US2570494A - Supersensitized silver halide emulsions containing a meso-alkoxyl substituted carbocyanine and a 2,2' cyanine - Google Patents
Supersensitized silver halide emulsions containing a meso-alkoxyl substituted carbocyanine and a 2,2' cyanine Download PDFInfo
- Publication number
- US2570494A US2570494A US762536A US76253647A US2570494A US 2570494 A US2570494 A US 2570494A US 762536 A US762536 A US 762536A US 76253647 A US76253647 A US 76253647A US 2570494 A US2570494 A US 2570494A
- Authority
- US
- United States
- Prior art keywords
- meso
- silver halide
- alkoxyl
- cyanine
- carbocyanine
- 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
- 239000000298 carbocyanine Substances 0.000 title claims description 24
- QWYZFXLSWMXLDM-UHFFFAOYSA-M pinacyanol iodide Chemical class [I-].C1=CC2=CC=CC=C2N(CC)C1=CC=CC1=CC=C(C=CC=C2)C2=[N+]1CC QWYZFXLSWMXLDM-UHFFFAOYSA-M 0.000 title claims description 16
- 239000000839 emulsion Substances 0.000 title claims description 10
- 229910052709 silver Inorganic materials 0.000 title claims description 7
- 239000004332 silver Substances 0.000 title claims description 7
- -1 silver halide Chemical class 0.000 title claims description 5
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 title description 2
- 239000000975 dye Substances 0.000 claims description 3
- 230000001235 sensitizing effect Effects 0.000 description 12
- 125000000217 alkyl group Chemical group 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 125000000623 heterocyclic group Chemical group 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 125000000547 substituted alkyl group Chemical group 0.000 description 2
- 241000501754 Astronotus ocellatus Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- KXNQKOAQSGJCQU-UHFFFAOYSA-N benzo[e][1,3]benzothiazole Chemical compound C1=CC=C2C(N=CS3)=C3C=CC2=C1 KXNQKOAQSGJCQU-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000005415 substituted alkoxy 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
- 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
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
- G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
- G03C1/08—Sensitivity-increasing substances
- G03C1/28—Sensitivity-increasing substances together with supersensitising substances
- G03C1/29—Sensitivity-increasing substances together with supersensitising substances the supersensitising mixture being solely composed of dyes ; Combination of dyes, even if the supersensitising effect is not explicitly disclosed
Definitions
- This invention relates to halide emulsions the spectral sensitivity of which has been modified by means of symmetrical or unsymmetrical carbocyanines containing an alkoxyl or substituted alkoxyl group at the central carbon atom of the trimethyne chain.
- a further object of our present invention is to provide photographic single or. multi-layer material comprising a light-sensitive silver halide emulsion layer containing a heretofore unknown carbocyanine dyestufi.
- halide emulsionone of the ineso-alkoxyl substituted carbocyanines which have an unexpected strong capacity for sensitizing photographic emulsions.
- These meso-alkoxyl substituted carbocyanines correspond to the following formula: 0R e 4' wherein Y and Z are the same or difiernt nonmetallic atoms necessary to complete a 5- or '6-membered N-containing heterocyclic nucleus including a substituted nucleus and a nucleus fused to another nucleus or to a ring system, B is alkyl, substituted alkyl; R, R are the same or different alkyl, substituted alkyl, aryl or aralkyl groups, and X is an acid residue.
- the meso-alkoxyl dyestuffs of our invention obtained in this way possess an absorption maximum which is shifted towards the short wave. region.
- Ezrample 1 A meso-alkoxyl carbocyanine usable as blue sensitizer of the probable formula:
- the following examples show alkoxyl substituted carbocyanines suitable for orthochromatic sensitizing of silver halide emulsions.
- Example 3 The sensitizer of the formula:
- a sensitizing maximum at 520 m the maximum of the corresponding meso-ethyl carbocyanine being at 630 m
- carbocyanine dyestuffs which'contain nuclei, such as quinoline and naphthothiazole which cause these dyes to absorb longer wave lengths and whereby some of these dyestufls spontaneously cause a second sensitizing maximum.
- Example 7 The sensitizer of the formula:
- --on NIT has a sensitizing maximum at 645 to 650 m (second maximum).
- the alkoxyl substituted carbocyanines according to the present invention are also most suitable for use in combination with other s'ensitiz'ers whereby often a strong sensitizing effect is obtained.
- the supersensitizing, for instance, of pseudocyanines is especially important.
- the dyestufis used until now for the supersensitizing of pseudocyanines in the ortho region generally had a too high red-sensitiveness whereas the dyestufis without this disadvantage are inferior supersensitizers.
- the compounds according to this invention overcome all of these disadvantages.
- Example 8 An excellent orthochromatic supersensitizing effect is obtained by combining the dyestufi of Example 3 with the known quinopseudocyanine ethyl bromide.
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- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Physics & Mathematics (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
Description
Patented Oct. 9, 1951 SUPERSENSITIZED' SILVER HALIDE EMUL- SIONS CONTAINING A MESO-ALKOXYL SUBSTITUTED CARBOCY ANINE AND A 2,2
CYANINE Marcel Adam Schouwenaars, Edegem-Antwerp, Leo Arnold. Van de Straete, Mortsel-Antwerp, and Oscar Hendrik Van den Broele, Wilrijk- Antwerp, Belgium, assignors to Gevaert Photo- Producten N. V., Mortsel-Antwerp, Belgium, a
company of Belgium No Drawing. Application July 21, 1947, Serial No. 762,536. In Germany December 31, 1943 Section 1, P'ublic as 690, August 8, 1946 Patent expires December 31, 1963 2 Claims.
This invention relates to halide emulsions the spectral sensitivity of which has been modified by means of symmetrical or unsymmetrical carbocyanines containing an alkoxyl or substituted alkoxyl group at the central carbon atom of the trimethyne chain.
According to the French Patent No. 742,639 it has been proposed to sensitize photographic emulsions by means of compounds considered as meso-alkoxyl substituted carbocyanines and manufactured by condensation of quaternary cycloammonium salts, which contain a reactive methyl group, with ,tetraalkyl orthocarbonic esters in the presence of piperidine or non-volatile alkalies as condensation agent. Carbocyaphotographic silver I nine dyestufis produced by the same process are described as suitable sensitizers of photographic emulsions by Piprianow, Ssytnik and Ssytsch in Chem. Zentr. I, 1936, page 4654, who also agree as to the formation of meso-alkoxyl substituted carbo-cyanines during the condensation. This assumption, however, has been found to be wrong. As explained hereinafter, no meso-alkoxyl substituted carbocyanines but the known meso-alkyl substituted carbocyanines are formed when using tetraalkyl orthocarbonic esters in the presence by incorporating therein a heretofore unknown meso-alkoxyl carbocyanine dyestuff.
A further object of our present invention is to provide photographic single or. multi-layer material comprising a light-sensitive silver halide emulsion layer containing a heretofore unknown carbocyanine dyestufi.
Further objects will become apparent from the following description.
We have found that these objects are accomplished by incorporatil lg in a photographic silver 7'. f
halide emulsionone of the ineso-alkoxyl substituted carbocyanines which have an unexpected strong capacity for sensitizing photographic emulsions. These meso-alkoxyl substituted carbocyanines correspond to the following formula: 0R e 4' wherein Y and Z are the same or difiernt nonmetallic atoms necessary to complete a 5- or '6-membered N-containing heterocyclic nucleus including a substituted nucleus and a nucleus fused to another nucleus or to a ring system, B is alkyl, substituted alkyl; R, R are the same or different alkyl, substituted alkyl, aryl or aralkyl groups, and X is an acid residue.
These carbocyanines are obtained by causing 2 (beta methyl beta alkoxyl vinyl) cycloammonium salts of the general formula:
to react, as described in the copending application Ser. No. 755,228, filed June 17, 1947, by Leo Arnold Van de Straete et al., now Patent No. 2,557,806, with a heterocyclic quaternary salt usable for cyanine condensations and containing an atom group capable of reacting with the CH3 group of the 2-(beta methyl-beta-alkoxylvinyl) -cycloammonium salts.
Compared with the corresponding alkyl substituted dyestuffs, the meso-alkoxyl dyestuffs of our invention obtained in this way possess an absorption maximum which is shifted towards the short wave. region. This means thatgthe meso-alkoxyl carbocyanines may be used-j for green or blue sensitized photographic emulsions whereas the corresponding carbocyanines bearing in meso-position the known substituents ar panchromatic sensitizers; l n.
Some specific examples illustrating our invention are given hereinafter.
Ezrample 1 A meso-alkoxyl carbocyanine usable as blue sensitizer of the probable formula:
has a sensitizing maximum at 505 m the maximum of the corresponding meso-methyl carbocyanine being at 560 m Example 2 A blue sensitizer oi the probable formula:
4 T OCH; O-CH=C-CH=C N/ \N Br- 0211 32115 has a sensitizing maximum at 520 m the maximum of the corresponding mesa-methyl carbocyanine being at 575 m The following examples show alkoxyl substituted carbocyanines suitable for orthochromatic sensitizing of silver halide emulsions.
Example 3 The sensitizer of the formula:
o-oH=coH=o Br N N 41H: ('33:
has a sensitizing maximum at 520 m the maximum of the corresponding meso-methyl carbocyanine being at 590 m Example 4 The sensitizer of the formula:
has a sensitizing maximum at 530 m the maximum of the corresponding meso-methyl carbocyanine being at 600 m Example 5 The sensitizer of the formula:
has a sensitizing maximum at 510 m.
T 0 cam c-oH=t:-cH=o I- N N Example 6 The sensitizer of the formula:
has a sensitizing maximum at 520 m the maximum of the corresponding meso-ethyl carbocyanine being at 630 m For panchromatic sensitizing carbocyanine dyestuffs may be used which'contain nuclei, such as quinoline and naphthothiazole which cause these dyes to absorb longer wave lengths and whereby some of these dyestufls spontaneously cause a second sensitizing maximum.
Example 7 The sensitizer of the formula:
on: --on NIT has a sensitizing maximum at 645 to 650 m (second maximum).
' The alkoxyl substituted carbocyanines according to the present invention are also most suitable for use in combination with other s'ensitiz'ers whereby often a strong sensitizing effect is obtained. In this respect the supersensitizing, for instance, of pseudocyanines is especially important. The dyestufis used until now for the supersensitizing of pseudocyanines in the ortho region generally had a too high red-sensitiveness whereas the dyestufis without this disadvantage are inferior supersensitizers. The compounds according to this invention overcome all of these disadvantages.
Example 8 An excellent orthochromatic supersensitizing effect is obtained by combining the dyestufi of Example 3 with the known quinopseudocyanine ethyl bromide.
It will be apparent that the above examples are illustrative of a few adaptations of the in- 2,570,494 5 symmetrical and unsymmetrical oarbooyanines REFERENCES CITED of the following general formula:
file of this patent:
j X- 5 UNITED STATES PATENTS I Number Name Date 2,066,966 Dieterle et a1. Jan. 5, 1937 wherein Y and Z are non-metallic atoms neces- 2.156.464 Schulz May 2, 1939 sary to complete a; heterocyclic N-containing "2,166,938 Carroll July 25, 1939 nucleus, R, R and R" are alkyl, and X is an acid residue, and a. 2,2'-cya.nine in order to obtain OR PATENTS a supersensitizing effect. Number Country t MARCEL SCHOUWENAARS- 42,245 France Mar. 21, 1933 LEO ARNOLD VAN STRAETE- 42,256 France Mar. 28, 1933 OSCAR HENDRIK VAN DEN BROELE. 15
The following references are of record in the
Claims (1)
- 2. A LIGHT-SENSITIVE PHOTOGRAPHIC SILVER HALIDE EMULSION CONTAINING A DYESTUFF SELECTED FROM THE GROUP CONSISTING OF MESO-ALKOXYL SUBSTITUTED SYMMETRICAL AND UNSYMMETRICAL CARBOCYANINES OF THE FOLLOWING GENERAL FORMULA:
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2570494X | 1943-12-31 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2570494A true US2570494A (en) | 1951-10-09 |
Family
ID=7996046
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US762536A Expired - Lifetime US2570494A (en) | 1943-12-31 | 1947-07-21 | Supersensitized silver halide emulsions containing a meso-alkoxyl substituted carbocyanine and a 2,2' cyanine |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2570494A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR42245E (en) * | 1931-02-07 | 1933-06-16 | Ig Farbenindustrie Ag | Process for sensitizing light-sensitive, silver halide emulsions to green, yellow and red |
| FR42256E (en) * | 1931-03-28 | 1933-06-21 | Ig Farbenindustrie Ag | Method for sensitizing silver halide emulsion layers |
| US2066966A (en) * | 1931-02-07 | 1937-01-05 | Agfa Ansco Corp | Manufacture of light sensitive materials |
| US2156464A (en) * | 1935-03-22 | 1939-05-02 | Schulz Otto Fritz | Production of polymethin dyestuffs |
| US2166938A (en) * | 1937-03-29 | 1939-07-25 | Eastman Kodak Co | Photographic emulsion |
-
1947
- 1947-07-21 US US762536A patent/US2570494A/en not_active Expired - Lifetime
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR42245E (en) * | 1931-02-07 | 1933-06-16 | Ig Farbenindustrie Ag | Process for sensitizing light-sensitive, silver halide emulsions to green, yellow and red |
| US2066966A (en) * | 1931-02-07 | 1937-01-05 | Agfa Ansco Corp | Manufacture of light sensitive materials |
| FR42256E (en) * | 1931-03-28 | 1933-06-21 | Ig Farbenindustrie Ag | Method for sensitizing silver halide emulsion layers |
| US2156464A (en) * | 1935-03-22 | 1939-05-02 | Schulz Otto Fritz | Production of polymethin dyestuffs |
| US2166938A (en) * | 1937-03-29 | 1939-07-25 | Eastman Kodak Co | Photographic emulsion |
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