CH197880A - Process for sensitizing a silver halide emulsion. - Google Patents
Process for sensitizing a silver halide emulsion.Info
- Publication number
- CH197880A CH197880A CH197880DA CH197880A CH 197880 A CH197880 A CH 197880A CH 197880D A CH197880D A CH 197880DA CH 197880 A CH197880 A CH 197880A
- Authority
- CH
- Switzerland
- Prior art keywords
- sensitizer
- polymethine dye
- formula
- sub
- group
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 38
- 239000000839 emulsion Substances 0.000 title claims description 7
- 230000001235 sensitizing effect Effects 0.000 title claims description 6
- -1 silver halide Chemical class 0.000 title claims description 6
- 229910052709 silver Inorganic materials 0.000 title claims description 3
- 239000004332 silver Substances 0.000 title claims description 3
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 230000009931 harmful effect Effects 0.000 claims description 3
- 125000000623 heterocyclic group Chemical group 0.000 claims description 3
- 125000000962 organic group Chemical group 0.000 claims description 3
- 206010070834 Sensitisation Diseases 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 125000003172 aldehyde group Chemical group 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- 150000004985 diamines Chemical class 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 125000004957 naphthylene group Chemical group 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229910017464 nitrogen compound Inorganic materials 0.000 claims description 2
- 229920000768 polyamine Polymers 0.000 claims description 2
- 230000008313 sensitization Effects 0.000 claims description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 1
- ZYDVNTYVDVZMKF-UHFFFAOYSA-N [Cl].[Ag] Chemical compound [Cl].[Ag] ZYDVNTYVDVZMKF-UHFFFAOYSA-N 0.000 claims 1
- IFVTZJHWGZSXFD-UHFFFAOYSA-N biphenylene Chemical group C1=CC=C2C3=CC=CC=C3C2=C1 IFVTZJHWGZSXFD-UHFFFAOYSA-N 0.000 claims 1
- 125000005843 halogen group Chemical group 0.000 claims 1
- 230000000737 periodic effect Effects 0.000 claims 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims 1
- 229910052711 selenium Inorganic materials 0.000 claims 1
- 239000011669 selenium Substances 0.000 claims 1
- 229910052717 sulfur Inorganic materials 0.000 claims 1
- 239000011593 sulfur Substances 0.000 claims 1
- 239000000975 dye Substances 0.000 description 14
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 235000002639 sodium chloride Nutrition 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ZTUKGBOUHWYFGC-UHFFFAOYSA-N 1,3,3-trimethyl-2-methylideneindole Chemical compound C1=CC=C2N(C)C(=C)C(C)(C)C2=C1 ZTUKGBOUHWYFGC-UHFFFAOYSA-N 0.000 description 1
- FYEHYMARPSSOBO-UHFFFAOYSA-N Aurin Chemical compound C1=CC(O)=CC=C1C(C=1C=CC(O)=CC=1)=C1C=CC(=O)C=C1 FYEHYMARPSSOBO-UHFFFAOYSA-N 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 1
- 239000000298 carbocyanine Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000003387 indolinyl group Chemical group N1(CCC2=CC=CC=C12)* 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- XXTISPYPIAPDGY-UHFFFAOYSA-N n,n-diphenylmethanimidamide Chemical compound C=1C=CC=CC=1N(C=N)C1=CC=CC=C1 XXTISPYPIAPDGY-UHFFFAOYSA-N 0.000 description 1
- CHMBIJAOCISYEW-UHFFFAOYSA-N n-(4-aminophenyl)acetamide Chemical compound CC(=O)NC1=CC=C(N)C=C1 CHMBIJAOCISYEW-UHFFFAOYSA-N 0.000 description 1
- AJDUTMFFZHIJEM-UHFFFAOYSA-N n-(9,10-dioxoanthracen-1-yl)-4-[4-[[4-[4-[(9,10-dioxoanthracen-1-yl)carbamoyl]phenyl]phenyl]diazenyl]phenyl]benzamide Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2NC(=O)C(C=C1)=CC=C1C(C=C1)=CC=C1N=NC(C=C1)=CC=C1C(C=C1)=CC=C1C(=O)NC1=CC=CC2=C1C(=O)C1=CC=CC=C1C2=O AJDUTMFFZHIJEM-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 150000003839 salts Chemical group 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000001043 yellow dye Substances 0.000 description 1
Landscapes
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
Description
'Verfahren zur Sensibilisierung einer Halogensilberemulsion. Es ist bereits bekannt, dass man Di- phenylformamidin mit quartären Salzen heterocyclischer Basen mit einer a-ständigen Methylgruppe in Reaktion treten lässt, wobei Verbindungen folgender Konstitution ent stehen:
EMI0001.0012
Der Reaktionsverlauf bei Herstellung eines derartigen Körpers ist folgender:
EMI0001.0014
Verbindungen der erwähnten Art dienen als Zwischenprodukte für die Herstellung von symmetrischen und unsymmetrischen Carbocyaninen, besitzen aber selbst keine sensibilisierende Wirkung, wie von vornherein nicht anders zu erwarten war.
Es wurde nun überraschenderweise ge funden, dass man eine Halogensilberemulsion, insbesondere eine Chlorsilberemulsion, da durch sensibilisieren kann, dass als Sensibili- sator mindestens ein Polymethinfarbstoff verwendet wird, wie er durch Kondensation eines Polyamins mit einem Aldehyd einer heterocyclischen Stickstoffverbindung erhal ten werden kann,
die in a-Stellung zum Stick stoff eine umsetzungsfähige Methylengruppe besitzt und bei der die Aldehydgruppe an Stelle eines Wasserstoffatomes der Methylen- gruppe steht.
Farbstoffe der vorliegenden Erfindung leiten sich beispielsweise von den bekannten Stoffen der oben angegebenen Formel und dem Verfahren ihrer Herstellung dadurch ab, dass an Stelle des einfachen Amins ein Di aurin (Triamin) zur Kondensation verwendet wird, und demgegenüber zwei (drei) Mole küle Aldehyd mit einem Molekül Diamin (Triamin) in Reaktion gebracht werden. Der Grundcharakter dieser Farbstoffe ist im we sentlichen der gleiche wie der der bekannten Klasse, nur ist die Farbe etwas bathochrom verschoben. Neu und vollkommen unerwartet ist, dass die Farbstoffe eine sensibilisierende Wirkung ausüben.
Die zur Ausführung des Verfahrens ge mäss der Erfindung zu verwendenden Farb stoffe haben beispielsweise die allgemeine Formel
EMI0002.0012
In dieser Formel ist Y, Z - Glied eines aromatischen Ringes, z. B.
EMI0002.0013
worin R, und R3 Alkylgruppen sind, R, = Alkyl, Ar = eine organische Gruppe, insbesondere aromatische Gruppe, beispiels weise Phenylen, Diphenylen, Naphthylen, X = ein beliebiger Säurerest, z. B. Halogen.
Weiterhin können die heterocyclischen Ringsysteme, sowie das aromatische Ring system, das die Aminogruppen trägt, ver schiedene Substituenten tragen, wobei die jenigen Substituenten ausgenommen sind, die eine ausgesprochen schädliche Wirkung auf die Sensibilisierung ausüben.
Durch die neue Klasse von Sensibilisa- toren ist die Technik der photographischen Emulsionen um eine ausserordentlich umfang reiche Gruppe von Farbstoffen bereichert werden, deren Fähigkeit zur Abwandlung durch weitgehende Substitutionsmöglichkeit eine sehr grosse ist.
Die Herstellung der Farbstoffe kann bei spielsweise nach dem Verfahren des franz. Patentes Nr. 809395 erfolgen.
Ein symmetrischer Farbstoff kann zum Beispiel wie folgt hergestellt werden: 1/" Mol des Aldehydes
EMI0002.0034
hergestellt nach Angaben der deutschen Pa tentschrift: Nr.<B>615130</B> (brit. Patentschrift Nr. 438603) werden in 10 cm' warmem Eis essig (zirka<B>50'</B> C) gelöst. Zu der gelb lichen Lösung wird in Portionen 1/0o Mol Benzidin eingetragen. Der Ansatz färbt sich sofort intensiv gelb.
Nach i/#stündigem Er wärmen auf<B>50'</B> wird mit 20 cm3 Wasser verdünnt, durch Hineinwerfen von etwas Eis abgekühlt und dann der Farbstoff durch 30%ige Kochsalzlösung ausgesalzen. Der Farbstoff wird aus Methanol umkristallisiert.
Unsymmetrische Farbstoffe können zum Beispiel in der Weise hergestellt werden, dass man zunächst etwa äquimolekulare Mengen eines aromatischen Monoacyldiamins und eines Aldehyds kondensiert, dann die Ace- tylgruppe verseift und schliesslich mit einer äquimolekularen Menge eines andern Alde hyds kondensiert.
Für die Herstellung eines unsymmetrischen Farbstoffes, bei dem sich auf beiden Seiten des Moleküls verschieden artige Indolinringe befinden, kann man zum Beispiel wie folgt vorgehen: '/so Mol 1.3.3-Trimethyl-2-methylen- indolin- )-aldehyd werden in 10 cm' Eisessig gelöst. Man gibt portionsweise 1/6o Mol Monoacetyl-para-phenylendiamin hinzu, er wärmt 1/2 Stunde auf 50 bis<B>60',</B> kühlt dann ab, verdünnt mit Wasser und salzt mit Koch salz aus.
Der abgesaugte gelbe Farbstoff wird zur Abspaltung der Acetylgruppe kurze Zeit mit 10%iger Salzsäure erwärmt. Man fügt dann 1/6o Mol 5-Methogy-1.3.3-tri- methyl-2-methylenindolin-cu-aldehyd (oder die entsprechende Menge eines andern co-A1- dehyds) hinzu und erwärmt nochmals 1/2 Stunde. Dann wird verdünnt, notfalls fil triert und mit Kochsalz ausgesalzen.
Um zu solchen unsymmetrischen Farb stoffen zu gelangen, bei denen Y und Z ver schieden sind, braucht man lediglich in dem angegebenen Beispiel 2 an Stelle des dort ver wendeten 5-Methogy-1.3.3-trimethyl-2-me- thylenindolin - c) - aldehyds einen Benzthia- zolin-Aldehyd oder einen andern heterocycli- schen. Aldehyd zu verwenden.
An den folgenden Beispielen werden weitere Farbstoffe beschrieben, die zur Aus führung, des Verfahrens Verwendung finden können: <I>Beispiel</I>
EMI0003.0031
EMI0003.0032
EMI0003.0033
EMI0003.0034
EMI0004.0001
EMI0004.0002
EMI0004.0003
EMI0004.0004
EMI0004.0005
EMI0004.0006
EMI0005.0001
EMI0005.0002
EMI0005.0003
Method for sensitizing a halide silver emulsion. It is already known that diphenylformamidine is allowed to react with quaternary salts of heterocyclic bases with a methyl group in the α position, resulting in compounds of the following constitution:
EMI0001.0012
The course of the reaction when producing such a body is as follows:
EMI0001.0014
Compounds of the type mentioned serve as intermediates for the preparation of symmetrical and asymmetrical carbocyanines, but do not themselves have a sensitizing effect, as was not to be expected from the outset.
It has now surprisingly been found that a halosilver emulsion, in particular a chlorosilver emulsion, can be sensitized by using at least one polymethine dye as sensitizer, as can be obtained by condensing a polyamine with an aldehyde of a heterocyclic nitrogen compound,
which has a reactive methylene group in the a-position to the nitrogen and in which the aldehyde group takes the place of a hydrogen atom of the methylene group.
Dyes of the present invention are derived, for example, from the known substances of the formula given above and the process of their preparation in that a di aurine (triamine) is used for condensation instead of the simple amine, and in contrast two (three) molecules of aldehyde a molecule of diamine (triamine) can be reacted. The basic character of these dyes is essentially the same as that of the known class, only the color is shifted somewhat bathochromically. What is new and completely unexpected is that the dyes have a sensitizing effect.
The dyes to be used for carrying out the method according to the invention have, for example, the general formula
EMI0002.0012
In this formula, Y, Z is a member of an aromatic ring, e.g. B.
EMI0002.0013
wherein R, and R3 are alkyl groups, R, = alkyl, Ar = an organic group, especially aromatic group, for example phenylene, diphenylene, naphthylene, X = any acid radical, e.g. B. Halogen.
Furthermore, the heterocyclic ring systems, as well as the aromatic ring system that carries the amino groups, can carry various substituents, with the exception of those substituents that have a particularly harmful effect on sensitization.
With the new class of sensitizers, the technology of photographic emulsions has been enriched by an extraordinarily extensive group of dyes, the ability of which can be modified by extensive substitution possibilities is very great.
The preparation of the dyes can for example by the method of the French. Patent No. 809395.
For example, a symmetrical dye can be made as follows: 1/ "mole of the aldehyde
EMI0002.0034
manufactured according to the German patent specification: No. 615130 (British patent specification No. 438603) are dissolved in 10 cm 'warm glacial vinegar (approx. 50' C). 1 / 0o mol of benzidine is added in portions to the yellow solution. The approach immediately turns an intense yellow.
After warming up to <B> 50 '</B> for 1.5 hours, it is diluted with 20 cm3 of water, cooled by throwing in some ice and then the dye is salted out with a 30% saline solution. The dye is recrystallized from methanol.
Unsymmetrical dyes can be prepared, for example, by first condensing approximately equimolecular amounts of an aromatic monoacyldiamine and an aldehyde, then saponifying the acetyl group and finally condensing it with an equimolecular amount of another aldehyde.
For the production of an unsymmetrical dye in which there are different types of indoline rings on both sides of the molecule, one can proceed as follows, for example: 1 / so moles of 1,3.3-trimethyl-2-methylene-indoline-) aldehyde are used in 10 cm 'glacial acetic acid dissolved. 1/60 mol of monoacetyl-para-phenylenediamine is added in portions, it is warmed to 50 to 60 'for 1/2 hour, then cools, diluted with water and salted out with sodium chloride.
The yellow dye which has been sucked off is heated for a short time with 10% hydrochloric acid to split off the acetyl group. 1/60 mole of 5-methogy-1,3.3-trimethyl-2-methyleneindoline-cu-aldehyde (or the corresponding amount of another co-aldehyde) is then added and the mixture is heated again for 1/2 hour. Then it is diluted, filtered if necessary and salted out with table salt.
To get to such asymmetrical dyes in which Y and Z are different, you only need in the given example 2 instead of the 5-methogy-1,3.3-trimethyl-2-methyleneindoline used there - c) - aldehyde a benzthiazoline aldehyde or another heterocyclic aldehyde. To use aldehyde.
The following examples describe further dyes that can be used to execute the process: <I> Example </I>
EMI0003.0031
EMI0003.0032
EMI0003.0033
EMI0003.0034
EMI0004.0001
EMI0004.0002
EMI0004.0003
EMI0004.0004
EMI0004.0005
EMI0004.0006
EMI0005.0001
EMI0005.0002
EMI0005.0003
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE197880X | 1935-10-24 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH197880A true CH197880A (en) | 1938-05-31 |
Family
ID=5756630
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH197880D CH197880A (en) | 1935-10-24 | 1936-10-20 | Process for sensitizing a silver halide emulsion. |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH197880A (en) |
-
1936
- 1936-10-20 CH CH197880D patent/CH197880A/en unknown
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