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DE1259701B - Process for the preparation of direct positive dye photographic images - Google Patents

Process for the preparation of direct positive dye photographic images

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Publication number
DE1259701B
DE1259701B DEA49535A DEA0049535A DE1259701B DE 1259701 B DE1259701 B DE 1259701B DE A49535 A DEA49535 A DE A49535A DE A0049535 A DEA0049535 A DE A0049535A DE 1259701 B DE1259701 B DE 1259701B
Authority
DE
Germany
Prior art keywords
products
amidrazones
phenyl
compounds
react
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
DEA49535A
Other languages
German (de)
Inventor
Dr Paul Marx
Dr Walter Pueschel
Dr Karl-Wilhelm Schranz
Dr Wolfgang Laessig
Dr Hans-Heinrich Credner
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.)
Agfa Gevaert AG
Original Assignee
Agfa Gevaert AG
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
Priority to DEA46672A priority Critical patent/DE1213241B/en
Priority to DEA49001A priority patent/DE1259700B/en
Application filed by Agfa Gevaert AG filed Critical Agfa Gevaert AG
Priority to DEA49534A priority patent/DE1257570B/en
Priority to DEA49535A priority patent/DE1259701B/en
Priority to US470615A priority patent/US3443942A/en
Priority to CH991765A priority patent/CH456343A/en
Priority to NL6509590A priority patent/NL6509590A/xx
Priority to GB31542/65A priority patent/GB1123782A/en
Priority to FR1592055D priority patent/FR1592055A/fr
Priority to BE667369D priority patent/BE667369A/xx
Publication of DE1259701B publication Critical patent/DE1259701B/en
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D215/38—Nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D215/38—Nitrogen atoms
    • C07D215/42—Nitrogen atoms attached in position 4
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/06—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D231/38—Nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D231/38—Nitrogen atoms
    • C07D231/42—Benzene-sulfonamido pyrazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
    • C07D277/62—Benzothiazoles
    • C07D277/68—Benzothiazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
    • C07D277/82—Nitrogen atoms
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/18—Processes for the correction of the colour image in subtractive colour photography
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)

Description

BUNDESREPUBLIK DEUTSCHLANDFEDERAL REPUBLIC OF GERMANY

G03cG03c

DEUTSCHESGERMAN

PATENTAMTPATENT OFFICE

AUSLEGESCHRIFTEDITORIAL

Int. CL:Int. CL:

Deutsche Kl.: 57 b -German class: 57 b -

Nummer:
Aktenzeichen:
Anmeldetag:
Auslegetag:Number:
File number:
Registration date:
Display day:

A49535IX a/57b
21.Juni 1965
25. Januar 1968A49535IX a / 57b
June 21, 1965
January 25, 1968

Das Hauptpatent betrifft ein Verfahren zur Herstellung von direktpositiven Farbstoffbildern unter Verwendung eines lichtempfindlichen Materials, das mindestens eine Halogensilberemulsionsschicht enthält, in die Amidrazone oder deren vinyloge, phenyloge oder azavinyloge Derivate eingebettet sind, die mit photographischen Schwarz-Weiß- oder Farbentwicklern zu farblosen Produkten reagieren, bei dem nach dem Entwickeln mit einem oxydierenden Bad gebleicht und anschließend fixiert wird, wobei die oxydierende Bleichung in Gegenwart von Verbindungen durchgeführt wird, die nicht oder nur unter Bildung farbloser Produkte oder solcher Produkte, die im Laufe des photographischen Verarbeitungsganges - farblos werden, mit Entwickler-Oxydationsprodukten reagieren, die vorzugsweise selbst keine Entwicklungswirkung besitzen und die sich mit den Oxydationsprodukten der Amidrazone zu farbigen Verbindungen umsetzen.The main patent relates to a process for the production of direct positive dye images under Use of a photosensitive material which contains at least one halogen silver emulsion layer, are embedded in the amidrazones or their vinylogous, phenylogous or azavinylogous derivatives, which react with photographic black and white or color developers to form colorless products which is bleached after developing with an oxidizing bath and then fixed, whereby the oxidative bleaching is carried out in the presence of compounds that are not or only with the formation of colorless products or those products which in the course of the photographic processing cycle - become colorless, react with developer oxidation products, which preferably themselves have no developmental effect and which are associated with the oxidation products of the amidrazones implement colored connections.

Bei der Weiterentwicklung des Verfahrens des Hauptpatentes wurde ■ nun gefunden, daß für den obigen Zweck l-Phenyl-J2-pyrazoline, insbesondere solche, die in 3,4- oder 5-Stellung oder am 1-Phenylring einen aliphatischen Rest bis zu 20 C-Atomen enthalten, geeignet sind. Durch oxidative Kupplung mit den Amidrazonen entstehen vorwiegend blaugrüne Farbstoffe. In the further development of the process of the main patent it has now been found that for the Above purpose l-phenyl-J2-pyrazolines, especially those in the 3,4- or 5-position or on the 1-phenyl ring contain an aliphatic radical of up to 20 carbon atoms, are suitable. By oxidative coupling with the amidrazones, mainly blue-green dyes are formed.

Besonders geeignet sind l-Phenyl-J2-pyrazoline der folgenden Formel:L-Phenyl-J2-pyrazolines of the following formula are particularly suitable:

worin die Substituenten R gleich oder verschieden sein können und die folgende Bedeutung besitzen: R gleich Wasserstoff, Carboxyl, verestertes Carboxyl, vorzugsweise mit aliphatischen Alkoholen bis zu 20 C-Atomen, Carbamyl, N-Alkylcarbamyl mit Alkylgruppen bis zu 20 C-Atomen, N-Phenylcarbamyl, Alkyl bis zu 20 C-Atomen, Aryl, wie Phenyl oder Naphthyl, oder Aralkyl, wie Benzyl oder Phenyläthyl, wobei die obigen Substituenten insbesondere die Phenylringe ihrerseits substituiert sein könnenin which the substituents R can be identical or different and have the following meanings: R is hydrogen, carboxyl, esterified carboxyl, preferably with aliphatic alcohols up to 20 carbon atoms, carbamyl, N-alkylcarbamyl with alkyl groups up to 20 carbon atoms, N-phenylcarbamyl, alkyl up to 20 carbon atoms, aryl, such as phenyl or Naphthyl, or aralkyl, such as benzyl or phenylethyl, the above substituents in particular the phenyl rings in turn can be substituted

Verfahren zur Herstellung von photographischen direktpositiven FarbstoffbildernProcess for the preparation of direct positive dye photographic images

Zusatz zum Patent: 1 213 241Addendum to the patent: 1 213 241

Anmelder:Applicant:

Agfa-Gevaert Aktiengesellschaft,Agfa-Gevaert Aktiengesellschaft,

5090 Leverkusen, Kaiser-Wilhelm-Allee 245090 Leverkusen, Kaiser-Wilhelm-Allee 24

Als Erfinder benannt:
Dr. Paul Marx, 5000 Köln-Buchheim;
Dr. Walter Püschel, 5090 Leverkusen;
Dr. Karl-Wilhelm Schranz, 5670 Opladen;
Dr. Wolfgang Lässig, 5000 Köln-Stammheim;
Dr. Hans-Heinrich Credner, 8000 MünchenNamed as inventor:
Dr. Paul Marx, 5000 Cologne-Buchheim;
Dr. Walter Püschel, 5090 Leverkusen;
Dr. Karl-Wilhelm Schranz, 5670 Opladen;
Dr. Wolfgang Lässig, 5000 Cologne-Stammheim;
Dr. Hans-Heinrich Credner, 8000 Munich

mit Substituenten, wie Nitro, Halogen, wie Chlor oder Brom, Alkyl mit vorzugsweise bis zu 5 C-Atomen, wie Methyl oder Äthyl, Hydroxyl, Alkoxy, ebenfalls mit vorzugsweise bis zu 5 C-Atomen, wie Methoxy oder Äthoxy, Carboxyl, Carboxyester mit vorzugsweise bis zu 5 C-Atomen, Amino, Alkylamino, Phenylamino, Acylamino, wobei die Acylgruppen vorzugsweise von aliphatischen Carbonsäuren abgeleitet sind, wie Acetylamino oder Benzylamino, ferner Sulfoamino, Sulfonyl, Alkysulfonyl oder Phenysulfonyl oder auch veresterte Sulfogruppen, insbesondere Ester mit aliphatischen Carbonsäuren, die bis zu 20 C-Atomen haben. Der Phenylring der obigen Formel kann ferner in einfacher Weise substituiert sein oder diese in anellierter Form enthalten.with substituents such as nitro, halogen, such as chlorine or bromine, alkyl with preferably up to 5 carbon atoms, such as methyl or ethyl, hydroxyl, alkoxy, also preferably with up to 5 carbon atoms, such as methoxy or ethoxy, carboxyl, carboxy ester with preferably up to 5 carbon atoms, amino, alkylamino, phenylamino, Acylamino, where the acyl groups are preferably derived from aliphatic carboxylic acids, such as acetylamino or benzylamino, also sulfoamino, Sulphonyl, alkysulphonyl or phenysulphonyl or also esterified sulpho groups, in particular esters with aliphatic carboxylic acids that have up to 20 carbon atoms. The phenyl ring of the above formula can can also be substituted in a simple manner or contain these in fused form.

Bevorzugt sind solche Verbindungen, die in 3-Stellung des Pyrazolinringes substituiert sind.Those compounds which are in the 3-position are preferred of the pyrazoline ring are substituted.

Der Phenylring der obigen Formel kann ferner durch weitere Phenyl- oder auch Naphthylringe in einfacher Weise substituiert sein oder diese in anellierter Form enthalten. Da selbstverständlich auch die Substituenten am Phenylring der obigen Formel ihrerseits substituiert sein können, ergeben sich vielfältige Variationsmöglichkeiten, wobei bestimmte Eigenschaften wie die Löslichkeit oder die Farbe des Umsetzungsproduktes mit den oxydierten Amidrazonen in vorteilhafter Weise modifiziert werden können. Bei der Auswahl der Substituenten istThe phenyl ring of the above formula can also be replaced by further phenyl or naphthyl rings in be easily substituted or contain them in fused form. Since, of course, that too Substituents on the phenyl ring of the above formula can in turn be substituted, there are many Possible variations, with certain properties such as solubility or color of the reaction product can be modified in an advantageous manner with the oxidized amidrazones can. When choosing the substituents is

709 720/453709 720/453

lediglich dafür Sorge zu tragen, daß die resultierenden nicht oder unter Bildung farbloser Produkte reagieren.only to ensure that the resulting products do not react or react with the formation of colorless products.

Produkte die photographischen Eigenschaften des Bevorzugt sind Verbindungen mit Substituenten, dieProducts having photographic properties of the Preferred are compounds with substituents that

Materials nicht negativ beeinflussen und unter den das Molekül diffusionsfest machen,Do not negatively affect the material and make the molecule diffusion-resistant under

üblichen photographischen Verarbeitungsbedingun- " Im einzelnen werden die folgenden VerbindungenUsual photographic processing conditions. Specifically, the following compounds

gen mit Entwicklern bzw. deren Oxydationsprodukten 5 erwähnt:genes with developers or their oxidation products 5 mentioned:

H2C-H2C H 2 CH 2 C

CH2 C = OCH 2 C = O

H IHI

C — CH2 — CH —C - CH 2 - CH -

H=IO-IOOH = IO-100

SO,HSO, H

H2C-H2C H 2 CH 2 C

CH2 C = OCH 2 C = O

H
— C-H
- C-

H IHI

- C — CH2 — CH —- C - CH 2 - CH -

— c-- c- ΛΛ NN υυ -CH2 -CH 2 CH
/CH
/ //

C=O C = OC = O C = O

NH OHNH OH

=to-100= to-100

Zur Darstellung von 3-subst.-J2-Pyrazolinen setzt man Vinylketone (wie z. B. Methylvinylketon, Mesityloxid und Chalkone) oder ß-Chloräthylenketone mit Phenylhydrazin um. In den überwiegenden Fällen tritt unmittelbarer Ringschluß ein, andernfalls erhitzt man die Hydrazone in Eisessig.To prepare 3-substituted-I2-pyrazolines, vinyl ketones (such as, for example, methyl vinyl ketone, mesityl oxide and chalcones) or ß-chloroethylene ketones with phenylhydrazine. In the majority of cases it occurs immediate ring closure, otherwise the hydrazones are heated in glacial acetic acid.

BeispieleExamples

a) CH3-C-CH = CH2 +
Oa) CH 3 -C -CH = CH 2 +
O

-NH,-NH,

CH,— CCH, - C

■=/ H■ = / H

b) R-C-CH2-CH2-Cl + / %—Nb) RC-CH 2 -CH 2 -Cl + / % -N

Il X=/ HII X = / H

NH,NH,

M. M air e, Bull. Soc. Chim. France (4) 3, 272 bis 280 (1908);M. Mair e, Bull. Soc. Chim. France (4) 3, 272-280 (1908);

K. v. A u ν e r s, A. K r e u d e r, Bd. 58, 1947 bis 1986 [1980] (1925).K. v. A u ν e r s, A. K r e u d e r, Vol. 58, 1947 to 1986 [1980] (1925).

C-O C-O

A. F. Plue, USA.-Patentschrift 2 976 295, 17.12. 1958/21.3.1961; General Aniline Film Corp. New York, N. Y.A. F. Plue, U.S. Patent 2,976,295, December 17. 1958 / March 21, 1961; General Aniline Film Corp. New York, N. Y.

Die Herstellung der Verbindung... sei im folgenden im einzelnen beschrieben: 63 g p-Nitrobenzalacetophenon, 300 ml Eisessig und 33 g Phenylhydrazin werden vereinigt und etwa 1 Stunde unter Rückfluß erhitzt. Nach dem Abkühlen wird das Reaktionsprodukt mit Wasser gefällt und abgesaugt; Fp. 1130C (Kristallisat aus Alkohol).The preparation of the compound ... is described in detail below: 63 g of p-nitrobenzalacetophenone, 300 ml of glacial acetic acid and 33 g of phenylhydrazine are combined and refluxed for about 1 hour. After cooling, the reaction product is precipitated with water and filtered off with suction; Mp. 113 0 C (crystals from alcohol).

Das Produkt wird anschließend in einem Gemisch von Methanol und Tetrahydrofuran gelöst und bei 50°C, 50 atü Wasserstoff mit Raney-Nickel hydriert. Das Lösungsmittelgemisch wird im Vakuum bis zur Trockne abdestilliert, der zähflüssige Rückstand in wenig Methanol aufgenommen, vom unlöslichen öl abgetrennt und die Aminoverbindung mit Wasser gefällt; Fp. 117°C (Methanol).The product is then dissolved in a mixture of methanol and tetrahydrofuran and at 50 ° C, 50 atm. Hydrogen hydrogenated with Raney nickel. The solvent mixture is in vacuo up to Distilled off dry, the viscous residue taken up in a little methanol, from the insoluble oil separated and the amino compound precipitated with water; M.p. 117 ° C (methanol).

5 g Polyvinylpyrrolidon-Maleinsäureanhydrid werden in 50 ml Eisessig, der auf 900C erwärmt worden ist, eingetragen. Dann werden sofort 5 g 1,3-Diphenyl-5-(p-aminophenyl)-2-pyrazolin — gelöst in 25 ml Dimethylformamid — zugegeben. Nach 20 Minuten bei 9O0C wird unter kräftigem Rühren auf Methanol ausgetragen, abgesaugt, zweimal mit Methanol nachgewaschen und getrocknet. Ausbeute: 7 g.5 g of polyvinylpyrrolidone-maleic anhydride are introduced into 50 ml of glacial acetic acid which has been heated to 90 0 C. Then immediately 5 g of 1,3-diphenyl-5- (p-aminophenyl) -2-pyrazoline - dissolved in 25 ml of dimethylformamide - are added. After 20 minutes at 9O 0 C is discharged with vigorous stirring to methanol, suction filtered, washed twice with methanol and dried. Yield: 7 g.

Als Amidrazone sind die in dem Hauptpatent beschriebenen Verbindungen geeignet. Dabei sind unter Amidrazonen allgemein Verbindungen zu verstehen, die die GruppierungThe compounds described in the main patent are suitable as amidrazones. Thereby are under Amidrazones generally mean compounds that represent the grouping

4545

N —N -

N-NN-N

enthalten oder deren vinylenhomologe, phenylenhomologe oder azavinylenhomologe Verbindungen. Unter den homologen Verbindungen sind solche zu N — NH2 Eisessig
Hcontain or their vinylene-homologous, phenylene-homologous or azavinylene-homologous compounds. Among the homologous compounds are those with N - NH 2 glacial acetic acid
H

verstehen, die die obige Gruppierung enthalten, wobei jedoch in der Formel zwischen dem Kohlenstoffatom und der Amingruppierung eine Vinylengruppierung, ein Phenylenrest oder eine Azomethingruppe enthalten ist.
Die folgende Verbindung ist besonders geeignet:which contain the above group, but in the formula, a vinylene group, a phenylene group or an azomethine group is contained between the carbon atom and the amine group.
The following connection is particularly suitable:

H
NH-C-C-C15H31 H
NH-CCC 15 H 31

O SO3HO SO 3 H

Die Amidrazone werden der Halogensilberemulsion in Mengen von 1 bis 120,vorzugsweise 15 bis 70 g pro Mol Halogensilber in einem beliebigen Stadium der Herstellung der Emulsion zugesetzt, vorzugsweise nach der chemischen Reifung vor dem Vergießen. Für die Durchführung des erfindungsgemäßen Verfahrens sind die üblichen Verarbeitungsbäder geeignet. The amidrazones are the halide silver emulsion in amounts of 1 to 120, preferably 15 to 70 g per Moles of halogen silver added at any stage in the preparation of the emulsion, preferably after chemical ripening before potting. For carrying out the method according to the invention the usual processing baths are suitable.

Die in der erfindungsgemäßen Weise verwendeten Amidrazone bzw. die 1-Phenyl- 12-pyrazoline können diffusionsfest, in gelöster oder einemulgierter Form den photographischen Schichten, insbesondere den lichtempfindlichen Silberhalogenidemulsionsschichten, zugesetzt werden.The amidrazones or the 1-phenyl-12-pyrazolines used in the manner according to the invention can diffusion-resistant, in dissolved or emulsified form, the photographic layers, especially the light-sensitive silver halide emulsion layers.

Die erfindungsgemäß zu verwendenden Pyrazoline werden den photographischen Schichten vorzugsweise in Mengen von 1 bis 120, insbesondere 15 bis 70 g pro Mol Halogensilber zugesetzt.The pyrazolines to be used in the present invention are preferred to the photographic layers added in amounts of 1 to 120, in particular 15 to 70 g per mole of halosilver.

Die Pyrazoline können jedoch auch nach dem bekannten Einentwicklungsverfahren angewendet werden, wobei sie einem zwischen den Entwickler und dem Bleichbad zu verwendenden Bad zugesetzt werden. The pyrazolines can, however, also be used according to the known development process, added to a bath to be used between the developer and the bleach bath.

Das erfindungsgemäße Verfahren ist sowohl zur Herstellung einfarbiger als auch mehrfarbiger Direktpbsitivbilder geeignet. Die zuerst genannten einfarbigen Bilder können dabei als Masken wirken. Im Fall sogenannter eingebauter Masken können die Farbbilder, in konventioneller Weise hergestellt werden. Für die Herstellung mehrfarbiger photographischer Bilder werden photographische Mehrschichtmaterialien verwendet, die in üblicher Weise lichtempfindliche Schichten enthalten, die gegenüber den drei Grundfarben des Spektrums empfindlich sind. Die Mehrfarbenbilder werden dabei nach dem bekannten subtraktiven Prinzip erzeugt.The method according to the invention is suitable for the production of both single-color and multicolor direct-print images suitable. The first-mentioned monochrome pictures can act as masks. In the case So-called built-in masks, the color images can be produced in a conventional manner. Multilayer photographic materials are used for the production of multicolor photographic images used, which in the usual way contain light-sensitive layers opposite the three Primary colors of the spectrum are sensitive. The multicolor images are made according to the known generated subtractive principle.

Beispiel Eine 1 g der Verbindung 1. und 1 g des AmidrazonsExample One 1 g of compound 1 and 1 g of the amidrazone

N —NH-SO,N -NH-SO,

auf 100 ml enthaltende Bromsilberemulsion wird auf einen geeigneten Träger aufgebracht, belichtet und 5 Minuten bei 20° C in dem nachstehenden Entwickler entwickelt:silver bromide emulsion containing 100 ml is applied to a suitable support and exposed to light and developed for 5 minutes at 20 ° C in the following developer:

4-Amino-N,N-butylbutansulfoanilin 5,0 g4-Amino-N, N-butylbutanesulfoaniline 5.0 g

Natriumsulfit sicc 1,0 gSodium sulfite sicc 1.0 g

Kaliumbromid 1,0 gPotassium bromide 1.0 g

Kaliumcarbonat 75,0 gPotassium carbonate 75.0 g

Wasser 11Water 11

Anschließend wird in üblicher Weise gebleicht und fixiert. Man erhält ein blaugrünes, positives Bild.Then it is bleached and fixed in the usual way. A blue-green positive is obtained Image.

Ähnliche Ergebnisse erhält man, wenn man im obengenannten Beispiel die Verbindung 1. durch eine der Verbindungen 2. bis 5. ersetzt.Similar results are obtained if the compound 1 in the above example is replaced by a of connections 2. to 5. replaced.

Claims (2)

Patentansprüche:Patent claims: 1. Verfahren zur Herstellung von photographischen direktpositiven Farbstoffbildern unter Verwendung eines lichtempfindlichen Materials, das mindestens eine Halogensilberemulsionsschicht enthält, in die Amidrazone oder deren vinyloge, phenyloge oder azavinyloge Derivate eingebettet sind, die mit photographischen Schwarz-Weiß- oder Farbentwicklern zu farblo.sen Produkten reagieren, bei dem nach dem Entwickeln mit einem" oxydierenden Bad gebleicht und. anschließend fixiert wird, wobei die oxydierende Bleichung in Gegenwart von Verbindungen durchgeführt wird, die nicht oder nur unter Bildung farbloser Produkte oder solcher Produkte, die im Laufe des photographischen Vprarbeitungsgariges farblos werden, mit Entwickleroxydationsprodukten reagieren, die vorzugsweise selbst keine Ent-CO — CH — CH — CH2 — CH —1. A process for the production of photographic direct positive dye images using a light-sensitive material which contains at least one halogen silver emulsion layer in which amidrazones or their vinylogous, phenylogous or azavinylogous derivatives are embedded, which react with photographic black-and-white or color developers to form colorless products in which, after developing, it is bleached with an "oxidizing bath" and then fixed, the oxidizing bleaching being carried out in the presence of compounds which do not or only produce colorless products or products which become colorless in the course of photographic processing, react with developer oxidation products, which preferably do not have any Ent-CO - CH - CH - CH 2 - CH - CH,CH, wicklungswirkung besitzen und die sich mit den Oxydationsprodukten der Amidrazone zu farbigen Verbindungen umsetzen, nach Patent 1 213 241, dadurch gekennzeichnet, daß als Verbindungen, die mit den Oxydationsprodukten der Amidrazone zu farbigen Verbindungen reagieren, 1-Phenyl-,12-Pyrazoline verwendet werden. have a winding effect and which become colored with the oxidation products of the amidrazones Implement connections, according to Patent 1 213 241, characterized in that as Compounds that react with the oxidation products of the amidrazones to form colored compounds, 1-phenyl-, 12-pyrazolines can be used. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß l-Phenyl-J2-pyrazoline der folgenden Formel verwendet werden:2. The method according to claim 1, characterized in that l-phenyl-J2-pyrazolines of the following Formula can be used: worin bedeutet R Wasserstoff, Carboxyl, verestertes Carboxyl, Carbamyl, N-Alkylcarbamyl, N-Phenylcarbamyl, Alkyl bis zu 20 C-Atomen, Aryl oder Aralkyl.where R is hydrogen, carboxyl, esterified carboxyl, carbamyl, N-alkylcarbamyl, N-phenylcarbamyl, alkyl up to 20 carbon atoms, aryl or aralkyl. 3, Verfahren nach den Ansprüchen 1 und 2, dadurch gekennzeichnet, daß diffusionsfeste 1-Phenyl-J2-pyrazolme verwendet werden, die in dje Halogensilberemulsionsschicht, die auch Amidrazone oder deren vinylenhomologe, phenylenhomolöge oder azavinylenhomologe Derivate enthält, eingebettet sind.3, method according to claims 1 and 2, characterized in that diffusion-resistant 1-phenyl-J2-pyrazolme used in dje halogen silver emulsion layer, which is also Amidrazone or contains their vinylene homologues, phenylene homologues or azavinylene homologous derivatives, are embedded.
DEA49535A 1964-07-24 1965-06-21 Process for the preparation of direct positive dye photographic images Pending DE1259701B (en)

Priority Applications (10)

Application Number Priority Date Filing Date Title
DEA46672A DE1213241B (en) 1964-07-24 1964-07-24 Process for the preparation of direct positive dye photographic images
DEA49001A DE1259700B (en) 1964-07-24 1965-04-22 Process for the preparation of direct positive dye photographic images
DEA49534A DE1257570B (en) 1964-07-24 1965-06-21 Process for the preparation of direct positive dye photographic images
DEA49535A DE1259701B (en) 1964-07-24 1965-06-21 Process for the preparation of direct positive dye photographic images
US470615A US3443942A (en) 1964-07-24 1965-07-08 Colored photographic direct positive images
CH991765A CH456343A (en) 1964-07-24 1965-07-15 Process for the production of direct positive color photographic images
NL6509590A NL6509590A (en) 1964-07-24 1965-07-23
GB31542/65A GB1123782A (en) 1964-07-24 1965-07-23 Colored photographic direct positive images
FR1592055D FR1592055A (en) 1964-07-24 1965-07-24
BE667369D BE667369A (en) 1964-07-24 1965-07-26

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DEA46672A DE1213241B (en) 1964-07-24 1964-07-24 Process for the preparation of direct positive dye photographic images
DEA49001A DE1259700B (en) 1964-07-24 1965-04-22 Process for the preparation of direct positive dye photographic images
DEA49534A DE1257570B (en) 1964-07-24 1965-06-21 Process for the preparation of direct positive dye photographic images
DEA49535A DE1259701B (en) 1964-07-24 1965-06-21 Process for the preparation of direct positive dye photographic images

Publications (1)

Publication Number Publication Date
DE1259701B true DE1259701B (en) 1968-01-25

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Application Number Title Priority Date Filing Date
DEA46672A Pending DE1213241B (en) 1964-07-24 1964-07-24 Process for the preparation of direct positive dye photographic images
DEA49001A Pending DE1259700B (en) 1964-07-24 1965-04-22 Process for the preparation of direct positive dye photographic images
DEA49535A Pending DE1259701B (en) 1964-07-24 1965-06-21 Process for the preparation of direct positive dye photographic images
DEA49534A Pending DE1257570B (en) 1964-07-24 1965-06-21 Process for the preparation of direct positive dye photographic images

Family Applications Before (2)

Application Number Title Priority Date Filing Date
DEA46672A Pending DE1213241B (en) 1964-07-24 1964-07-24 Process for the preparation of direct positive dye photographic images
DEA49001A Pending DE1259700B (en) 1964-07-24 1965-04-22 Process for the preparation of direct positive dye photographic images

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Application Number Title Priority Date Filing Date
DEA49534A Pending DE1257570B (en) 1964-07-24 1965-06-21 Process for the preparation of direct positive dye photographic images

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US (1) US3443942A (en)
BE (1) BE667369A (en)
CH (1) CH456343A (en)
DE (4) DE1213241B (en)
FR (1) FR1592055A (en)
GB (1) GB1123782A (en)
NL (1) NL6509590A (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5695914A (en) * 1995-09-15 1997-12-09 Eastman Kodak Company Process of forming a dye image
GB9716554D0 (en) * 1997-08-06 1997-10-08 Eastman Kodak Co New fogging solution for a reversal process

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE620977A (en) * 1961-08-02

Also Published As

Publication number Publication date
DE1259700B (en) 1968-01-25
DE1257570B (en) 1967-12-28
GB1123782A (en) 1968-08-14
FR1592055A (en) 1970-05-11
NL6509590A (en) 1966-01-25
CH456343A (en) 1968-07-15
DE1213241B (en) 1966-03-24
BE667369A (en) 1966-01-26
US3443942A (en) 1969-05-13

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