[go: up one dir, main page]

EP0225446B1 - Water-resistant photographic paper support - Google Patents

Water-resistant photographic paper support Download PDF

Info

Publication number
EP0225446B1
EP0225446B1 EP86113855A EP86113855A EP0225446B1 EP 0225446 B1 EP0225446 B1 EP 0225446B1 EP 86113855 A EP86113855 A EP 86113855A EP 86113855 A EP86113855 A EP 86113855A EP 0225446 B1 EP0225446 B1 EP 0225446B1
Authority
EP
European Patent Office
Prior art keywords
photographic paper
carrier according
carboxyl
paper carrier
modified polyvinyl
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
Application number
EP86113855A
Other languages
German (de)
French (fr)
Other versions
EP0225446A1 (en
Inventor
Alois-Bernhard Dr. Dipl.-Chem. Kerkhoff
Dietmar Dr. Dipl.-Chem. Bunke
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 AT86113855T priority Critical patent/ATE46221T1/en
Publication of EP0225446A1 publication Critical patent/EP0225446A1/en
Application granted granted Critical
Publication of EP0225446B1 publication Critical patent/EP0225446B1/en
Expired legal-status Critical Current

Links

Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/76—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
    • Y10T428/27—Web or sheet containing structurally defined element or component, the element or component having a specified weight per unit area [e.g., gms/sq cm, lbs/sq ft, etc.]
    • Y10T428/273—Web or sheet containing structurally defined element or component, the element or component having a specified weight per unit area [e.g., gms/sq cm, lbs/sq ft, etc.] of coating
    • Y10T428/277—Cellulosic substrate
    • 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]
    • Y10T428/31971—Of carbohydrate
    • Y10T428/31993—Of paper
    • Y10T428/31996—Next to layer of metal salt [e.g., plasterboard, etc.]

Definitions

  • the invention relates to a paper support for photographic layers provided on both sides with a polyolefin coating.
  • the paper core of the photographic support according to the invention is also largely protected against the action of the photographic treatment solutions at the edges which are caused by the cutting and is essentially free of dirt on the edges from the treatment solutions.
  • baryta papers the surfaces of which were provided with so-called baryta layers, which consisted essentially of barium sulfate and gelatin, were previously used as carrier materials for the inclusion of photosensitive layers, in particular layers for black / white and color silver salt photography.
  • waterproof photographic supports In order to be able to meet the requirements placed on the photographic support materials by the new automatic rapid development processes, waterproof photographic supports have been described which have been coated on both surfaces with a hydrophobic polyolefin.
  • the upper polyolefin coating layer of the waterproof photographic support to which a photographic emulsion layer is to be applied usually contains a white pigment to increase the sharpness of the photographic image.
  • the paper substrates coated on both sides with polyolefin are basically protected in both areas against the effects of conventional photographic treatment liquids. This protection is only interrupted at the edges of the coated papers, and the liquids have access to the paper core there. Due to the natural absorbency of paper, they penetrate the edges of the paper core and cannot be completely removed even in subsequent washing steps. Since the liquids often contain substances that change color dark when exposed to air or exposure to light, penetrated photographic treatment liquids appear as darker discolored edges after a short time, which leads to a reduction in the value of the photographic material.
  • the base paper is usually provided with a strong hydrophobizing inner sizing by adding sizing agents to the pulp suspension during the production of the paper.
  • the object of the invention is therefore to provide a waterproof photographic support which is free from the disadvantages described, i.e. which, even when used in an automatic rapid development process, has no dirt on the edges and whose paper core has the internal strength required for use in photographic supports and secure adhesion of the polyolefin coating.
  • the photographic support according to the invention has a basic structure consisting of a base paper and a polyolefin coating layer which is provided on both surfaces and which contains the light-reflecting white pigment (especially in the front coating) and, if appropriate, color pigments, optical brighteners and / or other additives such as antistatic compounds, dispersing aids for the white pigment and may contain antioxidants.
  • the base paper is produced in a known manner using a paper machine.
  • the paper pulp suspension is sized using alkyl ketene dimers or fatty acids or fatty acid salts, epoxidized fatty acid amides or anhydrides of fatty acids and mixtures thereof.
  • the paper pulp suspension can also contain synthetic fibers, mineral or organic fillers, white pigment, dye or color pigment, optical brighteners, antioxidants and / or other additives customary in the production of photographic supports, e.g. setting resins.
  • Base papers of any basis weight and of any density can be used.
  • the base paper is impregnated (surface-sized) with a solution of carboxyl-modified polyvinyl alcohol.
  • a carboxyl-modified polyvinyl alcohol is understood to mean, for example, a vinyl alcohol croton or iso crotonic acid polymer or a vinyl alcohol acrylic or methacrylic acid copolymer.
  • the vinyl alcohol-crotonic acid copolymer is preferred.
  • the carboxyl-modified polyvinyl alcohols have a viscosity of 20 to 50 mPa s in 4% solution at room temperature.
  • the average molecular weight is 5,000 to 20,000, preferably 7,000 to 10,000.
  • the carboxyl-modified polyvinyl alcohols used according to the invention are used as an aqueous solution using the known and customary ones Application procedure applied.
  • the application amount is 0 to 10 g / m 2, preferably 1 to 4.5 5 g / m2. If the application quantity is less than 0.5 g / m 2 , sufficient impregnation of the paper core (base paper) is not achieved and the penetration of the photographic treatment solutions into the edges and the contamination of the edges by the photographic treatment solutions are not avoided to the desired extent.
  • the improvement in properties is not linearly related to the number of carboxyl groups, so that the maximum does not occur with the carboxyl-modified polyvinyl alcohol with the largest carboxyl group content. Rather, the optimum is only achieved if carboxyl-modified polyvinyl alcohols are used which contain a carboxyl group content of 1 to 7 mol%, preferably 2.5 to 3.5 mol%.
  • carboxyl-modified polyvinyl alcohols which contain a carboxyl group content of 1 to 7 mol%, preferably 2.5 to 3.5 mol%.
  • the effect according to the invention is already achieved if a sized paper produced in a known manner is impregnated with a solution of the polyvinyl alcohol containing carboxyl groups. According to a preferred embodiment of the invention, however, the effect according to the invention is enhanced if polyvalent cations are additionally introduced into the paper.
  • These compounds can be selected from the group of alkaline earth metal compounds, for example calcium or magnesium chloride, from the group of aluminum salts, for example aluminum sulfate or aluminum chloride, and from the compounds of the transition metals.
  • the polyvalent cations are preferably added to the aqueous coating solution. However, they can also be added to the cellulose suspension or incorporated into the base paper before the polyvinyl alcohol solution according to the invention is used. Or they can be applied in the form of an aftertreatment (e.g.
  • the polyvalent cation compounds are in a weight ratio of 1/10 to 5/1 to the carboxylated polyvinyl alcohol. If the weight ratio falls below the value of 1/10, the enhancement of the described effect is not achieved. An increase in the weight ratio to values above 5/1 brings no further improvement in the effect according to the invention.
  • aqueous coating solution can also contain optical brighteners, defoamers, pigments, water repellents or crosslinking aids, such as, for example, dimethylolurea or trimethylolmelamine.
  • the paper support is treated with an aqueous coating mixture of the following composition:
  • the application amount is 2 g / m 2.
  • Crotonic acid-modified polyvinyl alcohols with the following carboxyl group proportions are used:
  • the treated paper is dried and extrusion coated with polyethylene in the usual way.
  • the Paper is treated with the coating mixture used in Example 1.
  • the order quantity is 3 g / m 2 .
  • Crotonic acid-modified polyvinyl alcohols with the following carboxyl groups are used.
  • the treated paper is dried and extrusion coated in a conventional manner with polyethylene.
  • An approximately 140 g / m 2 heavy paper sized with 0.3% by weight alkyl ketene dimer, 1.6% by weight fatty acid soap and 0.5% by weight aluminum ions is treated with an aqueous coating mixture, which contains a crotonic acid-modified polyvinyl alcohol with a degree of saponification of 98.5% and a carboxyl group content of 3.1 mol% in the amount of 40 g / l.
  • compounds of the following polyvalent cations are added:
  • the application quantity is 1.5 g / m 2 .
  • the treated paper is dried and extrusion coated with polyethylene in the usual way.
  • the order quantity is 4.5 g / m 2 .
  • the treated paper is dried and coated with a polyethylene coating mixture of the following composition:
  • the paper is treated on both sides in a second size press with the following polyvinyl alcohol solution.
  • the treated paper is dried and extrusion coated with polyethylene in the usual way.
  • both sides are successively sprayed with the following saline solution via a nozzle system:
  • the application quantity is 1.5 g / m 2 in the size press and 1.0_g / M 2 when spraying.
  • the treated paper is dried and extrusion coated with polyethylene in the usual way. In this case, the test of the carrier material was only carried out after 1 week of storage.
  • a paper produced according to Example 1 is treated with an aqueous coating mixture of the following composition:
  • the application amount is 3 g / m 2.
  • the treated paper is dried and extrusion-coated with polyethylene in the usual way.
  • a paper sheet produced according to Example 2 of DOS 32 41 599 is treated with the coating mixture described there (the application amount is 3 g / m 2 ), then dried and extrusion-coated with polyethylene in the usual way.
  • a paper sheet produced according to Example 3 is treated with the coating mixture described in Comparative Example V1.
  • the order quantity is 3 g / m 2 .
  • the treated paper is dried and coated with polyethylene in the usual way.
  • a paper of 140 g / m 2 produced according to Example 3 is treated (surface-sized) with the following coating mixture:
  • the treated paper is dried and extrusion coated with polyethylene in the usual way.
  • a 175 g / m 2 paper produced according to Example 1 is treated with the following coating mixture:
  • the treated paper is dried and extrusion coated with polyethylene in the usual way.
  • the treated papers are coated with polyethylene and then subjected to the following tests.
  • Treated paper is understood here to mean paper which has undergone the treatment of the base paper by the coating mixtures in the form of applications on both sides by dipping processes (size press), spraying, applications on both sides by means of roller application systems, slot casters or the like.
  • Test 1 Testing the impregnated base paper During the test, the developer absorption is determined by the paper (modified Cobb test). 14 x 14 cm test pieces are cut out of the paper web, precisely weighed and clamped in a cylindrical test device. 100 ml of a commercially available photographic developer are placed in the cylinder, left to act for a period of 50 seconds and then poured off. The test specimen is erased and weighed immediately. The extent of developer uptake is given in g / m 2 .
  • the test piece is subjected to a simulated photographic development process with a commercial developer containing benzyl alcohol at a temperature of about 30 ° C and for a period of 25 minutes.
  • the penetration of the photographic treatment solutions is measured on both edges of the test piece with a measuring magnifier.
  • the measured values are given as edge penetration (KE) in mm.
  • the test is carried out according to the method specified in TAPPI RC 308 with the Internal Bond Impact Tester Model B.
  • the measured values are measured in 1/1000 feet x pounds and were converted to the SI unit Nm according to the following equation.
  • Equation: ftpd.1.356 Nm
  • Test 2.3 Determination of the adhesive force between the polyethylene coating layer and the impregnated paper core
  • the test is carried out with a tensile strength measuring device from AB Lorentzen & Wettre on 15 mm wide and 18 cm long test strips.
  • the pull-off angle is 180 °
  • the pull-off speed is 70 mm / min.
  • the measured values are given in mN / 15 mm.
  • Comparative example V5 demonstrates that a degree of saponification of 88% for the polyvinyl alcohol used is not sufficient to achieve the desired effect.

Landscapes

  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Paper (AREA)
  • Laminated Bodies (AREA)

Abstract

A photographic paper support material for photographic purposes is disclosed with a polyolefin coating on both sides, wherein the base paper is internally sized by using a hydrophobizing sizing agent, and is surface sized with an aqueous coating mixture. The aqueous coating mixture contains a carboxyl-modified polyvinyl alcohol and optionally includes compounds with polyvalent cations. The paper support material is preferably used with such photographic layers as require wet development and wet fixing of the photographic image with photographic processing solutions.

Description

Die Erfindung betrifft einen beidseitig mit einem Polyolefinüberzug versehenen Papierträger für photographische Schichten.The invention relates to a paper support for photographic layers provided on both sides with a polyolefin coating.

Insbesondere betrifft sie beschichtete Papierträger für solche photographische Schichten, die einer Naßentwicklung oder Naßfixierung des photographischen Bildes mit Hilfe sogenannter photographischer Behandlungslösungen bedürfen.In particular, it relates to coated paper supports for those photographic layers which require wet development or wet fixation of the photographic image using so-called photographic processing solutions.

Der Papierkern des erfindungsgemäßen photographischen Trägers ist auch an den Kanten, die durch das Schneiden entstehen, weitestgehend gegen die Einwirkung der photographischen Behandlungslösungen geschützt und im wesentlichen von Verschmutzungen an den Kanten durch die Behandlungslösungen frei.The paper core of the photographic support according to the invention is also largely protected against the action of the photographic treatment solutions at the edges which are caused by the cutting and is essentially free of dirt on the edges from the treatment solutions.

Als Trägermaterialien für die Aufnahme photoempfindlicher Schichten, insbesondere von Schichten für die Schwarz/Weiß- und Farbsilbersalzphotographie, wurden früher sogenannte barytierte Papiere verwendet, deren Oberflächen mit sogenannten Barytschichten, die im wesentlichen aus Bariumsulfat und Gelatine bestanden, versehen waren.So-called baryta papers, the surfaces of which were provided with so-called baryta layers, which consisted essentially of barium sulfate and gelatin, were previously used as carrier materials for the inclusion of photosensitive layers, in particular layers for black / white and color silver salt photography.

Um den Anforderungen, die durch die neuen automatischen Schnellentwicklungsverfahren an die photographischen Trägermaterialien gestellt werden, genügen zu können, sind in neuerer Zeit wasserfeste photographische Träger beschrieben worden, die auf beiden Oberflächen mit einem hydrophoben Polyolefin beschichtet worden sind. Die obere Polyolefin- Überzugsschicht des wasserfesten photographischen Trägers, auf die eine photographische Emulsionsschicht aufgebracht werden soll, enthält gewöhnlich ein weißes Pigment, um die Schärfe des photographischen Bildes zu erhöhen.In order to be able to meet the requirements placed on the photographic support materials by the new automatic rapid development processes, waterproof photographic supports have been described which have been coated on both surfaces with a hydrophobic polyolefin. The upper polyolefin coating layer of the waterproof photographic support to which a photographic emulsion layer is to be applied usually contains a white pigment to increase the sharpness of the photographic image.

Die beidseitig mit Polyolefin überzogenen Papierträger sind grundsätzlich in beiden Flächen gegen die Einwirkung üblicher photographischer Behandlungsflüssigkeiten geschützt. Lediglich an den Kanten der beschichteten Papiere ist dieser Schutz unterbrochen, und die Flüssigkeiten haben dort Zutritt zum Papierkern. Aufgrund einer natürlichen Saugfähigkeit von Papier dringen sie an den Kanten in den Papierkern ein und können selbst in nachfolgenden Wässerungsschritten nicht mehr vollständig entfernt werden. Da die Flüssigkeiten vielfach Substanzen enthalten, die sich bei Luftzutritt oder bei Lichteinwirkung dunkel verfärben, treten eingedrungene photographische Behandlungsflüssigkeiten nach kurzer Zeit als dunkler verfärbte Ränder in Erscheinung, was zu einer Verringerung des Wertes des photographischen Materials führt.The paper substrates coated on both sides with polyolefin are basically protected in both areas against the effects of conventional photographic treatment liquids. This protection is only interrupted at the edges of the coated papers, and the liquids have access to the paper core there. Due to the natural absorbency of paper, they penetrate the edges of the paper core and cannot be completely removed even in subsequent washing steps. Since the liquids often contain substances that change color dark when exposed to air or exposure to light, penetrated photographic treatment liquids appear as darker discolored edges after a short time, which leads to a reduction in the value of the photographic material.

Um dem Problem des Kantenverschmutzens des photographischen Trägers zu begegnen, wird das Basispapier üblicherweise mit einer starken hydrophobierenden Innenleimung versehen, indem Leimungsmittel bei der Herstellung des Papiers der Faserstoffsuspension zugesetzt werden.In order to address the problem of soiling the edges of the photographic support, the base paper is usually provided with a strong hydrophobizing inner sizing by adding sizing agents to the pulp suspension during the production of the paper.

Es wurde auch versucht, hydrophobierende Mittel nach dem Schneiden auf die betroffenen, neu entstandenen Kanten aufzutragen.Attempts have also been made to apply hydrophobizing agents to the affected, newly formed edges after cutting.

Jedoch genügen die Ergebnisse dieser beiden Verfahrensweisen nicht den Anforderungen, die an ein qualitativ hochwertiges photographisches Material gestellt werden.However, the results of these two procedures do not meet the requirements placed on a high quality photographic material.

In der DOS 32 41 599 wurde vorgeschlagen, das Basispapier durch Auftragen eines mit Maleinsäure oder Itaconsäure carboxylierten Polyvinylalkohols abzudichten. Jedoch konnte das dort beschriebene Verfahren in Bezug auf die Kantenverschmutzung und vor allem die innere Festigkeit des Papierkerns nicht voll befriedigen. Außerdem war die Haftung zwischen dem Polyolefinüberzug und dem Basispapier nicht gleichmäßig gut. Haftungsprüfungen lieferten stark schwankende Werte.In DOS 32 41 599 it was proposed to seal the base paper by applying a polyvinyl alcohol carboxylated with maleic acid or itaconic acid. However, the process described there was not fully satisfactory in terms of edge contamination and, above all, the internal strength of the paper core. In addition, the adhesion between the polyolefin coating and the base paper was not equally good. Liability tests delivered strongly fluctuating values.

Augabe der Erfindung ist es daher, einen wasserfesten photographischen Träger zur Verfügung zu stellen, der frei von den beschriebenen Nachteilen ist, d.h. der auch bei der Verwendung in einem automatischen Schnellentwicklungsprozeß keine Verschmutzung der Kanten aufweist und dessen Papierkern die für die Verwendung in photographischen Trägern erforderliche innere Festigkeit und eine sichere Haftung des Polyolefinüberzugs besitzt.The object of the invention is therefore to provide a waterproof photographic support which is free from the disadvantages described, i.e. which, even when used in an automatic rapid development process, has no dirt on the edges and whose paper core has the internal strength required for use in photographic supports and secure adhesion of the polyolefin coating.

Diese Aufgabe wird durch die in den Ansprüchen beschriebenen Merkmale gelöst.This object is achieved by the features described in the claims.

Der erfindungsgemäße photographische Träger besitzt eine Grundstruktur aus einem Basispapier und einer Polyolefinüberzugsschicht, die auf beiden Oberflächen vorgesehen ist und die lichtreflektierendes Weißpigment (speziell in der Vorderseitenbeschichtung) sowie gegebenenfalls Farbpigmente, optische Aufheller und/oder andere Zusätze wie antistatisch wirkende Verbindungen, Dispergierhilfsmittel für das Weißpigment und Antioxidantien enthalten kann.The photographic support according to the invention has a basic structure consisting of a base paper and a polyolefin coating layer which is provided on both surfaces and which contains the light-reflecting white pigment (especially in the front coating) and, if appropriate, color pigments, optical brighteners and / or other additives such as antistatic compounds, dispersing aids for the white pigment and may contain antioxidants.

Das Basispapier wird in bekannter Weise mit Hilfe einer Papiermaschine hergestellt. Dabei wird die Papierfaserstoffsuspension unter Verwendung von Alkylketendimeren oder Fettsäuren bzw. Fettsäuresalzen, epoxidierten Fettsäureamiden oder Anhydriden von Fettsäuren sowie Mischungen hiervon geleimt. Darüber hinaus kann die Papierfaserstoffsuspension neben Zellstoffasern noch synthetische Faser, mineralische oder organische Füllstoffe, Weißpigment, Farbstoff oder Farbpigment, optische Aufheller, Antioxidantien und/oder andere bei der Herstellung photographischer Träger übliche Zusatzstoffe, z.B. verfestigende Harze, enthalten.The base paper is produced in a known manner using a paper machine. The paper pulp suspension is sized using alkyl ketene dimers or fatty acids or fatty acid salts, epoxidized fatty acid amides or anhydrides of fatty acids and mixtures thereof. In addition to pulp fibers, the paper pulp suspension can also contain synthetic fibers, mineral or organic fillers, white pigment, dye or color pigment, optical brighteners, antioxidants and / or other additives customary in the production of photographic supports, e.g. setting resins.

Es können Basispapiere beliebigen Flächengewichts und beliebiger Dichten verwendet werden.Base papers of any basis weight and of any density can be used.

Das Basispapier wird erfindungsgemäß mit einer Lösung von carboxylmodifiziertem Polyvinylalkohol imprägniert (oberflächengeleimt). Unter einem carboxylmodifizierten Polyvinylalkohol ist beispielsweise ein Vinylalkohol-Croton- oder -iso-Crotonsäurepolymer oder ein Vinylalkohol-Acryl oder -Methacrylsäurecopolymer zu verstehen. Erfindungsgemäß bevorzugt ist das Vinylalkohol-Crotonsäuerecopolymer.According to the invention, the base paper is impregnated (surface-sized) with a solution of carboxyl-modified polyvinyl alcohol. A carboxyl-modified polyvinyl alcohol is understood to mean, for example, a vinyl alcohol croton or iso crotonic acid polymer or a vinyl alcohol acrylic or methacrylic acid copolymer. According to the invention, the vinyl alcohol-crotonic acid copolymer is preferred.

Die carboxylmodifizierten Polyvinylalkohole zeigen in 4%iger Lösung bei Raumtemperatur eine Viskosität von 20 bis 50 mPa s. Das mittlere Molekulargewicht beträgt 5000 bis 20 000, bevorzugt 7000 bis 10 000.The carboxyl-modified polyvinyl alcohols have a viscosity of 20 to 50 mPa s in 4% solution at room temperature. The average molecular weight is 5,000 to 20,000, preferably 7,000 to 10,000.

Die erfindungsgemäß verwendeten carboxylmodifizierten Polyvinylalkohole werden als wäßrige Lösung unter Verwendung der bekannten und üblichen Auftragsverfahren aufgebracht. Die Auftragsmenge beträgt 0, bis 10 g/m2 vorzugsweise 1 bis 4,5 5 g/m2. Bei einer Auftragsmenge geringer als 0,5 g/m2 wird keine ausreichende Imprägnierung des Papierkerns (Basispapiers) erreicht und das Eindringen der photographischen Behandlungslösungen in die Kanten sowie das Verschmutzen der Kanten durch die photographischen Behandlungslösungen nicht im gewünschten Ausmaß vermieden.The carboxyl-modified polyvinyl alcohols used according to the invention are used as an aqueous solution using the known and customary ones Application procedure applied. The application amount is 0 to 10 g / m 2, preferably 1 to 4.5 5 g / m2. If the application quantity is less than 0.5 g / m 2 , sufficient impregnation of the paper core (base paper) is not achieved and the penetration of the photographic treatment solutions into the edges and the contamination of the edges by the photographic treatment solutions are not avoided to the desired extent.

Es wurde gefunden, daß der erfindungsgemäße Effekt nur bei Copolymeren mit einem Verseifungsgrad von wenigstens 96% erhalten wird.It has been found that the effect according to the invention is only obtained with copolymers with a degree of saponification of at least 96%.

Ist der Verseifungsgrad kleiner als 96% wird keine befriedigende Abdichtung des Papierkerns gegen das Eindringen der photographischen Behandlungslösungen erreicht.If the degree of saponification is less than 96%, a satisfactory sealing of the paper core against the penetration of the photographic treatment solutions is not achieved.

Es wurde ferner gefunden, daß die erfindungsgemäß beschriebenen Vorteile, nämlich die Verringerung des Eindringens photographischer Behandlungslösungen, Erhöhung der inneren Festigkeit des Papierkerns und der Haftung zwischen dem behandelten Basispapier und der Polyolefinüberzugsschicht, abhängig von der Anzahl der Carboxylgruppen in den verwendeten carboxylmodifizierten Polyvinylalkoholen ist.It has also been found that the advantages described according to the invention, namely the reduction in the penetration of photographic treatment solutions, the increase in the internal strength of the paper core and the adhesion between the treated base paper and the polyolefin coating layer, are dependent on the number of carboxyl groups in the carboxyl-modified polyvinyl alcohols used.

Und zwar steht die Verbesserung der Eigenschaften nicht in einem linearen Zusammenhang mit der Anzahl der Carboxylgruppen, so daß das Maximum nicht bei dem carboxylmodifizierten Polyvinylalkohol mit dem größten Carboxylgruppenanteil auftritt. Das Optimum wird vielmehr nur dann erzielt, wenn carboxylmodifizierte Polyvinylalkohole verwendet werden, die einen Carboxylgruppenanteil von 1, bis 7 mol-%, bevorzugt 2,5 bis 3,5 mol-%, enthalten. Der erfindungsgemäße Effekt wird bereits erreicht, wenn ein in bekannter Weise hergestelltes geleimtes Papier mit einer Lösung des Carboxylgruppen enthaltenden Polyvinylakohols imprägniert wird. Gemäß einer bevorzugten Ausführungsform der Erfindung ist der erfindugsgemäße Effekt jedoch verstärkt, wenn zusätzlich mehrwertige Kationen in das Papier eingebracht werden. Diese Verbindungen können aus der Gruppe der Erdalkali-Verbindungen, beispielsweise Calcium- oder Magnesiumchlorid, aus der Gruppe der Aluminiumsalze, beispielsweise Aluminiumsulfat oder Aluminiumchlorid, und aus den Verbindungen der Übergangsmetalle ausgewählt werden. Besonders bevorzugt werden Salze des Zirkoniums, beispielsweise Zirkoniumammoniumcarbonat oder Zirkoniumorthosulfat, und Verbindungen des Chroms, z.B. Chrom-Komplexe vom Werner-Typ. Die mehrwertigen Kationen werden vorzugsweise der wäßrigen Beschichtungslösung zugesetzt. Sie können aber auch vor Anwendung der erfindungsgemäßen Polyvinylalkohollösung der Zellstoffsuspension zugesetzt oder dem Basispapier inkorporiert werden. Oder sie können in Form einer Nachbehandlung (z.B. durch Sprühen) nach Imprägnierung mit der Polyvinylalkohollösung aufgebracht werden. Die mehrwertigen Kation-Verbindungen stehen zu dem carboxylierten Polyvinylalkohol in einem Gewichtsverhältnis von 1/10 bis 5/1. Unterschreitet das Gewichtsverhältnis den Wert von 1 /10, wird die Verstärkung des beschriebenen Effektes nicht erlangt. Eine Erhöhung des Gewichtsverhältnisses auf Werte über 5/1 bringt keine weitere Verbesserung des erfindungsgemäßen Effektes.In fact, the improvement in properties is not linearly related to the number of carboxyl groups, so that the maximum does not occur with the carboxyl-modified polyvinyl alcohol with the largest carboxyl group content. Rather, the optimum is only achieved if carboxyl-modified polyvinyl alcohols are used which contain a carboxyl group content of 1 to 7 mol%, preferably 2.5 to 3.5 mol%. The effect according to the invention is already achieved if a sized paper produced in a known manner is impregnated with a solution of the polyvinyl alcohol containing carboxyl groups. According to a preferred embodiment of the invention, however, the effect according to the invention is enhanced if polyvalent cations are additionally introduced into the paper. These compounds can be selected from the group of alkaline earth metal compounds, for example calcium or magnesium chloride, from the group of aluminum salts, for example aluminum sulfate or aluminum chloride, and from the compounds of the transition metals. Salts of zirconium, e.g. zirconium ammonium carbonate or zirconium orthosulfate, and compounds of chromium, e.g. Chromium complexes of the Werner type. The polyvalent cations are preferably added to the aqueous coating solution. However, they can also be added to the cellulose suspension or incorporated into the base paper before the polyvinyl alcohol solution according to the invention is used. Or they can be applied in the form of an aftertreatment (e.g. by spraying) after impregnation with the polyvinyl alcohol solution. The polyvalent cation compounds are in a weight ratio of 1/10 to 5/1 to the carboxylated polyvinyl alcohol. If the weight ratio falls below the value of 1/10, the enhancement of the described effect is not achieved. An increase in the weight ratio to values above 5/1 brings no further improvement in the effect according to the invention.

Weder durch die alleinige Verwendung der carboxylmodifizierten Polyvinylalkohole noch durch die Verwendung einer beschriebenen Kombination mit den Verbindungen mit mehrwertigen Kationen werden die photographischen Emulsionen beeinträchtigt.Neither the use of the carboxyl-modified polyvinyl alcohols alone nor the use of a combination described with the compounds with polyvalent cations impair the photographic emulsions.

Obwohl durch die Verwendung der erfindungsgemäß verwendeten Verbindungen bereits eine antistatische Ausrüstung des Papieres erreicht wird, kann der wäßrigen Beschichtungslösung, falls es gewünscht wird, zusätzlich Salz, beispielesweise Natriumchlorid oder Kaliumchlorid, zur Erhöhung der Leitfähigkeit der Papieroberfläche zugesetzt werden. Die wäßrige Beschichtungslösung kann außerdem optische Aufheller, Entschäumer, Pigmente, Hydrophobierungsmittel oder Vernetzungshilfsmittel, wie zum Beispiel Dimethylolharnstoff oder Trimethylolmelamin, enthalten.Although the use of the compounds used according to the invention already provides the paper with an antistatic finish, if desired, additional salt, for example sodium chloride or potassium chloride, can be added to the aqueous coating solution to increase the conductivity of the paper surface. The aqueous coating solution can also contain optical brighteners, defoamers, pigments, water repellents or crosslinking aids, such as, for example, dimethylolurea or trimethylolmelamine.

Die Erfindung wird anhand der nachfolgenden Beispiele näher erläutert.The invention is illustrated by the following examples.

Beispiel 1example 1

Ein ca. 175 g/m2 schweres Papier wird aus einer wäßrigen Faserstoffsuspension (LBKP/NBKP= 1/1), die zusätzlich 0,5 Gew.-% Polyamid-Polyamin-Epichlorhydrin, 0,5 Gew.-% kationisches Polyacrylamid, 0,5 Gew.-% anionisches Polyacrylamid und 0,4 Gew.-% Alkylketendimer mit Alkylgruppen mit 14 bis 16 Kohlenstoffatomen enthält, hergestellt. Der Papierträger wird mit einer wäßrigen Beschichtungsmischung folgender Zusammensetzung behandelt:An approximately 175 g / m 2 paper is made from an aqueous fiber suspension (LBKP / NBKP = 1/1), which additionally contains 0.5% by weight of polyamide-polyamine-epichlorohydrin, 0.5% by weight of cationic polyacrylamide, Contains 0.5 wt .-% anionic polyacrylamide and 0.4 wt .-% alkyl ketene dimer with alkyl groups with 14 to 16 carbon atoms. The paper support is treated with an aqueous coating mixture of the following composition:

Figure imgb0001
Figure imgb0001

Die Auftragsmenge beträgt 2 g/m2. Es werden Crotonsäure-modifizierte Polyvinylalkohole mit folgenden Carboxylgruppenanteilen verwendet:The application amount is 2 g / m 2. Crotonic acid-modified polyvinyl alcohols with the following carboxyl group proportions are used:

Figure imgb0002
Figure imgb0002

Das behandelte Papier wird getrocknet und mit Polyethylen in üblicher Weise extrusionsbeschichtet.The treated paper is dried and extrusion coated with polyethylene in the usual way.

Beispiel 2Example 2

Ein ca. 175 g/m2 schweres Papier wird aus einer wäßrigen Faserstoffsuspension (LBKP/NBKP = 2/1), die zusätzlich 5 Gew.-% Natriumstearat und 10 Gew.-% Aluminiumsulfat enthält, hergestellt. Das Papier wird mit der in Beispiel 1 verwendeten Beschichtungsmischung behandelt.A paper weighing approximately 175 g / m 2 is produced from an aqueous fiber suspension (LBKP / NBKP = 2/1) which additionally contains 5% by weight of sodium stearate and 10% by weight of aluminum sulfate. The Paper is treated with the coating mixture used in Example 1.

Die Auftragsmenge beträgt 3 g/m2.The order quantity is 3 g / m 2 .

Es werden Crotonsäure-modifizierte Polyvinylalkohole mit folgenden Carboxylgruppenanteilen verwendet.

Figure imgb0003
Crotonic acid-modified polyvinyl alcohols with the following carboxyl groups are used.
Figure imgb0003

Das behandelte Papier wird getrocknet und in üblicher Weise mit Polyethylen extrusionsbeschichtet.The treated paper is dried and extrusion coated in a conventional manner with polyethylene.

Beispiel 3Example 3

Ein ca. 140 g/m2 schweres mittels 0,3 Gew.-% Alkylketendimer, 1,6 Gew.-% Fettsäureseife und 0,5 Gew.-% Aluminium-lonen in der Papiermasse geleimtes Papier wird mit einer wäßrigen Beschichtungsmischung behandelt, die einen Crotonsäuremodifizierten Polyvinylalkohol mit einem Verseifungsgrad von 98,5% Und einem Carboxylgruppenanteil von 3,1 mol-% in der Menge von 40 g/I enthält. Außerdem werden Verbindungen folgender mehrwertiger Kationen zugesetzt:

Figure imgb0004
An approximately 140 g / m 2 heavy paper sized with 0.3% by weight alkyl ketene dimer, 1.6% by weight fatty acid soap and 0.5% by weight aluminum ions is treated with an aqueous coating mixture, which contains a crotonic acid-modified polyvinyl alcohol with a degree of saponification of 98.5% and a carboxyl group content of 3.1 mol% in the amount of 40 g / l. In addition, compounds of the following polyvalent cations are added:
Figure imgb0004

Die Auftragsmenge beträgt 1,5 g/m2. Das behandelte Papier wird getrocknet und mit Polyethylen in üblicher Weise extrusionsbeschichtet.The application quantity is 1.5 g / m 2 . The treated paper is dried and extrusion coated with polyethylene in the usual way.

Beispiel 4Example 4

Ein ca. 150 g/m2 schweres gemäß Beispiel 1 in der Papiermasse geleimtes Papier wird mit wäßrigen Beschichtungsmischungen folgender Zusammensetzung behandelt:

Figure imgb0005
An approximately 150 g / m 2 heavy paper sized according to Example 1 in the paper pulp is treated with aqueous coating mixtures of the following composition:
Figure imgb0005

Die Auftragsmenge beträgt 4,5 g/m2.The order quantity is 4.5 g / m 2 .

Das behandelte Papier wird getrocknet und mit einer Polyethylenüberzugsmischung folgender Zusammensetzung überzogen:

Figure imgb0006
The treated paper is dried and coated with a polyethylene coating mixture of the following composition:
Figure imgb0006

Beispiel 5Example 5

Ein ca. 140 g/m2 schweres Papier gemäß Beispiel 3 wird in der Papiermaschine in einer ersten Leimpresse mit der folgenden Salzlösung behandelt:

Figure imgb0007
An approximately 140 g / m 2 heavy paper according to Example 3 is treated in the paper machine in a first size press with the following saline solution:
Figure imgb0007

Nach einer Zwischentrocknung wird das Papier in einer zweiten Leimpresse mit folgender Polyvinylalkohollösung beidseitig behandelt.

Figure imgb0008
After intermediate drying, the paper is treated on both sides in a second size press with the following polyvinyl alcohol solution.
Figure imgb0008

Die Auftragsmengen betragen in beiden Fällen 1,5 g/m2.The application quantities in both cases are 1.5 g / m2 .

Das behandelte Papier wird getrocknet und mit Polyethylen in üblicher Weise extrusionsbeschichtet.The treated paper is dried and extrusion coated with polyethylene in the usual way.

Die Prüfung des Trägermaterials wurde in diesem Fall erst nach 1 wöchiger Lagerung durchgeführt.In this case, the test of the carrier material was only carried out after 1 week of storage.

Beispiel 6Example 6

Ein ca. 140 g/m2 schweres Papier gemäß Beispiel 3 wird in der Leimpresse einer Papiermaschine mit folgender Lösung behandelt:

Figure imgb0009
An approximately 140 g / m 2 paper according to Example 3 is treated in the size press of a paper machine with the following solution:
Figure imgb0009

Nach Trocknung werden nacheinander beide Seiten mit folgender Salzlösung über ein Düsensystem besprüht:

Figure imgb0010
After drying, both sides are successively sprayed with the following saline solution via a nozzle system:
Figure imgb0010

Die Auftragsmenge beträgt in der Leimpresse 1,5 g/m2 und beim Besprühen 1,0_g/M 2.The application quantity is 1.5 g / m 2 in the size press and 1.0_g / M 2 when spraying.

Das behandelte Papier wird getrocknet und mit Polyethylen in üblicher Weise extrusionsbeschichtet. Die Prüfung des Trägermaterials wurde in diesem Fall erst nach 1 wöchiger Lagerung durchgeführt.The treated paper is dried and extrusion coated with polyethylene in the usual way. In this case, the test of the carrier material was only carried out after 1 week of storage.

Vergleichsbeispiel V1Comparative Example V1

Ein nach Beispiel 1 hergestelltes Papier wird mit einer wäßrigen Beschichtungsmischung folgender Zusammensetzung behandelt:

Figure imgb0011
A paper produced according to Example 1 is treated with an aqueous coating mixture of the following composition:
Figure imgb0011

Die Auftragsmenge beträgt 3 g/m2. Das behandelte Papier wird getrocknet und mit Polyethylen in üblicher Weise extrusionsbeschichtet.The application amount is 3 g / m 2. The treated paper is dried and extrusion-coated with polyethylene in the usual way.

Vergleichsbeispiel V2Comparative example V2

Ein nach Beispiel 2 der DOS 32 41 599 hergestelltes Papierblatt wird mit der dort beschriebenen Beschichtungsmischung behandelt (die Auftragsmenge beträgt 3 g/m2), anschließend getrocknet und mit Polyethylen in der üblichen Weise extrusionsbeschichtet.A paper sheet produced according to Example 2 of DOS 32 41 599 is treated with the coating mixture described there (the application amount is 3 g / m 2 ), then dried and extrusion-coated with polyethylene in the usual way.

Vergleichsbeispiel V3Comparative Example V3

Ein nach Beispiel 3 hergestelltes Papierblatt wird mit der in Vergleichsbeispiel V1 beschriebenen Beschichtungsmischung behandelt. Die Auftragsmenge beträgt 3 g/m2. Das behandelte Papier wird getrocknet und mit Polyethylen in üblicher Weise beschichtet.A paper sheet produced according to Example 3 is treated with the coating mixture described in Comparative Example V1. The order quantity is 3 g / m 2 . The treated paper is dried and coated with polyethylene in the usual way.

Vergleichsbeispiel V4Comparative Example V4

Ein nach Beispiel 3 hergestelltes Papier von 140 g/m2 wird mit folgender Beschichtungsmischung behandelt (oberflächengeleimt):

Figure imgb0012
A paper of 140 g / m 2 produced according to Example 3 is treated (surface-sized) with the following coating mixture:
Figure imgb0012

Das behandelte Papier wird getrocknet und mit Polyethylen in üblicher Weise extrusionsbeschichtet.The treated paper is dried and extrusion coated with polyethylene in the usual way.

Vergleichsbeispiel V5Comparative Example V5

Ein nach Beispiel 1 hergestelltes Papier von 175 g/m2 wird mit folgender Beschichtungsmischung behandelt:

Figure imgb0013
A 175 g / m 2 paper produced according to Example 1 is treated with the following coating mixture:
Figure imgb0013

Das behandelte Papier wird getrocknet und mit Polyethylen in üblicher Weise extrusionsbeschichtet.The treated paper is dried and extrusion coated with polyethylene in the usual way.

1. Prüfung der Trägermaterialien1. Examination of the carrier materials

Die behandelten Papiere werden mit Polyethylen beschichtet und anschließend den folgenden Prüfungen unterzogen.The treated papers are coated with polyethylene and then subjected to the following tests.

Unter behandeltem Papier wird hierbei ein Papier verstanden, das die Behandlung des Basispapiers durch die Beschichtungsmischungen in Form von beidseitigen Anträgen durch Tauchvorgänge (Leimpresse), Besprühen, beidseitigen Anträgen mittels Walzenauftragssysteme, Schlitzgießern oder ähnlichem erfahren hat.Treated paper is understood here to mean paper which has undergone the treatment of the base paper by the coating mixtures in the form of applications on both sides by dipping processes (size press), spraying, applications on both sides by means of roller application systems, slot casters or the like.

Prüfung 1: Prüfung des imprägnierten Basispapiers Bei der Prüfung wird die Entwickleraufnahme durch das Papier bestimmt (modifizierter Cobb-Test). Es werden aus der Papierbahn Prüfstücke im Format 14 x 14 cm ausgeschnitten, genau gewogen und in einer zylinderförmigen Prüfvorrichtung festgeklemmt. In den Zylinder werden 100 ml eines handelsüblichen photographischen Entwicklers gegeben, über die Zeitdauer von 50 sec. einwirken gelassen und anschließend abgeschüttet. Der Prüfling wird abgelöscht und sofort gewogen. Das Ausmaß der Entwickleraufnahme wird in g/m2 angegeben.Test 1: Testing the impregnated base paper During the test, the developer absorption is determined by the paper (modified Cobb test). 14 x 14 cm test pieces are cut out of the paper web, precisely weighed and clamped in a cylindrical test device. 100 ml of a commercially available photographic developer are placed in the cylinder, left to act for a period of 50 seconds and then poured off. The test specimen is erased and weighed immediately. The extent of developer uptake is given in g / m 2 .

2. Prüfung des Polyethylen-beschichteten Papierträgers2. Testing the polyethylene-coated paper carrier

Prüfung 2. 1: Bestimmung des KanteneindringensTest 2. 1: Determination of edge penetration

Das Prüfstück wird einem simulierten photographischen Entwicklungsprozeß mit einem Benzylalkohol enthaltenden handelsüblichen Entwickler bei einer Temperatur von etwa 30°C und über eine Zeitdauer von 25 Minuten unterworfen. An beiden Kanten des Prüfstückes wird das Eindringen der photographischen Behandlungslösungen mit einer Meßlupe ausgemessen. Die Meßwerte werden als Kanteneindringen (KE) in mm angegeben.The test piece is subjected to a simulated photographic development process with a commercial developer containing benzyl alcohol at a temperature of about 30 ° C and for a period of 25 minutes. The penetration of the photographic treatment solutions is measured on both edges of the test piece with a measuring magnifier. The measured values are given as edge penetration (KE) in mm.

Prüfung 2.2: Bestimmung der inneren FestigkeitTest 2.2: Determination of the internal strength

(Spaltfestigkeit)(Gap strength)

Die Prüfung erfolgt nach der in TAPPI RC 308 angegebenen Methode mit dem Internal Bond Impact Tester Model B. Die Meßwerte werden in 1/1000 Fuß x Pfund gemessen und wurden gemäß folgender Gleichung auf die SI-Einheit Nm umgerechnet.The test is carried out according to the method specified in TAPPI RC 308 with the Internal Bond Impact Tester Model B. The measured values are measured in 1/1000 feet x pounds and were converted to the SI unit Nm according to the following equation.

Gleichung: ft·pd· 1,356 = NmEquation: ftpd.1.356 = Nm

In den Ergebnis-Tabellen sind die Meßwerte, in Klammern gesetzt, neben den umgerechneten Werten aufgelistet. Prüfung 2.3: Bestimmung der Haftkraft zwischen der Polyethylenüberzugsschicht und dem imprägnierten PapierkernIn the result tables, the measured values, in brackets, are listed next to the converted values. Test 2.3: Determination of the adhesive force between the polyethylene coating layer and the impregnated paper core

Die Prüfung erfolgt mit einem Zugfestigkeitsmeßgerät der Fa. A.B. Lorentzen & Wettre an 15 mm breiten und 18 cm langen Prüfstreifen. Der Abzugswinkel beträgt 180°, die Abzugsgeschwindigkeit 70 mm/min. Die Meßwerte werden in mN/15 mm angegeben.

Figure imgb0014
The test is carried out with a tensile strength measuring device from AB Lorentzen & Wettre on 15 mm wide and 18 cm long test strips. The pull-off angle is 180 °, the pull-off speed is 70 mm / min. The measured values are given in mN / 15 mm.
Figure imgb0014

Bewertung der ErgebnisseEvaluation of the results

Die Beispiele 1 bis 6 verdeutlichen den erfindungsgemäßen Effekt.Examples 1 to 6 illustrate the effect according to the invention.

Die obigen Prüfwerte zeigen, daß das Optimum in Bezug auf Kanteneindringen, Spaltfestigkeit und Haftung zur Polyethylenüberzugsschicht bei einem Carboxylgruppenanteil zwischen 2,5 und 3,5 mol-% liegt.The above test values show that the optimum in terms of edge penetration, gap strength and adhesion to the polyethylene coating layer is between 2.5 and 3.5 mol% with a carboxyl group fraction.

Die Gegenüberstellung zu den im Stand der Technik beschriebenen Beschichtungsmischungen (Vergleichsbeispiele V1 und V4), speziell zu der in der DOS 32 41 599 verwendeten Mischung (Vergleichsbeispiel V2), dokumentiert deutlich die Verbesserung der Werte durch die Verwendung der erfindungsgemäß beschriebenen Beschichtungslösungen. Mit dem Vergleichsbeispiel V5 wird demonstriert, daß ein Verseifungsgrad von 88% für den verwendeten Polyvinylalkohol nicht ausreicht, um den angestrebten Effekt zu erzielen.The comparison with the coating mixtures described in the prior art (Ver same examples V1 and V4), especially for the mixture used in DOS 32 41 599 (comparative example V2), clearly documents the improvement in the values through the use of the coating solutions described according to the invention. Comparative example V5 demonstrates that a degree of saponification of 88% for the polyvinyl alcohol used is not sufficient to achieve the desired effect.

Claims (15)

1. Waterproof photographic paper carrier comprising a base paper, which is sized using a water- repellent size and treated with a carboxyl-modified polyvinyl alcohol-containing aqueous coating mixture, and a polyolefin covering on both sides, characterized in that the carboxyl-modified polyvinyl alcohol is a copolymer of an unsaturated monocarboxylic acid with a carboxyl group fraction of 1.5 to 7 and preferably 2.5 to 3.5 mole % and the vinyl alcohol fraction has a saponification factor equal to or greater than 96%.
2. Waterproof photographic paper carrier according to claim 1, characterized in that the carboxyl- modified polyvinyl alcohol has an average molecular weight of 5,000 to 20,000.
3. Waterproof photographic paper carrier according to claims 1 and 2, characterized in that the carboxyl-modified polyvinyl alcohol is a crotonic or isocrotonic-vinyl alcohol copolymer.
4. Waterproof photographic paper carrier according to claim 1 and 2, characterized in that the carboxyl-modified polyvinyl alcohol is an acrylic or methacrylic acid-vinyl alcohol copolymer.
5. Waterproof photographic paper carrier according to claims 1 and 2, characterized in that the aqueous solutions of the carboxyl-modified polyvinyl alcohols have a viscosity of 20to 50 mPa.s at 20°C in a 4% aqueous solution.
6. Waterproof photographic paper carrier according to claims 1 to 5, characterized in that the carboxyl-modified polyvinyl alcohols are applied to the paper core in a quantity of 0.5 to 10 and preferably 1 to 4.5 g/m 2.
7. Waterproof photographic paper carrier according to claim 1 to 6, characterized in that, apart from the carboxyl-modified polyvinyl alcohol, the aqueous coating mixture contains compounds with polyvalent cations.
8. Waterproof photographic paper carrier according to claim 7, characterized in that the compound with polyvalent cations is a salt of alkaline earth metals, preferably calcium chloride or magnesium chloride.
9. Waterproof photographic paper carrier according to claim 7, characterized in that the compound with polyvalent cations is an aluminium salt, preferably aluminium sulphate or aluminium chloride.
10. Waterproof photographic paper carrier according to claim 7, characterized in that the compound with polyvalent cations is a transition metal compound.
11. Waterproof photographic paper carrier according to claim 10, characterized in that the transition metal compound is a zirconium compound, preferably zirconium ammonium carbonate or zirconium orthosulphate.
12. Waterproof photographic paper carrier according to claim 10, characterized in that the transition metal compound is a chromium compound, preferably a Werner-type chromium complex.
13. Waterproof photographic paper carrier according to claim 7, characterized in that the compound with polyvalent cations is in a weight ratio of 1:10to 5:1 to the carboxyl-modified polyvinyl alcohol.
14. Waterproof photographic paper carrier according to claims 1 to 6, characterized in that the base paper contains compounds with polyvalent cations.
15. Waterproof photographic paper carrier according to claim 1 to 6, characterized in that, following application to the paper, the carboxylmodified polyvinyl alcohol undergoes treatment with polyvalent cations.
EP86113855A 1985-12-10 1986-10-07 Water-resistant photographic paper support Expired EP0225446B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT86113855T ATE46221T1 (en) 1985-12-10 1986-10-07 WATERPROOF PHOTOGRAPHIC PAPER CARRIER.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3543597 1985-12-10
DE19853543597 DE3543597A1 (en) 1985-12-10 1985-12-10 WATERPROOF PHOTOGRAPHIC PAPER CARRIER

Publications (2)

Publication Number Publication Date
EP0225446A1 EP0225446A1 (en) 1987-06-16
EP0225446B1 true EP0225446B1 (en) 1989-09-06

Family

ID=6288090

Family Applications (1)

Application Number Title Priority Date Filing Date
EP86113855A Expired EP0225446B1 (en) 1985-12-10 1986-10-07 Water-resistant photographic paper support

Country Status (7)

Country Link
US (1) US4731291A (en)
EP (1) EP0225446B1 (en)
JP (1) JPH083608B2 (en)
AT (1) ATE46221T1 (en)
DE (2) DE3543597A1 (en)
ES (1) ES2010652B3 (en)
GR (1) GR3000239T3 (en)

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3668995D1 (en) * 1986-07-22 1990-03-15 Schoeller F Jun Gmbh Co Kg PHOTOGRAPHIC PAPER CARRIER AND METHOD FOR THE PRODUCTION THEREOF.
ES2042657T3 (en) * 1988-07-28 1993-12-16 Schoeller Felix Jun Papier WATER RESISTANT PHOTOGRAPHIC PAPER SUPPORT.
US4988559A (en) * 1988-11-15 1991-01-29 Oji Paper Co., Ltd. Support sheet for photographic printing sheet
JP2659578B2 (en) * 1989-02-06 1997-09-30 三菱製紙株式会社 Photographic support
US5102730A (en) * 1990-02-20 1992-04-07 Andrews Paper & Chemical Co., Inc. Erasable reproduction material
JP2793898B2 (en) * 1990-09-25 1998-09-03 富士写真フイルム株式会社 Photographic paper support
EP0553339B1 (en) * 1991-08-19 1997-12-17 Eastman Kodak Company Photographic paper with low oxygen permeability
DE69412062T2 (en) * 1993-12-08 1998-12-03 Fuji Photo Film Co., Ltd., Minami-Ashigara, Kanagawa Light-sensitive silver halide material containing a light-sensitive polymerizable layer and a cover layer containing polyvinyl alcohol with acidic groups or a salt thereof
US5464691A (en) * 1994-07-22 1995-11-07 Arizona Chemical Company Laminated barrier film
JP3311874B2 (en) * 1994-10-14 2002-08-05 富士写真フイルム株式会社 Composition for lithographic printing dampening solution
JP3571192B2 (en) * 1997-09-26 2004-09-29 ユニ・チャーム株式会社 Water-degradable cleaning sheet containing modified polyvinyl alcohol
MX357920B (en) * 2013-01-10 2018-07-31 Rivera Carmona Dalila Non-transparent art paper which prevents ink seepage.

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4994275A (en) * 1973-01-12 1974-09-06
DE2515823C2 (en) * 1975-04-11 1984-06-07 Felix Schoeller jr. GmbH & Co KG, 4500 Osnabrück Process for the production of a photographic support material to be dried by microwave treatment
JPS5684954A (en) * 1979-12-12 1981-07-10 Azona Kk Filmmpaper laminate and its manufacture
JPH0234371B2 (en) * 1981-11-10 1990-08-02 Fuji Photo Film Co Ltd SHASHININGASHOSHIJITAI
JPS59185690A (en) * 1983-04-07 1984-10-22 Jujo Paper Co Ltd Ink jet recording paper
JPS60217357A (en) * 1984-04-12 1985-10-30 Mitsubishi Paper Mills Ltd Photographic polyethylene coated paper

Also Published As

Publication number Publication date
ATE46221T1 (en) 1989-09-15
ES2010652B3 (en) 1989-12-01
EP0225446A1 (en) 1987-06-16
DE3543597C2 (en) 1992-03-05
DE3665505D1 (en) 1989-10-12
JPS62138848A (en) 1987-06-22
GR3000239T3 (en) 1991-03-15
US4731291A (en) 1988-03-15
DE3543597A1 (en) 1987-06-11
JPH083608B2 (en) 1996-01-17

Similar Documents

Publication Publication Date Title
DE3300025C2 (en)
EP0225446B1 (en) Water-resistant photographic paper support
DE4426620A1 (en) Paper base for photographic printing
DE2940870A1 (en) PHOTOGRAPHIC PAPER CARRIER WITH IMPROVED DURABILITY
DE3216840C2 (en) Water-resistant substrate for photographic materials
DE3636790C1 (en) Waterproof photographic paper carrier
DE3210621C2 (en)
DE3035318C2 (en)
DE3328463C2 (en)
EP0328756B1 (en) Base paper for photographic supports
DE3241599A1 (en) PHOTOGRAPHIC CARRIER
EP0235564B1 (en) Water-resistant photographic paper support
DE3238865C2 (en)
EP0213231B1 (en) Waterproof paper support for photographic layers
DE4110622C2 (en) Polyolefin coated substrate for photographic materials
EP0259548A1 (en) Photographic-paper support with a water-resistant polyolefinic coating
DE69215563T2 (en) Coated photographic paper supports
DE3306768C2 (en) Substrate for photographic recording materials
EP0356531B1 (en) Water-resistant photographic-paper support
DE3310979A1 (en) METHOD FOR PRODUCING A HIGHLY GLUE PAPER
DE3400125C2 (en) Process for making photographic paper supports
DE69127432T2 (en) Supports for photographic prints
DE3631835C2 (en)
DE69128405T2 (en) Photographic paper support
DE2344367C2 (en) Process for the production of a photographic paper support coated with a polyolefin

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE ES FR GB GR IT LI LU NL SE

17P Request for examination filed

Effective date: 19870714

17Q First examination report despatched

Effective date: 19880421

ITF It: translation for a ep patent filed
GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH DE ES FR GB GR IT LI LU NL SE

REF Corresponds to:

Ref document number: 46221

Country of ref document: AT

Date of ref document: 19890915

Kind code of ref document: T

ET Fr: translation filed
REF Corresponds to:

Ref document number: 3665505

Country of ref document: DE

Date of ref document: 19891012

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GR

Payment date: 19891219

Year of fee payment: 4

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

REG Reference to a national code

Ref country code: GR

Ref legal event code: FG4A

Free format text: 3000239

26N No opposition filed
ITTA It: last paid annual fee
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: THE PATENT HAS BEEN ANNULLED BY A DECISION OF A NATIONAL AUTHORITY

Effective date: 19910430

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 19920825

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: LU

Payment date: 19921014

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 19921020

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19921023

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 19921027

Year of fee payment: 7

EPTA Lu: last paid annual fee
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19931007

Ref country code: AT

Effective date: 19931007

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Effective date: 19931008

Ref country code: ES

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 19931008

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Effective date: 19940701

REG Reference to a national code

Ref country code: GR

Ref legal event code: MM2A

Free format text: 3000239

EUG Se: european patent has lapsed

Ref document number: 86113855.0

Effective date: 19940510

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19970915

Year of fee payment: 12

Ref country code: FR

Payment date: 19970915

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19970919

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 19970925

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 19971010

Year of fee payment: 12

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19981007

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19981031

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19981031

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19981031

BERE Be: lapsed

Owner name: FELIX SCHOELLER JR. G.M.B.H. & CO. K.G.

Effective date: 19981031

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990501

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19981007

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990630

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 19990501

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 19990601

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20051007