EP0039337A1 - Material for obtaining photographic prints by dry process - Google Patents

Material for obtaining photographic prints by dry process

Info

Publication number
EP0039337A1
EP0039337A1 EP19800901789 EP80901789A EP0039337A1 EP 0039337 A1 EP0039337 A1 EP 0039337A1 EP 19800901789 EP19800901789 EP 19800901789 EP 80901789 A EP80901789 A EP 80901789A EP 0039337 A1 EP0039337 A1 EP 0039337A1
Authority
EP
European Patent Office
Prior art keywords
image
light
dry process
photographic prints
silver salt
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.)
Withdrawn
Application number
EP19800901789
Other languages
German (de)
French (fr)
Inventor
Josef Rupp
Kanwaljit Purewal
Valentin Cavicchiolo
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.)
TONEC SA
Original Assignee
TONEC SA
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 TONEC SA filed Critical TONEC SA
Publication of EP0039337A1 publication Critical patent/EP0039337A1/en
Withdrawn legal-status Critical Current

Links

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
    • G03C1/494—Silver salt compositions other than silver halide emulsions; Photothermographic systems ; Thermographic systems using noble metal compounds
    • G03C1/498—Photothermographic systems, e.g. dry silver
    • G03C1/49809—Organic silver compounds

Definitions

  • the invention relates to an image capture material for the production of photographic copies in a dry way, which contains a light-insensitive silver salt.
  • the invention relates to a thermophotographic copying material for producing copies by, by means of heat-activated reduction of a silver salt of an organic acid, in the presence of a light-sensitive reducing agent, which copying material contains at least one layer of a silver salt of an organic acid and a light-resistant reducing agent for that contains silver ion.
  • the photosensitive, reducing organic compound is first made inactive and non-transferable by light by exposing imagewise in the presence of a compound which contributes to inactivating the reducing compound.
  • the reducing compound remaining in the unexposed or less exposed areas is then transferred by heat to the image-receiving layer with the silver salt of an organic acid and the light-resistant reducing agent for the silver ion, on which the color formation occurs.
  • Such compounds are, for example, 1 (2H) phthalazinol, barbituric acid, saccharin and 2-mercaptobenzoxanol.
  • 1 (2H) -pjtalazinone is used because these images have a deep black color.
  • the invention is based on the object of stabilizing the image-receiving material in such a way that the background remains white at the uncopied areas, but the image still appears deep black.
  • metal soaps with at least 14 carbon atoms which serve as a white pigment, can be used for this purpose.
  • Zinc palmitate is particularly suitable for this.
  • the metal soaps can be added to the layers in various amounts.
  • the optimal amount depends on the layer composition. In general, additions of 0.1-1 parts by weight, preferably 0.4-0.7 parts by weight, per part by weight of toner have been found to be most effective.
  • the metal soaps can be used in combination with the materials and compounds known for the respective heat development process.
  • Reducing compounds which have proven suitable for the thermally initiated reduction of these silver salts include, for example, pyrogallol, 4-stearoyl-pyrogallol, galloacetophenone, di-tert. Butyl-pyrogallol, butyl gallate, dodecyl gallate, gallic acid, ammonium gallate, 2,5-dihydroxy -benzoic acid, and -naphthols, 1-hydroxy-naphthoic acid- (2), phloroglucinol, pyrocatechol, hydroquinone, 1-phenyl-pyrazolidin-3-one, 4,4'-dihydroxybiphenyl, 1-hydroxy-4-methoxy- naphthalene, l-hydroxy-4-methoxy-dihydro-naphthalene, o- and p-phenylenediamine and acetoacetonitrile derivatives, for example in accordance with US Pat.
  • these reducing compounds are organic compounds in which an active hydrogen atom is bonded to a carbon, oxygen or nitrogen atom, which in turn is bonded to an atom of an aromatic or heterocyclic ring or in the case of the nitrogen atom can also be part of a heterocyclic ring.
  • the reactants can also be placed in a fibrous web.
  • pigments, fillers, fusible substances such as Waxes, dyes and various other additives can be incorporated.
  • the silver salt and the toner are preferably mixed together before casting. However, they can also be applied separately in adjacent layers from which the toner can diffuse to the metal salt, for example when the carrier film is heated.
  • the light sources customary in reproduction technology such as halogen lamps, iodine quartz lamps or incandescent lamps, can be used to expose the light-sensitive layers.
  • the spectral sensitivity of the light-sensitive material depends on the nature of the sensitizer dyes used.
  • the transfer of the image-forming compounds from the unexposed areas of the light-sensitive layers into the image-receiving layer takes place in the heat at temperatures between 80 and 200 ° C.
  • the heating can take place, for example, by guiding the exposed light-sensitive layer in contact with the image-receiving layer over hot plates or rollers or by irradiation with UR light.
  • the most favorable temperature and heating time naturally depend on the nature of the image-forming compound or the composition of the light-insensitive copying material containing silver salt; it can be determined by a few simple experiments.
  • the ready-to-use mixture is then poured onto a paper support in an amount of 150 g / m 2 and dried.
  • the photosensitive layer is exposed to light.
  • the exposure lasts 30 seconds and is carried out with a tungsten filament lamp of 1500 watts, which is attached at a distance of 5 cm from the light-sensitive material.
  • the exposed layer then becomes 5 at 125 ° C Brought into contact with the image-receiving layer for seconds. Deep black images with high density are obtained on a white background.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)

Abstract

La couche contient un sel d'argent photoresistant. Pour obtenir avec une image au noir contraste un fond blanc, on utilise un sel metallique d'acides gras avec au moins 14 atomes de carbone et en particulier le palmitate de zinc.The layer contains a photoresist silver salt. To obtain a black background contrasting with a white background, a metallic salt of fatty acids with at least 14 carbon atoms is used, in particular zinc palmitate.

Description

Bildempfangsmaterial für die Herstellung von photographischen Kopien auf trockenem Wege Image receiving material for the production of photographic copies by dry means
Die Erfindung bezieht sich auf ein Bilderapfangsmaterial für die Herstellung von photographischen Kopien auf trockenem Wege, die ein lichtunempfindliches Silbersalz enthält. Insbesondere betrifft die Erfindung ein thermophotogra- phisches Kopiermaterial zur Herstellung von Kopien, durch, mittels Wärme aktivierte Reduktion eines Silbersalzes einer organischen Säure, in Gegenwart eines li'chtempfindlichen Reduktionsmittels, welches Kopiermaterial in mindestens einer Schicht ein Silbersalz einer organischen Säure und ein lichtbeständiges Reduktionsmittel für das Silberion enthält.The invention relates to an image capture material for the production of photographic copies in a dry way, which contains a light-insensitive silver salt. In particular, the invention relates to a thermophotographic copying material for producing copies by, by means of heat-activated reduction of a silver salt of an organic acid, in the presence of a light-sensitive reducing agent, which copying material contains at least one layer of a silver salt of an organic acid and a light-resistant reducing agent for that contains silver ion.
Die lichtempfindliche, reduzierende organische Verbindung wird zunächst durch Licht inaktiv und nicht übertragbar gemacht, indem man bildmässig in Gegenwart einer Verbindung belichtet, die zur Inaktivierung der reduzierenden Verbindung beiträgt. Die in den unbelichteten oder weniger stark belichteten Stellen noch verbleibende, reduzierende Verbindung wird dann durch Wärme auf die Bildempfangsschicht mit dem Silbersalz einer organischen Säure und dem lichtbeständigen Reduktionsmittel für das Silberion übertragen, auf der die Farbbildung zustande kommt.The photosensitive, reducing organic compound is first made inactive and non-transferable by light by exposing imagewise in the presence of a compound which contributes to inactivating the reducing compound. The reducing compound remaining in the unexposed or less exposed areas is then transferred by heat to the image-receiving layer with the silver salt of an organic acid and the light-resistant reducing agent for the silver ion, on which the color formation occurs.
Bei diesem Verfahren werden nur gelbe bis hellbraune Silberbilder von geringem Kontrast erhalten. Es ist deshalb bekannt, dass man um Bilder mit genügender optischer Dichte zu erhalten, der Bildempfangsschicht sogenannte Toner zusetzt, die den Bildton nach braun bis schwarz verschieben.With this method, only yellow to light brown silver images of low contrast are obtained. It is therefore known that in order to obtain images with sufficient optical density, so-called toners are added to the image-receiving layer, which shift the image tone from brown to black.
Derartige Verbindungen sind z.B. 1(2H)-Phtalazinol, Barbitursäure, Saccharin und 2-Mercaptobenzoxanol. Wobei vorzugsweise l(2H)-Pjtalazinon eingesetzt wird, da diese Bilder eine tiefschwarze Farbe aufweisen.Such compounds are, for example, 1 (2H) phthalazinol, barbituric acid, saccharin and 2-mercaptobenzoxanol. Preferably 1 (2H) -pjtalazinone is used because these images have a deep black color.
Durch den Zusatz dieser Toner wird Jedoch das Bildempfangsmaterial empfindlicher gemacht, so dass der Grund der Kopie ebenfalls eine leichte Schwärzung erleidet. Gewünscht wird aber ein schwarzes Bild auf Weissem Grund.However, the addition of these toners makes the image-receiving material more sensitive, so that the base of the copy also suffers from a slight blackening. However, a black image on a white background is desired.
Der Erfindung liegt nun die Aufgabe zu Grunde, das Bildempfangsmaterial so zu stabilisieren, dass an den unkopierten Stellen der Grund weiss bleibt, das Bild jedoch immer noch tief schwarz erscheint.The invention is based on the object of stabilizing the image-receiving material in such a way that the background remains white at the uncopied areas, but the image still appears deep black.
Es wurde gefunden, dass Metallseifen mit mindestens 14 C-Atomen, die als Weisspigment dienen, zu diesem Zweck eingesetzt werden können.It has been found that metal soaps with at least 14 carbon atoms, which serve as a white pigment, can be used for this purpose.
Insbesondere eignet sich dazu Zinkpalmitat.Zinc palmitate is particularly suitable for this.
Die Metallseifen können den Schichten in verschiedenen Mengen zugesetzt werden. Die optimale Menge hängt jeweils von der Schichtzusammensetzung ab. Im Allgemeinen haben sich Zusätze von 0,1-1 Gew. Teilen, vorzugsweise 0,4- 0,7 Gew. Teile, pro Gew. Teil Toner als am wirksamsten erwiesen.The metal soaps can be added to the layers in various amounts. The optimal amount depends on the layer composition. In general, additions of 0.1-1 parts by weight, preferably 0.4-0.7 parts by weight, per part by weight of toner have been found to be most effective.
Die Metallseifen können in Kombination mit den für das jeweilige Wärmeentwicklungsverfahren bekannten Materialien und Verbindungen angewandt werden.The metal soaps can be used in combination with the materials and compounds known for the respective heat development process.
Zu reduzierenden Verbindungen, die sich zur thermisch initiierten Reduktion dieser Silbersalze als geeignet erwiesen haben, gehören z.B. Pyrogallol, 4-Stearoyl- pyrogallol, Galloacetophenon, Di-tert .butyl-pyrogallol, Butylgallat, Dodecylgallat, Gallussäure, Ammoniumgallat, 2,5-Dihydroxy-benzoesäure, und -Naphtole, 1-Hydroxy-naphtoe- säure-(2), Phloroglucinol, Brenzcatechin, Hydrochinon, 1- Phenyl-pyrazolidin-3-on, 4,4 '-Dihydroxybiphenyl, 1-Hydroxy- 4-methoxy-naphthalin, l-Hydroxy-4-methoxy-dihydro-naphthalin, o- und p-Phenylendiamin und Acetoacetonitril-Derivate, z.B. gemäss US-Patentschrift 3.619-239 oder deutscher Offenlegung- schrift 2.010.837. Andere Reduktionsmittel, die sich zur Verwendung bei höherer Temperatur eignen, sind Pyrazolin-5-on- Verbindungen mit zumindest einem Wasserstoffatom in der 4- Steilung. Geeignete Verbindungen der letztgenannten Art sind in der deutschen Offenlegungsschrift 2.117.053 besehrieben.Reducing compounds which have proven suitable for the thermally initiated reduction of these silver salts include, for example, pyrogallol, 4-stearoyl-pyrogallol, galloacetophenone, di-tert. Butyl-pyrogallol, butyl gallate, dodecyl gallate, gallic acid, ammonium gallate, 2,5-dihydroxy -benzoic acid, and -naphthols, 1-hydroxy-naphthoic acid- (2), phloroglucinol, pyrocatechol, hydroquinone, 1-phenyl-pyrazolidin-3-one, 4,4'-dihydroxybiphenyl, 1-hydroxy-4-methoxy- naphthalene, l-hydroxy-4-methoxy-dihydro-naphthalene, o- and p-phenylenediamine and acetoacetonitrile derivatives, for example in accordance with US Pat. No. 3,619-239 or German Offenlegungsschrift 2,010,837. Other reducing agents that are suitable for use at higher temperatures are pyrazolin-5-one compounds with at least one hydrogen atom in the 4-position. Suitable compounds of the latter type are described in German Offenlegungsschrift 2,117,053.
Wie aus der vorstehenden Aufzählung zu ersehen ist, handelt es sich bei diesen reduzierenden Verbindungen um organische Verbindungen, bei denen ein aktives Wasserstoff- atom an ein Kohlenstoff-, Sauerstoff- oder Stickstoffatom gebunden ist, das seinerseits an ein Atom eines aromatischen oder heterocycllschen Ringes gebunden oder im Falle des Stickstoffatoms auch Bestandteil eines heterocyclischen Ringes sein kann.As can be seen from the above list, these reducing compounds are organic compounds in which an active hydrogen atom is bonded to a carbon, oxygen or nitrogen atom, which in turn is bonded to an atom of an aromatic or heterocyclic ring or in the case of the nitrogen atom can also be part of a heterocyclic ring.
Bei der Auswahl der Bindemittel für die lichtempfindliche Schicht und die Bildempfangsschicht ist darauf zu achten, dass in der Wärme die Schichten nicht kleben. Diese Schwierigkeiten sind jedoch von anderen bekannten Verfahren, z.B. dem Silbersalzdiffusionsverfahren oder Wärmeentwicklungsverfahren, bekannt und unter Ausnutzung der Erfahrung auf diesen bekannten Gebieten ohne weiteres zu lösen.When selecting the binders for the light-sensitive layer and the image-receiving layer, care must be taken that the layers do not stick in the heat. However, these difficulties are related to other known methods, e.g. the silver salt diffusion process or heat development process, which can be easily solved using the experience in these known fields.
In Abwesenheit eines Bindemittels können die Reaktionsteilnehmer auch in eine faserige Bahn eingebracht werden. Um angestrebte Spezialeffekte zu erhalten, können Pigmente, Füllstoffe, schmelzbare Substanzen, wie z.B. Wachse, Farbstoffe und verschiedene andere Zusätze einverleibt werden.In the absence of a binder, the reactants can also be placed in a fibrous web. To obtain the desired special effects, pigments, fillers, fusible substances such as Waxes, dyes and various other additives can be incorporated.
Das Silbersalz und der Toner werden vorzugsweise vor dem Vergiessen miteinander- vermischt. Sie können jedoch auch getrennt in benachbarten Schichten aufgebracht werden, aus denen der Toner - z.B. beim Erhitzen der Trägerfolie - zum Metallsalz diffundieren kann. Zur Belichtung der lichtempfindlichen Schichten können die in der Reproduktionstechnik üblichen Lichtquellen, wie Halogenlampen, Jodquarzlampen oder Glühlampen verwendet werden. Die spektrale Empfindlichkeit des lichtempfindlichen Materials hängt von der Natur der verwendeten Sensibilisatorfarbstoffe ab. Die Ueberführung der bilderzeugenden Verbindungen von den unbelichteten Stellen der lichtempfindlichen Schichten in die Bildempfangsschicht geschieht in der Wärme bei Temperaturen zwischen 80 und 200ºC. Die Erwärmung kann erfolgen z.B. durch Führung der belichteten lichtempfindlichen Schicht in Kontakt mit der Bildempfangsschicht über heisse Platten oder Walzen oder auch durch Bestrahlung mit UR-Licht. Die güngstigste Temperatur und Erwärmungszeit hängt selbstverständlich von der Natur der bilderzeugenden Verbindung bzw. der Zusammensetzung des lichtunempfindlichen silbersalzhaltigen Kopiermaterials ab; sie kann durch wenige einfache Versuche ermittelt werden. The silver salt and the toner are preferably mixed together before casting. However, they can also be applied separately in adjacent layers from which the toner can diffuse to the metal salt, for example when the carrier film is heated. The light sources customary in reproduction technology, such as halogen lamps, iodine quartz lamps or incandescent lamps, can be used to expose the light-sensitive layers. The spectral sensitivity of the light-sensitive material depends on the nature of the sensitizer dyes used. The transfer of the image-forming compounds from the unexposed areas of the light-sensitive layers into the image-receiving layer takes place in the heat at temperatures between 80 and 200 ° C. The heating can take place, for example, by guiding the exposed light-sensitive layer in contact with the image-receiving layer over hot plates or rollers or by irradiation with UR light. The most favorable temperature and heating time naturally depend on the nature of the image-forming compound or the composition of the light-insensitive copying material containing silver salt; it can be determined by a few simple experiments.
Beispielexample
A. Herstellung des lichtempfindlichen Materials Ein Transparentpapier wird in einer Menge von 25 g/m2 mit der folgenden Mischung beschichtetA. Preparation of the Photosensitive Material A transparent paper is coated in an amount of 25 g / m 2 with the following mixture
(p-Chlorphenyl)-acetoacetonitrile 1,0 g(p-chlorophenyl) acetoacetonitrile 1.0 g
Erythrosin 440 mgErythrosin 440 mg
Aethylcellulose 50,0 gEthyl cellulose 50.0 g
Methyläthylketon 500 g anschliessend wie üblich trocknenThen dry methyl ethyl ketone 500 g as usual
B. Herstellung des BildempfangsmaterialsB. Preparation of Image Receiving Material
Aethylacetat 40 g Stearinsäure 4 g Silberstearat 5 g Zn-Palm!tat 2 g Polyäthylacrylat 5 g Phtalazinon 1 gEthyl acetate 40 g stearic acid 4 g silver stearate 5 g Zn-Palm! Tat 2 g polyethyl acrylate 5 g phthalazinone 1 g
Diese Mischung wird 24 h in einer Kugelmühle gemahlen. Zu dieser gemahlenen Masse werden vor dem Vergiessen zugebenThis mixture is ground in a ball mill for 24 h. Add to this ground mass before pouring
Aceton 20 gAcetone 20 g
2,6 Di-cyclohexyl-p-Kresol 1 g2,6 di-cyclohexyl-p-cresol 1 g
Die gebrauchsfertige Mischung wird dann in einer Menge von 150 g/m auf einen Papierträger gegossen und getrocknet.The ready-to-use mixture is then poured onto a paper support in an amount of 150 g / m 2 and dried.
Verarbeitung : Die lichtempfindliche Schicht wird bild mässig belichtet. Die Belichtung dauert 30 Sekunden und wird mit einer Wolframfadenlampe von 1500 Watt durchgeführt, die in einem Abstand von 5 cm vom lichtempfindlichen Material angebracht ist.Processing: The photosensitive layer is exposed to light. The exposure lasts 30 seconds and is carried out with a tungsten filament lamp of 1500 watts, which is attached at a distance of 5 cm from the light-sensitive material.
Anschliessend wird die belichtete Schicht bei 125ºC 5 Sek. lang mit der Bildempfangsschicht in Kontakt gebracht. Es werden tief schwarze Bilder mit hoher Dichte auf weissem Grund erhalten.The exposed layer then becomes 5 at 125 ° C Brought into contact with the image-receiving layer for seconds. Deep black images with high density are obtained on a white background.
Falls man das Zinkpalmitat weglässt, werden schwarze Bilder auf grau-schwarz punktiertem Grund erhalten. If you omit the zinc palmitate, black images will be obtained on a gray-black dotted background.

Claims

PATENTANSPRUECHE PATENT CLAIMS
1. Bildempfangsmaterial für die Herstellung von photographischen Kopien auf trockenem Wege, mit einer Schicht, die ein lichtunempfindliches Silbersalz enthält, dadurch gekennzeichnet, dass diese Schicht eine Metallseife mit mindestens 14-C-Atomen enthält.1. Image-receiving material for the production of photographic copies by dry means, with a layer containing a light-insensitive silver salt, characterized in that this layer contains a metal soap with at least 14 C atoms.
2. Bildempfangsmaterial nach Anspruch 1, dadurch gekennzeichnet, dass die Metallseife Zn-Palmitat ist. 2. Image receiving material according to claim 1, characterized in that the metal soap is Zn palmitate.
EP19800901789 1979-09-28 1980-09-26 Material for obtaining photographic prints by dry process Withdrawn EP0039337A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH872579 1979-09-28
CH8725/79 1979-09-28

Publications (1)

Publication Number Publication Date
EP0039337A1 true EP0039337A1 (en) 1981-11-11

Family

ID=4344007

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19800901789 Withdrawn EP0039337A1 (en) 1979-09-28 1980-09-26 Material for obtaining photographic prints by dry process

Country Status (2)

Country Link
EP (1) EP0039337A1 (en)
WO (1) WO1981000921A1 (en)

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1161777A (en) * 1966-02-21 1969-08-20 Fuji Photo Film Co Ltd Thermally Developable Light-sensitive Elements
JPS5057619A (en) * 1973-09-21 1975-05-20
US3885968A (en) * 1974-05-30 1975-05-27 Fuji Photo Film Co Ltd Thermally developable light-sensitive material
BE834856A (en) * 1974-10-24 1976-02-16 PROCESS FOR PREPARING COMPOSITIONS AND PHOTOSENSITIVE ELEMENTS DEVELOPABLE BY HEAT
GB1498406A (en) * 1975-05-22 1978-01-18 Kodak Ltd Heat-processable photosensitive material
JPS5334515A (en) * 1976-09-10 1978-03-31 Canon Inc Thermodevelopable photosensitive material

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO8100921A1 *

Also Published As

Publication number Publication date
WO1981000921A1 (en) 1981-04-02

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