example 3 CH 3 SO 3 (Example 6) is a compound with the formula Compound L is prepared as shown below from a leuco dye precursor designated by Compound L. 100 mg of compound L dissolved in 2 ml of glacial acetic acid
(0.115mM) solution of 0-chloranil 56.6mg
(0.23mM). After 1.5 hours, TLC shows no starting compound. Two drops of concentrated sulfuric acid are added, the mixture is left stirring for 1 hour and poured into 20 ml of ether. The precipitated product is taken, washed with ether and air dried to give the compound of Example 3. (Ethanol: λmax550nm - Epsilon 96000). 100 mg of compound L dissolved in 2 ml of glacial acetic acid
(0.115mM) solution of 0-chloranil 56.6mg
(0.23mM). Methanedisulfonic acid 2
Add drops after 1.5 hours. The mixture is left stirring for 1 hour and poured into 20 ml of ether to remove the precipitated product. The product is washed with ether and air dried to obtain the compound of Example 4. (ethanol/
H2O : λmax550nm - Epsilon 96000). 200 mg of compound L dissolved in 4 ml of glacial acetic acid
(0.23mM) solution to 113mg of 0-chloranil
(0.46mM). After 1.5 hours, TLC shows no starting compound present. 109.6 mg (0.46 mmol) of m-benzene-disulfonic acid are added all at once, stirring is continued for 0.5 h, then the reaction mixture is poured into 50 ml of ether. The precipitated product is collected, washed with ether and dried under reduced pressure to obtain 200.5 mg of the compound of Example 5. (ethanol:
λmax550nm - Epsilon approx. 82000). 0.5 g of compound L dissolved in 15 ml of methylene chloride
(0.58mM) solution to 283mg of 0-chloranil
(1.15mM) and add it all at once.
After 1.5 hours, TLC shows no starting compound present. The mixture is then cooled in an ice bath and 11 ml of methanesulfonic acid are added. 30 when the mixture is cold
Stir for 1 hour at room temperature, then ether
Pour into 200ml. Take the precipitated product,
Wash with ether and dry to give the product of Example 6 552
Get mg. (Ethanol: λmax550nm - Epsilon 94000; H2O : λmax547nm - Epsilon
93000). Example 7 (reference example) Formula production of compounds. Compound L500 dissolved in 10ml of dry methylene chloride
mg (0.57 mM) is treated with a solution of 0.084 ml of chlorsulfonic acid (â¡147 mg; 1.2 mM) in 5 ml of methylene chloride. A precipitate forms immediately. The mixture is left stirring at room temperature overnight, the methylene chloride is removed by decanation and the residue is washed with methylene chloride. TLC shows the presence of significant amounts of starting compounds. This residue (0.567g; 0.598mM) was dissolved in about 10ml of methanol, and 294mg of 0-chloranil was added.
(1.2mM) and heated at reflux for 30 minutes, then at room temperature for 2 hours. Remove the precipitate and evaporate the liquid under reduced pressure (approximately 200 mg). The liquid is processed by preparative TLC techniques to yield 96 mg of the monosulfonated dye product, a single spot of material corresponding to the title compound (soluble in chloroform; slightly soluble in methanol; insoluble in water). The title compound is
4 grafted onto hydroxyethylcellulose
-When incorporated into a layer of graft copolymer of vinyl-pyridine and vinylbenzyltrimethylammonium chloride, it has a λmax of 568 nm. Example 8 (reference example) Formula Manufacture of a compound having 500 mg of compound L dissolved in 5 ml of acetic anhydride
(0.57mM) solution of chlorsulfonic acid 0.084ml
(â¡147 mg; 1.2 mM) dropwise under nitrogen atmosphere. After 4 hours no precipitate is formed.
The mixture is left stirring at room temperature overnight. The mixture is then poured into 50 ml of ether. The precipitate was collected, washed with ether and dried under reduced pressure.
Obtain 0.56 g of solid. TLC of this solid shows the disulfonated product, the title compound, which should be the major product. Sulfonefluorescene dichloride is prepared as follows: In a five three neck round bottom flask equipped with a paddle stirrer, reflux condenser and thermometer, add ethyl acetate.
1.5 and then cooled to 0°C using an ice bath.
Add sulfonefluorescein (250 g) followed by 200 ml of thionyl chloride. The temperature will rise slightly. Allow the temperature to return to 0°C. 750 ml of N,N-dimethylformamide (DMF) are then added all at once. The temperature rises to about 30°C. After the addition is complete, stir the mixture for 1 hour. The ice bath is removed and the temperature of the reaction mixture is allowed to rise to room temperature, after which the mixture is placed on a steam bath and heated to reflux with stirring. During heating, the mixture becomes lighter in color and becomes viscous. (The color is brown). After refluxing for 10-15 minutes, the reaction mixture is placed in an ice bath and cooled to 0° C. with continuous stirring. The cold reaction mixture is filtered and washed with cold 15% DMF/ethyl acetate solution until the color of the precipitate is as light as possible, then with ether. After suctioning under the rubber dam,
Air dry the sulfonefluorescene dichloride. Yield 184.3g (68%); purity 99.7 by LC
%. The new ring-closing decomposition product formed when the xanthene compound used in the present invention undergoes irreversible decomposition in an alkaline aqueous solution has the formula (wherein R 1 , R 2 , R 3 and n have the same meanings as above). Although the alkyl substituent on the N atom of the death,
Desirable because it produces more highly colored compounds. A methanolic solution of the decomposition products of the present invention represented by Compounds A and B below and a methanolic solution of Compounds C to G having the following structures were prepared by adding 4,
Add to a series of buffer solutions, each with a PH of 5, 6, and 7, and measure the approximate PH at which these compounds become colored when the PH drops below the alkaline value. The results are shown in Table 1 below.
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瀺ãã[Table] The decomposition products (compounds A and B) of the xanthene dye used in the present invention are colorless at PH5, and PH4
Compound D is only weakly colored;
is also colorless at PH5, and it can be easily recognized by referring to Table 1 above that Compound C is only weakly colored at PH5. On the other hand, compounds E and F exhibit a weak color at PH6, and become strongly colored at PH4. Compound G exhibits a weak color at pH 7, and becomes very intensely colored as the pH decreases to 4. From this data, placing electron-withdrawing substituents on both 3,6-N-phenyl groups yields xanthene compounds whose decomposition products remain colorless even when the pH drops to about 4.5. On the other hand, the same xanthene compound with no electron-withdrawing substituent on the N-phenyl group or with only one such substituent on the N-phenyl group does not remain colorless even at a pH below 7; It can be seen that a product is produced. In addition to being colored in PH7, N,N
- The decomposition products of dialkyl compounds even exhibit stronger coloration at lower PH values. As mentioned above, the xanthene dyes used in the present invention undergo an irreversible decomposition reaction within a predetermined time at a predetermined PH and become colorless at a PH that typically increases during processing and subsequent bleaching periods. has the ability to completely and irreversibly decolorize in base by yielding a new colorless compound that remains
This new compound can therefore be carried in a photographic film unit, such as a light-sensitive element, without the possibility of reproducing color over time. Typically, the dye will be selected for use as an antihalation dye, for example in a non-light-sensitive layer located intermediate the light-sensitive silver halide emulsion layer and the support. The dye can also be selected for use as a color correction filter dye when absorption of light within a particular wavelength range during exposure is desired to achieve proper color balance. Representative film units in which the xanthene dyes used in the present invention can be advantageously used as antihalation dyes are described, for example, in British Patent No. 1,482,156. These film units consist, in the order in which the incident light passes, of an additive multicolor screen, a light-sensitive silver halide emulsion layer, an antihalation layer in which selected compounds may be disposed, and preferably an image-receiving layer. As described in that patent, exposure of the silver halide layer selectively transmits a predetermined portion of the incident light, such as red, green, and blue light, to the underlying light-sensitive silver halide layer. This is done through a screen with an optical filter element. Upon photographic processing with aqueous alkaline processing compositions, soluble silver complexes are transferred by diffusion and deposited in the stacked image-receiving layer as a function of the degree of exposure of the silver halide behind each filter element. The silver image thus formed can then serve to alter the amount of light passing through the filter element in the opposite direction during projection through the transparent support. In a preferred embodiment, the image-receiving layer is intermediate between the light-sensitive silver halide emulsion layer and the multicolor screen and remains in place as part of the integrated film unit before, during and after formation of the image. There is. Antihalation dyes are placed in the processing composition transparent layer adjacent to the photosensitive layer on the opposite side of the screen to prevent reflection or back scattering of incident light transmitted through the photosensitive layer, thus It functions to prevent silver halide grains from being exposed to light from other than the intended exposure path. As mentioned above, the dyes of the present invention are also useful in photographic film units comprising multilayer, multicolor photosensitive elements employing blue, green and red sensitive silver halide layers, especially when the image receiving layer carrying a color transfer image is developed after processing. It is also useful as a color correcting filter dye in an integrated negative-positive diffusion transfer film unit in which both elements are held together as a permanent laminate without being separated from the photosensitive layer. As part of the laminate, the image-bearing layer and the developed photosensitive layer (single layer or multilayer)
and a layer of light-reflecting material, preferably titanium dioxide, located between. A light-reflecting layer separating the image-bearing and photosensitive areas provides a white background for the transferred image and masks the developed photosensitive layer (single or multilayer). In addition to these layers, the laminate typically includes a dimensionally stable outer layer or support, at least one of which the resulting transferred image is visible by reflection against the background provided by the light-reflecting layer. As transparent as possible. Representative patents disclosing such film units include U.S. Pat. No. 2,983,606 issued to Howard G. Rogers on March 9, 1961;
U.S. Patent No. 3415644, U.S. Patent No. 3415645, and U.S. Patent No.
No. 3415646, July 20, 1971, by Howard G.
No. 3,594,164 and 3,594,165 issued to Rogers and dated March 7, 1972.
U.S. Patent No. issued to Edwin H.Land
There is number 3647437. Edwin H. Land, pending U.S. Patent Application No. 537,124, relates to a multicolor diffusion transfer film unit in which a layer of dye, preferably a dye releasable by a processing composition, is removed by photographic exposure. The dye layer is thus effective as a color correction filter. For convenience, this patent application is specifically incorporated herein. Whether used as antihalation dyes, as color-correcting filter dyes, or for other conventional photographic phototransmission applications, the dyes of the present invention, when placed in a processing composition permeable layer, convert colored dye compounds into new colorless ring closures. Upon contact with an aqueous alkaline treatment composition for the time required to transform the compound, it completely and irreversibly decolorizes. Decolorization, i.e. the time required to change from a colored compound to a colorless product by an irreversible decomposition reaction, can be measured at any given alkaline pH and by contacting and continuing the contact with a colored filter dye for the selected decolorization time. The PH must be at least as high as the predetermined PH to give the selected decolorization time. In the term T1/2, preferred compounds have a half-life (T1/2) of about 30 seconds or less in about 1N NaOH. The term T1/2 refers to the measured time during which half of the colored dye is bleached. The xanthene dyes used in this invention can be incorporated into the appropriate layers of a photographic film unit using any of the techniques known in the art. For example, the selected compound may be dissolved in a suitable solvent and then dispersed in a coating solution containing a hydrophilic colloid binder (e.g. gelatin), optionally in the presence of a wetting agent, and the resulting coating solution applied to the desired layer. , for example, a layer coated on a transparent support to provide an antihalation layer or on the outermost photosensitive layer of a multilayer multicolor photosensitive element to provide a color correction filter layer through which photographic exposure is carried out. Can be applied as a coated layer. The concentration of compounds in the layer varies depending on the product in which this filter layer is used, and is adjusted to provide the required optical density for the particular application.
It can be easily determined by experiment. It will be clear that the dyes of the invention can be used in combination with each other and also with other types of dyes conventionally used in antihalation, color correction and other filter layers. FIG. 1 of the accompanying drawings illustrates one embodiment of the invention, in which a number of primary red filter elements, a number of primary green filter elements and a number of blue filter elements are arranged in order on a single substantially single surface. an additive multicolor screen 3 arranged in a geometrically repeating distribution in parallel relationship on the branches; a non-photosensitive layer 5 carrying silver precipitation nuclei; a photosensitive layer 7 containing silver halide crystals. FIG. 1 is an enlarged cross-sectional view of an integrated diffusion transfer film unit comprising a transparent film base or support 1 carrying an antihalation layer 9 containing one or more of the optical screening dyes of the present invention; As explained in the aforementioned GB 1482156, the optical absorption of the antihalation layer in such film units can vary over a relatively wide range, but typically the antihalation layer has a
It has a transmission density range of 0.4-1.4. Transmission density is 0.6
Even when larger, multiple film units are used in adhesive relationship during exposure, the antihalation layer has sufficient density, i.e., to substantially prevent reflection and exposure of the underlying film unit. Preferably, it has absorption capacity. To determine the appropriate light absorption capacity for cyan, magenta, and yellow for color correction purposes, place a conventional "corrector" on the front of the camera lens.
(colorcompensating) filters can be used in a conventional manner as a convenient way to estimate the type and amount of excess desired. A layer containing suitable color correcting dye(s) in corresponding concentrations can be applied as a layer through which the photographic exposure is carried out. Multicolor diffusion transfer images are obtained using various arrangements of image-receiving layers and silver halide emulsions. Therefore,
These layers can be supported by conventional supports that are laminated after exposure. A particularly advantageous film structure is shown in U.S. Pat. No. 3,415,644, in which the required layers are in stacked relationship before and during exposure;
These layers also remain in stacked relationship as a permanent laminate after processing and imaging. Such film units typically carry an outer transparent layer or support through which exposure takes place and through which the final polychromatic image is visible, and at least a light-sensitive layer, and another outer layer that is opaque. Or have a support. Although the supports or sheet-like elements can simply be held in stacked relation, for example by joining the peripheral edges with tape, in a preferred embodiment the elements are laminated together before exposure.
This pre-lamination provides many benefits during both manufacturing and exposure times. These elements are delaminated by the distribution of the liquid treatment composition after exposure and bonded together as the treatment composition solidifies to form the desired permanent laminate. These two types of elements are combined into one before exposure.
The method of forming prelaminated film units that are laminated together in time is described, for example, in the March 28, 1972
No. 3,625,231 issued to Albert J. Backelder and Frederick J. Binda, US Pat. No. 3,652,282 issued to Edwin H. Land on March 28, 1972, and US Pat.
U.S. Patent No. issued to Edwin H.Land
Described in No. 3793023. A more detailed description of this aspect of the invention can be facilitated by reference to FIG. 2 of the accompanying drawings. FIG. 2 illustrates a diffusion transfer film unit suitable for providing integrated negative-positive reflection prints and employing a dye developer as the image dye. FIG. 2 illustrates a diffusion transfer film unit comprising a photosensitive element or component 2; a rupturable container 30; and an image receiving element or component 4. Photosensitive element 2 includes, in order, cyan dye developer layer 12, red-sensitive silver halide emulsion layer 14, interlayer 16, magenta dye developer layer 18, green-sensitive silver halide emulsion layer 20,
It consists of an opaque support carrying an intermediate layer 22, a yellow dye developer layer 24, a blue-sensitive silver halide emulsion layer 26 and an auxiliary layer 28. The positive or image-receiving layer is sequentially
It comprises a transparent support carrying a polymeric acid layer 42, a timeminder layer 44, and an image receiving layer 46 having a whiteable light screening dye according to the invention dispersed therein as a color correcting filter dye. These two elements are placed in a laminated and properly mated relationship, such as with a bonding tape (not shown), such that exposure of the silver halide emulsion layer is through an image-receiving layer 46 containing a bleachable dye.
Retained by The rupturable container 30 contains the treatment composition and is positioned such that upon rupture, the treatment composition is distributed between the stacked elements 2 and 4. By including a light-reflecting pigment, preferably titanium dioxide, in the treatment composition, a light-reflecting layer can be provided against which the transferred image formed on image-receiving layer 46 can be viewed. The light-reflecting layer masks the developed photosensitive layer from line of sight and remains as part of the permanent laminate along with the image-receiving layer 46. Rupturable container 3
0 is of the type shown in U.S. Pat. No. 2,543,181 and is located adjacent the long end of the film unit. When processing such a film unit, the film unit is advanced in relation to one another between a pair of pressurizing means, and the pressurizing means applies compressive pressure to the rupturable container 30 to release its liquid contents. A liquid mass is jetted between the photosensitive element 2 and the image receiving element 4 and then distributed between these sheets towards their three edges to form a substantially uniform preform of at least the same area as the image area. Form a layer of defined thickness. To ensure that the processing liquid is sufficient to form a layer of the required area and thickness between the sheets, excess processing liquid must be drained into container 3.
0, and trapping means
(not shown) may be provided for collection and retention of overflowing excess processing liquid. Details of the various layers and the various layers of the film unit of FIG. 1 can be found in the patents and patent applications cited above and need not be recited here. Processing of a film unit of the type illustrated in FIG. 2 begins by distributing a processing composition between predetermined layers of the film unit. In the exposed and developed areas, the dye developer becomes immobilized as a result of development. In the unexposed and undeveloped areas, the dye developer can be unreacted and diffused, and this results in point-to-point exposure of the silver halide layer, resulting in an image of the unoxidized dye developer being diffusible into the processing composition. Provide distribution. At least a portion of the imagewise distribution of the unoxidized dye developer is diffusely transferred to the image-receiving layer, thereby obtaining a desired transferred image. In an exemplary embodiment, the pH of the photographic system is adjusted to neutralize the alkali after a predetermined interval in accordance with the teachings of the aforementioned U.S. Pat. Controlled and reduced by reducing the PH which is non-diffusible. As will be readily appreciated, the details of such processing do not form part of the present invention and are well known; reference may be made to the aforementioned US patents for a more specific description of such processing. Polychromatic images are obtained by providing the required number of differently exposed silver halide emulsions, which silver halide emulsions are most commonly provided as individual layers coated in a stacked relationship. A film unit intended to provide a multicolor image has two or more selectively sensitized silver halide layers, each of which is combined therewith to provide a suitable image dye. The present invention provides an image dye having spectral absorption characteristics that are substantially complementary to the light of exposure of the silver halide with which the image dye-providing material is associated. The negative parts most commonly used to form multicolor images are "tripack" structures, with blue-, green-, and red-sensitive components having a combination of yellow, magenta, and cyan image dye-providing substances, respectively, in the same or adjacent layers. It has a silver halide emulsion layer. If desired, interlayers or spacer layers can be provided between each silver halide layer and the associated image dye-providing material or between other layers. This general type of integrated multicolor photosensitive element is
To Fdwin H.Land and Howard G.Rogers
U.S. Patent No. 3, issued October 3, 1967.
No. 3,345,163 as well as in the aforementioned U.S. patents, such as FIG. 9 of the aforementioned U.S. Pat. No. 2,983,606. Many modifications to the structure described in connection with FIG. 2 will themselves readily occur to those skilled in the art. So, for example, Edwin H.
No. 2,968,554 issued January 17, 1961 to Land, and U.S. Pat.
2983606, particularly in connection with FIG. 3 thereof, can be used in place of the multicolor multilayer negative. Image-dye-providing materials that can be used in such methods generally (1) are initially soluble or diffusible in the processing composition but become selectively non-diffusible in an imagewise pattern as a result of development; or ( 2) initially insoluble or non-diffusible in the processing composition, but producing a diffusive product in an imagewise pattern or becoming selectively diffusive as a result of development; be able to. These materials may be complete dyes or dye intermediates, such as color couplers. The necessary differences in mobility or solubility can be obtained, for example, by chemical effects such as redox reactions or coupling reactions. For examples of initially soluble or diffusible materials and their application in color diffusion transfer, see
For example, US Patent No. 2774668; US Patent No. 2968554;
Same No. 2983606; Same No. 3087817; Same No. 3185567
No. 3230082; No. 3345163; and No. 3345163;
The description in No. 3443943 can be mentioned. For initially non-diffusible materials and their application in color diffusion transfer systems, see U.S. Pat.
No. 3185567; No. 3719489; No. 3443939; No. 3443940; No. 3227550; No. 3227552;
and the substances and systems described in the same No. 4076529. Several types of image dye-providing materials and film units useful therein are described and referenced in the aforementioned US Pat. No. 3,647,437. It is also understood that "direct positive" silver halide emulsions can also be used depending on the particular image dye-providing material used and whether a positive or negative color transfer image is desired. Should. A suitable opacifying system to be included in the processing composition for off-camera processing is described in the aforementioned U.S. Pat. also contains an optical transmission density of greater than about 6.0 density units and an incident visible light active to the photosensitive silver halide when the processing composition is applied, at a pH greater than or equal to the pka of this optical filtering agent. The dispersion comprises a dispersion of an inorganic light reflecting agent at a concentration effective to provide a layer exhibiting an optical reflection density of less than about 1.0 density units to light. Instead of including a light-reflecting pigment in the processing composition, the light-reflecting pigment used to mask the photosensitive layer and provide a background for viewing the color transfer image formed in the image-receiving layer is initially incorporated into the film unit. It can also be present in whole or in part as a preformed layer. Examples of such pre-formed layers are the 1971
U.S. Patent No. 3,615,421, issued October 26, 1971;
Examples include those described in No. 3620724. Both reflectors were made by Edwin H.Land.
U.S. Patent No. 7, issued March 7, 1972
3647434 and 3647435. Dye developer (or other image dye-providing substance)
are preferably chosen for their ability to provide colors useful in the practice of subtractive color photography, namely cyan, magenta and yellow. These materials can be incorporated into the silver halide emulsions or, in preferred embodiments, in separate layers behind each silver halide emulsion. Thus, the dye developer can be, for example, a coating or layer behind each silver halide emulsion, such dye developer layer being a film-forming natural or Application using a coating solution having each dye developer distributed in a synthetic polymer (e.g. gelatin, polyvinyl alcohol, etc.) at a concentration calculated to give the desired dye developer coverage per unit area. can. As mentioned above, a dye developer is a compound containing a dye color forming system and also a silver halide developing group. The term "silver halide developing group" means a group suitable for developing exposed silver halide. Preferred silver halide developing groups include ortho-dihydroxyphenyl and ortho- and para-amino substituted hydroxyphenyl groups. Generally, developing groups include benzenoid developing groups, ie, aromatic developing groups that form quinonoid or quinone materials when oxidized. The image receiving layer may contain one of the materials known in the art such as polyvinyl alcohol, gelatin, etc. Suitable auxiliaries may also be included to mordant or otherwise fix the transferred image dye(s). Suitable materials are polyvinyl alcohol or gelatin containing dye mordants such as poly-4-vinylpyridine as described in U.S. Pat. No. 3,148,061 and 4-vinyl pyridine as described in U.S. Pat. No. 3,756,814. Includes graft copolymers containing pyridine. In various color diffusion transfer systems using the aforementioned and aqueous-alkaline processing compositions, subsequent to substantial dye transfer, the peripheral PH is lowered, image stability is increased and/or the image dye is initially diffusive. PH to a second (lower) PH that does not diffuse from these or
It is well known to use acid-reactive agents in the layers of the film unit to adjust the properties of the film. For example, the aforementioned US Pat. No. 3,415,644 discloses a system in which the desired PH reduction can be achieved by the application of a polymeric acid layer adjacent to the dyeable layer. These polymeric acids can be polymers containing acid groups capable of forming salts with alkali metals or organic bases, such as carboxylic and sulfonic acid groups; or potential acid-forming groups such as anhydrides or lactones. Suitable acid polymers contain free carboxyl groups. Alternatively, acid-reactive agents can be used according to Edwin H.Land.
U.S. Patent No. 30, issued March 30, 1971
As described in No. 3,573,043, it may be present in the layer adjacent to the silver halide furthest from the image-receiving layer. Another system for applying acid-reactive agents was described by Edwin H. Land on April 27, 1971.
No. 3,576,625 issued on D.A. The inert intermediate layer or spacer layer is used to prevent the development process from occurring too quickly or from interfering with the development process.
It can be, and is preferably, placed between the polymeric acid layer and the dyeable layer to control or "time" the PH reduction. Spacer or "timing" layers suitable for this purpose are inter alia U.S. Pat. No. 3,362,819;
No. 3421893; No. 3455686; and No. 3575701
It is stated in the number. The acid layer and the associated spacer layer are present in positive parts used in systems in which the dyeable layer and the photosensitive layer are on separate supports, e.g. between the support for the image receiving element and the dyeable layer. are preferably present in association with the dyeable layer or in an integrated film unit, for example on the side of the dyeable layer opposite the negative part, but they may also optionally be present, e.g. in U.S. Pat. It can also be present concomitantly with the photosensitive layer, as described in the above. U.S. Pat. No. 3,594,164 and U.S. Pat.
In film units such as those described in US Pat. No. 3,594,165, these layers can also be present on top of the coating layer being used to facilitate the application of processing liquids. As is well known and exemplified, for example, in the cited patents, liquid processing compositions used in the practice of multicolor diffusion transfer processes include at least an alkaline substance, such as an aqueous solution of sodium hydroxide, potassium hydroxide, etc. viscosity, preferably has a PH of greater than 12, and most preferably constitutes a film-forming material of such a type that the composition forms a relatively hard and relatively stable film when spread and dried. Including increasing compounds.
Preferred film-forming materials include high molecular weight polymers that are inert to alkaline solutions, such as polymeric water-soluble ethers, such as hydroxyethyl cellulose or sodium carboxymethyl cellulose. Other film-forming substances or thickening agents having the ability to increase viscosity may also be used without being substantially affected by allowing the solution to stand for extended periods of time. Film-forming substances at a temperature of approximately 24°C
Viscosity greater than 100Cps, preferably at this temperature
It is preferable to include it in the treatment composition in an amount suitable for imparting a viscosity of about 100,000 Cps to 200,000 Cps to the composition. In particularly useful embodiments, the transparent polymeric support prevents light-piping due to internal reflection within the transparent support and subsequent fog formation at its edges due to dissipation of active incident light from the surface of the photosensitive layer-bearing support. For this purpose, they contain small amounts of pigments such as carbon black; such elements are described in Belgian Patent No. 777407. It is advantageous if the transparent support contains a UV absorber. Example 9 (Example) For the purpose of illustrating the invention, a solution of a sample of the compound of Example 1 was applied to the image receiving layer 3 of an image receiving component having the following structure.
The compound is then formulated by mixing it with a solution of the graft copolymer and applying the mixture onto the top surface of the timing layer to complete the receiver component. A clear 4 mil (0.1 mm) polyethylene terephthalate film base is coated in the following order: 1. Approximately 9 parts polyethylene partial butyl ester/maleic anhydride copolymer, 1 part polyvinyl butyral, and 1 part polyvinyl butyral as the polymeric acid layer. A mixture of about 2500
Apply at a coverage of mg/ft 2 (26900 mg/m 2 ); 2 60-30- of butyl acrylate, diacetone acrylamide, styrene and methacrylic acid
Contains a 14:1 ratio mixture of 4-6 quaternary polymer and polyvinyl alcohol, producing 500 mg/ ft2 (5380
Timing layer applied at a coverage of 3 mg/ m2 ); 2.2/1/2.2 of 4-vinylpyridine and vinylbenzyltrimethylammonium chloride grafted onto hydroxyethyl cellulose.
300mg/ft 2 (3228mg/m 2 ) of graft copolymer
to form an image-receiving layer containing the selected dye compound at a coverage of 22 mg/ft 2 (118 mg/m 2 ). An image receiving component containing a dye compound is placed on a piece of gelatin-coated Mylar, red (R),
The transmission density for green (G) and blue (B) is recorded with a transmission densitometer. A few drops of aqueous 1N KOH are then added onto the gelatin sheet and the receiver part is gently pressed against the gelatin sheet to "bleach" the dye compounds. After about 60 seconds, the transmission density is again measured for the red (R) and green (G) of this "Sandermanch" structure.
and blue (B). The results are shown in the table below.
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ããªããã®ãšè§£éãããã¹ãã§ããã[Table] The densitometer was set at 0.00 for R, G, and B using two pieces of gelatin-coated Mylar in the light beam. The compound of Example 2 also absorbed in the green region when applied to a copolymer layer similar to layer 3 and decolorized when contacted with an aqueous alkaline treatment composition having a PH>14. These results demonstrate that the dyes of the present invention are effective at absorbing radiation within a wavelength range and are "bleached" or decolorized when treated with aqueous alkali. It will be apparent that a variety of solvents can be used to disperse the dye in the image-receiving layer or other suitable layer of a photographic product, and that useful solvents can be readily selected for a given compound. Also,
The dye can be placed outside the silver halide emulsion layer (single or multilayer) and its migration in a given matrix or binder when the anion may have a deleterious effect on the photosensitive material. Depending on the nature of the dye, it may be desirable to use matrix-binding or immobilizing groups to prevent dye migration, especially if the photographic product is exposed to high temperature and humidity conditions before use. . Furthermore, when the dyes of the invention are used for color balance correction, for example in multicolor diffusion transfer photographic film units, the light-sensitive element can be exposed to a suitable multicolor step-wedge and a given It will be appreciated that the processing composition and image receiving element can be used to effect diffusion transfer. Blue, green and red Dlog E of the resulting multicolor transfer image (sample image)
Next create the curve. A review of these Dlog E curves will indicate to those skilled in the art the extent and manner in which individual Dlog E curves deviate from the desired curve shape in color photographic sensitometry. From this consideration, routine analysis and experimentation can determine how much excess is needed in which wavelength range (range or ranges) to obtain a more desirable color balance. Another film unit of the photosensitive element having the same photosensitive element, receiver element and processing composition as that used to obtain the sample image, as required to produce the desired change in the Dlog E curve of the sample image. The same exposure is applied through a conventional color correction filter(s) of estimated color and density. Blue, green, and red Dlog E curves of the resulting test multicolor transfer image are generated and compared with those of the sample. Determining the most effective color filter to provide the desired Dlog E curve shape change may require one or more "tests";
Such tests can be performed quickly and easily. Once the appropriate color range has been determined, a layer containing color-correcting dye(s) that absorbs light in the relevant wavelength range (one or more ranges) is applied to the transparent support at the required density. Apply a coverage calculated to give . This "test" color correcting dye layer is placed in the exposure path and the exposure test described above is repeated. Analysis of the Dlog E curve of the resulting multicolor transfer image will show what changes, if necessary, should be made to the spectral absorption range and density before combining the corresponding color-correcting dye layer into the diffusion transfer film unit. Probably. When the exposure is carried out through the layer containing the xanthene dye(s) used in this invention, the light absorbed by the color correcting dye(s) will absorb the exposed silver halide layer (single layer or one or more dyes of the present invention in combination with other filter dyes to produce individual red, green, and blue dyes; It will be appreciated that one, two or all three of the Dlog E curves can be used to effect changes effective in achieving the desired color balance. The xanthene dyes used in this invention are particularly useful in diffusion transfer and other photographic film units where it is desired to bleach the dye(s) during processing after exposure through the dye layer (single or multiple). Although found to have properties, the dyes of the present invention can also be used in diffusion transfer or other film units where the dye is located such that the dye concentration does not contribute to the transferred or final image. "Unbleached" when the filter dye layer through which the exposure takes place is not part of the transferred image, or when the final image is masked from the line of sight as some kind of integrated negative-positive reflective print structure. The filter dye should be non-diffusible into the image-receiving layer containing the transferred image. The necessary non-diffusivity can be achieved by the use of suitable mordants, by the use of long-chain "ballast" or "anchor"substituents;
and/or by other techniques known in the art. As shown in the example above, in the integrated diffusion transfer film unit, color correction dye (one or more)
can be incorporated into the image-receiving layer. The selection of the location of the color correcting dye(s) depends in large part on determining at what stage of manufacture such color correcting dye is to be incorporated. As will be readily apparent, the application of color-correcting dye(s) to a separate layer has the advantage of allowing modification after this area has been sufficiently "matured" and of the same lot. The advantage is obtained that it is also possible to modify parts of the positive part differently. Supports for the various layers can be of any type known in the art to be useful. In preferred embodiments in which integrated negative-positive reflective prints are obtained, the support should be dimensionally stable and may be a polyethylene terephthalate or other polymer based film base as described in the related cited patents. sell. The transferred image formed following film-wise exposure and processing of the type illustrated in FIG. 2 is a geometrically opposite image to the subject. Therefore, in order to form a transfer image that is not geometrically opposed, such film-by-film exposure is
As described in U.S. Patent No. 3,447,437 issued June 3, 1969 to B. Tiffany:
This should be done through an image reversing optical system, such as a camera having an image reversing optical system using mirror optics. When the expression "positive image" is used, this expression is used to indicate an image produced on the image-bearing layer such that it is reversed in a positive-negative sense with respect to the image in the light-sensitive emulsion layer. , are used primarily for illustrative purposes and should not be construed in a limiting sense. Another example of the meaning of "positive image" is when a photosensitive element is exposed to actinic light through a negative transparency. In this case, the latent image in the light-sensitive emulsion layer is positive and the image formed on the image-bearing layer is negative. The expression "positive image" is therefore intended to include images formed on the image-bearing layer as well as transferred images obtained by using a direct positive silver halide emulsion to provide a "positive" image of the subject. do. Although the utility of the xanthene dyes used in the present invention has been illustrated in the context of application to an integral diffusion transfer film unit in which the transferred image is held together with a developed photosensitive element as part of a permanent laminate, the present invention The xanthene dyes used in the invention may also be used in antihalation, color correction or other photosensitive layers in diffusion transfer film units where the silver or dye transfer image is separated from the developed photosensitive layer (single layer or multilayer) after processing. It will be appreciated that it can also be used to apply (single or multiple layers). Although the image dye-providing material is preferably a dye developer, it will be apparent that other types of image dyes or dye intermediates may be used in forming dye transfer images. In addition to their usefulness in diffusion transfer photographic products and methods, the xanthene dyes used in this invention can also be used in filter layers of conventional photographic materials, such as antihalation layers or color correction layers in conventional negatives, as desired. can be placed in the relevant layer (single layer or multilayer) in an amount sufficient to obtain an overeffect of Selection and formulation of xanthene dyes for the desired hyperactivity can be carried out in a known manner using conventional techniques and is well known to those skilled in the art. For example, for color correction purposes, the selected dye(s) may absorb light within a particular wavelength range, such as blue, green or red light, or a combination of several wavelength ranges. It is incorporated into the layer through which exposure takes place. For certain supported cases, it may be desirable to pass through two different wavelength ranges of light in proportions such that one silver halide emulsion receives more overexposure than the other emulsion. As in the case of diffusion transfer film units, the dye(s) selected for color correction is applied to the photosensitive element after it has been allowed to age to "age", i.e., as manufactured. It is advantageous to apply this after the sensitometry no longer changes significantly over time. When the dyes of the invention are used for antihalation purposes, these dyes can be incorporated, for example, in a layer on one or both sides of a support carrying a photosensitive layer (single or multilayer), and When these dyes are used as optical filtering agents, it is of course important that these dyes do not interfere with the imagewise exposure of the photosensitive layer (single or multilayer) or interfere with the act of viewing the final image. , so as to prevent fogging due to subsequent exposure during room light processing. All that is contained in the foregoing description and examples is by way of illustration only, since the invention is susceptible to certain modifications within the scope of the claims without departing from the scope of the invention. shall be construed as having no limiting meaning.
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FIG. 1 is an enlarged cross-sectional view of a diffusion transfer film unit having an antihalation layer containing the xanthene dye of the present invention; and FIG. FIG. 3 is an enlarged cross-sectional view of another diffusion transfer film unit having the structure shown in FIG.
Claims (1)
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補åã ïŒïŒ æè²ååç©ãåŒ ïŒåŒäžïŒ¡ã¯ã¢ããªã³ã§ããïŒãæãããç¹èš±è«æ±
ã®ç¯å²ç¬¬ïŒïŒé ã«èšèŒã®åç補åãClaims: 1 Enveloping a multilayer comprising a support and at least one light-sensitive silver halide emulsion layer carried on the support, at least one of these layers having the formula and (In the formula, each R 1 is lower alkyl; each R 2 is nitro; cyano; âSO 2 CH 3 ; [Formula] [Formula] COCH 3 ; âSO 2 N (CH 2 Ph) 2 (However, Ph is phenyl); and -SO 2 N(CH 3 ) 2 ; X is [Formula]; R 3 is a lower alkyl group; Y is R 2 1. A photographic product containing a colored xanthene compound selected from compounds having an electron-withdrawing group as defined in , n is zero or 1, and A is an anion. 2. A photographic product according to claim 1, wherein the colored compound is dispersed in a processing composition permeable layer on the same side of the support as the silver halide emulsion layer (single or multilayer). 3. A photographic product according to claim 2, comprising, in order, a support, a light-sensitive silver halide emulsion layer and a colored compound-containing layer. 4 supported on the support or on a second support and arranged to receive a silver diffusion transfer image upon application of an aqueous alkaline processing composition providing a silver halide developer and a silver halide solvent; Claim 3 includes a silver precipitated layer
Photo products listed in section. 5 In order, the above support, an additive multicolor screen,
5. A photographic product according to claim 4, comprising the silver precipitate layer, the light-sensitive silver halide emulsion layer and the colored compound layer, the support being transparent. 6. Claim 2, wherein the support is transparent and the colored compound is arranged in a layer between the support and the silver halide emulsion layer (single layer or multilayer). photo products. 7. The method according to claim 2, further comprising a layer of the colored compound coated on the opposite surface of the support, on the light-sensitive silver halide emulsion layer furthest from the support. Photo products. 8 Claims in which the silver halide emulsion layers are a red-sensitive silver halide emulsion, a green-sensitive silver halide emulsion and a blue-sensitive silver halide emulsion, and each emulsion layer has an image dye-providing material associated therewith. Photographic products as described in item 2 of the scope. 9 The colored compound is a compound of the above formula,
A photographic product according to claim 1. 10. A photographic product according to claim 1, wherein said colored compound is a compound of the above formula. 11 The above colored compound has the formula A photographic product according to claim 1, wherein A is an anion. 12 The above colored compound has the formula A photographic product according to claim 1, having: 13 The above colored compound has the formula A photographic product according to claim 1, wherein A is an anion. 14 A first support carrying a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a blue-sensitive silver halide emulsion layer, which silver halide emulsion layers are combined therein to form a cyan image, respectively. a first sheet-like element containing a dye-providing material, a magenta image dye-providing material, and a yellow image dye-providing material;
a second sheet-like element comprising a second support; this treatment being arranged to allow the release of an aqueous alkaline treatment composition between a pair of predetermined layers carried by said support; a rupturable container holding the composition in a releasable manner; one of the above supports;
an image-receiving layer carried on one of the supports; and a processing composition permeable layer carried on one of the supports, in which a colored xanthene compound is dispersed; The sheet-like element and the second sheet-like element are in or suitable for stacking with their supports on the outside; at least one of said supports passes through which the silver halide emulsion is applied. transparent to allow exposure to light; and the xanthene compound has the formula and (In the formula, each R 1 is lower alkyl; each R 2 is nitro; cyano; âSO 2 CH 3 ; [Formula] [Formula] âCOCH 3 ; âSO 2 N (CH 2 Ph) 2 (However, Ph is phenyl); and -SO 2 N(CH 3 ) 2 ; X is [Formula]; R 3 is a lower alkyl group; Y is R 2 , n is zero or 1, and A is an anion) for multicolor diffusion transfer imaging. 15. A photographic product according to claim 14, wherein the colored compound is arranged so that the exposure of the silver halide emulsion layer takes place therethrough. 16. The photograph of claim 15, wherein the second support is transparent and the image-receiving layer and the light screening dye are carried by a transparent second sheet of this second sheet-like element. product. 17. A photographic product according to claim 14, wherein the product has means for providing a layer of white pigment between the image-receiving layer and the silver halide emulsion. 18. A photographic product according to claim 17, wherein the means for providing a layer of white pigment comprises a white pigment dispersed in the processing composition. 19. A photographic product according to claim 17, wherein the means for providing a layer of white pigment is a preformed layer of white pigment. 20. Photographic product according to claim 16, in which a colored compound is arranged in the image-receiving layer. 21. Photographic product according to claim 19, in which the colored compound is arranged in a preformed layer of white pigment. 22. The photographic product of claim 14, wherein each image dye-providing material is an image dye-providing material selected from image dyes and image dye intermediates. 23. The photographic product of claim 22, wherein each image dye-providing substance is a dye. 24. The photographic product of claim 23, wherein each dye is a dye developer. 25. The photographic product of claim 14, wherein the first sheet-like element and the second sheet-like element are in a stacked relationship. 26. A photographic product according to claim 14, wherein the second sheet-like element is suitable for being in stacked relationship with the first sheet-like element. 27. The photographic product of claim 16, wherein the first support is opaque. 28. The photographic product of claim 15, wherein the first support and the second support are transparent. 29. Photographic product according to claim 14, wherein the colored compound is a compound of the above formula. 30. Photographic product according to claim 14, wherein the colored compound is a compound of the above formula. 31 A colored compound has the formula 15. A photographic product according to claim 14, wherein A is an anion. 32 A colored compound has the formula A photographic product according to claim 14, having: 33 A colored compound has the formula 15. A photographic product according to claim 14, wherein A is an anion.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10690179A | 1979-12-26 | 1979-12-26 |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS56135555A JPS56135555A (en) | 1981-10-23 |
JPH0132974B2 true JPH0132974B2 (en) | 1989-07-11 |
Family
ID=22313869
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP18366580A Granted JPS56135555A (en) | 1979-12-26 | 1980-12-24 | Novel xanthene compound and photographic product and method employing it |
Country Status (1)
Country | Link |
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JP (1) | JPS56135555A (en) |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4416971A (en) * | 1982-12-28 | 1983-11-22 | Polaroid Corporation | Novel xanthene compounds and their photographic use |
JP5836200B2 (en) * | 2012-05-30 | 2015-12-24 | å¯å£«ãã€ã«ã æ ªåŒäŒç€Ÿ | Compound having xanthene skeleton, coloring composition, ink for ink jet recording, and ink jet recording method |
EP2669338B1 (en) * | 2012-05-31 | 2017-04-05 | Fujifilm Corporation | Coloring composition, ink for inkjet recording and inkjet recording method |
JP5946174B2 (en) * | 2012-06-07 | 2016-07-05 | æ¥æ¬åè¬æ ªåŒäŒç€Ÿ | Xanthene-based soluble precursor compounds and colorants |
JP5978015B2 (en) * | 2012-06-07 | 2016-08-24 | äœåååŠæ ªåŒäŒç€Ÿ | Method for producing compound |
JP6009246B2 (en) * | 2012-07-02 | 2016-10-19 | äžå€åææ ªåŒäŒç€Ÿ | Xanthene dye and method for producing the same |
JP6062560B2 (en) * | 2013-09-30 | 2017-01-18 | å¯å£«ãã€ã«ã æ ªåŒäŒç€Ÿ | Compound having xanthene skeleton, coloring composition, ink for ink jet recording, ink jet recording method, ink jet printer cartridge, and ink jet recorded matter |
KR102092333B1 (en) * | 2014-06-13 | 2020-03-23 | ëì° íìžìŒ 죌ìíì¬ | Method for producing dye master batch |
-
1980
- 1980-12-24 JP JP18366580A patent/JPS56135555A/en active Granted
Also Published As
Publication number | Publication date |
---|---|
JPS56135555A (en) | 1981-10-23 |
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