DE1112282B - Process for hardening gelatin layers, in particular photographic emulsions - Google Patents

Process for hardening gelatin layers, in particular photographic emulsions

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Publication number
DE1112282B
DE1112282B DEV15860A DEV0015860A DE1112282B DE 1112282 B DE1112282 B DE 1112282B DE V15860 A DEV15860 A DE V15860A DE V0015860 A DEV0015860 A DE V0015860A DE 1112282 B DE1112282 B DE 1112282B
Authority
DE
Germany
Prior art keywords
hardening
photographic emulsions
gelatin layers
polyoxyaromatics
particular photographic
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.)
Pending
Application number
DEV15860A
Other languages
German (de)
Inventor
Dipl-Chem Dr Emil-Joachim Birr
Dipl-Chem Dr Werner Walther
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Filmfabrik Wolfen VEB
Original Assignee
Filmfabrik Wolfen VEB
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Filmfabrik Wolfen VEB filed Critical Filmfabrik Wolfen VEB
Priority to DEV15860A priority Critical patent/DE1112282B/en
Priority claimed from FR795919A external-priority patent/FR1227588A/en
Publication of DE1112282B publication Critical patent/DE1112282B/en
Pending legal-status Critical Current

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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
    • G03C1/30—Hardeners
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C47/00—Compounds having —CHO groups
    • C07C47/52—Compounds having —CHO groups bound to carbon atoms of six—membered aromatic rings
    • C07C47/56—Compounds having —CHO groups bound to carbon atoms of six—membered aromatic rings containing hydroxy groups
    • C07C47/57—Compounds having —CHO groups bound to carbon atoms of six—membered aromatic rings containing hydroxy groups polycyclic

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Description

BUNDESREPUBLIK DEUTSCHLAND KL.39b 17 FEDERAL REPUBLIC OF GERMANY KL. 39b 17

INTERNAT.Ki. C 08 hINTERNAT.Ki. C 08 h

DEUTSCHESGERMAN

PATENTAMTPATENT OFFICE

AUSLEGESCHRIFT 1112 282EXPENDITURE 1112 282

Vl5860IVb/39bVl5860IVb / 39b

ANMELDETAG: 30. JANUAR 1959REGISTRATION DATE: JANUARY 30, 1959

BEKANNTMACHUNG
DER ANMELDUNG
UNDAUSGABEDER
AUSLEGESCHRIFT: 3. AU GU S T 1961 NOTICE
THE REGISTRATION
ANDOUTPUTE
EDITORIAL: 3rd AU GU ST 1961

Es ist bekannt, photographischen Halogensilber-Gelatine-Emulsionen zur Beschleunigung der Härtung oder zur Vermeidung des Nachhärtens neben dem üblichen Härtungsmittel einen sogenannten Härtungsbeschleuniger zuzusetzen. Bei diesem Beschleuniger handelt es sich im allgemeinen um ein Polyoxybenzol, das gegebenenfalls durch eine Aldehydgruppe substituiert ist. Das bekannteste Beispiel dieser Gruppe ist der 2,4-Dioxy-benzaldehyd oder Resorcylaldehyd(a).It is known to use silver halide photographic gelatin emulsions to accelerate hardening or to avoid post-hardening, a so-called hardening accelerator can be added in addition to the usual hardening agent. With this accelerator it is generally a polyoxybenzene, which is optionally substituted by an aldehyde group is. The best-known example of this group is 2,4-dioxy-benzaldehyde or resorcylaldehyde (a).

Es wurde nun gefunden, daß man eine Beschleunigung der Härtung über den bisherigen Stand der Technik hinaus erzielen kann, wenn man als Härtungsbeschleuniger solche Polyoxyaromaten oder bzw. und solche ihrer Aldehydderivate anwendet, die mindestens zwei Benzolkerne in nichtkondensierter Form enthalten. It has now been found that there is an acceleration the hardening can be achieved beyond the previous state of the art if such polyoxyaromatic compounds or / and uses those of their aldehyde derivatives which contain at least two benzene nuclei in non-condensed form.

Als besonders geeignet im Sinne der Erfindung haben sich beispielsweise erwiesen:For example, the following have proven to be particularly suitable for the purposes of the invention:

(b) 2,4,2',5'-Tetraoxydiphenyl-(l,l'); Resorcyl-hydrochinon (b) 2,4,2 ', 5'-tetraoxydiphenyl- (1,1'); Resorcyl hydroquinone

OHOH

OHOH

OHOH

OH Verfahren zum Härten von Gelatineschichten, insbesondere photographischen EmulsionenOH Process for hardening gelatin layers, especially photographic emulsions

Anmelder:Applicant:

VEB Filmfabrik Agfa Wolfen, Wolfen (Kr. Bitterfeld)VEB Filmfabrik Agfa Wolfen, Wolfen (district of Bitterfeld)

Dipl.-Chem. Dr. Emil-Joachim Birr und Dipl.-Chem. Dr. Werner Walther,Dipl.-Chem. Dr. Emil-Joachim Birr and Dipl.-Chem. Dr. Werner Walther,

Wolfen (Kr. Bittelfeld), sind als Erfinder genannt wordenWolfen (Kr. Bittelfeld) have been named as the inventor

(e) 3,4,3',4'-Tetraoxy-(l,l')-diphenyl-(5,5')-disulfonsäure-dimethylmethan (e) 3,4,3 ', 4'-tetraoxy- (l, l') -diphenyl- (5,5 ') -disulfonic acid-dimethylmethane

SOoHSOoH

OHOH

(c) 3,4,2',5'-Tetraoxydiphenyl-(l,l'); Brenzcatechinyl-hydrochinon (c) 3,4,2 ', 5'-tetraoxydiphenyl- (1,1'); Catechinyl hydroquinone

OHOH

OHOH

OHOH

OHOH

(f) 3,4,3',4'-Tetraoxy-(l,l')-diphenyl-methanol(f) 3,4,3 ', 4'-tetraoxy- (l, l') -diphenyl-methanol

OH-OH-

CHOH- <CHOH- <

>—OH> —OH

OHOH

OHOH

(d) 3,4,3',4'-Tetraoxy-diphenyl-(l,l')-dimethylmethan (g) 2,4,2',5'-Tetraoxy-(l,l')-diphenyl-5-aldehyd(d) 3,4,3 ', 4'-tetraoxy-diphenyl- (l, l') -dimethylmethane (g) 2,4,2 ', 5'-tetraoxy- (l, l') -diphenyl-5 -aldehyde

CH3 CH3 CH 3 CH 3

OHOH

CHO
—OHCHO
-OH

OHOH

OH OH OHOH OH OH

109 650/430109 650/430

(h) 3,4,2',5'-Tetraoxy-(l,l')-diphenyl-5-aldehyd
OH CHO(h) 3,4,2 ', 5'-tetraoxy- (l, l') -diphenyl-5-aldehyde
OH CHO

-OH-OH

OHOH

OHOH

(i) 2,4,2',4'-Tetraoxydiphenyl-(l,l')-sulfon
OH— ζ (i) 2,4,2 ', 4'-tetraoxydiphenyl (1,1') sulfone
OH— ζ

OHOH

OHOH

Diese Verbindungen lassen sich beispielsweise in hier nicht beanspruchter Weise folgendermaßen herstellen: These connections can be established as follows, for example, in a manner not claimed here:

Brenzcatechinyl-hydrochinonCatechinyl hydroquinone

22 g Brenzcatechin werden mit 21,6 g Chinon im Ölbad geschmolzen. Es tritt heftige Reaktion ein. Danach erwärmt man noch 30 Minuten, läßt erkalten und kocht mit Benzol aus. Beim Erkalten dieser benzolischen Lösung fällt das Brenzcatechinyl-hydrochinon aus.22 g of catechol are melted with 21.6 g of quinone in an oil bath. A violent reaction occurs. Then it is heated for another 30 minutes, allowed to cool and boiled with benzene. When this cools down The catechinyl hydroquinone precipitates in a benzene solution.

3,4,3',4'-Tetraoxy-diphenyl-(l, 1 ')-dimethylmethan3,4,3 ', 4'-tetraoxydiphenyl- (1,1') -dimethylmethane

29 g Brenzcatechin werden mit 7,2 cm3 Aceton und 20 cm3 konzentrierter Salzsäure 6 Stunden unter Rückfluß erhitzt. Nach 3 Stunden beginnt das Produkt auszufallen. Zur Reinigung wäscht man mit heißem Wasser. Fp. 284 bis 2860C.29 g of pyrocatechol are refluxed for 6 hours with 7.2 cm 3 of acetone and 20 cm 3 of concentrated hydrochloric acid. After 3 hours the product begins to precipitate. Wash with hot water for cleaning. Mp. 284 to 286 0 C.

3,4,3',4'-Tetraoxy-(l, 1 ')-diphenyl-(5,5')-disulfonsäure-dimethylmethan 3,4,3 ', 4'-tetraoxy- (1,1') -diphenyl- (5,5 ') -disulfonic acid-dimethylmethane

Die Darstellung erfolgt analog dem vorigen Beispiel mit Brenzcatechinsulfonsäure oder durch Sulfurierung des Tetraoxy-diphenyl-(l,l')-dimethylmethans mit Aminosulfonsäure.The representation is analogous to the previous example with catechol sulfonic acid or by sulfurization of tetraoxydiphenyl- (l, l ') - dimethylmethane with aminosulfonic acid.

2,4,2',5-Tetraoxy-(l, 1 ')-diphenyl-5-aldehyd2,4,2 ', 5-tetraoxy- (1,1') -diphenyl-5-aldehyde

109 g Resorcyl-hydrochinon werden in 600 cm3 Äther gelöst und mit 88 g trockenem Zinkcyanid versetzt. Unter Rühren und guter Kühlung leitet man trockenen Chlorwasserstoff bis zur Sättigung ein. Man dekantiert vom entstandenen Imidchlorid und zersetzt dieses mit 10%iger Schwefelsäure. Fp. 1720C.109 g of resorcyl hydroquinone are dissolved in 600 cm 3 of ether and 88 g of dry zinc cyanide are added. With stirring and good cooling, dry hydrogen chloride is passed in until it is saturated. The imide chloride formed is decanted and decomposed with 10% sulfuric acid. Mp. 172 0 C.

2,4,2',4'-Tetraoxydiphenyl-(l,l')-sulfon2,4,2 ', 4'-tetraoxydiphenyl (l, l') sulfone

Die Darstellung erfolgt durch Oxydation des entsprechenden Sulfids mit Wasserstoffsuperoxyd in Eisessig auf dem Wasserbad (Journ. Am. Chem. Soc, 53 [1931], S. 3466).It is represented by oxidation of the corresponding sulfide with hydrogen peroxide in Glacial acetic acid on a water bath (Journ. Am. Chem. Soc, 53 [1931], p. 3466).

Als Beispiel für die Wirksamkeit der Verbindungen, die selbst in den in der nachstehenden Tabelle angeführten Mengen praktisch keine oder nur eine geringe Härtungswirkung aufweisen, sei ihre An-Wendung zusammen mit Diacetyl als Härtungsmittel in einer Ammoniak-Bromjodsilber-Gelatine-Emulsion angeführt. Pro Liter Emulsion sind 0,33 bzw. 0,66 g Diacetyl sowie 0,13 g des Härtungsbeschleunigers (a bis i) angewandt worden. Die angegebenen Schmelzpunkte sind sofort nach dem Vergießen und nach einer Aufbewahrung von 2 Tagen bei 5O0C festgestellt worden.As an example of the effectiveness of the compounds, which even in the amounts listed in the table below have practically no or only a slight hardening effect, their use together with diacetyl as hardening agent in an ammonia-bromoiodosilver-gelatin emulsion is given. 0.33 and 0.66 g of diacetyl and 0.13 g of the curing accelerator (a to i) were used per liter of emulsion. The melting points given are determined immediately after casting and after storage of 2 days at 5O 0 C.

Diacetyl
pro Liter
EmulsionDiacetyl
per liter
emulsion Beschleuniger
0,13 g pro Liter
Emulsionaccelerator
0.13 g per liter
emulsion Schme]
sofortSchme]
immediately zpunkte
nach
2 Tagenzpoints
after
2 days SS. bei 50° Cat 50 ° C 31,631.6 32,032.0 0,330.33 —- 32,032.0 35,035.0 0,660.66 —- 32,332.3 42,042.0 0,330.33 aa 34,334.3 36,336.3 0,660.66 aa 36,036.0 58,258.2 0,330.33 bb 35,035.0 49,049.0 0,330.33 CC. 35,235.2 70,070.0 0,660.66 dd 36,736.7 65,065.0 0,660.66 ee 36,536.5 68,068.0 0,330.33 ff 32,532.5 39,039.0 0,660.66 gG 37,637.6 70,070.0 0,660.66 hH 35,835.8 70,070.0 0,330.33 ii 32,332.3 39,039.0

Die gemeinsame Verwendung von Härtungsmittel und Härtungsbeschleuniger kann in verschiedener Weise vorgenommen werden. Man kann diese Mittel so anwenden, daß sie gleichzeitig oder nacheinander auf die zu härtende Schicht wirken. So können die Substanzen zusammen der zu vergießenden Emulsion,The joint use of curing agent and curing accelerator can be in various Way to be made. One can use these remedies in such a way that they can be used simultaneously or one after the other act on the layer to be hardened. So the substances can be used together in the emulsion to be poured,

einer Unterschicht oder einem Überguß zugesetzt werden, oder der eine der beiden Reaktionsteilnehmer kann der einen und der zweite einer anderen der genannten Schichten zugefügt werden, so z. B. das Härtungsmittel der Emulsion und der Härtungs-be added to an underlayer or an overcoat, or one of the two reactants one and the second can be added to another of the layers mentioned, e.g. B. that Hardeners of the emulsion and hardening

beschleuniger dem Überzug oder umgekehrt.accelerate the coating or vice versa.

Als Härtungsmittel können beispielsweise angewandt werden: Aldehyde oder Aldehyd abspaltende Verbindungen wie Formaldehyd, Glyoxal, Mucochlorsäure oder Trimethylolmelamin, ferner Diketone wie Diacetyl, oder Nitroalkohole wie Nitropropandiol.Examples of hardening agents that can be used are: aldehydes or aldehyde-releasing agents Compounds such as formaldehyde, glyoxal, mucochloric acid or trimethylolmelamine, and also diketones such as Diacetyl, or nitro alcohols such as nitropropanediol.

Beispiel 1example 1

Einer Bromsüber-Gelatine-Emulsion werden vor dem Vergießen 0,40 g Glyoxal und 0,15 g Brenzcatechinyl-hydrochinon pro 11 Emulsion zugesetzt. Nach dem Trocknen erhält man eine tropenfeste Filmschicht.0.40 g of glyoxal and 0.15 g of catechinyl-hydroquinone are added to a bromine-over-gelatine emulsion before pouring added per 11 emulsion. After drying, a tropicalized film layer is obtained.

Beispiel 2Example 2

Einer Bromjodsilber-Gelatine-Emulsion werden vor dem Vergießen 0,45 g Diacetyl pro Liter zugesetzt. Der darübergegossene Überzug erhält einen Zusatz von 1 g 3,4,3',4'-Tetraoxy-diphenyl-(l,l')-dimethylmethan pro Liter. Das auf diese Weise erhaltene Material läßt sich in Lösungen bei erhöhter Temperatur verarbeiten.0.45 g of diacetyl per liter are added to a silver bromide gelatin emulsion before pouring. The coating poured over it receives an addition of 1 g of 3,4,3 ', 4'-tetraoxydiphenyl- (l, l') - dimethylmethane per liter. The material obtained in this way can be dissolved in solutions at elevated temperature to process.

Claims (2)

PATENTANSPRÜCHE:PATENT CLAIMS: 1. Verfahren zum Härten von Gelatineschichten, insbesondere photographischen Emulsionen, unter Verwendung von Polyoxyaromaten als Härtungsbeschleuniger neben Härtungsmitteln, dadurch gekennzeichnet, daß man solche Polyoxyaromaten oder bzw. und solche ihrer Aldehydderivate anwendet, die mindestens zwei Benzolkerne in nichtkondensierter Form enthalten.1. A process for hardening gelatin layers, especially photographic emulsions, using polyoxyaromatics as hardening accelerators in addition to hardeners, characterized in that polyoxyaromatics or those of their aldehyde derivatives which contain at least two benzene nuclei in non-condensed form are used. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die Härtungsmittel und Polyoxyaromaten so angewandt werden, daß sie gleichzeitig oder nacheinander auf die zu härtende Schicht einwirken.2. The method according to claim 1, characterized in that the curing agents and polyoxyaromatics be applied so that they act simultaneously or sequentially on the layer to be hardened. In Betracht gezogene Druckschriften:
Deutsche Patentschrift Nr. 837 955.Considered publications:
German patent specification No. 837 955. © 109 650/430 7.61© 109 650/430 7.61
DEV15860A 1959-01-30 1959-01-30 Process for hardening gelatin layers, in particular photographic emulsions Pending DE1112282B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
DEV15860A DE1112282B (en) 1959-01-30 1959-01-30 Process for hardening gelatin layers, in particular photographic emulsions

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEV15860A DE1112282B (en) 1959-01-30 1959-01-30 Process for hardening gelatin layers, in particular photographic emulsions
FR795919A FR1227588A (en) 1959-05-28 1959-05-28 Process for hardening gelatin layers, in particular photographic emulsions

Publications (1)

Publication Number Publication Date
DE1112282B true DE1112282B (en) 1961-08-03

Family

ID=26001333

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3236652A (en) * 1963-01-10 1966-02-22 Eastman Kodak Co Stabilized silver halide emulsions
WO2008148747A2 (en) * 2007-06-08 2008-12-11 University Of Copenhagen Pdz domain modulators
WO2019039565A1 (en) * 2017-08-24 2019-02-28 三菱ケミカル株式会社 Dihydroxybiphenyl compound, bisphosphite compound, catalyst, method for producing aldehydes, and method for producing alcohol

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE837955C (en) * 1948-12-16 1952-05-05 Gen Aniline & Film Corp Hardened photographic films with improved properties

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE837955C (en) * 1948-12-16 1952-05-05 Gen Aniline & Film Corp Hardened photographic films with improved properties

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3236652A (en) * 1963-01-10 1966-02-22 Eastman Kodak Co Stabilized silver halide emulsions
WO2008148747A2 (en) * 2007-06-08 2008-12-11 University Of Copenhagen Pdz domain modulators
WO2008148747A3 (en) * 2007-06-08 2009-07-09 Univ Copenhagen Pdz domain modulators
WO2019039565A1 (en) * 2017-08-24 2019-02-28 三菱ケミカル株式会社 Dihydroxybiphenyl compound, bisphosphite compound, catalyst, method for producing aldehydes, and method for producing alcohol
JPWO2019039565A1 (en) * 2017-08-24 2020-10-01 三菱ケミカル株式会社 Method for producing dihydroxybiphenyl compound, bisphosphite compound, catalyst, aldehydes and alcohol
US10793497B2 (en) 2017-08-24 2020-10-06 Mitsubishi Chemical Corporation Dihydroxybiphenyl compound, bisphosphite compound, catalyst, production method of aldehydes, and production method of alcohol

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