US2289300A - Photographic sensitizer - Google Patents
Photographic sensitizer Download PDFInfo
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- US2289300A US2289300A US234604A US23460438A US2289300A US 2289300 A US2289300 A US 2289300A US 234604 A US234604 A US 234604A US 23460438 A US23460438 A US 23460438A US 2289300 A US2289300 A US 2289300A
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- sensitizes
- methine
- aldehyde
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- -1 silver halide Chemical class 0.000 description 27
- KIWBPDUYBMNFTB-UHFFFAOYSA-N Ethyl hydrogen sulfate Chemical compound CCOS(O)(=O)=O KIWBPDUYBMNFTB-UHFFFAOYSA-N 0.000 description 14
- 239000000839 emulsion Substances 0.000 description 12
- 230000001235 sensitizing effect Effects 0.000 description 8
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 description 7
- 101150065749 Churc1 gene Proteins 0.000 description 7
- 102100038239 Protein Churchill Human genes 0.000 description 7
- 239000000975 dye Substances 0.000 description 6
- LBHSDLLXNOMENU-UHFFFAOYSA-M 5-chloro-3-ethyl-2-methyl-1-phenylbenzimidazol-3-ium;ethyl sulfate Chemical compound CCOS([O-])(=O)=O.C12=CC=C(Cl)C=C2[N+](CC)=C(C)N1C1=CC=CC=C1 LBHSDLLXNOMENU-UHFFFAOYSA-M 0.000 description 5
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 230000035945 sensitivity Effects 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- GKGRHBSXWAZUKF-UHFFFAOYSA-N S(=O)(=O)(OCC)[O-].[NH+]1=CNC2=C1C=CC=C2 Chemical compound S(=O)(=O)(OCC)[O-].[NH+]1=CNC2=C1C=CC=C2 GKGRHBSXWAZUKF-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 230000003595 spectral effect Effects 0.000 description 4
- KRXXWINWRGUIBJ-UHFFFAOYSA-N 1,3,3-trimethyl-2h-indole Chemical compound C1=CC=C2N(C)CC(C)(C)C2=C1 KRXXWINWRGUIBJ-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 125000003710 aryl alkyl group Chemical group 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 238000012937 correction Methods 0.000 description 3
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- RAJJBUDOSMZCOF-UHFFFAOYSA-M 1-ethyl-2-methyl-3-phenylbenzimidazol-1-ium;iodide Chemical compound [I-].C12=CC=CC=C2[N+](CC)=C(C)N1C1=CC=CC=C1 RAJJBUDOSMZCOF-UHFFFAOYSA-M 0.000 description 2
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- MCIDGHHVKNZHRD-UHFFFAOYSA-N 1,2,2-trimethyl-3h-indole Chemical compound C1=CC=C2CC(C)(C)N(C)C2=C1 MCIDGHHVKNZHRD-UHFFFAOYSA-N 0.000 description 1
- AIGNCQCMONAWOL-UHFFFAOYSA-N 1,3-benzoselenazole Chemical compound C1=CC=C2[se]C=NC2=C1 AIGNCQCMONAWOL-UHFFFAOYSA-N 0.000 description 1
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical compound C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 description 1
- IQXKPWLWEOWSER-UHFFFAOYSA-N 1H-benzimidazol-3-ium methyl sulfate Chemical compound COS(=O)(=O)[O-].[NH+]1=CNC2=C1C=CC=C2 IQXKPWLWEOWSER-UHFFFAOYSA-N 0.000 description 1
- LNRBYOQBXDEFFJ-UHFFFAOYSA-N 3-ethyl-5-methoxy-2H-1,3-benzoselenazole Chemical compound C(C)N1C[Se]C2=C1C=C(C=C2)OC LNRBYOQBXDEFFJ-UHFFFAOYSA-N 0.000 description 1
- 101100382267 Caenorhabditis elegans cah-1 gene Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical group [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- MDYSZUUHPDCHPG-UHFFFAOYSA-N methyl sulfate 1H-pyrrol-1-ium Chemical compound [NH2+]1C=CC=C1.COS([O-])(=O)=O MDYSZUUHPDCHPG-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-M toluene-4-sulfonate Chemical compound CC1=CC=C(S([O-])(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-M 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
- G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
- G03C1/08—Sensitivity-increasing substances
- G03C1/10—Organic substances
- G03C1/12—Methine and polymethine dyes
- G03C1/14—Methine and polymethine dyes with an odd number of CH groups
- G03C1/18—Methine and polymethine dyes with an odd number of CH groups with three CH groups
Definitions
- Our present invention relates to photographic sensitizers.
- sensitizers comprising particularly members of the cyanine-group which serve to sensitize silver halide emulsions for green and green-yellow; that is to say, they are orthochromatic sensitizers.
- the spectral composition of the light in the darkroom must be shifted as far as possible towards the short wave lengths, i. e. towards bright red or orange. The limit is set on this condition by the initial sensitivity of the emulsion to certain wave lengths.
- the intensity of the spectral sensitivity at these wave lengths is practically of no importance in working exposures, for it amounts only to a fraction of the intensity of the sensitivity at the sensitizing maximum.
- This small sensitivity sulfices to fog the emulsion when the light of the darkroom falls within that spectral region.
- Such emulsions therefore, can only be worked up with correspondingly longer Wave lengths, that is to say with light physiologically darker.
- the sensitizing curve of which falls away as strongly as possible towards the long wave lengths, or a generally more selective sensitizer the spectral composition of the light in the darkroom may be nearer to the sensitizing zone. Similar advantages of a highly selective sensitizing occur when there is a gap in the green, in which case the processing is conducted in green light.
- a further object is the provision of trimethinecyanines containing at least one benzimidazole ring.
- a still further object is to provide trimethinecyanines with a benzimidazole ring which contains at the nitrogen atoms alkyl, aralkyl or aryl groups.
- the new sensitizers have the following general formula:
- R1 alkyl
- A,B hydrogen, alkyl or aryl, A and B together may also represent unsubstituted or substituted aryl of the benzene series.
- heterocyclic w-aldehydes that is to say an aldehyde in which the aldehyde group is asubs'tituent in a methine group attached in 2-position to the nitrogen atom; for example benzthiazole-, benzselenazole-, benzoxazole-, or trimethylindoline 2 methine-w-aldehyde may be used,
- This (ll-aldehyde is caused to react with 1 mol of 2-methyl-N,N-dialkyl(arylalkyl) -benzimidazolium halide in the presence of a condensing agent, for example pyridine and piperidine.
- a condensing agent for example pyridine and piperidine.
- Example 2 The dyestuif produced from 1.1.3- trimethyl-G-methoxyindoline-Z-methine-w aldehyde and 1.3-diethyl-2-methyl 6 ethoxybenz imidazolium iodide and corresponding with the following formula sensitizes a silver halide emulsion in the green with a maximum at 545 m and without a gap in the green.
- Example 3 The dyestuff obtained by means of 1.1.S-trimethyl-6-methoxyindoline2-methinew-aldehyde and 1-ethyl-2-methyl-3-phenyl-benzimidazolium iodide and corresponding to the following formula:
- Example 4 The dyestufi obtained from 1.1.3- trimethylindoline-2-methine-w-aldehyde and 1- ethyl-2-methyl-3-phenyl-benzimidazolium iodide has the following formula:
- Example 7 The unsymmetrical dyestuff obtained from 3-ethyl-benzthiazole-2-methine-waldehyde and l-ethyl-2-methyl-3-phenyl-benzimidazolium ethyl sulfate and having the formula:
- Example 8 The dyestuff produced. from 3- ethyl-benzthiazole-2-methine-w-aldehyde and 1- ethyl-2-methyl-3-phenyl 6 chlorobenzimidazolium ethyl sulfate and having the formula:
- Example 11 The dyestuif from 1.1.3-trimethylindoline-2-methine-w-aldehyde and 1- ethyl 2 methyl-3-(4-bromophenyl) -6-chloro benzimidazolium ethyl sulfate has the formula and sensitizes to 5'75 m l with a maximum at 580 m
- Example 12. The dyestuff obtained by means of l".
- 1.3-trimethyl-indoline 2 methine-w-aldehyde and 1-eth'yl-2-methyl-3(4'- methoxyphenyD-benzimidazolium ethyl sulfate has the following formula and sensitizes to 565 m with a maximum at 540.
- Example 13 The dyestuff from 1.1.3-trimethylindoline-2-methine-w-aldehyde and 1- ethyl-Z-methyl 3-phenyl 6 chloro benzimidazolium-ethyl sulfate has the formula and sensitizes to 580 m l with a maximum at 550.
- Example 14 The dyestufi obtained from 1.1.3 trimethylindoline 2 methine-w-aldehyde and 1ethYl-2-methyl;3 -phenyl 5.6 dichlorobenzimidazolium ethyl sulfate and corresponding with the following formula sensitizes to 590 m with a maximum at 560 m
- Example 15. The trimethinecyanine obtained from 1.1.3 trimethylindoline-2-methine-w-aldehyde and 1-ethyl-2.5-dimethyl-3-phenyl-benzimidazolium ethyl sulfate and corresponding with the formula sensitizes to 565 ml with a maximum at 540 mp.
- trimethinecyanine produced from 1-ethyl-2-methyl-3-acet0xypropyl-6-ch1orobenzimidazolium-ethyl sulfate and N-ethyl- 555 III/1..
- Example 27 The trimethinecyanine produced from 1-ethyl-2-methyl-3-phenyl-6-chlorobenzimidazolium-ethyl sulfate and N-ethyl-5-methoxy benzselenazole 2 methine-w-aldehyde has the following formula and. sensitizes to 610 m with a maximum at 575 m l,
- Example 28 The trimethinecyanine produced from l-ethyl-2-methyl-3-phenyl-6-chloro-benzimidazolium ethyl sulfate and 1.1.3-trimethyl-6- methoxy-indoline-2-methine-w-aldehyde has the following formula and sensitizes to 600 nm with a maximum at 570 my.
- Example 29 The trimethinecyanine produced from 1-ethyl-2-methyl-3-pheny1-6-chloro-benzimidazolium ethyl sulfate and 1.1.3.6-tetramethylindQIine-Z-methine-w-aldehyde has the following formula and sensitizes to 590 m with a maximum at 558 mp"
- Example 30 The trimethinecyanine produced from 1.2 dimethyl-3-phenyl-6-chlorobenzimidazolium-methylsulfate and 1.1.3-trimethyl-indoline-2-methine-w-aldehyde has the following formula and sensitizes to 580 m with a maximum at 550 Ina.
- trimethine cyam'ne produced from 1 -ethyl-2-methyl-3- (4-ch1oropheny1-) benzimidazolium ethyl sulfate and N ethyl-thiazoline- Z-methine-w-aldehyde has the following formula and sensitizes from 450 to 510 m with a maximum at 493 mp.
- dimethyl benzselenazole-Z-methine-w-aldehyde has the following formula I OCHa
- Example 36 The trimethinecyanine produced from 1-propy1-2-methyl-3-phenyl-6-chlor0benzimidazoliumiodide and 1.1.3-trimethyl-indoline- Z-methine-w-aIdehyde has the following formula and sensitizes to 580 my with a maximum at 550
- Example 37. The trimethinecyanine produced from 1-ethy1-2-methyl-3-phenyl-6-chloro-benzimidazolium-ethyl sulfate and N-propyl-Ll-dimethyl-indoline-Z-methine-w aldehyde has the following formula CH3 CzHa CaH1 6 5 and. sensitizes to 580 ma with a maximum at 550 m l.
- Example 45 The trirnethinecyanine produced from 1-propyl-2-methyl-3-phenyl-6-chloro-benzimidazolium-iodide and N-ethyl-thiazoline-Z- methine-w-aldehyde has the following formula and sensitizes from 450 to 520 m with a maximum at 503 mu.
- Example 46' The trimethinecyanine produced from 1-ethyl-2.5-dimethy1-3-phenyl-benzimidazoline-ethyl-sulfate and N-ethyl-thiazoline-Z- methine-w-aldehyde has the following formula and sensitizes from 450 to 510 m with a maxi mum at 493 m
- Example 49 The trimethinecyanine produced from l-ethyl-2-methyl-3-phenyl-6-chlorobenzimidazolium ethyl sulfate
- Example 50 The trimethinecyanine produced from 1-ethyl-2-methyl-3- (4'-chlorophenyl-) -6- trifiuoromethyl-benzimidazolium ethyl sulfate and 1.1.3 trimethyl-indoline-Z -methine-w-aldeand sensitizes to 580 m with a maximum at 550 m
- Example 51 The trimethinecyanine produced from 1 ethyl 2 methyl-3-aoetoXypropy1-benzimidazolium ethyl sulfate and 1.1.3-trimethylindoline-2-methine-w-aldehyde has the following formula and sensitizes to 550 m with a maximum at 528 mp.
- tetramethyl-indoline-2-methine-w-aldehyde has the following formula CHa CaHs and sensitizes to 575 m with a maximum at 540 mu.
- Example 54 The trimethinecyanine produced from 1-ethy1-2-methyl-3-acetoxypropy1-6-ch1oro-benzimidazolium-ethyl sulfate and 1.1.3-trimethyl 6 methoxy indoIine-Z-methine-w-aldehyde has the following formula CH3 (fall;
- trimethinecyanine produced from 1-ethyl-2-methyl-3-acet0Xyethyl-6-chlorobenzimidazolium ethyl sulfate and N-ethyl-thiazoline-Z-methine-w-aldehyde has the following formula and sensitizes from 450 to 520 m with a maximum at 498 m
- N-ethyl-thiazo- Iine-Z-methine-w-aldehyde has the following formula and sensitizes from 450 to 520 m l with a maximum at 498 m
- Example 58. The trimethinecyanine produced from 1-ethyl-Z-methyl-B-benzyl benzimidazolium-ethylsulfate and 1.1.B-trimethyl-indoline- 2-methinew-aldehyde has the following formula and sensitizes from 450 to 520 ml with a maximum at 498 m
- Example 60. The trimethinecyanine produced from 1-ethyl-Z-methyl-3-isobutyl-6-chloro-benzimidazolium ethyl sulfate and N-ethyl-thiazo- 1ine-2-methine-w-aldehyde has the following formula and sensitizes from 450 to 520 m with a maximum at 498 my
- Example 61 The trimethinecyanine produced from 1.Z-dimethyl-3-isobuty1-fi-chloro-benzimidazolium-methylsulfate and N-ethyl-thiazoline- 2methinewaldehyde has the following formula CHa
- Example 62 The trimethinecyanine produced from 1 ethyl 2 methyl 3 acetoxypropyl-4- chloro-benzimidazolium ethyl sulfate and 1.1.3 lrimethyl indoline 2 methine-w-aldehyde has the following formula CH3 CzHa l I -CHa N vand sensitizes to 560 mp with a maximum of 630 ma.
- Example 63.l-The trimethinecyanine produced from 1.2-dimethyl-3 acetoxypropyl 4 chlorobenzimidazolium methylsulfate and N ethylthiazoline-2-methine-w-aldehyde has the following formula and sensitizes from 450 to 510 ml with a maximum at 493 mp.
- Example 64 The trimethinecyanine produced from 1.2-dirnethyl-3 acetoxypropyl 6 chlorobenzimidazolium-methyl sulfate and 1.1.3.6- tetramethyl-indo1ine-2-methine-w-aldehyde has the following formula and sensitizes to 575 m with a maximum at 540 ma.
- Example 65 The trimethinecyanine produced from 1.2-dimethyl-3 acetoxypropyl benzimidazolium-methylsulfate and N-ethyl-thiazoline-Z- methine-w-aldehyde has the following formula.
- Example 66 The trimethinecyanine produced from 1.2-dimethyl-3-benzyl 6-chloro-benzimid azolium-methylsulfate and N-ethyl-thiazoline-2;- methine-w-aldehycle has the following formula and sensitizes from 450 to 525 m with a maximum at 500 m
- Example 67 The trimethinecyanine produced from 1-ethy-2 methyl 3 isobutyl-G-trifiuoromethyl-benzimidazolium ethyl sulfate and N- ethyl-thiazoline-Z-methine-w-aldehyde has the following formula and sensitizes from 450 to 525 mm with a maximum at 500 m
- Example 68 The trimethinecyanine produced from l-ethyl 2 methyl-3-isobutyl-6-trifluoromethyl-benzimidazolium ethyl sulfate and 1.1.3
- R2 is acetoxyalkyl
- X is an acid radical
- Y is a member selected from the group consisting of O, S, Se, and
- D is an o-phenylene radical
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- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Spectroscopy & Molecular Physics (AREA)
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- Engineering & Computer Science (AREA)
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- General Physics & Mathematics (AREA)
- Plural Heterocyclic Compounds (AREA)
Description
Patented July 7, 1942 PHOTOGRAPHIC SENSITIZER Gustav Oskar Riester, Dessau,
Wilmanns, Wolfen,
Kreis Bitterfeld, and Karl Kumetat,
Wolfen, Kreis Bitterfeld, Germany, assignors, by mesne assignments, to General Aniline & Film Corporation, New York, N. Y., a corporation of Delaware No Drawing. Application October 12, 1938, Serial No. 234,604. In Germany October 18, 1937 3 Claims.
Our present invention relates to photographic sensitizers.
There is a series of sensitizers comprising particularly members of the cyanine-group which serve to sensitize silver halide emulsions for green and green-yellow; that is to say, they are orthochromatic sensitizers. In order to be able to use the brightest light possible in processing the sensitized material in the dark-room, the spectral composition of the light in the darkroom must be shifted as far as possible towards the short wave lengths, i. e. towards bright red or orange. The limit is set on this condition by the initial sensitivity of the emulsion to certain wave lengths. If the sensitizing curve rises from yellow or yellowgreen very gradually and flatly, the intensity of the spectral sensitivity at these wave lengths is practically of no importance in working exposures, for it amounts only to a fraction of the intensity of the sensitivity at the sensitizing maximum. This small sensitivity sulfices, however, to fog the emulsion when the light of the darkroom falls within that spectral region. Such emulsions, therefore, can only be worked up with correspondingly longer Wave lengths, that is to say with light physiologically darker. If, however, a sensitizer is used the sensitizing curve of which falls away as strongly as possible towards the long wave lengths, or a generally more selective sensitizer, the spectral composition of the light in the darkroom may be nearer to the sensitizing zone. Similar advantages of a highly selective sensitizing occur when there is a gap in the green, in which case the processing is conducted in green light.
It is one object of our invention to provide ortho-chromatic emulsions having sensitizing curves which fall away steeply and also have pronounced definite and limited positions of the sensitizing region.
A further object is the provision of trimethinecyanines containing at least one benzimidazole ring.
A still further object is to provide trimethinecyanines with a benzimidazole ring which contains at the nitrogen atoms alkyl, aralkyl or aryl groups.
Other objects of our invention will appear from the description following hereinafter.
The new sensitizers have the following general formula:
A f A T ]I C'-CH=CHCH=C\ i B N/ 1 B xit R2 in which:
Y=O, S, Se, CH=CH, or
R1=alkyl,
R2=alkyl, aryl, aralkyl or acetoxyalkyl X=acid radical, such as Cl, Br, I, S04, C104 or para-toluene sulfonate,
A,B=hydrogen, alkyl or aryl, A and B together may also represent unsubstituted or substituted aryl of the benzene series.
For the production of the unsymmetrical dyestuffs one starts from heterocyclic w-aldehydes, that is to say an aldehyde in which the aldehyde group is asubs'tituent in a methine group attached in 2-position to the nitrogen atom; for example benzthiazole-, benzselenazole-, benzoxazole-, or trimethylindoline 2 methine-w-aldehyde may be used, This (ll-aldehyde is caused to react with 1 mol of 2-methyl-N,N-dialkyl(arylalkyl) -benzimidazolium halide in the presence of a condensing agent, for example pyridine and piperidine.
The dyestulf may contain substituents in the 40 benzene ring. The benzene ring of the benzimidazole may carry a fused-on benzene ring.
The dyestufi is incorporated with the emulsion especially in an' emulsion ripened with the use of ammonia emulsion or with the finished layer in any usual manner.
methine-w-aldehyde and 1.3-diethyl-2-methyl-6- ethoxybenzimidazolium iodide and corresponding with the following formula sensitizes a silver bromide emulsion in the green with a maximum at 570 ma with a very steep falling-away of the sensitivity curve towards the region of long waves.
Example 2.The dyestuif produced from 1.1.3- trimethyl-G-methoxyindoline-Z-methine-w aldehyde and 1.3-diethyl-2-methyl 6 ethoxybenz imidazolium iodide and corresponding with the following formula sensitizes a silver halide emulsion in the green with a maximum at 545 m and without a gap in the green.
Example 3.-The dyestuff obtained by means of 1.1.S-trimethyl-6-methoxyindoline2-methinew-aldehyde and 1-ethyl-2-methyl-3-phenyl-benzimidazolium iodide and corresponding to the following formula:
sensitizes without a gap in the green and with a maximum at 560 m Example 4.-The dyestufi obtained from 1.1.3- trimethylindoline-2-methine-w-aldehyde and 1- ethyl-2-methyl-3-phenyl-benzimidazolium iodide has the following formula:
and sensitizes without a gap in the green and with a maximum at 540 m Example 5.The dyestufi produced by means of 3-ethyl-benzselenazole-Z-methine-w-aIdehyde and 1-ethyl-2-methyl-3-phenyl-benzimidazolium ethyl sulfate and corresponding to the following formula:
zHs 5 sensitizes to about 585 m without a gap and with a maximum at 557 m Example 6.The unsymmetrical dyestuff obtained from 3-ethyl-benzselenazole-2-methinew-aldehyde and 1-ethyl-2-methyl-3-phenyl-6 chloro-benzimidazolium ethyl sulfate and having the following composition:
sensitizes to about 600 m with a maximum at 567 my Example 7.-The unsymmetrical dyestuff obtained from 3-ethyl-benzthiazole-2-methine-waldehyde and l-ethyl-2-methyl-3-phenyl-benzimidazolium ethyl sulfate and having the formula:
CzHn
2 5 CnHs sensitizes to 585 m witha'maximum at 555 my.
Example 8.The dyestuff produced. from 3- ethyl-benzthiazole-2-methine-w-aldehyde and 1- ethyl-2-methyl-3-phenyl 6 chlorobenzimidazolium ethyl sulfate and having the formula:
CzHs I 0 l sensitizes to 550 m with a maximum at 525 m Example 10.The trimethinecyanine from 3 ethyl-5.13 naphthoxazole-Z-methine-wealdehyde and 1-ethyl-2-methyl-3-phenyl-6-chloro-benzimidazolium ethyl sulfate has the formula:
and sensitizes to 560 m with a maximum at 538 m Example 11.The dyestuif from 1.1.3-trimethylindoline-2-methine-w-aldehyde and 1- ethyl 2 methyl-3-(4-bromophenyl) -6-chloro benzimidazolium ethyl sulfate has the formula and sensitizes to 5'75 m l with a maximum at 580 m Example 12.-The dyestuff obtained by means of l".1.3-trimethyl-indoline 2 methine-w-aldehyde and 1-eth'yl-2-methyl-3(4'- methoxyphenyD-benzimidazolium ethyl sulfate has the following formula and sensitizes to 565 m with a maximum at 540.
Example 13.-The dyestuff from 1.1.3-trimethylindoline-2-methine-w-aldehyde and 1- ethyl-Z-methyl 3-phenyl 6 chloro benzimidazolium-ethyl sulfate has the formula and sensitizes to 580 m l with a maximum at 550.
Example 14.-The dyestufi obtained from 1.1.3 trimethylindoline 2 methine-w-aldehyde and 1ethYl-2-methyl;3 -phenyl 5.6 dichlorobenzimidazolium ethyl sulfate and corresponding with the following formula sensitizes to 590 m with a maximum at 560 m Example 15.--The trimethinecyanine obtained from 1.1.3 trimethylindoline-2-methine-w-aldehyde and 1-ethyl-2.5-dimethyl-3-phenyl-benzimidazolium ethyl sulfate and corresponding with the formula sensitizes to 565 ml with a maximum at 540 mp.
Example 16.--The trimethinecyanine produced by means of 1.1.3-trimethylindo1ine-2-methinew-aldehyde and 1-ethyl-2-methyl-3-phenyl-6 trifluoromethyl-benzimidazolium ethyl sulfate and corresponding with the formula:
CH3 CH3 sensitizes to 570 m with a maximum at 542 m Example 18.The trimethinecyanine obtained from N-ethyl-thiazoline-2-methineu-a1dehyde and! 1-ethy1-2-methyl-3-phenyl-6-chloro-ben3zimidazolium ethyl sulfate and having the formula C2115 CaHs sensitizes with a maximum at 510 m Example 19.The trimethinecyanine produced from 1.1v.3-trimethylindoline-2-methine-w-aldehyde and 1-ethyl-2-methy1-3-acetoxy-propyl-6- chloro-benzimidazolium ethyl sulfate and having the following structural formula sensitizes to 570 m with a maximum at 545 m Example 20.--The trimethinecyanine produced from N-ethyl-thiazoline-2-methine-w-aldehyde, and 1-ethyl-2-methyl-3-acetoxypropyl-6-chlorobenzimidazolium ethyl sulfate has the following structural formula and sensitizes with a maximum at 503 mp.
Example 21 .--The trimethinecyanine produced from 1.2-dimethyl-3-acetoxypropyl-6-oh1orobenzimidazolium methyl sulfate and N-ethyl-benzselenazole-2-methine-w-aldehyde having the following formula I Se I Cl 'CH=CH-CH=C I 021:, on, x-
CH2 $H2 O.CO.CH:
and sensitizing to 590 ml with a maximum at Example 22.The trimethinecyanine produced from 1-ethyl-2-methyl-3-acet0xypropyl-6-ch1orobenzimidazolium-ethyl sulfate and N-ethyl- 555 III/1..
Example 23.The trimethinecyanine produced from 1-ethyl-2-methyl-3-phenyl-6-chlorobenzimidazolium ethyl sulfate and N-ethyl-quinoline-2-methine-w-aldehyde has the following formula and sensitizes to 650 m with a maximum at 600 m and a gap at 500 m Example 24.-The trimethinecyanine produced from 1-ethyl-2-methy1-3-pheny1-benzimidazolium-ethyl sulfate and N-ethyl- 5.6-dimethylbenzselenazole-2-methine-w-aldehyde has the following formula C 2H5 I N H3C- Se JZ'CH=CHCH=C 7 I I CgHs CtHs and sensitizes to 590 m with a maximum at 563 m Example 25.The trimethinecyanine produced from 1-ethyl-2-methyl-S-phenyl-G-chlorobenzimidazolium-ethyl sulfate and N-ethyl-5.6-dimethylbenzselenazole-2-methine-w-aldehyde has the following formula and sensitizes to 610 m with a maximum at 575 m Example 26.--The trimethinecyanine produced from 1-ethyl-2-methyl-3-phenyl-benzimidazo1ium-ethyl sulfate and N-ethyl-5-methoxy-benzselenazole-2-methine-w-aldehyde has the following formula and sensitizes to 600 m with a maximum at 565 ma.
Example 27.--The trimethinecyanine produced from 1-ethyl-2-methyl-3-phenyl-6-chlorobenzimidazolium-ethyl sulfate and N-ethyl-5-methoxy benzselenazole 2 methine-w-aldehyde has the following formula and. sensitizes to 610 m with a maximum at 575 m l,
Example 28.The trimethinecyanine produced from l-ethyl-2-methyl-3-phenyl-6-chloro-benzimidazolium ethyl sulfate and 1.1.3-trimethyl-6- methoxy-indoline-2-methine-w-aldehyde has the following formula and sensitizes to 600 nm with a maximum at 570 my.
Example 29.-The trimethinecyanine produced from 1-ethyl-2-methyl-3-pheny1-6-chloro-benzimidazolium ethyl sulfate and 1.1.3.6-tetramethylindQIine-Z-methine-w-aldehyde has the following formula and sensitizes to 590 m with a maximum at 558 mp" Example 30.-The trimethinecyanine produced from 1.2 dimethyl-3-phenyl-6-chlorobenzimidazolium-methylsulfate and 1.1.3-trimethyl-indoline-2-methine-w-aldehyde has the following formula and sensitizes to 580 m with a maximum at 550 Ina.
Example 31.The trimethinecyanine produced from 1-ethyl-2-methyl-3- (4'-ch1orophenyl) benzimidazolium ethyl sulfate and 1.1.3-trimethylindoline-2-methine-w-aldehyde has the following formula duced from 1-ethyl-2-methyl-3-(4'-chloropheny1-)-benzimidazoliumethy1 sulfate and. 1.1.3.6- tetramethyl-2-methine-w-aldehyde has the following formula and sensitizes to 575 m with a maximum at 548 Example 33.The trimethine cyam'ne produced from 1 -ethyl-2-methyl-3- (4-ch1oropheny1-) benzimidazolium ethyl sulfate and N ethyl-thiazoline- Z-methine-w-aldehyde has the following formula and sensitizes from 450 to 510 m with a maximum at 493 mp.
Example 34.The trimethinecyanine produced from l-ethyl-Z-m e t h y 1-3- (4'-chlorophenyl-) benzimidazolium ethyl sulfate and. Nethyl-5.6- dimethyl benzselenazole-2-methine-w-aldehyde has the following formula and sensitizes to 600 mu with amaximum at 565 Example 35 .The trimethinecyanine produced from 1 -ethyl-2-methyl-3- (4'-methoxyphenyl-) benzimidazolium-ethyl sulfate and N-methyl5.6
dimethyl benzselenazole-Z-methine-w-aldehyde has the following formula I OCHa Example 36.--The trimethinecyanine produced from 1-propy1-2-methyl-3-phenyl-6-chlor0benzimidazoliumiodide and 1.1.3-trimethyl-indoline- Z-methine-w-aIdehyde has the following formula and sensitizes to 580 my with a maximum at 550 Example 37.-The trimethinecyanine produced from 1-ethy1-2-methyl-3-phenyl-6-chloro-benzimidazolium-ethyl sulfate and N-propyl-Ll-dimethyl-indoline-Z-methine-w aldehyde has the following formula CH3 CzHa CaH1 6 5 and. sensitizes to 580 ma with a maximum at 550 m l.
from 1-ethy1-2-methy1-3-pheny1-5-chloro-benzimidazolium ethyl sulfate and 1.1.3-trimethy1- indoline-2-methine-w-aldehyde has the following formula and sensitizes to 580 ma with a maximum at 550 m Example 39.-The trimethinecyanine produced from 1-ethyl-2-methyl-3-phenyl-5-chloro-benzimidazolium-ethylsulfate and. N-ethyl-thiazoline- 2-methine-w-aldehyde has the following formula and sensitizes from 450 to 525 III/.0 with a maximum at 503 m and sensitizes to 595 m with a maximum at 562 Example 38.'1l1e trimethinecyam'ne produced Example 40.-The trimethinecyanine produced from 1-ethyl-2-methyl-3- (4' -methoxyphenyl) benzimidazolium ethyl sulfate and N-ethyl-thiazoline-Z-methine-w-aldehyde has the following formula and sensitizes from 450 to 510 m with a maximum at 439 mu.
Example 41.The trimethinecyanine produced from 1-ethyl-2-methyl-3-phenyl-5.6-dichlorobenzimidazolium-ethylsulfate and N-ethyl-thiazoline-2-methine-w-aldehyde has the following formula CaHa I EFF-S 7 C1 '-CH=CHCH=JJ and sensitizes from 450 to 530 m with a maximum at 508 mu.
Example 42.The trimethinecyanine produced from 1-ethyl-2-methyl-3-phenyl-benzimidazolium ethyl sulfate and N-ethyl-thiazoline-2-methine-w-aldehyde has the following formula and sensitizes from 450 to 510 m with a maximum at 493 m Example 43.The trimethinecyanine produced from l-ethyl-2-methyl-3-(4-bromopheny1) -benzimidazolium ethyl sulfate and 1.1.3-trimethylindoline-2-methine-w-aldehyde has the following formula and sensitizes to 560 m l with a maximum at 540 m Example 44.-The trimethinecyanine produced from 1-ethyl-2-methyl-3-(4-bromophenyl) -benzimidazolium ethyl sulfate and N-ethyl-thiazoline-2-methine-w-aldehyde has the following formula and sensitizes from 450 to 510 m with a maximum at 493 my.
Example 45.The trirnethinecyanine produced from 1-propyl-2-methyl-3-phenyl-6-chloro-benzimidazolium-iodide and N-ethyl-thiazoline-Z- methine-w-aldehyde has the following formula and sensitizes from 450 to 520 m with a maximum at 503 mu.
Example 46'.-The trimethinecyanine produced from 1-ethyl-2.5-dimethy1-3-phenyl-benzimidazoline-ethyl-sulfate and N-ethyl-thiazoline-Z- methine-w-aldehyde has the following formula and sensitizes from 450 to 510 m with a maxi mum at 493 m Example 48.-The trimethinecyanine produced from l-ethyl-2-methyl-3- (4='-chlorophenyl-) -6- chloro-benzimidazolium ethyl sulfate and 1.1.3- trimethyl indoline 2 methine-w-aldehyde has the following formula Cans and sensitizes to 580 m with a maximum at 550 m Example 49.-The trimethinecyanine produced from l-ethyl-2-methyl-3-phenyl-6-chlorobenzimidazolium ethyl sulfate and 1.1.3-trimethy1-6- chloro -indo1ine 2 methine-w-aldehyde has the following formula and sensitizes to 580 ml with a maximum at 550 ma.
Example 50.--The trimethinecyanine produced from 1-ethyl-2-methyl-3- (4'-chlorophenyl-) -6- trifiuoromethyl-benzimidazolium ethyl sulfate and 1.1.3 trimethyl-indoline-Z -methine-w-aldeand sensitizes to 580 m with a maximum at 550 m Example 51.The trimethinecyanine produced from 1 ethyl 2 methyl-3-aoetoXypropy1-benzimidazolium ethyl sulfate and 1.1.3-trimethylindoline-2-methine-w-aldehyde has the following formula and sensitizes to 550 m with a maximum at 528 mp.
Example 52.The trimethinecyanine produced from 1 ethyl 2 methyl-3-aoetoXypropyl-benzimidazolium ethyl sulfate and N-ethyl-thiazoline- 2-methine-w-aldehyde has the following formula and sensitizes from 450 to 510 m with a maximum at 493 ma.
Example 53.The trimethinecyanine produced from 1-ethyl-2-methyl-3acetoxypropyl-6-chloro-benzimidazolium ethyl sulfate and 1.1.3.6-
tetramethyl-indoline-2-methine-w-aldehyde has the following formula CHa CaHs and sensitizes to 575 m with a maximum at 540 mu.
Example 54.-The trimethinecyanine produced from 1-ethy1-2-methyl-3-acetoxypropy1-6-ch1oro-benzimidazolium-ethyl sulfate and 1.1.3-trimethyl 6 methoxy indoIine-Z-methine-w-aldehyde has the following formula CH3 (fall;
and sensitizes to 585 ml with a maximum at 550 m Example 55.The trimethinecyanine produced from 1.2 dimethyl 3 acetoxypropyl-G-ohlorobenzimidazolium-methylsulfate and N-ethylthiazoline-Z-methine-(ll-aldehyde has the following formula C'CIEI=CHCH=(IJ H N N X- z s CH: w w 0.0 0.0m
and sensitizes from 450 to 520 mu with a maximum at 498 m Example 56.The trimethinecyanine produced from 1-ethyl-2-methyl-3-acet0Xyethyl-6-chlorobenzimidazolium ethyl sulfate and N-ethyl-thiazoline-Z-methine-w-aldehyde has the following formula and sensitizes from 450 to 520 m with a maximum at 498 m Example 57.-The trimethinecyanine produced from 1.Z-dimethyl-3-acetoxyethyl-fi-ohloro-benzimidazolium-methylsulfate and. N-ethyl-thiazo- Iine-Z-methine-w-aldehyde has the following formula and sensitizes from 450 to 520 m l with a maximum at 498 m Example 58.--The trimethinecyanine produced from 1-ethyl-Z-methyl-B-benzyl benzimidazolium-ethylsulfate and 1.1.B-trimethyl-indoline- 2-methinew-aldehyde has the following formula and sensitizes from 450 to 520 ml with a maximum at 498 m Example 60.-The trimethinecyanine produced from 1-ethyl-Z-methyl-3-isobutyl-6-chloro-benzimidazolium ethyl sulfate and N-ethyl-thiazo- 1ine-2-methine-w-aldehyde has the following formula and sensitizes from 450 to 520 m with a maximum at 498 my.
Example 61 .-The trimethinecyanine produced from 1.Z-dimethyl-3-isobuty1-fi-chloro-benzimidazolium-methylsulfate and N-ethyl-thiazoline- 2methinewaldehyde has the following formula CHa | C1115 CH2 and sensitizes from 450 to 520 ml with a maximum at 498 mp.
Example 62.-The trimethinecyanine produced from 1 ethyl 2 methyl 3 acetoxypropyl-4- chloro-benzimidazolium ethyl sulfate and 1.1.3 lrimethyl indoline 2 methine-w-aldehyde has the following formula CH3 CzHa l I -CHa N vand sensitizes to 560 mp with a maximum of 630 ma.
Example 63.l-The trimethinecyanine produced from 1.2-dimethyl-3 acetoxypropyl 4 chlorobenzimidazolium methylsulfate and N ethylthiazoline-2-methine-w-aldehyde has the following formula and sensitizes from 450 to 510 ml with a maximum at 493 mp.
Example 64.-The trimethinecyanine produced from 1.2-dirnethyl-3 acetoxypropyl 6 chlorobenzimidazolium-methyl sulfate and 1.1.3.6- tetramethyl-indo1ine-2-methine-w-aldehyde has the following formula and sensitizes to 575 m with a maximum at 540 ma.
Example 65.-The trimethinecyanine produced from 1.2-dimethyl-3 acetoxypropyl benzimidazolium-methylsulfate and N-ethyl-thiazoline-Z- methine-w-aldehyde has the following formula.
and sensitizes from 450 to 520 m with a maximum at 493 mp. V
Example 66.The trimethinecyanine produced from 1.2-dimethyl-3-benzyl 6-chloro-benzimid azolium-methylsulfate and N-ethyl-thiazoline-2;- methine-w-aldehycle has the following formula and sensitizes from 450 to 525 m with a maximum at 500 m Example 67.The trimethinecyanine produced from 1-ethy-2 methyl 3 isobutyl-G-trifiuoromethyl-benzimidazolium ethyl sulfate and N- ethyl-thiazoline-Z-methine-w-aldehyde has the following formula and sensitizes from 450 to 525 mm with a maximum at 500 m Example 68.The trimethinecyanine produced from l-ethyl 2 methyl-3-isobutyl-6-trifluoromethyl-benzimidazolium ethyl sulfate and 1.1.3- trimethyl-indoline-2-methine-w-aldehyde has the following formula and sensitizes to 570 m with a maximum at 540 mu.
Example 69.The trimethinecyanine produced from 1.2.3-trimethyl benzimidazolium methyl- 7 sulfate and N-ethyl-thiazoline-2-methine-w-a1- dehyde has the following formula C Ha and sensitizes from 450 to 520 mil with a maximum at 490 I'll 1..
Example 70.--The trimethinecyanine produced from 1-ethyl-2.3-dimethyl-benzimidazolium-ethyl-sulfate and N-ethyl-thiazoline-2-methine-waldehyde has the following formula I HzS N A B2 C'-OH=CHCH= and sensitizes from 450 to 520 m with a maximum at 490 my.
Est-ample 71 .-The trimethinecyanine produced from 1.2.3-trimethyl benzimidazolium methylsulfate and N-ethyl-benselenazole-2-methine-waldehyde has the following formula CH3 C2115 and sensitizes to 580 m with a maximum at 545 mp.
Example 73.-The trimethinecyanine produced from 1-ethyl-2-methy1-3-dodecyl 6 chlorobenzimidazolium-ethylsulfate and 1.1.3-trimethy1- indoline-Z-methine-w-aldehyde has the following formula and sensitizes to 570 m with a maximum at 540 m Example 74.The trimethinecyanine produced from 1.2-dimethyl-3-dodecyl-S-chlorobenzimidazolium-methylsulfate and N-ethyl-benzselenazole-2-methine-w-aldehyde has the following formula I Se l]l c1 5 (L'CH=CHCH=O and sensitizes to 590 m l with a maximum at 560 m Example 75.-The trimethinecyanine produced from 1.2-dimethyl-3-dodecyl-6-chlorobenzimidazolium-methylsulfate and N-ethyl-thiazoline-2- 15 methine-w-aldehyde has the following formula (13H: H:? 01 c -o H=C HCH=C I (11H; 01TH and sensitizes from 450 to 520 m with a maximum at 500 m In the above formulae 3: stands for an alkyl sulfate radical such as ethyl or methyl sulfate.
We claim:
1. A trimethinecyanine corresponding with the following general formula:
| r r E CCH=CHCH=O D X I". l.
in which R1 is ethyl, 40
R2 is acetoxyalkyl, X is an acid radical,
Y is a member selected from the group consisting of O, S, Se, and
D is an o-phenylene radical,
E is a member selected from the group consisting ofCH2CH2-, an o-phenylene radical, and an o-naphthylene radical,
2. A trimethinecyanine corresponding with the following formula:
in which X is an acid radical.
3. A trimethinecyanine corresponding with the following formula:
in which X is an acid radical.
GUSTAV WILMANNS. OSKAR RIESTER. KARL KUMETAT.
Certificate of Correction Patent No. 2,289,300. July 7, 1942.
GUSTAV WILMANN S ET AL.
It is hereby certified that errors appear in the printed specification of the above numbered patent requiring correction as follows: Page 1, second column, line 44, after the Word ammonia strike out emulsion; same line, after finished insert emulsion; page 6, first column, lines 19 and 20, for maximum at 439 my read maximum at 493 my; page 8, second column, lines 33 and 34, for of 630 my read at 580 my; and that the said Letters Patent should be read with these corrections therein that the same may conform to the record of the case in the Patent Office.
Signed and sealed this 30th day of March, A. D. 1943.
[SEAL] HENRY VAN ARSDALE,
Acting Commissioner of Patents.
m iiiiiiiii a Hn.u q .r
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2289300X | 1937-10-18 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2289300A true US2289300A (en) | 1942-07-07 |
Family
ID=7993756
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US234604A Expired - Lifetime US2289300A (en) | 1937-10-18 | 1938-10-12 | Photographic sensitizer |
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| Country | Link |
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| US (1) | US2289300A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2437465A (en) * | 1942-07-13 | 1948-03-09 | Ici Ltd | Manufacture of new coloring matters |
| US2463264A (en) * | 1942-12-23 | 1949-03-01 | Ciba Ltd | Derivatives of cyclic amidines and process of making same |
| US2481464A (en) * | 1945-12-29 | 1949-09-06 | Gen Aniline & Film Corp | Photographic emulsions containing nu-aryloxy-, arylthio-and arylselenoalkyl cyanine dyes |
| US2504615A (en) * | 1945-12-29 | 1950-04-18 | Gen Aniline & Film Corp | Photographic emulsions containing nu-aryloxy-, arylthio-, and arylselenoalkyl cyanine dyes |
| US2544322A (en) * | 1939-04-24 | 1951-03-06 | Bela Gaspar | Sensitized photographic emulsions |
| US3628964A (en) * | 1967-07-17 | 1971-12-21 | Fuji Photo Film Co Ltd | Photographic supersensitized silver halide emulsions |
-
1938
- 1938-10-12 US US234604A patent/US2289300A/en not_active Expired - Lifetime
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2544322A (en) * | 1939-04-24 | 1951-03-06 | Bela Gaspar | Sensitized photographic emulsions |
| US2437465A (en) * | 1942-07-13 | 1948-03-09 | Ici Ltd | Manufacture of new coloring matters |
| US2463264A (en) * | 1942-12-23 | 1949-03-01 | Ciba Ltd | Derivatives of cyclic amidines and process of making same |
| US2481464A (en) * | 1945-12-29 | 1949-09-06 | Gen Aniline & Film Corp | Photographic emulsions containing nu-aryloxy-, arylthio-and arylselenoalkyl cyanine dyes |
| US2504615A (en) * | 1945-12-29 | 1950-04-18 | Gen Aniline & Film Corp | Photographic emulsions containing nu-aryloxy-, arylthio-, and arylselenoalkyl cyanine dyes |
| US3628964A (en) * | 1967-07-17 | 1971-12-21 | Fuji Photo Film Co Ltd | Photographic supersensitized silver halide emulsions |
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