EP0202410B1 - Material for carriers for heat-developable photographic layers - Google Patents
Material for carriers for heat-developable photographic layers Download PDFInfo
- Publication number
- EP0202410B1 EP0202410B1 EP86103383A EP86103383A EP0202410B1 EP 0202410 B1 EP0202410 B1 EP 0202410B1 EP 86103383 A EP86103383 A EP 86103383A EP 86103383 A EP86103383 A EP 86103383A EP 0202410 B1 EP0202410 B1 EP 0202410B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- layers
- photographic
- coated
- image
- thermally developable
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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- 239000000463 material Substances 0.000 title claims abstract description 31
- 239000000969 carrier Substances 0.000 title description 2
- 230000005865 ionizing radiation Effects 0.000 claims abstract description 11
- 239000011230 binding agent Substances 0.000 claims abstract description 10
- 238000000576 coating method Methods 0.000 claims abstract description 9
- 239000011248 coating agent Substances 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 5
- 238000009792 diffusion process Methods 0.000 claims abstract description 4
- 239000010410 layer Substances 0.000 description 44
- 239000000203 mixture Substances 0.000 description 9
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- -1 salt compound Chemical class 0.000 description 7
- 239000000126 substance Substances 0.000 description 6
- 239000012876 carrier material Substances 0.000 description 5
- 238000010894 electron beam technology Methods 0.000 description 5
- 239000011241 protective layer Substances 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- 238000003851 corona treatment Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- 108010010803 Gelatin Proteins 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 229920000159 gelatin Polymers 0.000 description 2
- 239000008273 gelatin Substances 0.000 description 2
- 235000019322 gelatine Nutrition 0.000 description 2
- 235000011852 gelatine desserts Nutrition 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- AQRYNYUOKMNDDV-UHFFFAOYSA-M silver behenate Chemical compound [Ag+].CCCCCCCCCCCCCCCCCCCCCC([O-])=O AQRYNYUOKMNDDV-UHFFFAOYSA-M 0.000 description 2
- 239000012463 white pigment Substances 0.000 description 2
- UDATXMIGEVPXTR-UHFFFAOYSA-N 1,2,4-triazolidine-3,5-dione Chemical compound O=C1NNC(=O)N1 UDATXMIGEVPXTR-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- UKMSUNONTOPOIO-UHFFFAOYSA-M behenate Chemical compound CCCCCCCCCCCCCCCCCCCCCC([O-])=O UKMSUNONTOPOIO-UHFFFAOYSA-M 0.000 description 1
- 229940116224 behenate Drugs 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- POULHZVOKOAJMA-UHFFFAOYSA-M dodecanoate Chemical compound CCCCCCCCCCCC([O-])=O POULHZVOKOAJMA-UHFFFAOYSA-M 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229940070765 laurate Drugs 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 231100000957 no side effect Toxicity 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000019612 pigmentation Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229940114926 stearate Drugs 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003536 tetrazoles Chemical class 0.000 description 1
- 229920002397 thermoplastic olefin Polymers 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 239000003232 water-soluble binding agent Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
- G03C8/40—Development by heat ; Photo-thermographic processes
- G03C8/4013—Development by heat ; Photo-thermographic processes using photothermographic silver salt systems, e.g. dry silver
- G03C8/4046—Non-photosensitive layers
- G03C8/4073—Supports
-
- 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
- G03C1/49872—Aspects relating to non-photosensitive layers, e.g. intermediate protective layers
Definitions
- the invention relates to a carrier material for thermally developable photographic layers. It relates in particular to the use of a coated paper as a support for such photographic layers.
- Photographic materials that can be developed by exposure to heat are known and are described, for example, in "Imaging Systems” on page 122 f of K.I. Jacobsen and R.E. Jacobsen (The Focal Press, London, 1976) and in “Neblette's Handbook of Photography and Reprography", 7th edition, 1978, on pages 32, 33 and 570 (Van Nostrand Reinhold Company). They are also commercially available as so-called “dry silver” materials).
- thermally developable photographic layers are at least one organic metal salt compound and at least one reducing agent. This principle applies both to thermally developable black and white image layers and to thermally developable color image layers.
- silver halide, antifoggants, sensitizers, color formers, activators, catalysts and / or other additives for improving the image quality or image stability can be contained in one or more image layers or in adjacent layers.
- the binder of a thermally developable photographic layer is either a water-insoluble plastic, e.g. Polyvinyl butyral, or a common water soluble binder e.g. Gelatin or polyvinyl alcohol, and the photographic layer is spread as a spreadable preparation using known coating methods and dried.
- a water-insoluble plastic e.g. Polyvinyl butyral
- a common water soluble binder e.g. Gelatin or polyvinyl alcohol
- the organic metal compound is preferably an organic silver salt (for example Ag laurate, stearate, behenate, urazole, triazole, benzotriazole, tetrazole, carbazole, imidazole, or the like).
- organic silver salt for example Ag laurate, stearate, behenate, urazole, triazole, benzotriazole, tetrazole, carbazole, imidazole, or the like.
- organometallic compounds such as Hg - , Fe (III) - and above all Te compounds. Characteristic of thermally developable photographic materials is not so much the type of oxidizing metal compound but rather the fact that a visible photographic image is obtained in the exposed material after heat treatment and without the known use of aqueous process solutions. By heat treatment it is meant that the imagewise coated material is brought to a temperature between 80 and 250 ° C (preferably 100 to 200 ° C).
- polyester film is the preferred backing material, but the papers coated with resin (e.g. polyethylene), which are commonly used for wet development, are also occasionally used.
- resin e.g. polyethylene
- Film carriers are particularly suitable when transparency of the carrier is desired. However, they have disadvantages if the carrier material is to be reflective. The reflectance of 85 to 90% that is common with white film material (see EP 119 830) is not always sufficient to achieve optimal image sharpness. In addition, footage is relatively inflexible and expensive.
- the known resin-coated papers for example polyethylene-coated papers
- the resin layer therefore deforms at development temperatures of 100 ° or more, and a separation between the photographic layer and the resin layer was even observed in individual cases when developed by means of hot rollers.
- thermally developable photographic materials have also become known, in which a color image is formed which is transferred to an image-receiving material during or after thermal development by diffusion transfer.
- the processes and materials are described, for example, in EP 76 492, EP 79 056, DOS 3 345 023, EP 119 470, EP 118 078, DOS 3 407 228, EP 121 765, EP 123166, EP 125 521, EP 131161 or DOS 3 422 455.
- conventional resin-coated papers are less suitable as an image-receiving material because of the thermoplasticity of the resin layers.
- a paper is used as a carrier material for thermally developable photographic layers or as an image receiving material for thermally developed color images, which contains a crosslinked binder or at least a crosslinked on a surface.
- Bearing layer which is produced from radiation-curable material, the crosslinkable starting material consisting predominantly of unsaturated monomeric, oligomeric or polymeric substances and is crosslinked in or on the paper by means of ionizing radiation.
- EP-A 159 493 discloses a photographic support material which contains a coating on at least one side, the binder component of which is predominantly made from unsaturated compounds and which is cured by means of low-energy rays. To prevent discoloration and fogging, this material additionally contains at least one unsaturated monomeric, oligomeric or polymeric hydroxyl functional substance, the molar concentration of the hydroxyl groups being equal to or greater than 2, specifically for layers to be developed wet as well as for layers to be developed dry.
- Reducing substances of this type are often also a component of the thermally developable photographic layers and are jointly responsible for image formation.
- the layers hardened with ionizing radiation directly as a substrate for thermally developed photographic layers or also as a receiving material for thermally developed color images, because the unsaturated compounds used for the production of the radiation-hardened layers in the commercial form always come with the addition of polymerization inhibitors are stabilized.
- Papers coated with radiation-hardened binder can be translucent to transparent. In this form, they are preferably used for thermally developable black-and-white layers, such as those used for generating weather maps. On the other hand, they can be reflective due to the addition of white pigment and are mainly used in this form for supervisory images.
- Papers coated or impregnated with non-pigmented radiation-curable mixtures for transparent images show a more uniform transparency after curing than papers coated or impregnated with solvent-containing preparations and then dried.
- Papers coated with pigmented radiation-curable mixtures primarily benefit from the possible degree of pigmentation of the coating.
- white pigment e.g. titanium dioxide
- reflectance levels of up to 95% were measured on such layers, which enables the production of particularly sharp and brilliant top views.
- impregnations and coatings made from radiation-curable mixtures are very temperature-resistant after curing by means of ionizing radiation.
- the layers do not deform even when briefly used at a higher temperature of 200 ° C or more, and the coated or impregnated papers are more dimensionally stable than previously used papers with minor changes in their moisture content.
- such papers can be applied using a contact hardening process, for example. according to DOS 30 22 709 have a surface quality comparable to that of foils combined with the flexibility of a coated paper.
- all base papers suitable for photographic applications are suitable, which can be treated in a known manner with all radiation-curable mixtures known in principle and after hardening by means of ionizing radiation (for example electron beams or other high-energy radiation) directly or after use known adhesion-promoting intermediate steps such as the corona treatment or an adhesive layer with one or more photographic layers for thermal development and optionally a protective layer and / or optionally an antihalation layer or further auxiliary layers are coated.
- the thermally developable photographic layers can belong to the group of black and white image layers or to the group of color image layers.
- Against side receives a protective layer of Uchthof according to the composition in Example 4 of European Patent Application No. 119 830.
- An approx. 130 g / m 2 heavy photographic base paper with a pre-sealing coating consisting essentially of polyvinyl alcohol and barium sulfate, which is coated on one side with about 25 g / m 2 of a mixture hardened under protective gas by means of electron beams with an energy dose of 35 J / g is coated after corona treatment with about 2 g / m 2 of a 1: 1 mixture of gelatin and trimethylvinylbenzylammonium chloride copolymer and used as an image-receiving material for a thermally developable photographic color image according to DOS 33 45 023.
- the image-receiving material is brought into contact with the exposed layer of the photo material, and the image is developed by means of a heated drum and transferred to the image-receiving material by diffusion transfer of the dyes.
- a paper with a reflective coating according to Example 2 is used as a carrier material for a thermally developable photographic layer and an antihalation layer in accordance with EP 119 830.
Abstract
Description
Die Erfindung betrifft ein Trägermaterial für thermisch entwickelbare fotografische Schichten. Sie betrifft insbesondere die Verwendung eines beschichteten Papieres als Träger für solche fotografischen Schichten.The invention relates to a carrier material for thermally developable photographic layers. It relates in particular to the use of a coated paper as a support for such photographic layers.
Fotografische Materialien, die durch Wärmeeinwirkung entwickelt werden können, sind bekannt und beispielsweise in "Imaging Systems" auf Seite 122 f von K.I. Jacobsen und R.E. Jacobsen (The Focal Press, London, 1976) sowie in "Neblette's Handbook of Photography and Reprographie", 7. Auflage, 1978, auf den Seiten 32, 33 und 570 (Van Nostrand Reinhold Company) beschrieben. Sie sind femer als sogenannte "Dry Silver"-Materialien im Handel).Photographic materials that can be developed by exposure to heat are known and are described, for example, in "Imaging Systems" on page 122 f of K.I. Jacobsen and R.E. Jacobsen (The Focal Press, London, 1976) and in "Neblette's Handbook of Photography and Reprography", 7th edition, 1978, on pages 32, 33 and 570 (Van Nostrand Reinhold Company). They are also commercially available as so-called "dry silver" materials).
Die wichtigsten Bestandteile thermisch entwickelbarer fotografischer Schichten sind wenigstens eine organische Metallsalzverbindung und wenigstens ein Reduktionsmittel. Dieses Prinzip gilt sowohl für thermisch entwickelbare Schwarzweiß-Bildschichten als auch für thermisch entwickelbare Colorbildschichten. Daneben können Silberhalogenid, Antischleiermittel, Sensibilisatoren, Farbbildner, Aktivatoren, Katalysatoren und/oder andere Zusätze zur Verbesserung der Bildqualität oder Bildstabilität in einer oder mehreren Bildschichten oder in benachbarten Schichten enthalten sein.The most important components of thermally developable photographic layers are at least one organic metal salt compound and at least one reducing agent. This principle applies both to thermally developable black and white image layers and to thermally developable color image layers. In addition, silver halide, antifoggants, sensitizers, color formers, activators, catalysts and / or other additives for improving the image quality or image stability can be contained in one or more image layers or in adjacent layers.
Das Bindemittel einer thermisch entwickelbaren fotografischen Schicht ist entweder ein wasserunlöslicher Kunststoff, z.B. Polyvinylbutyral, oder ein üblicher wasserlöslicher Binder, z.B. Gelatine oder Polyvinylalkohol, und die fotografische Schicht wird als streichfähige Zubereitung mit Hilfe bekannter Beschichtungsverfahren auf einen Träger gebracht und getrocknet.The binder of a thermally developable photographic layer is either a water-insoluble plastic, e.g. Polyvinyl butyral, or a common water soluble binder e.g. Gelatin or polyvinyl alcohol, and the photographic layer is spread as a spreadable preparation using known coating methods and dried.
Die organische Metallverbindung ist vorzugsweise ein organisches Silbersalz (z.B. Ag-laurat, - stearat, -behenat, -urazol, -triazol, -benzotriazol, - tetrazol, -carbazol, imidazol, o.a.). In der Patentliteratur sind aber auch andere Organo-Metallverbindungen wie Hg-, Fe(III)- sowie vor allem Te-Verbindungen beschrieben. Kennzeichnend für thermisch entwickelbare Fotomaterialien ist nicht so sehr die Art der oxidierend wirkenden Metallverbindung sondern die Tatsache, daß ein sichtbares fotografisches Bild im belichteten Material nach einer Wärmebehandlung und ohne die bekannte Anwendung wässriger Prozeßlösungen erhalten wird. Mit Wärmebehandlung ist gemeint, daß das bildmäßig beschichtete Material auf eine Temperatur zwischen 80 und 250°C (vorzugsweise 100 bis 200°C) gebracht wird.The organic metal compound is preferably an organic silver salt (for example Ag laurate, stearate, behenate, urazole, triazole, benzotriazole, tetrazole, carbazole, imidazole, or the like). The patent literature also describes other organometallic compounds such as Hg - , Fe (III) - and above all Te compounds. Characteristic of thermally developable photographic materials is not so much the type of oxidizing metal compound but rather the fact that a visible photographic image is obtained in the exposed material after heat treatment and without the known use of aqueous process solutions. By heat treatment it is meant that the imagewise coated material is brought to a temperature between 80 and 250 ° C (preferably 100 to 200 ° C).
Als Trägermaterialien für thermisch entwickelbare fotografische Schichten sind Papiere und verschiedene Filmmaterialien in Gebrauch. Gemäß EP 118 078 und EP 119 380 gilt Polyesterfilm als bevorzugtes Trägermaterial, aber auch die für Naßentwicklung gebräuchlichen mit Harz (z.B. Polyethylen) beschichteten papiere kommen gelegentlich zur Anwendung.Papers and various film materials are used as carrier materials for thermally developable photographic layers. According to EP 118 078 and EP 119 380, polyester film is the preferred backing material, but the papers coated with resin (e.g. polyethylene), which are commonly used for wet development, are also occasionally used.
Filmträger sind besonders geeignet, wenn Transparenz der Trägers gewünscht ist. Sie haben jedoch Nachteile, wenn das Trägermaterial reflektierend sein soll. Der bei weißem Filmmaterial übliche Remissionsgrad von 85 bis 90 % (vergl. EP 119 830) ist für die Erreichung optimaler Bildschärfen nicht immer ausreichend. Außerdem ist Filmmaterial relativ unflexibel und teuer.Film carriers are particularly suitable when transparency of the carrier is desired. However, they have disadvantages if the carrier material is to be reflective. The reflectance of 85 to 90% that is common with white film material (see EP 119 830) is not always sufficient to achieve optimal image sharpness. In addition, footage is relatively inflexible and expensive.
Andererseits besitzen die bekannten harzbeschichteten Papiere, z.B. polyethylenbeschichtete Papiere, zwar alle guten Eigenschaften eines Papieres, haben aber nur begrenzte Einsatzmöglichkeiten, weil das thermoplastische Polyolefinharz bereits bei relativ geringfügig erhöhten Temperaturen erweicht. Bei Entwicklungstemperaturen von 100° ' oder mehr verformt sich daher die Harz-Schicht, und bei Entwicklung mittels heißer Walzen wurde im Einzelfall sogar eine Trennung zwischen fotografischer Schicht und Harzschicht beobachtet.On the other hand, the known resin-coated papers, for example polyethylene-coated papers, have all the good properties of a paper, but have only limited possible uses because the thermoplastic polyolefin resin already softens at relatively slightly elevated temperatures. The resin layer therefore deforms at development temperatures of 100 ° or more, and a separation between the photographic layer and the resin layer was even observed in individual cases when developed by means of hot rollers.
Neuerdings wurden ferner thermisch entwickelbare fotografische Materialien bekannt, bei denen ein Farbbild entsteht, das während oder nach der thermischen Entwicklung durch Diffusionstransfer auf ein Bildempfangsmaterial übertragen wird. Die Verfahren und Materialien sind beispielsweise in EP 76 492, EP 79 056, DOS 3 345 023, EP 119 470, EP 118 078, DOS 3 407 228, EP 121 765, EP 123166, EP 125 521, EP 131161 oder DOS 3 422 455 beschrieben. Auch hier erweist sich, daß konventionelle harzbeschichtete Papiere wegen der Thermoplastizität der Harzschichten sich weniger gut als Bildempfangsmaterial eignen.Recently, thermally developable photographic materials have also become known, in which a color image is formed which is transferred to an image-receiving material during or after thermal development by diffusion transfer. The processes and materials are described, for example, in EP 76 492, EP 79 056, DOS 3 345 023, EP 119 470, EP 118 078, DOS 3 407 228, EP 121 765, EP 123166, EP 125 521, EP 131161 or DOS 3 422 455. Here, too, it has been found that conventional resin-coated papers are less suitable as an image-receiving material because of the thermoplasticity of the resin layers.
Aufgabe der vorliegenden Erfindung ist es daher, ein besser geeignetes Trägermaterial für thermisch entwickelbare fotografische Schichten und ein besser geeignetes Bildempfangsmaterial für thermisch entwickelte farbfotografische Bilder vorzuschlagen und insbesondere ein Material auszuwählen, das durch seine Wärmebeständigkeit gute Gebrauchseigenschaften hat und darüber hinaus die thermisch entwickelbaren fotografischen Schichten nicht in unerwünschter Weise beeinflußt.It is therefore an object of the present invention to propose a more suitable support material for thermally developable photographic layers and a more suitable image receiving material for thermally developed color photographic images, and in particular to select a material which has good thermal properties due to its heat resistance and, moreover, does not provide the thermally developable photographic layers influenced in an undesirable manner.
Diese Aufgabe wird dadurch gelöst, daß als Trägermaterial für thermisch entwickelbare fotografische Schichten oder als Bildempfangsmaterial für thermisch entwickelte Farbbilder ein Papier verwendet wird, das ein vernetztes Bindemittel enthält oder wenigstens auf einer Oberfläche eine vernetzte. Schicht trägt, die aus strahlenhärtbarem Material erzeugt ist, wobei das vernetzbare Ausgangsmaterial überwiegend aus ungesättigten monomeren, oligomeren oder polymeren Substanzen besteht und in bzw. auf dem papier mittels ionisierender Strahlung vernetzt ist. Unter ungesättigten Substanzen sollen Stoffe mit wenigstens einer C=C-Doppelbindung verstanden sein, beispielsweise Acrylat-oder Methacrylatverbindungen.This object is achieved in that a paper is used as a carrier material for thermally developable photographic layers or as an image receiving material for thermally developed color images, which contains a crosslinked binder or at least a crosslinked on a surface. Bearing layer which is produced from radiation-curable material, the crosslinkable starting material consisting predominantly of unsaturated monomeric, oligomeric or polymeric substances and is crosslinked in or on the paper by means of ionizing radiation. Unsaturated substances are to be understood as meaning substances with at least one C = C double bond, for example acrylate or methacrylate compounds.
Die Verwendung solcherart beschichteter Papier für übliche naß zu entwickelnde Silberhalogenid enthaltende fotografische Schichten ist in DOS 30 22 451 beschrieben, und es hat sich erwiesen, daß die mittels ionisierender Strahlung (z.B. Elektronenstrahlen) unter Luftausschluß gehärteten Schichten aus strahlenhärtbarem Material in aufliegenden naß entwickelbaren Silberhalogenidschichten Schleier erzeugen. Als eine mögliche Ursache dieser Schleierbildung wurde der in den härtbaren Materialien üblicherweise enthaltene Polymerisationsinhibitor bzw. ein Umsetzungsprodukt davon diskutiert, weil als Inhibitoren verwendete Substanzen, z.B.. Hydrochinon, auch als fotografische Entwickler verwendet werden können.The use of paper coated in this way for conventional photographic layers containing silver halide to be wet-developed is described in DOS 30 22 451, and it has been found that the layers of radiation-curable material hardened by means of ionizing radiation (for example electron beams) with exclusion of air in overlying wet-developable silver halide layers are veils produce. One of the possible causes of this fogging was the polymer which is usually present in the curable materials onsinhibitor or a reaction product thereof discussed because substances used as inhibitors, for. Hydroquinone, can also be used as a photographic developer.
Aus der EP-A 159 493 ist ein fotografisches Trägermaterial bekannt, das zumindest einseitig einen Uberzug enthält, dessen Binderkomponente überwiegend aus ungesättigten Verbindungen hergestellt ist und der mittels energieliefemder Strahlen ausgehärtet ist. Zur Verhinderung von Verfärbung und Schleierbildung enthält dieses Material außerdem zusätzlich zumindest eine ungesättigte monomere, oligomere oder polymere hydroxifunktionelle Substanz, wobei die molale Konzentration der Hydroxigruppen gleich oder größer als 2 ist, und zwar für naß zu entwickelnde Schichten als auch für trocken zu entwickelnde Schichten.EP-A 159 493 discloses a photographic support material which contains a coating on at least one side, the binder component of which is predominantly made from unsaturated compounds and which is cured by means of low-energy rays. To prevent discoloration and fogging, this material additionally contains at least one unsaturated monomeric, oligomeric or polymeric hydroxyl functional substance, the molar concentration of the hydroxyl groups being equal to or greater than 2, specifically for layers to be developed wet as well as for layers to be developed dry.
Reduzierend wirkende Substanzen dieser Art sind vielfach auch ein Bestandteil der thermisch entwickelbaren fotografischen Schichten und sind mitverantwortlich für die Bilderzeugung. Infolgedessen bestanden erhebliche Bedenken, die mit ionisierender Strahlung gehärteten Schichten direkt als Substrat für thermisch zu entwickelnde fotografische Schichten oder auch als Empfangsmaterial für thermisch entwickelte Farbbilder zu verwenden, weil die für die Erzeugung der strahlengehärteten Schichten gebrauchten ungesättigten Verbindungen in der Handelsform immer durch Zusatz von Polymerisationsinhibitoren stabilisiert sind.Reducing substances of this type are often also a component of the thermally developable photographic layers and are jointly responsible for image formation. As a result, there were considerable doubts about using the layers hardened with ionizing radiation directly as a substrate for thermally developed photographic layers or also as a receiving material for thermally developed color images, because the unsaturated compounds used for the production of the radiation-hardened layers in the commercial form always come with the addition of polymerization inhibitors are stabilized.
Überraschenderweise führte die Verwendung der aus inhibitorhaltigen ungesättigten Verbindungen erzeugten Schichten, die durch ionisierende Strahlung gehärtet wurden, jedoch nicht zu den befürchteten nachteiligen Auswirkungen auf thermisch entwickelbare fotografische Schichten. Vielmehr erwiesen sich solcherart imprägnierte oder beschichtete Papiere als gut geeignete und vielseitig verwendbare Träger, die keine Nebenwirkungen auf thermisch entwickelte fotografische Schichten zeigten und auch als Bildempfangsmaterial für thermisch entwickelte farbfotografische Bilder gut geeignet sind.Surprisingly, however, the use of the layers produced from inhibitor-containing unsaturated compounds which have been hardened by ionizing radiation did not lead to the feared adverse effects on thermally developable photographic layers. Rather, such impregnated or coated papers have proven to be highly suitable and versatile supports which have no side effects on thermally developed photographic layers and are also well suited as image-receiving material for thermally developed color photographic images.
Papiere, die mit strahlengehärtetem Bindemittel überzogen sind, können einerseits durchscheinend bis transparent sein. In dieser Form finden sie vorzugsweise Verwendung für in der Durchsicht zu betrachtende thermisch entwickelbare Schwarz-weiß-Schichten wie sie beispielsweise bei Erzeugung von Wetterkarten zum Einsatz kommen. Sie können andererseits aufgrund von Weißpigmentzusatz reflektierend sein und finden in dieser form vorwiegend Verwendung für Aufsichtsbilder.Papers coated with radiation-hardened binder can be translucent to transparent. In this form, they are preferably used for thermally developable black-and-white layers, such as those used for generating weather maps. On the other hand, they can be reflective due to the addition of white pigment and are mainly used in this form for supervisory images.
Mit nicht pigmentierten strahlenhärtbaren Mischungen überzogene oder imprägnierte Papiere für Durchsichtsbilder zeigen nach Härtung eine gleichmäßigere Transparenz als vergleichsweise mit Lösungsmittel enthaltenden Zubereitungen beschichtete oder imprägnierte und dann getrocknete Papiere.Papers coated or impregnated with non-pigmented radiation-curable mixtures for transparent images show a more uniform transparency after curing than papers coated or impregnated with solvent-containing preparations and then dried.
Mit pigmentierten strahlenhärtbaren Mischungen überzogene Papiere gewinnen vor allem durch den möglichen Pigmentierungsgrad des Überzugs. So können Überzüge mit 30 bis 60 Gewichtsprozent an Weißpigment (z.B. Titandioxid) hergestellt werden. Nach Härtung mittels ionisierender Strahlung wurden an solchen Schichten Remissionsgrade bis zu 95 % gemessen, wodurch die Herstellung besonders scharfer und brillanter Aufsichtsbilder ermöglicht wird.Papers coated with pigmented radiation-curable mixtures primarily benefit from the possible degree of pigmentation of the coating. In this way, coatings with 30 to 60 percent by weight of white pigment (e.g. titanium dioxide) can be produced. After hardening by means of ionizing radiation, reflectance levels of up to 95% were measured on such layers, which enables the production of particularly sharp and brilliant top views.
Weitere für die erfindungsgemäße Verwendung wichtige Vorteile sind, daß Imprägnierungen und Beschichtungen aus strahlenhärtbaren Mischungen nach der mittels ionisierenderStrahlung vorgenommenen Härtung sehr temperaturbeständig sind. Die Schichten verformen sich auch bei kurzzeitiger Anwendung höhererTemperatur von 200°C oder mehr - nicht, und die beschichteten oder imprägnierten Papiere sind bei kleineren Änderungen ihres Feuchtegehaltes dimensionsstabiler als bisher verwendete Papiere. Schließlich können solche Papiere bei Anwendung eines Kontakthärtungsverfahrens z/B. gemäß DOS 30 22 709 eine durchaus mit Folien vergleichbare Oberflächenqualität verbunden mit der Flexibilität eines beschichteten Papieres haben.Further important advantages for the use according to the invention are that impregnations and coatings made from radiation-curable mixtures are very temperature-resistant after curing by means of ionizing radiation. The layers do not deform even when briefly used at a higher temperature of 200 ° C or more, and the coated or impregnated papers are more dimensionally stable than previously used papers with minor changes in their moisture content. Finally, such papers can be applied using a contact hardening process, for example. according to DOS 30 22 709 have a surface quality comparable to that of foils combined with the flexibility of a coated paper.
Für die Herstellung der gemäß der Erfindung verwendeten Trägermaterialien eignen sich alle für fotografische Anwendungen geeigneten Basispapiere, die in bekannter Weise mit allen im Prinzip bekannten strahlenhärtbaren Mischungen behandelt werden können und nach Härtung mittels ionisierender Strahlung (z.B. Elektronenstrahlen oder anderer energiereicher Strahlung) direkt oder nach Anwendung bekannter haftungsvermittelnder Zwischenschritte wie die Coronabehandlung oder eine Haftschicht mit einer oder mehreren fotografischen Schichten für thermische Entwicklung sowie gegebenenfalls einer Schutzschicht und/oder gegebenenfalls einer Lichthofschutzschicht oder weiteren Hilfsschichten überzogen werden. Die thermisch entwickelbaren fotografischen Schichten können zur Gruppe der Schwarzweißbild-Schichten oder zur Gruppe der Colorbild-Schichten gehören. In den nachstehenden Beispielen sind einige Verwendungen beschrieben, ohne daß diese Beispiele beschränkend für die Erfindung sind.For the production of the support materials used according to the invention, all base papers suitable for photographic applications are suitable, which can be treated in a known manner with all radiation-curable mixtures known in principle and after hardening by means of ionizing radiation (for example electron beams or other high-energy radiation) directly or after use known adhesion-promoting intermediate steps such as the corona treatment or an adhesive layer with one or more photographic layers for thermal development and optionally a protective layer and / or optionally an antihalation layer or further auxiliary layers are coated. The thermally developable photographic layers can belong to the group of black and white image layers or to the group of color image layers. Some uses are described in the examples below, without these examples being restrictive for the invention.
Ein ca. 70 g/m2 schweres fotografisches Basispapier, das in Schutzgasatmosphäre mit etwa 12 g/m2 einer Mischung aus
Ein ca. 70 g/m2 schweres fotografisches Basispapier mit einer Oberflächenleimung aus carboxiliertem Polyvinylalkohol, das einseitig mit etwa 20 g/m2 eines unter Schutzgas mittels Elektronenstrahlen mit einer Energiedosis von 40 J/g ausgehärteten Mischung aus
Ein ca. 130 g/m2 schweres fotografisches Basispapier mit einem Vorabdichtungsüberzug aus im wesentlichen Polyvinylalkohol und Bariumsulfat, das einseitig mit etwa 25 g/m2 eines unter Schutzgas mittels Elektronenstrahlen mit einer Energiedosis von 35 J/g ausgehärteten Mischung aus
Ein gemäß Beispiel 2 reflektierend beschichtetes Papier wird als Trägermaterial für eine thermisch entwickelbare fotografische Schicht und eine Lichthofschutzschicht ggemäß EP 119 830 verwendet.A paper with a reflective coating according to Example 2 is used as a carrier material for a thermally developable photographic layer and an antihalation layer in accordance with EP 119 830.
Claims (1)
- Use of a photographic paper support, which contains a binding agent cross-linked by ionizing radiation and/or is coated on at least one surface with a coating, the binding agent of which has been cross-linked by ionizing radiation, the binding agent when not cross-linked containing unsaturated compounds, for thermally developable colour-photographic recording materials according to the diffusion transfer process.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT86103383T ATE46220T1 (en) | 1985-05-21 | 1986-03-13 | BASE MATERIAL FOR THERMALLY DEVELOPABLE PHOTOGRAPHIC COATINGS. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3518113 | 1985-05-21 | ||
| DE19853518113 DE3518113A1 (en) | 1985-05-21 | 1985-05-21 | CARRIER MATERIAL FOR THERMALLY DEVELOPABLE PHOTOGRAPHIC LAYERS |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0202410A2 EP0202410A2 (en) | 1986-11-26 |
| EP0202410A3 EP0202410A3 (en) | 1988-01-07 |
| EP0202410B1 true EP0202410B1 (en) | 1989-09-06 |
Family
ID=6271176
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP86103383A Expired EP0202410B1 (en) | 1985-05-21 | 1986-03-13 | Material for carriers for heat-developable photographic layers |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US4952486A (en) |
| EP (1) | EP0202410B1 (en) |
| JP (1) | JPS61267044A (en) |
| AT (1) | ATE46220T1 (en) |
| DE (2) | DE3518113A1 (en) |
| ES (1) | ES8704643A1 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07120013B2 (en) * | 1987-04-20 | 1995-12-20 | 富士写真フイルム株式会社 | Image forming method |
| CA1329335C (en) * | 1986-12-17 | 1994-05-10 | Akihiko Nagumo | Image-forming method employing light-sensitive material |
| US4752559A (en) * | 1987-03-24 | 1988-06-21 | Helland Randall H | Primer/antihalation coating for photothermographic constructions |
| US5424182A (en) * | 1993-01-15 | 1995-06-13 | Labelon Corporation | Aqueous coating composition for thermal imaging film |
| DE19728093C2 (en) * | 1997-07-02 | 1999-06-24 | Schoeller Felix Jun Foto | Image receiving material for image recording processes |
| WO2001010640A1 (en) * | 1999-08-05 | 2001-02-15 | Rexam Graphics Inc. | Uv cured glossy support for ink jet recording material |
| US6326415B1 (en) * | 1999-08-05 | 2001-12-04 | Rexam Graphics Inc. | UV cured glossy support for ink jet recording material |
| US20060088674A1 (en) * | 2004-10-27 | 2006-04-27 | Hladik Molly L | Ultraviolet curable barrier layers |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3582337A (en) * | 1968-06-27 | 1971-06-01 | Eastman Kodak Co | Light-sensitive photographic paper |
| US3667959A (en) * | 1970-05-01 | 1972-06-06 | Eastman Kodak Co | Photosensitive and thermosensitive element,compositions and process |
| DE2940870C2 (en) * | 1979-10-09 | 1986-10-02 | Felix Schoeller jr. GmbH & Co KG, 4500 Osnabrück | Coated paper support for photographic layers |
| US4311774A (en) * | 1980-03-19 | 1982-01-19 | Polaroid Corporation | Irradiation treatment of polymeric photographic film supports |
| DE3022451A1 (en) * | 1980-06-14 | 1982-01-07 | Felix Schoeller jr. GmbH & Co KG, 4500 Osnabrück | WATERPROOF PHOTOGRAPHIC PAPER |
| DE3022709A1 (en) * | 1980-06-18 | 1982-01-07 | Felix Schoeller jr. GmbH & Co KG, 4500 Osnabrück | WATERPROOF PHOTOGRAPHIC PAPER AND METHOD FOR THE PRODUCTION THEREOF |
| GB8307022D0 (en) * | 1983-03-15 | 1983-04-20 | Minnesota Mining & Mfg | Photothermographic element |
| JPS59178456A (en) * | 1983-03-30 | 1984-10-09 | Fuji Photo Film Co Ltd | Color image forming method |
| JPS6061747A (en) * | 1983-09-16 | 1985-04-09 | Konishiroku Photo Ind Co Ltd | Thermodevelopable photosensitive material |
| US4594315A (en) * | 1983-09-21 | 1986-06-10 | Konishiroku Photo Industry Co., Ltd. | Light-sensitive silver halide photographic element with electron beam cured interlayer |
| DE3415215A1 (en) * | 1984-04-21 | 1985-10-24 | Felix Schoeller jr. GmbH & Co KG, 4500 Osnabrück | RESISTANT TO PHOTOGRAPHIC BAEDER PHOTOGRAPHIC CARRIER MATERIAL |
| JPS60230133A (en) * | 1984-04-27 | 1985-11-15 | Fuji Photo Film Co Ltd | Heat developable photosensitive material |
| DE3435639A1 (en) * | 1984-09-28 | 1986-04-10 | Felix Schoeller jr. GmbH & Co KG, 4500 Osnabrück | PHOTOGRAPHIC CARRIER MATERIAL FOR BLACK / WHITE AND COLOR PHOTOGRAPHY |
-
1985
- 1985-05-21 DE DE19853518113 patent/DE3518113A1/en active Granted
-
1986
- 1986-03-13 AT AT86103383T patent/ATE46220T1/en not_active IP Right Cessation
- 1986-03-13 DE DE8686103383T patent/DE3665503D1/en not_active Expired
- 1986-03-13 EP EP86103383A patent/EP0202410B1/en not_active Expired
- 1986-05-16 ES ES554995A patent/ES8704643A1/en not_active Expired
- 1986-05-19 JP JP61112833A patent/JPS61267044A/en active Granted
-
1989
- 1989-10-10 US US07/420,616 patent/US4952486A/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| DE3665503D1 (en) | 1989-10-12 |
| ATE46220T1 (en) | 1989-09-15 |
| JPS61267044A (en) | 1986-11-26 |
| DE3518113A1 (en) | 1986-11-27 |
| ES8704643A1 (en) | 1987-04-16 |
| US4952486A (en) | 1990-08-28 |
| DE3518113C2 (en) | 1987-03-19 |
| JPH0555070B2 (en) | 1993-08-16 |
| EP0202410A2 (en) | 1986-11-26 |
| ES554995A0 (en) | 1987-04-16 |
| EP0202410A3 (en) | 1988-01-07 |
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