US2671021A - Polymeric magenta color former - Google Patents
Polymeric magenta color former Download PDFInfo
- Publication number
- US2671021A US2671021A US203025A US20302550A US2671021A US 2671021 A US2671021 A US 2671021A US 203025 A US203025 A US 203025A US 20302550 A US20302550 A US 20302550A US 2671021 A US2671021 A US 2671021A
- Authority
- US
- United States
- Prior art keywords
- chloride
- bis
- amino
- mole
- color former
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- -1 SILVER HALIDE Chemical class 0.000 claims description 73
- 239000000839 emulsion Substances 0.000 claims description 36
- 239000004332 silver Substances 0.000 claims description 23
- 229910052709 silver Inorganic materials 0.000 claims description 23
- 150000001875 compounds Chemical class 0.000 claims description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 49
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 24
- 229920000642 polymer Polymers 0.000 description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 125000003118 aryl group Chemical group 0.000 description 14
- 239000000203 mixture Substances 0.000 description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- 239000002253 acid Substances 0.000 description 12
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 11
- JEXVQSWXXUJEMA-UHFFFAOYSA-N pyrazol-3-one Chemical class O=C1C=CN=N1 JEXVQSWXXUJEMA-UHFFFAOYSA-N 0.000 description 11
- 238000003756 stirring Methods 0.000 description 10
- 125000000217 alkyl group Chemical group 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 7
- 229940051880 analgesics and antipyretics pyrazolones Drugs 0.000 description 7
- 125000003710 aryl alkyl group Chemical group 0.000 description 7
- 108010010803 Gelatin Proteins 0.000 description 6
- 229920000159 gelatin Polymers 0.000 description 6
- 239000008273 gelatin Substances 0.000 description 6
- 235000019322 gelatine Nutrition 0.000 description 6
- 235000011852 gelatine desserts Nutrition 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 150000001299 aldehydes Chemical class 0.000 description 4
- 239000003085 diluting agent Substances 0.000 description 4
- 125000000623 heterocyclic group Chemical group 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- GVNWZKBFMFUVNX-UHFFFAOYSA-N Adipamide Chemical compound NC(=O)CCCCC(N)=O GVNWZKBFMFUVNX-UHFFFAOYSA-N 0.000 description 3
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical compound NC1=NC=NN1 KLSJWNVTNUYHDU-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- PWAXUOGZOSVGBO-UHFFFAOYSA-N adipoyl chloride Chemical compound ClC(=O)CCCCC(Cl)=O PWAXUOGZOSVGBO-UHFFFAOYSA-N 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- 125000000753 cycloalkyl group Chemical group 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- ZRHUHDUEXWHZMA-UHFFFAOYSA-N 1,4-dihydropyrazol-5-one Chemical compound O=C1CC=NN1 ZRHUHDUEXWHZMA-UHFFFAOYSA-N 0.000 description 2
- YGHRJJRRZDOVPD-UHFFFAOYSA-N 3-methylbutanal Chemical compound CC(C)CC=O YGHRJJRRZDOVPD-UHFFFAOYSA-N 0.000 description 2
- QNGVNLMMEQUVQK-UHFFFAOYSA-N 4-n,4-n-diethylbenzene-1,4-diamine Chemical compound CCN(CC)C1=CC=C(N)C=C1 QNGVNLMMEQUVQK-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 description 2
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 125000005026 carboxyaryl group Chemical group 0.000 description 2
- VDBXLXRWMYNMHL-UHFFFAOYSA-N decanediamide Chemical compound NC(=O)CCCCCCCCC(N)=O VDBXLXRWMYNMHL-UHFFFAOYSA-N 0.000 description 2
- WMPOZLHMGVKUEJ-UHFFFAOYSA-N decanedioyl dichloride Chemical compound ClC(=O)CCCCCCCCC(Cl)=O WMPOZLHMGVKUEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- JARKCYVAAOWBJS-UHFFFAOYSA-N hexanal Chemical compound CCCCCC=O JARKCYVAAOWBJS-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 125000006501 nitrophenyl group Chemical group 0.000 description 2
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- ZLYYJUJDFKGVKB-OWOJBTEDSA-N (e)-but-2-enedioyl dichloride Chemical compound ClC(=O)\C=C\C(Cl)=O ZLYYJUJDFKGVKB-OWOJBTEDSA-N 0.000 description 1
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- GUUUPLGXSAZRQX-UHFFFAOYSA-N 1-ethyl-1-(2-ethylphenyl)hydrazine Chemical compound CCN(N)C1=CC=CC=C1CC GUUUPLGXSAZRQX-UHFFFAOYSA-N 0.000 description 1
- REHQLKUNRPCYEW-UHFFFAOYSA-N 1-methylcyclohexane-1-carboxylic acid Chemical compound OC(=O)C1(C)CCCCC1 REHQLKUNRPCYEW-UHFFFAOYSA-N 0.000 description 1
- PKZJLOCLABXVMC-UHFFFAOYSA-N 2-Methoxybenzaldehyde Chemical compound COC1=CC=CC=C1C=O PKZJLOCLABXVMC-UHFFFAOYSA-N 0.000 description 1
- DYNFCHNNOHNJFG-UHFFFAOYSA-N 2-formylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C=O DYNFCHNNOHNJFG-UHFFFAOYSA-N 0.000 description 1
- VQBBXLZPRXHYBO-UHFFFAOYSA-N 2-methoxyterephthalic acid Chemical compound COC1=CC(C(O)=O)=CC=C1C(O)=O VQBBXLZPRXHYBO-UHFFFAOYSA-N 0.000 description 1
- UFMBOFGKHIXOTA-UHFFFAOYSA-N 2-methylterephthalic acid Chemical compound CC1=CC(C(O)=O)=CC=C1C(O)=O UFMBOFGKHIXOTA-UHFFFAOYSA-N 0.000 description 1
- YNAKESQZGPZDDZ-UHFFFAOYSA-N 2-n,2-n-diethylbenzene-1,2-diamine Chemical compound CCN(CC)C1=CC=CC=C1N YNAKESQZGPZDDZ-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- ZTFYJIXFKGPCHV-UHFFFAOYSA-N 2-propan-2-ylnaphthalene-1-sulfonic acid Chemical compound C1=CC=CC2=C(S(O)(=O)=O)C(C(C)C)=CC=C21 ZTFYJIXFKGPCHV-UHFFFAOYSA-N 0.000 description 1
- UELIBMUMKLRTKJ-UHFFFAOYSA-N 3-amino-1,4-dihydropyrazol-5-one Chemical class NC1=NNC(=O)C1 UELIBMUMKLRTKJ-UHFFFAOYSA-N 0.000 description 1
- XQJSXPXELXFGQE-UHFFFAOYSA-N 3-methoxybenzaldehyde 4-methoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C=C1.COC=1C=C(C=O)C=CC1 XQJSXPXELXFGQE-UHFFFAOYSA-N 0.000 description 1
- BKZMFCVWBWMBEM-UHFFFAOYSA-N 3-methylbenzaldehyde;4-methylbenzaldehyde Chemical compound CC1=CC=C(C=O)C=C1.CC1=CC=CC(C=O)=C1 BKZMFCVWBWMBEM-UHFFFAOYSA-N 0.000 description 1
- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical group C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 description 1
- SKIBELYSXFYZPS-UHFFFAOYSA-N 4-n-ethylbenzene-1,4-diamine Chemical compound CCNC1=CC=C(N)C=C1 SKIBELYSXFYZPS-UHFFFAOYSA-N 0.000 description 1
- VROZMOZSNFUILE-UHFFFAOYSA-N 5-amino-2-(3-chlorophenyl)-4h-pyrazol-3-one Chemical compound O=C1CC(N)=NN1C1=CC=CC(Cl)=C1 VROZMOZSNFUILE-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241001446467 Mama Species 0.000 description 1
- BZORFPDSXLZWJF-UHFFFAOYSA-N N,N-dimethyl-1,4-phenylenediamine Chemical compound CN(C)C1=CC=C(N)C=C1 BZORFPDSXLZWJF-UHFFFAOYSA-N 0.000 description 1
- 101100285000 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) his-3 gene Proteins 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 description 1
- 235000009470 Theobroma cacao Nutrition 0.000 description 1
- GCXUHGZBBGZTII-UHFFFAOYSA-N a828071 Chemical compound ClC(Cl)=O.ClC(Cl)=O GCXUHGZBBGZTII-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- IZKFFGYHEVUVFE-UHFFFAOYSA-N acetaldehyde butanal formaldehyde propanal Chemical compound O=C.CC=O.CCC=O.CCCC=O IZKFFGYHEVUVFE-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 244000240602 cacao Species 0.000 description 1
- 125000004181 carboxyalkyl group Chemical group 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000001246 colloidal dispersion Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- CNXXEPWXNDFGIG-UHFFFAOYSA-N dodecanedioyl dichloride Chemical compound ClC(=O)CCCCCCCCCCC(Cl)=O CNXXEPWXNDFGIG-UHFFFAOYSA-N 0.000 description 1
- 229910001651 emery Inorganic materials 0.000 description 1
- 239000012458 free base Substances 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 description 1
- ABMFBCRYHDZLRD-UHFFFAOYSA-N naphthalene-1,4-dicarboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=C(C(O)=O)C2=C1 ABMFBCRYHDZLRD-UHFFFAOYSA-N 0.000 description 1
- HGEVGSTXQGZPCL-UHFFFAOYSA-N nonanedioyl dichloride Chemical compound ClC(=O)CCCCCCCC(Cl)=O HGEVGSTXQGZPCL-UHFFFAOYSA-N 0.000 description 1
- BTFQKIATRPGRBS-UHFFFAOYSA-N o-tolualdehyde Chemical compound CC1=CC=CC=C1C=O BTFQKIATRPGRBS-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 150000002895 organic esters Chemical class 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- HKOOXMFOFWEVGF-UHFFFAOYSA-N phenylhydrazine Chemical compound NNC1=CC=CC=C1 HKOOXMFOFWEVGF-UHFFFAOYSA-N 0.000 description 1
- 125000005936 piperidyl group Chemical group 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- GJAWHXHKYYXBSV-UHFFFAOYSA-N quinolinic acid Chemical compound OC(=O)C1=CC=CN=C1C(O)=O GJAWHXHKYYXBSV-UHFFFAOYSA-N 0.000 description 1
- 125000005493 quinolyl group Chemical group 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- ADPUQRRLAAPXGT-UHFFFAOYSA-M sodium;2-formylbenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1C=O ADPUQRRLAAPXGT-UHFFFAOYSA-M 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- MHSKRLJMQQNJNC-UHFFFAOYSA-N terephthalamide Chemical compound NC(=O)C1=CC=C(C(N)=O)C=C1 MHSKRLJMQQNJNC-UHFFFAOYSA-N 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
- G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
- G03C7/32—Colour coupling substances
- G03C7/327—Macromolecular coupling substances
Definitions
- This invention relates to the production or pbo czraphic dye mag b co r e m n and particularly to polymeric pyrazolones as coloreforming couplers therefor.
- Modern methods of color photography utilize multilayer materials having differently sensitized superimposed silver halide emulsion layers, each containing color-forming components fast to diffusion which, upon development with a primary aromatic amino, developing agent, yield subtractively colored dyestufi images.
- magenta components most frequently employedare derivatives; which are ren dered fast to difiuslon by the inclusion of a suitable group which imparts a substantive character to the molecule of the component, or of a, long chain aliphatic hydrocarbon radical which nrevcnts difiusiqc at the. cqmpqnent the em l sion. 'Dye images. produced by such components are not entirely satisfactory.
- Another object is to provide photographic emulsions, containing, pqlymeria pyra olone; c9 9 formers capable-E yielding, upon: color development, dye images of excellent color, high brilllanceistability. and ery. fine grain,
- a further object is to. provide photographic emulsions containing polymeric pyrazolones which do not afiect the sensitivity of photographic emulsions and do not cause stain.
- R is an; alkyl group, e. g., methyl, ethyl; propyl, isopropyl, butyl, isobutyl, amyl, isoamyl, hexyl, heptyl, octyl, an aryl group, e. g;., phenyl, tolyl, methoxyphenyl, phenoxyphenyl, chlorophen-yl, nitrophenyl, naphthyl, an aralkyl group, a a, be li, ethalbe t en: ethyl, or a heterocyclic nucleus, e.
- R is an; alkyl group, e. g., methyl, ethyl; propyl, isopropyl, butyl, isobutyl, amyl, isoamyl, hexyl, heptyl, octyl, an
- thiazolyl hen c'thiazqly quin01sl,, xridyl,and t e m B; is hydrogen or an alkyl, e. g., methyl, ethyl, prop b ts/l; isobut amyl, y hept-yl, ctyl. carbogryalkyl, e. g., carboxymethyl, carboxyethyl, carbqxypropyl, carboxybutyl, carboxyamyl, cycloalkyl, e. g., cyclopentyl, cyclohexyl, aryl, e.
- phenyl, tolyl methoxyphenyl, ethoxyphenyl, dimethoxyphenyi, naphthyl, carboxyaryl, e. g., carboxyphenyl, carboxytolyl, carboxynaphthyl, sulfoaryl, e. g., sulfophenyl, sulfoto1yl, sulfonaphthyl, aralkyl, e .v g, benzyl, phenethyl and heterocyclic radicals, e. g., pyridyl, quinolyl, nicotenyl,
- polymeric pyrazolones embraced Polymer of N.N'-bls-3-[l-phenyLS-pymzolonn]m-carboxycinnamicdiamide with formaldehyde Polymer of N.N'-b1s-3-[l-phenyl'fi-pyrazolonoJ-a'fi'GiethyI- succinamlde with formaldehyde 'one'molarequivalent of the dihalidei' of a. dioic condensingapproximatelytwomolar.
- the preferred solvent-diluents for the polymerization of: the:bis amidopyrazolone with the aldehyde are dioxa-ne;pyridine;andldimethyl or' 21x32 33833: diethylacetamide. It ism bernoted; however; that Azelayl chloride solvent-diluents otherthan thosementioned sebacyl chloride above may also be employed; theweleetibn de- Hendecanedioyl hl rid pending.
- a suitable solvent such as an aqueous, alcoholic or -aqueous-alcoholic one normal solution of sodium or potassium hydroxide.
- Dispersing agents such as isopropylnaphthalene sulfonic acid or other suitable dispersing agents, for example, those disclosed .in United States Patent 2,186,717, may be used in preparing the suspensions of the polymeric pyrazolones for incorporation into silver halideemulsions.
- the polymericpyrazolones may be' incorporated into other colloidal materials such as water dispersible organic esters of cellulose, polyamides, hydroxyethylcellulose, or modified polyvinyl. .alcohol..
- the polymeric" pyrazolones have the unique property of being compatible not only with gelatinous silver halide emulsions but also with those which contain a synthetic colloidal carrier as a substitute for gelatin. 2'
- suitable aromatic primary amino developing agents which maybe employed for the development of the color forming polymersof the present invention, there may be mentioned l-aminoaniline, 4-ethylaminoaniline, 2- diethylaminoaniline, l-dialkylaminoanilines, e. g., 4-dimethylaminoaniline, 4 diethylaminoaniline, 4- [N-fm-hydroxyethyl) -Nethyl] amin'oaniline, 4- 3,5 dihydroxyethyl) aminoaniline, 4 -amino-N- ylaniline sulfate and the like.
- These developing agents are preferably used in the form of their salts, such as the hydrochloride, since they are more soluble and stable than the free base. They are characterized by the presence of a free or primary amino group in the aromatic nucleus r Grams 4-'diethylaminoaniline hydrochloride 2 Sodium carbonate (anhydrous) '50 Sodium sulfite (anhydrous) 2 Potassium bromide 0.2 Water to make 1 liter.
- the exposed silver halide emulsions containing the polymeric color-formers are developed inlth'e abovesoluti'onirrthe usual manner. Abl'a'ck and absorption maximum at 535 my. and" did not? white first developer and a: second exposure are show any indications of diffusibility'.
- the invention is flurther illustrated; by the folistability on storage at elevated temperatures and lowing. examples, but it is to; be understood that high humidity as. well as: increased. resistance to the: invention not: to be restricted thereto; acid. fumes.
- Example II Polymer of N,N'-bis-3- [1-phenyl-5-pyrazolono]adipamide with formaldehyde
- Example I 42.5 grams (0.24 mole) of l-phenyl-d-amino- 1 5'-pyrazolone and 120 mls. of pyridine were H HOHN NH H:OH heated. together on a steam-bath. Te this mixture, 2'3 grams (0&125 mole) of adipyl chloride were. added dropwise with stirring. After 2 mixture was poured into 300 mls. of water.
- Example III X Polymer of N',N-bis-3-[I- (3'-toly1)-5-pyrazolono]adipamide with benzaldehyde-Z-sulfonic.afiid 1.87 grams (0.005 mole) of the above bis- 46 grams (0.24 mole) of 1-(3"-tolyl)-3'-aminoamidopyrazelene, 25 mls. of dioxane, 0.4 of S-pyrazolone and 120 mls. of pyridine were a 37% solution of. formalin (0.005 mole) and ten 00 heated together on a steam bath. To this mixdrops of pyridine were mixed.
- Example VII 1 61 er whit nes 1* m a, a
- Example 111 wherein R represents a member selected from the class consisting of alkyl, aryl, aralkyl and hetez 'ocyclic groups, R1 represents a member select'ed the class consisting or hydrogen;
- wb -fio represents a radical of a ol carBoxy-Ho acid of not more than 18- carbonatoms and is selected from the class consisting of aliphatic, cycloaliphatic, aromatic, aliphaiti' aromatic; and heteroeyclie dicarboxylie acids, and- X represehts the mmilier of repeated: units the polymer and ism integer greatest-hair 2.
- R represents a member selected from the class consisting oi alkyl, aryl, aralkyl, and
- R1 represents a member selected from the class consisting of hydrogen
- OCA--CO represents a radical of a dicarboxylic acid of not more than 18 carbon atoms and is selected from the class consistingofaliphati -v cycloaliphatic, aromatic, aliphaticearomatic and heterocyclic dicarboxylic acids
- X represents thenumber of repeated units in the polymer and is an integer greater than2.
- the method of producing a magenta photographic image in a silver halide emulsion layer which comprises exposingand developing it with a solution of an aromatic primary amino developing agent, said emulsion containing as a magenta color former, the polymer of N,N'-bis-3- [1-phenyl-5-pyrazolon0]urea with formaldehyde.
- the method of producing a magenta'photographic image in a silver halide emulsion layer which comprises exposing and developing it with a solution of an aromatic primary amino developing agent, said emulsion containing as a magenta color former, the polymer of N,N-bis-3- [1- (3-tolyl) -5-pyrazolono adipamide with benzaldehyde-Z-sulfonic acid.
- veloping agent said emulsion containing as a, ma genta color former, the polymer of N,N'-bis-3- [l phenyl-S-pyrazclono]sebacamide with form-' aldehyde.
- the method of producing a magenta photographic image in a silver halide emulsionlayer which comprises exposing and developing it with a solution of an aromatic primary amino developing agent, said emulsion containing asa magenta color former, the polymer of N,N-bis- 3 [1 phenyl 5 pyrazolonolsebacamide with. phthalaldehydic acid.
- a photographic element comprising a support and a -silver halide emulsion layer,-,said1 emulsion layer containing as a color iormerior the magenta image, a polymeric coupler compound of the classconsisting of compounds hav-. ing the following formulae: .7.
- R. represents a member selected from the class consisting of alkyl, aryl, aralkyl, and heterocyclic groups
- R1 represents a. member selected from the class consisting of hydrogen, alkyl, carboxyalkyl, cycloalkyl, aryl, sulfoaryl, carboxyaryl, aralkyl, and heterocyclic radicals
- OC-ACO-- represents a radical: ofsa dicarboxylicgacidr'oiLnot more than 18 port and a silver halide emulsion layer, said emulsion layer containing as a color former for the magenta image, the polymer of N,N'-bis-3- [1-(3-tolyl) -5-pyrazolonoladipamide with benzaldehyde-Z-sulfonic acid.
- a photographic element comprising a support and a silver halide emulsion layer, said emulsion layer containing as a color former for 'themagenta image, the polymer of N,N'-bis-3- E l-phenyl-5-pyrazolono l terephthalamide with formaldehyde.
- a photographic element comprising a support and a silver halide emulsion layer, said emulsion layer containing as a color former for themagenta image, the polymer of N,N'-bis-3- [1-phenyl-5-pyrazolonolsebacamide with formaldehyde.
- a photographicelement comprising a sup port and a silver halide emulsion layer, said emulsion layer containing as a color former for the magenta image, the polymer of N,N-bis-3- [1-phenyl-5-pyrazolonolsebacamide with phthal- SARAH c. KLEIGER.
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Description
Patented Mar. 2, 1954 POLYMERIC MAGENTA cocoa FORMER Sarah C. Kleiger and Henry J. Hugos, Binghamton, N. Y., assignors to General Aniline & Film Corporation, New York N. Y., a corporation of Delaware No Drawing. Application Deeember"27,'1Q5'0,
. iserialNo. 203,025
18 Claims. (Cl'. 957-6 This invention relates to the production or pbo czraphic dye mag b co r e m n and particularly to polymeric pyrazolones as coloreforming couplers therefor.
Modern methods of color photography utilize multilayer materials having differently sensitized superimposed silver halide emulsion layers, each containing color-forming components fast to diffusion which, upon development with a primary aromatic amino, developing agent, yield subtractively colored dyestufi images.
The magenta components most frequently employedare derivatives; which are ren dered fast to difiuslon by the inclusion of a suitable group which imparts a substantive character to the molecule of the component, or of a, long chain aliphatic hydrocarbon radical which nrevcnts difiusiqc at the. cqmpqnent the em l sion. 'Dye images. produced by such components are not entirely satisfactory. The principal disadvantage of these components is their generally waxy character which renders their purification extremely diificult, thus leading to, a loss in speed and contrast, undesired color shifts, and stain, The removal of the impurities which cause these undesirable photographic efiects is very timercqnsumiaa, exefinsive and. not always, very effective. I i
It has also been proposed to react pyrazolones with aliphatic aldehydes to yield dimeric or polymeric color formers. These too, sufier from the above shortcomings and have the added disadvanta e. of not being interchangeably compatible with; gelatin emulsions and other colloidal dispersions, such as modified polyvinyl alcohol which may; be used in place of gelatin as a colloidal carrier.
It. is an object of the present invention to provide a class of polymeric pyrazolone color formers for producing magenta dye images Another object is to provide photographic emulsions, containing, pqlymeria pyra olone; c9 9 formers capable-E yielding, upon: color development, dye images of excellent color, high brilllanceistability. and ery. fine grain,
A further object is to. provide photographic emulsions containing polymeric pyrazolones which do not afiect the sensitivity of photographic emulsions and do not cause stain.
Other objects and advantages of this invention will be apparent from the following specifications in which its preferred details and embodiments are described.
The above and other-objects are accomplished by the use of linear polymers obtained by condensing a dihalide Off a dioic acid with a l-substituted-3-aminopyrazolone to yield a bis-3-amidopyrazolone which is subsequently reacted with an aldehyde,
l t 2: wherein R is an; alkyl group, e. g., methyl, ethyl; propyl, isopropyl, butyl, isobutyl, amyl, isoamyl, hexyl, heptyl, octyl, an aryl group, e. g;., phenyl, tolyl, methoxyphenyl, phenoxyphenyl, chlorophen-yl, nitrophenyl, naphthyl, an aralkyl group, a a, be li, ethalbe t en: ethyl, or a heterocyclic nucleus, e. g., thiazolyl, hen c'thiazqly quin01sl,, xridyl,and t e m B; is hydrogen or an alkyl, e. g., methyl, ethyl, prop b ts/l; isobut amyl, y hept-yl, ctyl. carbogryalkyl, e. g., carboxymethyl, carboxyethyl, carbqxypropyl, carboxybutyl, carboxyamyl, cycloalkyl, e. g., cyclopentyl, cyclohexyl, aryl, e. g., phenyl, tolyl, methoxyphenyl, ethoxyphenyl, dimethoxyphenyi, naphthyl, carboxyaryl, e. g., carboxyphenyl, carboxytolyl, carboxynaphthyl, sulfoaryl, e. g., sulfophenyl, sulfoto1yl, sulfonaphthyl, aralkyl, e .v g, benzyl, phenethyl and heterocyclic radicals, e. g., pyridyl, quinolyl, nicotenyl,
piperidyl, and wherein OC-ACO-. is a, di-
acyl radical of a dicarboxylic acid oi not more than 18 carbon atoms and selected from the class consisting of aliphatic, cycloaliphatic, aromatic, aromaticraliphatic, and heterocyclicdicarboxylic acids, e, g., oxalic, nalon-ic, succinic, glutaric, adipic, pimelic, suberic, azel'ai'c, sebacic, hendecanedioic, dodecanedioic, brassylic, tetradecanedioic, pentadecanedioic, thapsic, fumaric, glutaconic, a-hYdl'OlllllCOIlic, fi-hydromuconic, 2-octenedioic, phthalic, isophthalic, terephthalic, 2- methyl-1,4-benzenedicarboxylic, 2-methoxy-1,4- benzenedicarboxylic, 4,4'-dicarboxybiphenyl, 1,4- naphthalenedicarboxylic, 3-carboxylphenylacetyl, 3-carboxynaphthylacetyl, carboxycinnamic, carboxycyclohexaneacetic, camphoric, 1,4-cyclohexanedicarboxylic, pyrazolone dicarboxylic acid pyridinedicarboxylic and the like, which may be further substituted, for example, by alkyl, alkoxy and halogen, and X represents the number of repeated units in the polymer and is an integer greater than 2.
Examples of polymeric pyrazolones embraced Polymer of N.N'-bls-3-[l-phenyLS-pymzolonn]m-carboxycinnamicdiamide with formaldehyde Polymer of N.N'-b1s-3-[l-phenyl'fi-pyrazolonoJ-a'fi'GiethyI- succinamlde with formaldehyde 'one'molarequivalent of the dihalidei' of a. dioic condensingapproximatelytwomolar. e uivzflm ableldihalidesiof'dioic (dicarbo'Xylio) acid whioh 01" a, 1-subsfitut'ed'-3 amihopyrazolone"havihg' a may beused in'the preparation -orthe bisa;mld'o reactive methylene group" in" the" 4"-posit1o1r with py lon Carbonyl dichloride (phosgene) I Oxalyl chloride 60 Malonyl chloride Malonyl bromide Succinyl chloride Suocinyl bromide a, 8-Dimethy1succiny1 chloride 65 a,px-Diethy1succinyl chloride a,,B-Dibromosuccinyl bromide Glutaryl chloride Adipyl chloride acid" in the presence of a suitable soli'enf-diliterlt suclr as" pyridine, quino'line; orpicolin'e, a; high boiling aliphatic" amine such as" triethylamine or-tripropylamine; orin the presenceof dibxane which may contain a; small" amount ofan organic base such as-tfietliylmihe, and reactingthe resulting bis-amidbpyrazolone witli a email excess of s molar equivalent or an'- aldehyde iii the'pres ence of a solvent-diluent.
The preferred solvent-diluents for the polymerization of: the:bis amidopyrazolone with the aldehyde are dioxa-ne;pyridine;andldimethyl or' 21x32 33833: diethylacetamide. It ism bernoted; however; that Azelayl chloride solvent-diluents otherthan thosementioned sebacyl chloride above may also be employed; theweleetibn de- Hendecanedioyl hl rid pending. onttheeresistancerof thaseleeted diluent a-Butyl-a-ethylglutaryl chloride tomartioipatiomin: theweactiom 75 Dodecanedioyl chloride 15 Brassylyl chloride Tetradecanedioyl chloride Pentadecanedioyl chloride Thapsyl chloride Fumaryl chloride Glutaconyl chloride 2-hexenedioyl chloride 3-hexenedloyl chloride z-octenedioyl chloride 4-amyl-2,5-heptadienedioy1 chloride '7 2,9-dimethyl-2,4,6,8-decatetraenedioyl chlorid Hexadecanedioyl chloride Phthalyoyl chloride Isophthaloyl chloride Terephthaloyl chloride 2-methyl-1,4-benzenedicarboxyl chloride 2-methoxy-lA-benzenedicarboxyl chloride 1,4-naphthalenedicarboxyl chloride 3-carboxylcinnamoyl dichloride 3-carboxyldihydrocinnamoyl dichloride 3-carboxylphenylacetyl dichloride 3-carboxylnaphthylacetyl dichloride 4,4'-dicarboxyldiphenyl chloride 1,4-cyclohexanedicarboxyl chloride Camphoryl chloride (2-carboxyl-2-methylcyclohexane)acetyl dichloride 4,5-pyrazoledicarboxyl chloride 3,5-pyridinedicarboxyl chloride The following compounds are illustrative exam ples of suitable 3-amino-5-pyrazolones:
3-amino-l-phenyl-S-pyrazolone 3 -amino-1- (3 -methylphenyl) -5-pyrazolone 3-aminc-l- (4'-methoxyphenyl) -5-py1'azolone 3-amino- 1 (4'-phenoxyphenyl) -5-pyrazolone 3 amino 1 [4 (p. tert. butylphenoxy)- phenyl] 5 pyrazolone 3 amino 1 [4' (m tolyloxylphenyl] 5- pyrazolone v 3 amino 1 [4 (3,5" dimethylphenoxylphenyl] -5-pyrazolone 3-amino-1- [3 -chlorophenyl] -5-pyrazolone 3-amino-1- (4' nitrophenyl) -5-pyraz0lone B-amino-l- (2'-benzothiazolyl) -5-pyrazolone 3-amino-1- 1 -naphthyl) -5-pyrazolone 3-amino-l- (2'-naphthyl) -5-pyrazolone 3-amino-1-benzyl-5-pyrazolone 3-amino-l-phenethyl-5-pyrazolone 3-a-mino-1- (2-pyridyl) -5-pyrazolone S-amino-l- (2-quinolyl) -5-pyrazolone f1he-following are illustrative examples'of suitable aldehydes which may be utilized in the polymerization with the bis-amidopyrazolones:
Formaldehyde Acetaldehyde Propionaldehyde Butyraldehyde Iso-butyraldehyde Valeraldehyde Iso-Valeraldehyde Caproaldehyde Glyoxylic acid Formylacetic acid fi-Formylpropionic acid Formylsuccinic acid E-Formylcaproic acid Cyclopentanecarboxaldehyde Benzaldehyde l-naphthaldehyde o-Tolualdehyde m-Tolualdehyde p-Tolualdehyde "16 4-methoxybenzaldehyde 3-methoxybenzaldehyde 2-'methoxybenzaldehyde l-piperidine carboxaldhyd'e 2-pyridylpropionaldehyde Phenylacetaldehyde Phenylpropionaldehyde The polymeric pyrazolones prepared in accordance with the present invention are added to thesilver halide emulsion in the form of a solution or a suspension. in a suitable solvent such as an aqueous, alcoholic or -aqueous-alcoholic one normal solution of sodium or potassium hydroxide. Dispersing agents such as isopropylnaphthalene sulfonic acid or other suitable dispersing agents, for example, those disclosed .in United States Patent 2,186,717, may be used in preparing the suspensions of the polymeric pyrazolones for incorporation into silver halideemulsions. Instead of gelatin, the polymericpyrazolones may be' incorporated into other colloidal materials such as water dispersible organic esters of cellulose, polyamides, hydroxyethylcellulose, or modified polyvinyl. .alcohol.. The polymeric" pyrazolones have the unique property of being compatible not only with gelatinous silver halide emulsions but also with those which contain a synthetic colloidal carrier as a substitute for gelatin. 2'
As examples of suitable aromatic primary amino developing agents which maybe employed for the development of the color forming polymersof the present invention, there may be mentioned l-aminoaniline, 4-ethylaminoaniline, 2- diethylaminoaniline, l-dialkylaminoanilines, e. g., 4-dimethylaminoaniline, 4 diethylaminoaniline, 4- [N-fm-hydroxyethyl) -Nethyl] amin'oaniline, 4- 3,5 dihydroxyethyl) aminoaniline, 4 -amino-N- ylaniline sulfate and the like. These developing agentsarepreferably used in the form of their salts, such as the hydrochloride, since they are more soluble and stable than the free base. They are characterized by the presence of a free or primary amino group in the aromatic nucleus r Grams 4-'diethylaminoaniline hydrochloride 2 Sodium carbonate (anhydrous) '50 Sodium sulfite (anhydrous) 2 Potassium bromide 0.2 Water to make 1 liter.
The exposed silver halide emulsions containing the polymeric color-formersare developed inlth'e abovesoluti'onirrthe usual manner. Abl'a'ck and absorption maximum at 535 my. and" did not? white first developer and a: second exposure are show any indications of diffusibility'. The ma;- only employed: if the desiredv image is ta be: or genta image: was characterized by the fineness. the reversal type. of its grain, and showed greater than average- The invention is flurther illustrated; by the folistability on storage at elevated temperatures and lowing. examples, but it is to; be understood that high humidity as. well as: increased. resistance to the: invention not: to be restricted thereto; acid. fumes.
- Example II Polymer of N,N'-bis-3- [1-phenyl-5-pyrazolono]adipamide with formaldehyde Example I 42.5 grams (0.24 mole) of l-phenyl-d-amino- 1 5'-pyrazolone and 120 mls. of pyridine were H HOHN NH H:OH heated. together on a steam-bath. Te this mixture, 2'3 grams (0&125 mole) of adipyl chloride were. added dropwise with stirring. After 2 mixture was poured into 300 mls. of water. The precipitated: bis-amidopyrazolone was filtered; and first washed with water and then with dilute- Pelynrer ofi N,N'-bis-3- [.l-phenylL-fi-pyrazofono]urea with Mir-28kg formaldehyde: A mixtureconsisting. of 11.5 grams (0.025 mole)- 335 grams (0.05 mole) of 1-phenyl-3-amino-5- or. the dried bis-amidopyrazolone,y125- mls. of pyrazolone and. 25 mls. of pyridine were mixed dlOXaIle, 2 1 Of a formal-ill (0-025 111016)- I hours of continued stirring;' and heating... the
1 ammonia- The residue was dried and melted and warmed on a steam bath. 7.3 grams of. a. and 50 drops of pyridine Was t d un solution of phosgene in benzene. (containing 35 flux on a steam bath far hours- An additiflnall 2.56 grams or 0.025 mole of phosgene) were added Of ffl Was dd d in Order D dropwise tothe mixture. Heating and stirring vide a slight excess of formalin and eu were continued for an additional mmutes. continued for 1 hour. An insoluble p fld lfit Was- The reaction mixture was cooled to room tem-- filtered f the 11011 miXture a d Was ed perature. A White product separated which was 40 d 10 grams of the pr decomposing filtered ofi, washed with pyridine and dried in above 270 C. were obtained.
vacuo at room temperature using, concentrated A bright and t s magenta dy image sulfuric acid as a desiccant. The product can s a xi m abs p at 0 e Was p be further purified by recrystallization from hot duced by utilizing the above color former as in pyridine. The product decomposes when heated Ex ple I. The dye image Was Characterized above 260 C. by the fineness of its grain.
Example III X Polymer of N',N-bis-3-[I- (3'-toly1)-5-pyrazolono]adipamide with benzaldehyde-Z-sulfonic.afiid 1.87 grams (0.005 mole) of the above bis- 46 grams (0.24 mole) of 1-(3"-tolyl)-3'-aminoamidopyrazelene, 25 mls. of dioxane, 0.4 of S-pyrazolone and 120 mls. of pyridine were a 37% solution of. formalin (0.005 mole) and ten 00 heated together on a steam bath. To this mixdrops of pyridine were mixed. and refluxed for ture, 23 grams (0.125 mole) of adipyl chloride two hours. In order to provide a slight excess were added dropwise with stirring. After 2. hours of formaldehyde, 0.1 ml. of formalin was added of continued stirring and heating, the mixture at this point and the heating continued for an was poured into 300 mls. of Water. The preadditional 3 hours. The mixture was filtered (i5 cipitated .bis-amidopyrazolone was filtered, and
while hot and the residue washed with dioxane. first washed with water and then with dilute The yield of the dried material was 1.79 grams. ammonia, and subsequently dried. v i
0.35 gram of the above color former was dis-. A mixture of 11.9 grams (0.027 mole) of the persed in a small volume of dilute aqueous alkali dried bis-amidopyrazolone and 250 mls. of diand the dispersion added to 50 mls. of a gelatin oxane was heated on a steam bath. To this ous silver halide emulsion. The emulsion was mixture, 5 grams (0.028 mole) of the sodium salt coated onto a suitable support and dried. The. of benzaldehyde-Z-sulfonic acid and 50 drops of dried film was sensitometrically exposed and depyridine were added and the mixture was heated veloped in a 4-diethylaminoaniline developer. 'for dhcursonth'e steam gbath under refl'mi': The The brilliant magenta image obtained had an mixture was'filteredwh'ile hot and the filtrate 19 poured into approximately 1 liter of cold water. 77 grams (0.44 mole) of l-phenyl-3-amino-5'- The resultant solution was acidified by the addipyrazolone were mixed with 220 mls. of pyridine tion of hydrochloric acid until a polymerization and warmed on a steam bath with stirring. 53 product separated as a fine, tan-colored precipigrams (0.22 mole) of sebacyl chloride were added tate. 5 dropwise with stirring. Heating and stirring were The final product can be further purified by continued for 3 hours. After cooling, the mixture washing with hot ethanol. A bright and dense was poured into 500 mls. of cold water while magenta image was obtained by utilizing the stirring. The precipitated product was purified color former as in Example I. The dye image ,by stirring with dilute ammonia, washed with was characterized by the fineness of its grain. water and dried. Further purification can be ob- Ezample IV H-LCHGHNOCC C 0-NH(I}('3H-0H21OH t l C=o N \N Polymer of N,N-bis-3-[1- henyl-5-pyrazolono1terephthalamide wit formaldehyde 17.5 grams (0.1 mole) of 1-phenyl-3-amino tained by consecutive washings with alcohol and pyrazolone were dissolved in 60 mls. of hot pyriether. The'product melted at 251-3 C. dine and the solution heated to reflux. 10.3 2.1 grams (0.004 mole) of the bis-amidopyrazgrams (0.05 mole) of terephthalyl chloride disolone were dispersed in 25 mls. of dioxane, solved in 50 mls. of dioxane were added gradtreated with 0.4 ml. of 37% of formalin (0.15 ually to the boiling mixture. After the addition gram or 0.005 mole of formaldehyde) and 10 drops had been completed, refluxing was continued for of pyridine. The mixture was heated under reanother hour. The larger portion of the solvents flux on a steam bath for 5 hours. The solution present was then distilled off and the hot residue was filtered hot and poured into 100 mls. of water. poured into water. 7 A tarry product separated The finely divided product was made more readily which became granular upon acidification with filterable by the addition of hydrochloric acid. hydrochloric acid. The precipitate was filtered A magenta dye image of good density and brilofi, washed with water and dried in a vacuo over liance was obtained when the above color former concentrated sulfuric acid. The final product was utilized in the silver halide emulsion as in can be further purified by boiling out with hot Example I. The dye image obtained was charethanol. acterized by the fineness of its grain.
Ewample VI H (JHCHNOO(CH:)aGONHCCH--(EH- OH SOaH Polymer of N,N'-bis-3-[l-phenyl-E-pyrazolono]sebacamide with benzaldehyde-2-sulfonic acid 2.4 grams (0.005 mole) of the above bis-amido- 1 gram (0.0019 mole) of the bis-amidopyrazpyrazolone and 25 mls. of dioxane were mixed olone of Example V was mixed with 0.4 gram with 0.4 ml. formalin (containing 0.15 gram or (0.0019 mole) of the sodium salt of benzaldehyde- 0.005 mole of formaldehyde) and 10 drops of pyri- 2-sulfonic acid in 25 mls. of dioxane. The susdine. The mixture washeated for 4 hours on a pension was refluxed for 3 hours to yield a clear steam bath under reflux. The dioxane-insoluble light'brown solution. The solution was filtered fraction was filtered off and purified by washing and the filtrate diluted with 100 mls. of water to with dioxane. A bright and dense magneta dye give a milky suspension which was acidified with imag was produced by utilizing the above color hydrochloric acid, whereupon the polymer sepformer as in Example I. The dye image was aratedinafilterable form.
characterized by the fineness of its grain. A bright and dense magenta image was ob- ExampZeV H (|JH (|3-HNO C(CH2)8C 0NHC--CHCH::|OH
' o=o c=o Polymer of N,N'-bis-3-[i-phenyl-ii-pyrazolono]sebacamlde g with formaldehyde 7 .1,
tained when this polymeric color former was m corporated in a gelatin silver halide emulsiontas in Example I. It was particularly characterized by the fineness or: the" developed color grains.
Example VII 1 61 er whit nes 1* m a, a
0 witlrp'hdr xybgzaf hyd ple VI was remotes-with the exception: that h ydroxybenzaidehydo used in place or 0.4 gram (0.0019 more) or the sodium salt or henzaldehyde-flqultunic When a dispersion of this color former was-added to a silver halide emulsion, a magenta image of above average emery and fineness of grain was obtainea after'color-development.
Example 111 wherein R represents a member selected from the class consisting of alkyl, aryl, aralkyl and hetez 'ocyclic groups, R1 represents a member select'ed the class consisting or hydrogen;
some} simmido aiiz' i, m1, arallc rl and woman mamas,
wb -fio represents a radical of a ol carBoxy-Ho acid of not more than 18- carbonatoms and is selected from the class consisting of aliphatic, cycloaliphatic, aromatic, aliphaiti' aromatic; and heteroeyclie dicarboxylie acids, and- X represehts the mmilier of repeated: units the polymer and ism integer greatest-hair 2.
I Polymerpi NJV-bis B-[1 phonyl-5=pyraqolono-Isebacaiirl'de v I with fmtliafaldhyclic acid 2.1 grams (0.005 mole) of the sebacylamido bismyrazoloneoi Example V1,;25-mlar '01? diexa'rie, 10. drops of pyridine and. 0.15 grain. (0.005 mole). of phthalaldehydio acid were refluxed-for 5 hours to yield a dark brown. solutiom. The solution was. filtered while hot and the filtrate-poured into- 100 mls. of water. The finely divided precipitate-"was aggregatediby the addition of -'strong hydrochloric acid. The precipitate was filtered; washed with water, and dried in vacuo to'g-ive a light colored lowing formulae:
N N it i l 0 formaldehyde,
2. A. photographic silver halide eimlsioa cohtaming: as a: color former; theifioli mer or kiss s-{l1whenyi fi pyrazoiono l urea with; formaldehyde; r v
3-; a photographic silver halide mlfiim fiit taming as a color former, the polymer of NQN-" benza1dehyde-2-sulfonic acid. I w
i. A photographic saver-halide emulsion contailii flg as a color formerrtnepoiymer or Miif f' his 3 E 1 ph'eriyi' '5 pyrazomirolterephthah amide with fomiaidehycie;
5. A; ohotograohic silver halide emulsion con-"Q tainiiig as a color former, the olymer of NN bis-'3 E 1 -phenyl-5-pyrazol0no lsebacamidewith? 6; A nhotographiosilver" halide emulsion-con taming aaa color. formers the polymer of MN bis-B-l;hphenykE-pyrafiolonolsebacamide with.
phthalaldchydicvacid; 7, The method-cf? producing amagenta photographicimage a silver halide emulsion la er which comprises exposing thelayei an'erdeveiop mg it iwitira solution. of an aromatic primary ammo dwelofiihg agent, said emulsion Iay'er" eontaiifiirg as amagenta colorforiner, e; poly-r merit coaster compound or the class consisting of compounds "havii ig the folfowing general};
formulae hi -Z 23". andf wherein R represents a member selected from the class consisting oi alkyl, aryl, aralkyl, and
heterocyclic groups, R1 represents a member selected from the class consisting of hydrogen,
alkyl, cycloalkyl, aryl, aralkyl, and heterocyclic' radicals, OCA--CO represents a radical of a dicarboxylic acid of not more than 18 carbon atoms and is selected from the class consistingofaliphati -v cycloaliphatic, aromatic, aliphaticearomatic and heterocyclic dicarboxylic acids, and X represents thenumber of repeated units in the polymer and is an integer greater than2. Y 1 V 8. The method of producing a magenta photographic image in a silver halide emulsion layer which comprises exposingand developing it with a solution of an aromatic primary amino developing agent, said emulsion containing as a magenta color former, the polymer of N,N'-bis-3- [1-phenyl-5-pyrazolon0]urea with formaldehyde.
9. The method of producing a magenta'photographic image in a silver halide emulsion layer which comprises exposing and developing it with a solution of an aromatic primary amino developing agent, said emulsion containing as a magenta color former, the polymer of N,N-bis-3- [1- (3-tolyl) -5-pyrazolono adipamide with benzaldehyde-Z-sulfonic acid.
. 10. The method of producing a magentaphotographic image in a'silver halide emulsion layer which comprises exposing and developingit with a solution of an aromatic primary amino de-.- veloping agent, said emulsion containing as a magenta color former, the polymer of N,N'-bis-3- [1 phenyl 5 pyrazolonolterephthalamide and formaldehyde. 1 g 1 11. The method of producing a magenta photographic image in a silver halide emulsion layer which comprises exposing and developing it with a solution of an aromatic primary amino-de-. veloping agent, said emulsion containing as a, ma genta color former, the polymer of N,N'-bis-3- [l phenyl-S-pyrazclono]sebacamide with form-' aldehyde.
12. The method of producing a magenta photographic image in a silver halide emulsionlayer which comprises exposing and developing it with a solution of an aromatic primary amino developing agent, said emulsion containing asa magenta color former, the polymer of N,N-bis- 3 [1 phenyl 5 pyrazolonolsebacamide with. phthalaldehydic acid.
. 13. A photographic element comprising a support and a -silver halide emulsion layer,-,said1 emulsion layer containing as a color iormerior the magenta image, a polymeric coupler compound of the classconsisting of compounds hav-. ing the following formulae: .7.
1 E saant enera r wherein R. represents a member selected from the class consisting of alkyl, aryl, aralkyl, and heterocyclic groups, R1 represents a. member selected from the class consisting of hydrogen, alkyl, carboxyalkyl, cycloalkyl, aryl, sulfoaryl, carboxyaryl, aralkyl, and heterocyclic radicals, and wherein OC-ACO-- represents a radical: ofsa dicarboxylicgacidr'oiLnot more than 18 port and a silver halide emulsion layer, said emulsion layer containing as a color former for the magenta image, the polymer of N,N'-bis-3- [1-(3-tolyl) -5-pyrazolonoladipamide with benzaldehyde-Z-sulfonic acid.
aldehydic acid.
16. A photographic element comprising a support and a silver halide emulsion layer, said emulsion layer containing as a color former for 'themagenta image, the polymer of N,N'-bis-3- E l-phenyl-5-pyrazolono l terephthalamide with formaldehyde.
1'7. A photographic element comprising a support and a silver halide emulsion layer, said emulsion layer containing as a color former for themagenta image, the polymer of N,N'-bis-3- [1-phenyl-5-pyrazolonolsebacamide with formaldehyde.
18. A photographicelement comprising a sup port and a silver halide emulsion layer, said emulsion layer containing as a color former for the magenta image, the polymer of N,N-bis-3- [1-phenyl-5-pyrazolonolsebacamide with phthal- SARAH c. KLEIGER.
HENRY J. nuoos.
.References" Cited in the file of this patent UNITED STATES PA'IENTS Number Date
Claims (1)
1. A PHOTOGRAPHIC SILVER HALIDE EMULSION CONTAINING A POLYMERIC COUPLER COMPOUND OF THE CLASS CONSISTING OF COMPOUNDS HAVING THE FOLLOWING FORMULAE:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US203025A US2671021A (en) | 1950-12-27 | 1950-12-27 | Polymeric magenta color former |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US203025A US2671021A (en) | 1950-12-27 | 1950-12-27 | Polymeric magenta color former |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2671021A true US2671021A (en) | 1954-03-02 |
Family
ID=22752148
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US203025A Expired - Lifetime US2671021A (en) | 1950-12-27 | 1950-12-27 | Polymeric magenta color former |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2671021A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4171975A (en) * | 1977-02-10 | 1979-10-23 | Konishiroku Photo Industry Co., Ltd. | Light-sensitive silver halide color photographic materials |
| US4762777A (en) * | 1984-12-15 | 1988-08-09 | Agfa-Gevaert Ag | Polyurea and polyurethane compounds containing a photographically useful group, and a photographic recording material containing such compounds |
| US4874689A (en) * | 1986-05-24 | 1989-10-17 | Fuji Photo Film Co., Ltd. | Silver halide color photographic material |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2186734A (en) * | 1936-11-02 | 1940-01-09 | Ig Farbenindustrie Ag | Color photography |
| US2186849A (en) * | 1935-08-07 | 1940-01-09 | Agfa Ansco Corp | Manufacture of photographic silver halide emulsions |
| GB562675A (en) * | 1940-10-31 | 1944-07-12 | Du Pont Film Mfg Corp | Improvements in or relating to dyestuff intermediates |
| US2380032A (en) * | 1938-10-05 | 1945-07-10 | Du Pont | Processes of color photography |
| US2511231A (en) * | 1949-03-26 | 1950-06-13 | Eastman Kodak Co | 1-cyanophenyl-3-acylamino-5-pyrazolone couplers for color photography |
-
1950
- 1950-12-27 US US203025A patent/US2671021A/en not_active Expired - Lifetime
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2186849A (en) * | 1935-08-07 | 1940-01-09 | Agfa Ansco Corp | Manufacture of photographic silver halide emulsions |
| US2186734A (en) * | 1936-11-02 | 1940-01-09 | Ig Farbenindustrie Ag | Color photography |
| US2380032A (en) * | 1938-10-05 | 1945-07-10 | Du Pont | Processes of color photography |
| GB562675A (en) * | 1940-10-31 | 1944-07-12 | Du Pont Film Mfg Corp | Improvements in or relating to dyestuff intermediates |
| US2511231A (en) * | 1949-03-26 | 1950-06-13 | Eastman Kodak Co | 1-cyanophenyl-3-acylamino-5-pyrazolone couplers for color photography |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4171975A (en) * | 1977-02-10 | 1979-10-23 | Konishiroku Photo Industry Co., Ltd. | Light-sensitive silver halide color photographic materials |
| US4762777A (en) * | 1984-12-15 | 1988-08-09 | Agfa-Gevaert Ag | Polyurea and polyurethane compounds containing a photographically useful group, and a photographic recording material containing such compounds |
| US4874689A (en) * | 1986-05-24 | 1989-10-17 | Fuji Photo Film Co., Ltd. | Silver halide color photographic material |
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