EP0253911A1 - Photographic-paper support and process for its production - Google Patents

Photographic-paper support and process for its production Download PDF

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Publication number
EP0253911A1
EP0253911A1 EP86110061A EP86110061A EP0253911A1 EP 0253911 A1 EP0253911 A1 EP 0253911A1 EP 86110061 A EP86110061 A EP 86110061A EP 86110061 A EP86110061 A EP 86110061A EP 0253911 A1 EP0253911 A1 EP 0253911A1
Authority
EP
European Patent Office
Prior art keywords
photographic
support material
polyolefin
photographic support
material according
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.)
Granted
Application number
EP86110061A
Other languages
German (de)
French (fr)
Other versions
EP0253911B1 (en
Inventor
Wolfram Chem.-Ing. Wysk (Grad.)
Bernd Dipl.-Ing. Scholz
Ralf-Burckhard Dr. Dipl.-Chem. Dethlefs
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.)
Felix Schoeller Jr Foto und Spezialpapiere GmbH
Felex Schoeller Jr and GmbH and Co KG
Original Assignee
Felix Schoeller Jr Foto und Spezialpapiere GmbH
Felex Schoeller Jr and GmbH and Co KG
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 Felix Schoeller Jr Foto und Spezialpapiere GmbH, Felex Schoeller Jr and GmbH and Co KG filed Critical Felix Schoeller Jr Foto und Spezialpapiere GmbH
Priority to EP86110061A priority Critical patent/EP0253911B1/en
Priority to AT86110061T priority patent/ATE50369T1/en
Priority to DE8686110061T priority patent/DE3668995D1/en
Priority to JP61278934A priority patent/JPH0660992B2/en
Priority to HU871855A priority patent/HU201581B/en
Priority to ES8701428A priority patent/ES2003722A6/en
Priority to AU72932/87A priority patent/AU594153B2/en
Priority to CN87104888.4A priority patent/CN1031299C/en
Priority to US07/072,406 priority patent/US4895757A/en
Priority to YU133187A priority patent/YU45949B/en
Priority to GR871154A priority patent/GR871154B/en
Publication of EP0253911A1 publication Critical patent/EP0253911A1/en
Application granted granted Critical
Publication of EP0253911B1 publication Critical patent/EP0253911B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D21H19/56—Macromolecular organic compounds or oligomers thereof obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
    • G03C1/775—Photosensitive materials characterised by the base or auxiliary layers the base being of paper
    • G03C1/79—Macromolecular coatings or impregnations therefor, e.g. varnishes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31725—Of polyamide
    • Y10T428/3175—Next to addition polymer from unsaturated monomer[s]
    • Y10T428/31757—Polymer of monoethylenically unsaturated hydrocarbon
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/3188—Next to cellulosic
    • Y10T428/31895—Paper or wood
    • Y10T428/31899—Addition polymer of hydrocarbon[s] only
    • Y10T428/31902—Monoethylenically unsaturated
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/31909—Next to second addition polymer from unsaturated monomers
    • Y10T428/31913—Monoolefin polymer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31971—Of carbohydrate
    • Y10T428/31989—Of wood

Definitions

  • the invention relates to a photographic paper support which is coated with a waterproof pigment-containing polyolefin layer.
  • waterproof photographic paper supports consist of a base paper with synthetic resin coatings applied on both sides.
  • the resin coatings on the base paper can be made of polyolefin, e.g. Polyethylene, exist and have been applied to the paper by means of extrusion coating, but they can also be composed of organic lacquer mixtures which are layered onto the paper by means of immersion or spray processes and solidified by means of high-energy radiation.
  • One or more photosensitive coatings based on silver halide are applied to one of the synthetic resin layers.
  • the light-sensitive layers can be black and white as well as color photographic layers.
  • the synthetic resin coating (front coating) arranged under the light-sensitive layers usually contains light-reflecting white pigment and, if appropriate, color pigments, optical brighteners and / or other additives such as antistatic compounds, dispersants for the white pigment and antioxidants.
  • the synthetic resin film (backside coating) arranged on the paper side opposite the light-sensitive layers can be pigmented or unpigmented and / or contain other additives which result from the respective use of the laminate as a photographic support.
  • This layer can also be coated with other functional layers (for example layers for writing, antistatic layers, sliding layers, adhesive layers or antihalation layers as well as layers for flatness).
  • the coating of a photographic base paper with polyolefin by extrusion through a slot die is a known process.
  • the polyolefin extrusion coating occurs at a point where the paper web enters the nip between a cooling roll and a rubber roll through which the polyolefin layer is adhered to the paper web.
  • the cooling roller also serves to design the surface structure of the polyolefin layer. Depending on the nature of the cooling roller surface, shiny, matt or structured, e.g. silky, polyolefin surfaces can be produced.
  • the rhythmic detachment of the polyolefin film which is not entirely uniform, also leads to a deterioration in the desired, uniformly high-gloss surface finish of the polyolefin film.
  • There are hair-like elevations across the paper web which are visible under the influence of light in the border area of total reflection, but cannot be detected by surface measurements, and which occur at a distance of about 1 mm from each other.
  • release agent to the polyolefin in order to reduce the adhesion of the polyolefin layer to the cooling roller and to achieve a uniformly easy separation of the extruded film.
  • release agents include the metal salts of fatty acids mentioned in Japanese Patent Laid-Open JP 32 442/1982, JP 46 818/1982 and JP 46 819/1982, e.g. Zinc or magnesium stearate.
  • amides such as e.g. Use oleamide and erucic acid amide, but also polyolefin waxes and stearin as release agents.
  • these release agents have to be used in the usual pigment-containing polyolefin mixtures in relatively high concentrations (0.5 - 2%) in order to achieve the desired effect.
  • These high concentrations not only reduce the adhesion of the polyolefin to the chill roll in a manner that is desirable per se, but also significantly weaken the adhesion of the polyolefin to the paper carrier. This results in disadvantages in the further processing of the photographic support, for example in the form of detachment of the polyolefin layer from the paper when subjected to stress in the photographic process solutions or even during the coating with the photographic layers.
  • these release agents for example stearic acid, stearates or stearic acid amide, sweat profusely at the extrusion temperatures Polyolefin melt, so that there is drop formation and then visible, grease-stained deposits on the polyolefin layer.
  • polyethylene glycols with a molecular weight of 400 to 4000 can be suitable release agents in order to facilitate the detachment of unpigmented low density polyethylene types from the cooling roll of an extrusion coating system.
  • 500 - 600 ppm of polyethylene glycol for 0.924 density polyethylene and 900 to 1200 ppm of polyethylene glycol for 0.915 density polyethylene are mentioned as additional amounts.
  • polyalkylene oxides are known to the person skilled in the art as substances which sensitize photographic silver salt layers. (Neblette's Handbook of Photography and Reprography, 1977). As a result, their use in the support material appeared fundamentally undesirable because the migration from there to the photographic layers cannot be controlled. On the other hand, it is known that polyalkylene oxides attach to the pigment surface and make it hydrophilic.
  • the object of the invention is therefore to provide a polyolefin-coated carrier material with a high-gloss surface of the pigment-containing polyolefin coating, in which the pigment-containing polyolefin layer is easily and uniformly detached from the high-gloss cooling roller and nevertheless adheres well to the base paper and has no effect on the sensitivity of overlying photographic layers.
  • a photographic base paper is coated on the side lying first of the photographic layers with a polyolefin mixture which contains at least one polyoxyalkylene glycol in addition to polyolefin and white pigment.
  • the pigmented polyolefin mixture contains, in addition to polyalkylene oxide, a fatty acid soap of a polyvalent metal or a fatty acid amide.
  • polyolefins are used to coat a photographic base paper, e.g. Polyethylene, polypropylene or an olefin copolymer individually or as a mixture in question.
  • the preferred coating resin is polyethylene, which can be used with both high and low density, and as a blend of both types.
  • preferred white pigment is a titanium dioxide or a mixture of titanium dioxide with another white pigment or filler. Small amounts of colored pigments, dyes, optical brighteners or other known additives may also be present.
  • the polyolefin coating composition can be applied to one or both sides of the paper.
  • the application is carried out by means of extrusion coating using a slot die at temperatures of 270 to 330 ° C.
  • the paper base to be coated with a polyethylene mixture containing pigment according to the invention can be any photographic base paper which is either neutral sized using alkyl ketene dimer or has a known acidic size based on precipitated resin or fatty acid soaps.
  • the base paper can be made exclusively from cellulose fibers or from mixtures of cellulose fibers with synthetic fibers. It can have a basis weight of 60 to 300 g / m2 (preferably 70 to 200 g / m2) and contain a surface sizing in addition to the inside sizing.
  • General a photographic base paper is understood to mean a bright white paper with a uniform transparency, which is secured against penetration of the photographic treatment solutions by a special strong sizing and yet shows no photochemical effects on photographic layers.
  • the polyoxyalkylene glycol added to the polyolefin / pigment mixture is preferably a polyethylene glycol with a molecular weight between 100 and 35,000, preferably between 400 and 20,000, or a polypropylene glycol with a molecular weight between 400 and 10,000, preferably between 2,000 and 10,000.
  • the polyoxyalkylene glycol used as a release agent can be added to the polyethylene mixture in any known manner, but it is preferred to introduce the polyoxyalkylene glycol via a premix (masterbatch).
  • the amount of polyoxyalkylene glycol used is between 40 ppm and 1% based on the total amount of polyethylene, but preferably between 100 ppa and 0.5%.
  • the formation of the transverse markings is completely avoided, but the adhesion of the polyolefin film to the base paper is not adversely affected.
  • the effect according to the invention is achieved even at the very low release agent concentration of 40 ppm polyoxyalkylene glycol based on the total amount of the polyethylene / pigment mixture.
  • the release agents already described for use in photographic supports only take effect at much higher concentrations.
  • the effect according to the invention is retained over a large concentration range without visible exudates.
  • the entire range ie also at concentrations of 0.5 to 1%, in which the release agents usually used are introduced, when using polyether glycols according to the invention the polyethylene film easily detaches from the cooling roller and the adhesion of the polyethylene film to the paper carrier remains good to satisfactory, whereas in the case of the previously known release agents the defects already described occur.
  • the cooling roller is not contaminated by sticking on short-chain polyolefin constituents, nor is there any drop formation and the associated contamination of the extruded polyolefin film by excessively exudated release agent, nor are changes in sensitivity observed in overlying photographic layers.
  • polyoxyalkylene glycol amounts of less than 40 ppm, based on the total amount of the polyethylene mixture, are used, however, the detachment of the polyethylene film from the chill roll is clearly worse than described according to the invention and the markings described appear in the surface of the photographic support material.
  • the separation of the polyethylene film from the cooling roller takes place easily and uniformly, but adequate adhesion to the paper carrier is generally no longer ensured.
  • the photographic base paper is coated with a white pigment-containing polyolefin mixture which, in addition to a polyoxyalkylene glycol, also contains a fatty acid salt of a polyvalent metal, for example Al stearate, Mg stearate, Zn stearate or the like, or a fatty acid amide.
  • a white pigment-containing polyolefin mixture which, in addition to a polyoxyalkylene glycol, also contains a fatty acid salt of a polyvalent metal, for example Al stearate, Mg stearate, Zn stearate or the like, or a fatty acid amide.

Abstract

1. Photographic support material, consisting of photographic base paper and at least one polyolefin layer containing white pigment disposed on the base paper, characterized in that the polyolefin layer additionally contains a polyalkylene glycol in a proportion of between 40 ppm and 1%, referred to the total quantity of the polyolefin layer.

Description

Die Erfindung betrifft einen fotografischen Papierträger, der mit einer wasserfesten pigmenthaltigen Polyolefinschicht überzogen ist.The invention relates to a photographic paper support which is coated with a waterproof pigment-containing polyolefin layer.

Wasserfeste fotografische Papierträger bestehen bekanntlich aus einem Basispapier mit auf beiden Seiten aufgebrachten Kunstharz­überzügen. Die auf dem Basispapier befindlichen Kunstharzüberzüge können aus Polyolefin, z.B. Polyethylen, bestehen und mittels Extrusionsbeschichtung auf das Papier aufgebracht worden sein, sie können aber auch aus organischen Lackmischungen zusammengesetzt sein, die mittels Tauch- oder Sprühverfahren auf das Papier geschichtet und mittels energiereicher Strahlung verfestigt werden.As is well known, waterproof photographic paper supports consist of a base paper with synthetic resin coatings applied on both sides. The resin coatings on the base paper can be made of polyolefin, e.g. Polyethylene, exist and have been applied to the paper by means of extrusion coating, but they can also be composed of organic lacquer mixtures which are layered onto the paper by means of immersion or spray processes and solidified by means of high-energy radiation.

Auf einer der Kunstharzschichten sind eine oder mehrere auf Silberhalogenid basierende lichtempfindliche Überzüge angebracht. Bei den lichtempfindlichen Schichten kann es sich sowohl um schwarz/weiß- als auch um farbfotografische Schichten handeln.One or more photosensitive coatings based on silver halide are applied to one of the synthetic resin layers. The light-sensitive layers can be black and white as well as color photographic layers.

Der unter der bzw. den lichtempfindlichen Schichten angeordnete Kunstharzüberzug (Vorderseitenbeschichtung) enthält üblicherweise lichtreflektierendes Weißpigment sowie gegebenenfalls Farbpigmente, optische Aufheller und/oder andere Zusätze wie antistatisch wirkende Verbindungen, Dispergierhilfsmittel für das Weißpigment und Anti­oxidantien.The synthetic resin coating (front coating) arranged under the light-sensitive layers usually contains light-reflecting white pigment and, if appropriate, color pigments, optical brighteners and / or other additives such as antistatic compounds, dispersants for the white pigment and antioxidants.

Der auf der den lichtempfindlichen Schichten entgegengesetzten Papierseite angeordnete Kunstharzfilm (Rückseitenbeschichtung) kann pigmentiert oder unpigmentiert sein und/oder andere Zusätze enthalten, die sich aus der jeweiligen Verwendung des Laminates als fotografischer Träger ergeben. Diese Schicht kann außerdem mit weiteren funktionellen Schichten (z.B. Schichten für die Beschreibbarkeit, antistatische Schichten, Gleitschichten, Kleberschichten oder Lichthofschutzschichten sowie Schichten für die Planlage) überzogen sein.The synthetic resin film (backside coating) arranged on the paper side opposite the light-sensitive layers can be pigmented or unpigmented and / or contain other additives which result from the respective use of the laminate as a photographic support. This layer can also be coated with other functional layers (for example layers for writing, antistatic layers, sliding layers, adhesive layers or antihalation layers as well as layers for flatness).

Die Beschichtung eines fotografischen Basispapiers mit Polyolefin mittels Extrusion durch eine Breitschlitzdüse ist ein an sich bekanntes Verfahren. Die Polyolefinextrusionsbeschichtung erfolgt an einer Stelle, wo die Papierbahn in den Spalt zwischen einer Kühlwalze und einer Gummiwalze eintritt, durch die die Polyolefinschicht zur Haftung auf die Papierbahn gebracht wird. Die Kühlwalze dient außerdem der Gestaltung der Oberflächen­struktur der Polyolefinschicht. Entsprechend der Beschaffenheit der Kühlwalzenoberfläche können glänzende, matte oder strukturierte, z.B. seidenartige, Polyolefinoberflächen erzeugt werden.The coating of a photographic base paper with polyolefin by extrusion through a slot die is a known process. The polyolefin extrusion coating occurs at a point where the paper web enters the nip between a cooling roll and a rubber roll through which the polyolefin layer is adhered to the paper web. The cooling roller also serves to design the surface structure of the polyolefin layer. Depending on the nature of the cooling roller surface, shiny, matt or structured, e.g. silky, polyolefin surfaces can be produced.

Die Erzeugung von hochglänzenden Oberflächen ist bislang mit Mängeln behaftet. Das betrifft in besonderem Maße hochglänzende Oberflächen von pigmenthaltigen Polyolefinüberzügen, die nach oxidierender Vorbehandlung direkt oder mit einer dünnen haftvermittelnden Schicht überzogen die fotografischen Schichten tragen und daher bestimmend für das Erscheinungsbild des endgültigen fotografischen Materials sind.The production of high-gloss surfaces has so far been flawed. This applies in particular to high-gloss surfaces of pigment-containing polyolefin coatings, which after oxidizing pretreatment carry the photographic layers directly or coated with a thin adhesion-promoting layer and are therefore decisive for the appearance of the final photographic material.

Aufgrund der hochglänzenden Oberfläche der Kühlwalze kommt es, verglichen mit matten und strukturierten Kühlwalzenoberflächen, zu größeren Haftkräften zwischen der Polyolefinoberfläche und der Kühlwalzenoberfläche. Daraus kann, selbst bei konstanter, gleichmäßiger Papierbahnbewegung, eine rhythmische Ablösung des Polyethylenfilms von der Kühlwalze resultieren. In extremen Fällen erfolgt sogar eine Ablagerung kurzkettiger Polyolefin­bestandteile an der Kühlwalze, die zu einer starken Beeinträch­tigung der Oberflächengüte des Polyolefinfilms führen kann, indem sie eine leichte Mattierung vortäuscht.Due to the high-gloss surface of the cooling roller, there are greater adhesive forces between the polyolefin surface and the cooling roller surface compared to matt and structured cooling roller surfaces. This can result in a rhythmic detachment of the polyethylene film from the chill roll, even with constant, even paper web movement. In extreme cases, short-chain polyolefin components are even deposited on the chill roll, which can severely impair the surface quality of the polyolefin film by simulating a slight matting.

Auch die nicht ganz gleichförmige, sondern rhythmische Ablösung des Polyolefinfilms bewirkt eine Verschlechterung der ange­strebten gleichmäßig hochglänzenden Oberflächenbeschaffenheit des Polyolefinfilms. Es entstehen quer zum Papierbahnverlauf haarfeine Erhebungen, die unter Lichteinfall im Grenzbereich der Totalreflexion sichtbar, durch Oberflächenmessungen jedoch nicht erfaßbar sind, und die in einem Abstand zueinander von ungefähr 1 mm auftreten.The rhythmic detachment of the polyolefin film, which is not entirely uniform, also leads to a deterioration in the desired, uniformly high-gloss surface finish of the polyolefin film. There are hair-like elevations across the paper web, which are visible under the influence of light in the border area of total reflection, but cannot be detected by surface measurements, and which occur at a distance of about 1 mm from each other.

Diese Erhebungen bleiben auch nach der Beschichtung mit einer fotografischen Emulsion erkennbar und werden nach bildmäßiger Belichtung und anschließender Entwicklung besonders in dunklen Bildbereichen als störend empfunden.These elevations remain recognizable even after they have been coated with a photographic emulsion and, after image-wise exposure and subsequent development, are found to be particularly annoying in dark areas of the image.

Um die Entstehung der fehlerhaften Markierungen zu unterbinden, mußte bislang die Extrusionsgeschwindigkeit drastisch verringert werden. Wegen des Auftretens von Ablagerungen mußte außerdem die glänzende Kühlwalze häufiger gereinigt werden.In order to prevent the formation of the faulty markings, the extrusion speed had to be reduced drastically. Because of the appearance of deposits, the glossy cooling roller also had to be cleaned more frequently.

Eine weitere Maßnahme zur Verhinderung der querverlaufenden Markierungen besteht darin, dem Polyolefin ein Trennmittel zuzusetzen, um dadurch die Haftung der Polyolefinschicht an der Kühlwalze zu verringern und eine gleichmäßig leichte Abtrennung des extrudierten Films zu erreichen. Zu diesen Trennmitteln sind die in den japanischen Offenlegungsschriften JP 32 442/1982, JP 46 818/1982 und JP 46 819/1982 genannten Metallsalze von Fettsäuren, z.B. Zink- oder Magnesiumstearat, zu zählen. Es ist außerdem bekannt, Amide, wie z.B. Oleamid und Erucasäureamid, aber auch Polyolefinwachse und Stearin als Trennmittel zu verwenden.Another measure to prevent the transverse markings is to add a release agent to the polyolefin in order to reduce the adhesion of the polyolefin layer to the cooling roller and to achieve a uniformly easy separation of the extruded film. These release agents include the metal salts of fatty acids mentioned in Japanese Patent Laid-Open JP 32 442/1982, JP 46 818/1982 and JP 46 819/1982, e.g. Zinc or magnesium stearate. It is also known to use amides such as e.g. Use oleamide and erucic acid amide, but also polyolefin waxes and stearin as release agents.

Diese bereits für die Verwendung bei der Herstellung foto­grafischer Träger beschriebenen Trennmittel weisen jedoch gravierende Nachteile auf.However, these release agents already described for use in the production of photographic supports have serious disadvantages.

Zum einen müssen diese Trennmittel bei den üblichen pigment­haltigen Polyolefinmischungen in relativ hohen Konzentrationen (0,5 - 2%) eingesetzt werden, um den gewünschten Effekt zu erzielen. Durch diese hohen Konzentrationen wird aber nicht nur die Haftung des Polyolefins an der Kühlwalze in an sich erwünschter Weise verringert, sondern es wird auch die Haftung des Polyolefins am Papierträger merklich geschwächt. Dadurch ergeben sich Nachteile bei der weiteren Verarbeitung des fotografischen Trägers, z.B. in Form des Ablösens der Poly­olefinschicht vom Papier bei der Beanspruchung in den fotografischen Prozeßlösungen oder sogar während der Beschichtung mit den fotografischen Schichten. Darüber hinaus schwitzen diese Trennmittel, z.B. Stearinsäure, Stearate oder Stearinsäureamid, bei den Extrusionstemperaturen stark aus der Polyolefinschmelze aus, so daß es zur Tropfenbildung und anschließend sichtbaren, fettfleckartigen Ablagerungen auf der Polyolefinschicht kommt.On the one hand, these release agents have to be used in the usual pigment-containing polyolefin mixtures in relatively high concentrations (0.5 - 2%) in order to achieve the desired effect. These high concentrations not only reduce the adhesion of the polyolefin to the chill roll in a manner that is desirable per se, but also significantly weaken the adhesion of the polyolefin to the paper carrier. This results in disadvantages in the further processing of the photographic support, for example in the form of detachment of the polyolefin layer from the paper when subjected to stress in the photographic process solutions or even during the coating with the photographic layers. In addition, these release agents, for example stearic acid, stearates or stearic acid amide, sweat profusely at the extrusion temperatures Polyolefin melt, so that there is drop formation and then visible, grease-stained deposits on the polyolefin layer.

In US 37 78 404 ist ferner beschrieben, daß Polyethylen­glykole mit dem Molekulargewicht 400 bis 4000 geeignete Trennmittel sein können, um die Ablösung von nicht pigmen­tierten Polyethylen-Typen mit niedriger Dichte von der Kühlwalze einer Extrusionsbeschichtungsanlage zu erleichtern. Dabei werden als Zusatzmengen 500 - 600 ppm Polyethylenglykol bei Polyethylen der Dichte 0,924 und 900 bis 1200 ppm Poly­ethylenglykol bei Polyethylen der Dichte 0,915 genannt.In US 37 78 404 it is further described that polyethylene glycols with a molecular weight of 400 to 4000 can be suitable release agents in order to facilitate the detachment of unpigmented low density polyethylene types from the cooling roll of an extrusion coating system. 500 - 600 ppm of polyethylene glycol for 0.924 density polyethylene and 900 to 1200 ppm of polyethylene glycol for 0.915 density polyethylene are mentioned as additional amounts.

Eine Übertragung des Zusatzes von Polyethylenglykol auf pigmentierte Polyolefinmischungen für fotografische Träger­papiere war jedoch aus verschiedenen Gründen keineswegs naheliegend. Polyalkylenoxide sind dem Fachmann einerseits als Stoffe bekannt, die fotografische Silbersalzschichten sensibi­lisieren. (Neblette's Handbook of Photography and Reprography, 1977). Infolgedessen erschien ihre Verwendung im Trägermaterial grundsätzlich unerwünscht, weil die Migration von dort in die fotografischen Schichten nicht kontrollierbar ist. Andererseits ist bekannt, daß Polyalkylenoxide sich an der Pigmentoberfläche anlagern und diese hydrophilieren. Diese Anlagerung führt nicht nur zu einer festen Bindung an der Pigmentoberfläche sondern auch zu einer Verstärkung der Feuchtezurückhaltung in der Polyethylen/Pigment-Mischung, und es war eine Verstärkung des bekannten "lacing"-Effekts bei Extrusionsbeschichtung von Mischungen mit mehr als 10 % Pigment zu befürchten. Schließlich hatte eine Nacharbeitung der US 37 78 404 ergeben, daß die Polyolefinhaftung am Basispapier durch den Zusatz von z.B. 600 ppm Polyethylenglykol 600 zum Polyethylen meßbar verschlechtert wird.A transfer of the addition of polyethylene glycol to pigmented polyolefin mixtures for photographic base papers was, however, by no means obvious for various reasons. On the one hand, polyalkylene oxides are known to the person skilled in the art as substances which sensitize photographic silver salt layers. (Neblette's Handbook of Photography and Reprography, 1977). As a result, their use in the support material appeared fundamentally undesirable because the migration from there to the photographic layers cannot be controlled. On the other hand, it is known that polyalkylene oxides attach to the pigment surface and make it hydrophilic. This attachment not only leads to a firm bond to the pigment surface but also to an increase in moisture retention in the polyethylene / pigment mixture, and it was an enhancement of the known "lacing" effect when extrusion coating mixtures with more than 10% pigment fear. Finally, a revision of US 37 78 404 had shown that the polyolefin adhesion to the base paper by the addition of e.g. 600 ppm polyethylene glycol 600 is measurably deteriorated to polyethylene.

Aufgabe der Erfindung ist es daher, ein Polyolefin-beschichtetes Trägermaterial mit hochglänzender Oberfläche des pigmenthaltigen Polyolefinüberzugs zu schaffen, bei dem sich die pigmenthaltige Polyolefinschicht leicht und gleichmäßig von der hochglänzenden Kühlwalze löst und trotzdem gut auf dem Basispapier haftet und keine die Empfindlichkeit aufliegender fotografischer Schichten verändernde Wirkungen hat.The object of the invention is therefore to provide a polyolefin-coated carrier material with a high-gloss surface of the pigment-containing polyolefin coating, in which the pigment-containing polyolefin layer is easily and uniformly detached from the high-gloss cooling roller and nevertheless adheres well to the base paper and has no effect on the sensitivity of overlying photographic layers.

Diese Aufgabe wird dadurch gelöst, daß ein fotografisches Basispapier auf der den fotografischen Schichten zunächst liegenden Seite mit einer Polyolefinmischung überzogen wird, die neben Polyolefin und Weißpigment mindestens ein Polyoxyalkylenglykol enthält. In einer besonderen Ausführungs­form enthält die pigmentierte Polyolefinmischung neben Polyalkylenoxid noch eine Fettsäureseife eines mehrwertigen Metalls oder ein Fettsäureamid.This object is achieved in that a photographic base paper is coated on the side lying first of the photographic layers with a polyolefin mixture which contains at least one polyoxyalkylene glycol in addition to polyolefin and white pigment. In a particular embodiment, the pigmented polyolefin mixture contains, in addition to polyalkylene oxide, a fatty acid soap of a polyvalent metal or a fatty acid amide.

Zur Beschichtung eines fotografischen Basispapieres kommen verschiedene Polyolefine, z.B. Polyethylen, Polypropylen oder ein Olefincopolymer einzeln oder in Mischung in Frage. Das bevorzugte Beschichtungsharz ist jedoch Polyethylen, das sowohl mit hoher als auch mit niedriger Dichte, sowie als Abmischung beider Typen verwendet werden kann.Various polyolefins are used to coat a photographic base paper, e.g. Polyethylene, polypropylene or an olefin copolymer individually or as a mixture in question. However, the preferred coating resin is polyethylene, which can be used with both high and low density, and as a blend of both types.

In fotografischen Trägermaterialien ist bevorzugtes Weißpigment ein Titandioxid oder eine Mischung von Titandioxid mit einem anderen Weißpigment oder Füllstoff. Außerdem können kleine Mengen farbiger Pigmente, Farbstoffe, optischer Aufheller oder andere bekannte Zusätze enthalten sein.In photographic support materials, preferred white pigment is a titanium dioxide or a mixture of titanium dioxide with another white pigment or filler. Small amounts of colored pigments, dyes, optical brighteners or other known additives may also be present.

Die Polyolefinbeschichtungsmasse kann auf einer oder beiden Papierseiten aufgetragen sein. Der Auftrag erfolgt mittels Extrusionsbeschichtung unter Verwendung einer Breitschlitzdüse bei Temperaturen von 270 bis 330°C.The polyolefin coating composition can be applied to one or both sides of the paper. The application is carried out by means of extrusion coating using a slot die at temperatures of 270 to 330 ° C.

Die mit einer erfindungsgemäßen Pigment enthaltenden Polyethylen-­Mischung zu beschichtende Papierunterlage kann ein beliebiges fotografisches Basispapier sein, das entweder unter Verwendung von Alkylketendimer neutral geleimt ist oder eine bekannte saure Leimung auf der Basis von gefällten Harz- oder Fettsäure­seifen hat. Das Basispapier kann ausschließlich aus Zellstoff­fasern oder aus Mischungen von Zellstofffasern mit synthetischen Fasern hergestellt sein. Es kann ein Flächengewicht von 60 bis 300 g/m² (vorzugsweise 70 bis 200 g/m²) haben und zusätzlich zur Innenleimung eine Oberflächenleimung enthalten. Allgemein wird unter einem fotografischen Basispapier ein hochweißes Papier mit gleichmäßiger Durchsicht verstanden, das durch eine spezielle starke Leimung gegen ein Eindringen der fotografischen Behandlungslösungen gesichert ist und trotzdem keine fotochemischen Wirkungen auf fotografische Schichten zeigt.The paper base to be coated with a polyethylene mixture containing pigment according to the invention can be any photographic base paper which is either neutral sized using alkyl ketene dimer or has a known acidic size based on precipitated resin or fatty acid soaps. The base paper can be made exclusively from cellulose fibers or from mixtures of cellulose fibers with synthetic fibers. It can have a basis weight of 60 to 300 g / m² (preferably 70 to 200 g / m²) and contain a surface sizing in addition to the inside sizing. General a photographic base paper is understood to mean a bright white paper with a uniform transparency, which is secured against penetration of the photographic treatment solutions by a special strong sizing and yet shows no photochemical effects on photographic layers.

Bei dem der Polyolefin/Pigment-Mischung zugesetzten Polyoxyalkylenglykol handelt es sich vorzugsweise um ein Polyethylenglykol mit einem Molekulargewicht zwischen 100 und 35 000, bevorzugt zwischen 400 und 20 000, oder um ein Polypropylenglykol mit einem Molekulargewicht zwischen 400 und 10 000, bevorzugt zwischen 2 000 und 10 000.The polyoxyalkylene glycol added to the polyolefin / pigment mixture is preferably a polyethylene glycol with a molecular weight between 100 and 35,000, preferably between 400 and 20,000, or a polypropylene glycol with a molecular weight between 400 and 10,000, preferably between 2,000 and 10,000.

Das als Trennmittel verwendete Polyoxyalkylenglykol kann der Polyethylenmischung auf jede bekannte Weise zugesetzt werden, bevorzugt ist jedoch die Einbringung des Polyoxyal­kylenglykols über eine Vormischung (Masterbatch).The polyoxyalkylene glycol used as a release agent can be added to the polyethylene mixture in any known manner, but it is preferred to introduce the polyoxyalkylene glycol via a premix (masterbatch).

Die verwendete Menge des Polyoxyalkylenglykols liegt zwischen 40 ppm und 1% bezogen auf die Gesamtmenge des Polyethylens, vorzugsweise jedoch zwischen 100 ppa und 0,5 %.The amount of polyoxyalkylene glycol used is between 40 ppm and 1% based on the total amount of polyethylene, but preferably between 100 ppa and 0.5%.

In dem angegebenen Mengenbereich wird die Entstehung der querverlaufenden Markierungen vollständig vermieden, die Haftung des Polyolefinfilms auf dem Basispapier jedoch nicht nachteilig beeinflußt.In the specified quantity range, the formation of the transverse markings is completely avoided, but the adhesion of the polyolefin film to the base paper is not adversely affected.

Dieses Ergebnis ist in mehrfacher Hinsicht überraschend.This result is surprising in several ways.

Erstens wird der erfindungsgemäße Effekt schon bei der sehr geringen Trennmittelkonzentration von 40 ppm Polyoxyalkylen­glykol bezogen auf die Gesamtmenge der Polyethylen/Pigment-­Mischung erreicht. Die für die Verwendung in fotografischen Trägern bereits beschriebenen Trennmittel entfalten ihre Wirkung erst bei wesentlich höheren Konzentrationen.First, the effect according to the invention is achieved even at the very low release agent concentration of 40 ppm polyoxyalkylene glycol based on the total amount of the polyethylene / pigment mixture. The release agents already described for use in photographic supports only take effect at much higher concentrations.

Zweitens bleibt der erfindungsgemäße Effekt ohne sichtbare Ausschwitzungen über einen großen Konzentrationsbereich erhalten. Im gesamten Bereich, d.h. auch bei Konzentrationen von 0,5 bis 1%, in denen die üblicherweise verwendeten Trennmittel eingebracht werden, löst sich bei der Verwendung von Polyether­glykolen gemäß der Erfindung der Polyethylenfilm leicht von der Kühlwalze und die Haftung des Polyethylenfilms auf dem Papier­träger bleibt gut bis befriedigend, während bei den bislang bekannten Trennmitteln die bereits beschriebenen Mängel auftreten.Second, the effect according to the invention is retained over a large concentration range without visible exudates. In the entire range, ie also at concentrations of 0.5 to 1%, in which the release agents usually used are introduced, when using polyether glycols according to the invention the polyethylene film easily detaches from the cooling roller and the adhesion of the polyethylene film to the paper carrier remains good to satisfactory, whereas in the case of the previously known release agents the defects already described occur.

Darüber hinaus tritt bei der Verwendung der erfindungsgemäßen Trennmittel weder eine Verschmutzung der Kühlwalze durch Ankleben kurzkettiger Polyolefinbestandteile auf, noch ist eine Tropfenbildung und die damit verbundene Verunreinigung des extrudierten Polyolefinfilms durch übermäßig stark ausgeschwitztes Trennmittel zu beachten, noch werden Empfindlichkeitsänderungen in aufliegenden fotografischen Schichten beobachtet.In addition, when the release agents according to the invention are used, the cooling roller is not contaminated by sticking on short-chain polyolefin constituents, nor is there any drop formation and the associated contamination of the extruded polyolefin film by excessively exudated release agent, nor are changes in sensitivity observed in overlying photographic layers.

Bei der Verwendung von Polyoxyalkylenglykolmengen geringer als 40 ppm bezogen auf die Gesamtmenge der Polyethylenmischung wird jedoch die Ablösung des Polyethylenfilms von der Kühlwalze eindeutig schlechter als erfindungsgemäß beschrieben und es zeigen sich die beschriebenen Markierungen in der Oberfläche des fotografischen Trägermaterials.If polyoxyalkylene glycol amounts of less than 40 ppm, based on the total amount of the polyethylene mixture, are used, however, the detachment of the polyethylene film from the chill roll is clearly worse than described according to the invention and the markings described appear in the surface of the photographic support material.

Bei einem Polyoxyalkylenglykolgehalt größer als 1% bezogen auf die Polyethylenmischung erfolgt zwar die Abtrennung des Polyethylenfilms von der Kühlwalze leicht und gleichmäßig, eine ausreichende Haftung auf dem Papierträger ist jedoch im allgemeinen nicht mehr gegeben.If the polyoxyalkylene glycol content is greater than 1%, based on the polyethylene mixture, the separation of the polyethylene film from the cooling roller takes place easily and uniformly, but adequate adhesion to the paper carrier is generally no longer ensured.

In einer besonderen Ausführungsform der Erfindung wird das fotografische Basispapier mit einer Weißpigment enthaltenden Polyolefinmischung überzogen, die neben einem Polyoxyalkylen­glykol noch ein Fettsäuresalz eines mehrwertigen Metalls, z.B. Al-Stearat, Mg-Stearat, Zn-Stearat o.a., oder ein Fettsäureamid enthält. Diese kombinierte Verwendung von Polyglykol mit einem an sich als Trennmittel bekannten Fettsäurederivat zeigte in Pigment enthaltenden Polyolefin­mischungen überraschenderweise einen synergistischen Effekt.In a special embodiment of the invention, the photographic base paper is coated with a white pigment-containing polyolefin mixture which, in addition to a polyoxyalkylene glycol, also contains a fatty acid salt of a polyvalent metal, for example Al stearate, Mg stearate, Zn stearate or the like, or a fatty acid amide. This combined use of polyglycol with a fatty acid derivative known per se as a release agent surprisingly showed a synergistic effect in pigment-containing polyolefin mixtures.

Dieser drückt sich darin aus, daß die Trennung vom Kühlzylinder bei kombiniertem Einsatz von Polyglykol und Fettsäurederivat leichter und sauberer geschieht als bei Einzeleinsatz der Komponenten. Sonst übliche Ablagerungen auf der Walze unter­bleiben und die Haftung der Schicht am Basispapier ist überraschend gut.This is expressed in the fact that the separation from the cooling cylinder is easier and cleaner when the polyglycol and fatty acid derivative are used than when the components are used individually. Otherwise usual deposits on the roller are avoided and the adhesion of the layer to the base paper is surprisingly good.

Der erfinderische Gedanke wird durch die folgenden Beispiele näher erläutert.The inventive idea is explained in more detail by the following examples.

Beispiel 1example 1

Ein ca. 160 g/m² schweres unter Verwendung von Alkylketendimer gleimtes fotografisches Basispapier wurde mittels Extrusions­beschichtung mit einer Polyethylenmischung folgender Zusammensetzung überzogen:
50 Gew.-% Niederdruckpolyethylen (Dichte 0,963, Schmelzindex 10)
40 Gew.-% Hochdruckpolyethylen (Dichte 0,918, Schmelzindex 7)
10 Gew.-% TiO₂ (Rutil-Typ)An approx. 160 g / m² heavy photographic base paper glued using alkyl ketene dimer was coated by extrusion coating with a polyethylene mixture of the following composition:
50% by weight low-pressure polyethylene (density 0.963, melt index 10)
40% by weight high-pressure polyethylene (density 0.918, melt index 7)
10% by weight TiO₂ (rutile type)

Der Mischung wurden vor der Extrusion Polyethylenglykole folgender Molekulargewichte in Form einer Vormischung (Masterbatch) zugesetzt

Figure imgb0001
Before the extrusion, polyethylene glycols of the following molecular weights were added to the mixture in the form of a premix (masterbatch)
Figure imgb0001

Beispiel 2Example 2

Ein ca. 160 g/m² schweres unter Verwendung von Alkylketendimer geleimtes fotografisches Basispapier wurde mittels Extrusions­beschichtung mit einer Polyethylenmischung folgender Zusammensetzung überzogen:
50 Gew.-% Niederdruckpolyethylen (Dichte 0,963, Schmelzbinder 10)
40 Gew.-% Hochdruckpolyethylen (Dichte 0,918, Schmelzindex 7)
10 Gew.-% TiO₂ (Rutil-Typ)An approx. 160 g / m² heavy photographic base paper sized using alkyl ketene dimer was extrusion coated with a polyethylene mixture of the following composition:
50% by weight low-pressure polyethylene (density 0.963, melt binder 10)
40% by weight high-pressure polyethylene (density 0.918, melt index 7)
10% by weight TiO₂ (rutile type)

Der Mischung wurden vor der Extrusion Polypropylenglykole folgender Molekulargewichte in Form einer Vormischung (Masterbatch) zugesetzt:

Figure imgb0002
Before the extrusion, polypropylene glycols of the following molecular weights were added to the mixture in the form of a premix (master batch):
Figure imgb0002

Beispiel 3Example 3

Ein ca. 160 g/m² schweres unter Verwendung von Alkylketendimer geleimtes fotografisches Basispapier wurde mittels Extrusions­beschichtung mit einer Polyethylenmischung folgender Zusammensetzung überzogen:
50 Gew.-% Niederdruckpolyethylen (Dichte 0,963, Schmelzindex 10)
40 Gew.-% Hochdruckpolyethylen (Dichte 0,918, Schmelzindex 7)
10 Gew.-% TiO₂ (Anatas-Typ)An approx. 160 g / m² heavy photographic base paper sized using alkyl ketene dimer was extrusion coated with a polyethylene mixture of the following composition:
50% by weight low-pressure polyethylene (density 0.963, melt index 10)
40% by weight high-pressure polyethylene (density 0.918, melt index 7)
10% by weight TiO₂ (anatase type)

Der Mischung wurden vor der Extrusion Polypropylenglykole in folgenden Mengen in Form einer Vormischung (Masterbatch) zugesetzt:

Figure imgb0003
Before extrusion, the mixture was added to the mixture in the following amounts in the form of a premix (masterbatch):
Figure imgb0003

Beispiel 4Example 4

Ein ca. 160 g/m² schweres unter Verwendung von Alkylketendimer geleimtes fotografisches Basispapier wurde mittels Extrusions­beschichtung mit einer Polyethylenmischung folgender Zusammensetzung überzogen:
50 Gew.-% Niederdruckpolyethylen (Dichte 0,963, Schmelzindex 10)
40 Gew.-% Hochdruckpolyethylen (Dichte 0,918, Schmelzindex 7)
10 Gew.-% TiO₂ (Anatas-Typ)An approx. 160 g / m² heavy photographic base paper sized using alkyl ketene dimer was extrusion coated with a polyethylene mixture of the following composition:
50% by weight low-pressure polyethylene (density 0.963, melt index 10)
40% by weight high-pressure polyethylene (density 0.918, melt index 7)
10% by weight TiO₂ (anatase type)

Der Mischung wurden vor der Extrusion Polypropylenglykole in folgenden Mengen in Form einer Vormischung (Masterbatch) zugesetzt:

Figure imgb0004
Before extrusion, the mixture was added to the mixture in the following amounts in the form of a premix (masterbatch):
Figure imgb0004

Beispiel 5Example 5

Ein ca. 100 g/m² schweres unter Verwendung von Fettsäureseifen sauer geleimtes fotografisches Basispapier wurde mittels Extrusionsbeschichtung mit einer Polyethylenmischung folgender Zusammensetzung:
25 Gew.-% Niederdruckpolyethylen (Dichte 0,963, Schmelzindex 10)
63 Gew.-% Hochdruckpolyethylen (Dichte 0,918, Schmelzindex 7)
versetzt mit den Zusätzen gemäß der Zusammenstellung in Tabelle 1, überzogen.

Figure imgb0005
An approx. 100 g / m² heavy photographic base paper that was acid-sized using fatty acid soaps was extrusion-coated with a polyethylene mixture of the following composition:
25% by weight low-pressure polyethylene (density 0.963, melt index 10)
63% by weight high-pressure polyethylene (density 0.918, melt index 7)
mixed with the additives according to the compilation in Table 1, coated.
Figure imgb0005

Beispiel 6Example 6

Ein ca. 200 g/m² schweres unter Verwendung von Alkylketendimer geleimtes fotografisches Basispapier mit einer Oberflächen­leimung aus Stärke und Natriumsulfat wurde mittels Extrusions­beschichtung mit einer Polyethylenmischung folgender Zusammensetzung überzogen:
20 Gew.-% Niederdruckpolyethylen (Dichte 0,963, Schmelzindex 10)
70 Gew.-% Hochdruckpolyethylen (Dichte 0,918, Schmelzindex 7)
9,8 Gew.-% TiO₂
0,1 Gew.-% optischer Aufheller
0,1 Gew.-% Stabilisator
300 ppm Polyoxyalkylenglykol

  • 6a: Das Polyoxyalkylenglykol ist ein Polyethylenglykol (MW 600) und wird in Form einer Vormischung zugesetzt.
  • 6b: Das Polyoxyalkylenglykol ist ein Polyethylenglykol (MW 600) und wird in die Extrusionsschmelze mittels einer Dosierpumpe eingebracht.
  • 6c: Das Polyoxyalkylenglykol ist ein Polypropylenglykol (MW 2000) und wird in Form einer Vormischung zugesetzt.
  • 6d: Das Polyoxyalkylenglykol ist ein Polypropylenglykol (MW 2000) und wird in die Extrusionsschmelze mittels einer Dosierpumpe eingebracht.
An approx. 200 g / m² heavy photographic base paper sized using alkyl ketene dimer with a surface size made of starch and sodium sulfate was extrusion coated with a polyethylene mixture of the following composition:
20% by weight low-pressure polyethylene (density 0.963, melt index 10)
70% by weight high-pressure polyethylene (density 0.918, melt index 7)
9.8% by weight of TiO₂
0.1% by weight of optical brighteners
0.1 wt% stabilizer
300 ppm polyoxyalkylene glycol
  • 6a: The polyoxyalkylene glycol is a polyethylene glycol (MW 600) and is added in the form of a premix.
  • 6b: The polyoxyalkylene glycol is a polyethylene glycol (MW 600) and is introduced into the extrusion melt by means of a metering pump.
  • 6c: The polyoxyalkylene glycol is a polypropylene glycol (MW 2000) and is added in the form of a premix.
  • 6d: The polyoxyalkylene glycol is a polypropylene glycol (MW 2000) and is introduced into the extrusion melt by means of a metering pump.

Beispiel 7Example 7

Ein ca. 160 g/m² schweres unter Verwendung von Alkylketendimer Natriumstearat, Aluminiumsalz und epoxidiertem Fettsäureamid geleimtes und mit carboxiliertem Polyvinylalkohol oberflächen­geleimtes fotografisches Basispapier wurde mittels Extrusions­beschichtung mit einer Polyethylenmischung folgender Zusammensetzung überzogen:
30 Gew.-% Niederdruckpolyethylen (Dichte 0,963, Schmelzindex 9)
57 Gew.-% Hochdruckpolyethylen (Dichte 0,915, Schmelzindex 7)
12,9 Gew.-% Titandioxid (Rutiltyp)
0,03 Gew.-% Ultramarinblau
0,01 Gew.-% phenolisches Antioxidans
0,06 Gew.-% sterisch gehindertes polymeres Amin (M = ca. 2500)An approx. 160 g / m² heavy photographic base paper sized using alkyl ketene dimer sodium stearate, aluminum salt and epoxidized fatty acid amide and surface-sized with carboxylated polyvinyl alcohol was coated by extrusion coating with a polyethylene mixture of the following composition:
30% by weight low-pressure polyethylene (density 0.963, melt index 9)
57% by weight high-pressure polyethylene (density 0.915, melt index 7)
12.9% by weight titanium dioxide (rutile type)
0.03 wt% ultramarine blue
0.01% by weight phenolic antioxidant
0.06% by weight of sterically hindered polymeric amine (M = approx. 2500)

Der Mischung wurden vor der Extrusion die folgenden Kombinationen von Trennmitteln in Form von Vormischungen mit Polyethylen (Masterbatch) zugesetzt:

  • 7a: 200 ppm Polyethylenglykol 600
    0,4 % Magnesiumstearat
  • 7b: 100 ppm Polyethylenglykol 600
    0,4 % Aluminumstearat
  • 7c: 200 ppm Polyethylenglykol 600
    0,1 % Erucasäureamid
  • 7d: 200 ppm Polyethylenglykol 600
    0,3 % Aluminiumstearat
    100 ppm Erucasäureamid
  • 7e: 400 ppm Polyethylenglykol 600
    0,2 % Aluminiumstearat
  • 7f: 400 ppm Polyethylenglykol 1000
    0,1 % Magnesiumstearat
    300 ppm Erucasäureamid
  • 7g: 300 ppm Polyethylenglykol 10000
    0,2 % Zinkstearat
    300 ppm Erucasäureamid
  • 7h: 500 ppm Polyethylenglykol 10000
    0,1 % Aluminiumstearat
    500 ppm Behensäureamid
The following combinations of release agents in the form of premixes with polyethylene (masterbatch) were added to the mixture before the extrusion:
  • 7a: 200 ppm polyethylene glycol 600
    0.4% magnesium stearate
  • 7b: 100 ppm polyethylene glycol 600
    0.4% aluminum stearate
  • 7c: 200 ppm polyethylene glycol 600
    0.1% erucic acid amide
  • 7d: 200 ppm polyethylene glycol 600
    0.3% aluminum stearate
    100 ppm erucic acid amide
  • 7e: 400 ppm polyethylene glycol 600
    0.2% aluminum stearate
  • 7f: 400 ppm polyethylene glycol 1000
    0.1% magnesium stearate
    300 ppm erucic acid amide
  • 7g: 300 ppm polyethylene glycol 10000
    0.2% zinc stearate
    300 ppm erucic acid amide
  • 7h: 500 ppm polyethylene glycol 10000
    0.1% aluminum stearate
    500 ppm behenic amide

Vergleichsbeispiel 1VComparative Example 1V

Ein ca. 160 g/m² schweres unter Verwendung von Alkylketendimer geleimtes fotografisches Basispapier wurde mittels Extrusions­beschichtung mit einer Polyethylenmischung folgender Zusammensetzung überzogen:
50 Gew.-% Niederdruckpolyethylen (Dichte 0,963, Schmelzindex 10)
40 Gew.-% Hochdruckpolyethylen (Dichte 0,918, Schmelzindex 7)
10 Gew.-% TiO₂ (Anatastyp)An approx. 160 g / m² heavy photographic base paper sized using alkyl ketene dimer was extrusion coated with a polyethylene mixture of the following composition:
50% by weight low-pressure polyethylene (density 0.963, melt index 10)
40% by weight high-pressure polyethylene (density 0.918, melt index 7)
10% by weight TiO₂ (anatase type)

Der Mischung wurde vor der Extrusion Zinkstearat, Magnesium­stearat, Aluminiumstearat oder Erucasäureamid in folgenden Mengen in Form einer Vormischung (Masterbatch) zugesetzt:

Figure imgb0006
Before the extrusion, zinc stearate, magnesium stearate, aluminum stearate or erucic acid amide were added to the mixture in the following amounts in the form of a premix (masterbatch):
Figure imgb0006

Vergleichsbeispiel 2VComparative Example 2V

Ein ca. 100 g/m² schweres unter Verwendung von Fettsäureseifen sauer geleimtes fotografisches Basispapier wird mit Polyethylen­mischungen folgender Zusammensetzungen überzogen:
25 Gew.-% Niederdruckpolyethylen (Dichte 0,963, Schmelzindex 10)
63 Gew.-% Hochdruckpolyethylen (Dichte 0,918, Schmelzindex 7)
10 Gew.-% TiO₂ (Rutiltyp)
0,60 Gew.-% Kobaltblau
0,78 Gew.-% Kobaltviolett
0,05 Gew.-% optischer Aufheller
0,01 Gew.-% phenolisches Antioxidans
0,06 Gew.-% sterisch gehindertes Amin (M = ca. 2500)
sowie

  • 2V/a 0,5 Gew.-% Zinkstearat
  • 2V7b 0,5 Gew.-% Magnesiumstearat
  • 2V/c 0,5 Gew.-% Erucasäureamid
An approx. 100 g / m² heavy photographic base paper that is acid-sized using fatty acid soaps is coated with polyethylene mixtures of the following compositions:
25% by weight low-pressure polyethylene (density 0.963, melt index 10)
63% by weight high-pressure polyethylene (density 0.918, melt index 7)
10% by weight TiO₂ (rutile type)
0.60% by weight cobalt blue
0.78 wt% cobalt violet
0.05% by weight optical brightener
0.01% by weight phenolic antioxidant
0.06% by weight of sterically hindered amine (M = approx. 2500)
such as
  • 2V / a 0.5% by weight zinc stearate
  • 2V7b 0.5% by weight magnesium stearate
  • 2V / c 0.5% by weight erucic acid amide

Prüfung der TrägermaterialienExamination of the carrier materials

Für die Prüfung der Trägermaterialien wurden drei Kriterien herangezogen:

  • 1.) das Ablösen des Polyethylenfilms von der Kühlwalze.
    Das Ablösen läßt sich visuell beurteilen und mit den drei Noten leichtes Ablösen ("leicht"), befriedigendes Ablösen ("mittel") oder schlechtes Ablösen ("schlecht") beschreiben.
  • 2.) das Auftreten der fehlerhaften Markierungen auf den Oberflächen bei Beschichtungs­geschwindigkeiten von 100 und 150 m/min. Diese Markierungen können stark ("++") oder vereinzelt ("+") oder gar nicht ("0") auftreten.
  • 3.) die Haftung des Polyethylenfilms am Papierträger bei der Beschichtungs­geschwindigkeit von 100 m/min. Zur Bestimmung der Haftung wird der Poly­ethylenfilm von dem Papierträger in einem Winkel von 180° abgezogen.
    Läßt sich der Polyethylenfilm ohne Beschädigung des Faserfilzes des Papierträgers abziehen, so wird die Haftung mit "5" benotet. Je nach Ausmaß der Schädigung des Faserfilzes erhält man Haftungsnoten von "4" (ausreichende Haftung), "3" (befriedigende Haftung) oder "2"(gute Haftung).
Figure imgb0007
Figure imgb0008
Figure imgb0009
Figure imgb0010
Figure imgb0011
Figure imgb0012
Figure imgb0013
Figure imgb0014
 Three criteria were used to test the carrier materials:
  • 1.) the peeling of the polyethylene film from the cooling roll.
    The detachment can be assessed visually and described with the three notes easy detachment ("easy"), satisfactory detachment ("medium") or poor detachment ("bad").
  • 2.) the appearance of the faulty markings on the surfaces at coating speeds of 100 and 150 m / min. These markings can appear heavily ("++") or occasionally ("+") or not at all ("0").
  • 3.) the adhesion of the polyethylene film to the paper support at a coating speed of 100 m / min. To determine the adhesion, the polyethylene film is pulled off the paper backing at an angle of 180 °.
    If the polyethylene film can be removed without damaging the fiber felt of the paper backing, the liability is rated "5". Depending on the extent of the damage to the fiber felt, adhesion ratings of "4" (sufficient adhesion), "3" (satisfactory adhesion) or "2" (good adhesion) are obtained.
Figure imgb0007
Figure imgb0008
Figure imgb0009
Figure imgb0010
Figure imgb0011
Figure imgb0012
Figure imgb0013
Figure imgb0014

Claims (14)

1. Fotografisches Trägermaterial bestehend aus fotografischem Basispapier und mindestens einer auf dem Papier angeordneten Weißpigment enthaltenden Polyolefinschicht, dadurch gekennzeichnet, daß die Polyolefinschicht zusätzlich ein Polyalkylenglykol enthält und daß das Polyalkylenglykol in der Menge zwischen 40 ppm und 1% bezogen auf die Gesamt­menge der Polyolefinmischung enthalten ist.1. Photographic support material consisting of photographic base paper and at least one arranged on the paper white pigment-containing polyolefin layer, characterized in that the polyolefin layer additionally contains a polyalkylene glycol and that the polyalkylene glycol is contained in the amount between 40 ppm and 1% based on the total amount of the polyolefin mixture . 2. Fotografisches Trägermaterial gemäß Anspruch 1, dadurch gekennzeichnet, daß das Polyalkylenglykol Polyethylenglykol ist.2. Photographic support material according to claim 1, characterized in that the polyalkylene glycol is polyethylene glycol. 3. Fotografisches Trägermaterial gemäß Anspruch 1, dadurch gekennzeichnet, daß das Polyalkylenglykol Polypropylenglykol ist.3. Photographic support material according to claim 1, characterized in that the polyalkylene glycol is polypropylene glycol. 4. Fotografisches Trägermaterial gemäß Anspruch 1 und 2, dadurch gekennzeichnet, daß das Polethylenglykol ein Molekulargewicht von 100 bis 35 000, vorzugsweise von 400 bis 20 000, besitzt.4. Photographic support material according to claim 1 and 2, characterized in that the polyethylene glycol has a molecular weight of 100 to 35,000, preferably from 400 to 20,000. 5. Fotografisches Trägermaterial gemäß Anspruch 1 und 3, dadurch gekennzeichnet, daß das Polypropylenglykol ein Molekulargewicht von 400 bis 10 000, vorzugsweise 2000 bis 4000, besitzt.5. Photographic support material according to claim 1 and 3, characterized in that the polypropylene glycol has a molecular weight of 400 to 10,000, preferably 2000 to 4000. 6. Fotografisches Trägermaterial gemäß Anspruch 1, dadurch gekennzeichnet, daß das Polyalkylenglykol vorzugsweise in einer Menge von 100 ppa bis 0,5% bezogen auf die Gesamtmenge der Polyolefinmischung enthalten ist.6. Photographic support material according to claim 1, characterized in that the polyalkylene glycol is preferably contained in an amount of 100 ppa to 0.5% based on the total amount of the polyolefin mixture. 7. Fotografisches Trägermaterial bestehend aus einem fotografischen Basispapier und mindestens einer auf dem Papier angeordneten Weißpigment enthaltenden Polyolefinschicht, dadurch gekennzeichnet, daß die Polyolefinschicht zusätzlich wenigstens ein Polyalkylen­glykol und wenigstens ein Fettsäurederivat aus der Gruppe der Seifen und der Fettsäureamide enthält.7. Photographic support material consisting of a photographic base paper and at least one polyolefin layer containing white pigment arranged on the paper, characterized in that the polyolefin layer additionally contains at least one polyalkylene glycol and at least one fatty acid derivative from the group of soaps and fatty acid amides. 8. Fotografisches Trägermaterial gemäß Anspruch 7, dadurch gekennzeichnet, daß die Fettsäureseife eine Seife eines mehrwertigen Metalles ist.8. Photographic support material according to claim 7, characterized in that the fatty acid soap is a soap of a polyvalent metal. 9. Fotografisches Trägermaterial gemäß Anspruch 7, dadurch gekennzeichnet, daß das Fettsäurederivat von einer C₁₄- bis C₂₄-Fettsäure abgeleitet ist.9. Photographic support material according to claim 7, characterized in that the fatty acid derivative is derived from a C₁₄ to C₂₄ fatty acid. 10. Fotografisches Trägermaterial bestehend aus einem fotografischen Basispapier und mindestens einer auf dem Papier angeordneten Weißpigment enthaltenden Polyolefinschicht, dadurch gekennzeichnet, daß die Polyolefinschicht zusätzlich ein Polyalkylenglykol, eine Fettsäureseife und ein Fettsäureamid enthält.10. Photographic support material consisting of a photographic base paper and at least one polyolefin layer containing white pigment arranged on the paper, characterized in that the polyolefin layer additionally contains a polyalkylene glycol, a fatty acid soap and a fatty acid amide. 11. Fotografisches Trägermaterial gemäß Anspruch 1, 7 oder 10, dadurch gekennzeichnet, daß die Gegenseite ebenfalls mit Polyolefin beschichtet ist.11. Photographic support material according to claim 1, 7 or 10, characterized in that the opposite side is also coated with polyolefin. 12. Fotografisches Trägermaterial gemäß Anspruch 1, 7 oder 10, dadurch gekennzeichnet, daß die vorder­seitige Schicht durch physikalische oder chemische Vorbehandlung für die Aufnahme einer fotografischen Schicht vorbereitet ist.12. Photographic support material according to claim 1, 7 or 10, characterized in that the front layer is prepared by physical or chemical pretreatment for the inclusion of a photographic layer. 13. Verfahren zur Herstellung eines fotografischen Trägermaterials gemäß Anspruch 1, dadurch gekennzeichnet, daß das Basispapier mittels Extrusionsbeschichtung mit einer Weißpigment enthaltenden Polyolefinmischung beschichtet wird, die ein Polyalkylenglykol enthält.13. A method for producing a photographic support material according to claim 1, characterized in that the base paper is coated by means of extrusion coating with a polyolefin mixture containing white pigment, which contains a polyalkylene glycol. 14. Verfahren zur Herstellung eines fotografischen Träger­materials gemäß Anspruch 7, dadurch gekennzeichnet, daß das Basispapier mittels Extrusionsbeschichtung mit einer Weißpigment enthaltenden Polyolefinmischung beschichtet wird, die wenigstens ein Polyalkylenglykol und wenigstens ein Fettsäurederivat aus der Gruppe der Seifen und der Fettsäureamide enthält.14. A method for producing a photographic support material according to claim 7, characterized in that the base paper is coated by means of extrusion coating with a white pigment-containing polyolefin mixture which contains at least one polyalkylene glycol and at least one fatty acid derivative from the group of soaps and fatty acid amides.
EP86110061A 1986-07-22 1986-07-22 Photographic-paper support and process for its production Expired - Lifetime EP0253911B1 (en)

Priority Applications (11)

Application Number Priority Date Filing Date Title
EP86110061A EP0253911B1 (en) 1986-07-22 1986-07-22 Photographic-paper support and process for its production
AT86110061T ATE50369T1 (en) 1986-07-22 1986-07-22 PHOTOGRAPHIC PAPER SUPPORT AND PROCESS FOR ITS MANUFACTURE.
DE8686110061T DE3668995D1 (en) 1986-07-22 1986-07-22 PHOTOGRAPHIC PAPER CARRIER AND METHOD FOR THE PRODUCTION THEREOF.
JP61278934A JPH0660992B2 (en) 1986-07-22 1986-11-25 Photographic carrier material and manufacturing method thereof
HU871855A HU201581B (en) 1986-07-22 1987-04-27 Photographic carrier metters
ES8701428A ES2003722A6 (en) 1986-07-22 1987-05-13 Photographic-paper support and process for its production.
AU72932/87A AU594153B2 (en) 1986-07-22 1987-05-14 Photographic carrier paper and method for its manufacture
CN87104888.4A CN1031299C (en) 1986-07-22 1987-06-10 Photographic paper base and mfg. process therefor
US07/072,406 US4895757A (en) 1986-07-22 1987-07-13 Photographic paper support manufacture
YU133187A YU45949B (en) 1986-07-22 1987-07-16 PHOTOGRAPHIC PAPER CARRIER AND PROCEDURE FOR ITS PRODUCTION
GR871154A GR871154B (en) 1986-07-22 1987-07-21 Photographic paper carrier and production method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP86110061A EP0253911B1 (en) 1986-07-22 1986-07-22 Photographic-paper support and process for its production

Publications (2)

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EP0253911A1 true EP0253911A1 (en) 1988-01-27
EP0253911B1 EP0253911B1 (en) 1990-02-07

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EP (1) EP0253911B1 (en)
JP (1) JPH0660992B2 (en)
CN (1) CN1031299C (en)
AT (1) ATE50369T1 (en)
AU (1) AU594153B2 (en)
DE (1) DE3668995D1 (en)
ES (1) ES2003722A6 (en)
GR (1) GR871154B (en)
HU (1) HU201581B (en)
YU (1) YU45949B (en)

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EP0362823A2 (en) * 1988-10-04 1990-04-11 Fuji Photo Film Co., Ltd. Paper for photographic purposes

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DE3716269C2 (en) * 1987-05-15 1993-12-09 Schoeller Felix Jun Papier Waterproof substrate for light-sensitive materials
JP2711483B2 (en) * 1991-03-20 1998-02-10 富士写真フイルム株式会社 Photographic paper support
DE4110622C2 (en) * 1991-04-02 1995-12-21 Schoeller Felix Jun Papier Polyolefin coated substrate for photographic materials
JPH05323495A (en) * 1992-03-17 1993-12-07 Fuji Photo Film Co Ltd Base for photographic printing paper
US5464691A (en) * 1994-07-22 1995-11-07 Arizona Chemical Company Laminated barrier film
US6312822B1 (en) * 1998-05-28 2001-11-06 Eastman Chem Co Dispersion aids for optical brighteners in polyolefins
US6416626B1 (en) * 2000-09-28 2002-07-09 Weyerhaeuser Company Polyethylene glycol-containing paper

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US3778404A (en) * 1970-06-19 1973-12-11 Nat Distillers Chem Corp Hot melt coating composition and method
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EP0362823A3 (en) * 1988-10-04 1990-10-31 Fuji Photo Film Co., Ltd. Paper for photograph

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US4895757A (en) 1990-01-23
ATE50369T1 (en) 1990-02-15
YU133187A (en) 1988-10-31
HU201581B (en) 1990-11-28
CN1031299C (en) 1996-03-13
EP0253911B1 (en) 1990-02-07
GR871154B (en) 1987-08-20
CN87104888A (en) 1988-02-03
JPH0660992B2 (en) 1994-08-10
ES2003722A6 (en) 1988-11-01
AU594153B2 (en) 1990-03-01
JPS6330841A (en) 1988-02-09
YU45949B (en) 1992-09-07
AU7293287A (en) 1988-01-28
DE3668995D1 (en) 1990-03-15
HUT44103A (en) 1988-01-28

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