EP1757731A2 - Prepreg - Google Patents
Prepreg Download PDFInfo
- Publication number
- EP1757731A2 EP1757731A2 EP06119238A EP06119238A EP1757731A2 EP 1757731 A2 EP1757731 A2 EP 1757731A2 EP 06119238 A EP06119238 A EP 06119238A EP 06119238 A EP06119238 A EP 06119238A EP 1757731 A2 EP1757731 A2 EP 1757731A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- impregnating
- resin solution
- free
- polymer dispersion
- combination
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
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
- D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
- D21H27/18—Paper- or board-based structures for surface covering
- D21H27/22—Structures being applied on the surface by special manufacturing processes, e.g. in presses
- D21H27/26—Structures being applied on the surface by special manufacturing processes, e.g. in presses characterised by the overlay sheet or the top layers of the structures
-
- 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
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/63—Inorganic compounds
- D21H17/70—Inorganic compounds forming new compounds in situ, e.g. within the pulp or paper, by chemical reaction with other substances added separately
-
- 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
- D21H25/00—After-treatment of paper not provided for in groups D21H17/00 - D21H23/00
- D21H25/04—Physical treatment, e.g. heating, irradiating
- D21H25/06—Physical treatment, e.g. heating, irradiating of impregnated or coated paper
Definitions
- the invention relates to prepregs, a process for their preparation and decorative coating materials obtainable therefrom.
- Decorative films based on prepregs are already more or less deeply soaked within the paper machine, immediately after sheet formation and drying, with a resin mixture, depending on the basis weight of the base paper. After drying and smoothing, usually also within the paper machine, the paper or the film must be crosslinked and thus be gap-resistant, so that during the subsequent processing steps of the finish coating and lamination on corresponding carrier no fiber separation occurs within the decorative film.
- the prepregs for further processing high coverage and surface quality, good printability in rotogravure, good paintability (high paint level), good flatness and bondability with chip and MDF boards (medium-density fiberboard) required.
- the thermally crosslinkable impregnating resins commonly used for the preparation of prepregs are water-dilutable, formaldehyde-containing resin solutions based on urea, melamine or phenolic resins. Since their sole use leads to relatively brittle products, these resin solutions are generally used in combination with water-dilutable, thermally crosslinkable polymer dispersions based on acrylic acid, acrylic acid ester, styrene, butadiene, vinyl acetate or acrylonitrile.
- the resin absorption can be between 5 and 35% by weight, with the proportion of resin solutions generally penetrating deeper into the base paper than the proportion of polymer dispersions. The latter accumulate more or less on the top and bottom of the paper and ensure good smoothability and thus printability and surface impermeability and thus paintability (paint level) of the papers.
- the resin solutions are intended to ensure the good gap strength and flatness of the prepreg by crosslinking the fiber-resin composite during further processing.
- thermosetting, formaldehyde-free resin solution By using a thermosetting, formaldehyde-free resin solution, the first at a heat treatment of the pre-impregnate over a period of about 40 seconds at about 132 ° C according to DE 101 34 302 C1 largely crosslinked (degree of crosslinking of at most 85%), these disadvantages are avoided.
- the resin solution used for this purpose, its production and possible uses, inter alia for the impregnation of papers for decorative applications, are in the DE 197 35 959 A1 described.
- the disadvantage is that such until the H adoptedverpressung on the carrier material (eg chipboard) as the last further processing step completely uncrosslinked pre-impregnate according to the DE 101 34 302 C2 until then has no better or even worse internal strengths than known formaldehyde-free or -contaminated prepregs.
- the carrier material eg chipboard
- it has up to the hot pressing a poorer surface impermeability and thus poorer paint (lower paint level) and a poorer flatness during the lamination (bonding) than previously known formaldehyde-free and -containing pre-impregnate.
- the invention is therefore based on the object to provide partially crosslinked prepregs that already largely avoid the disadvantages mentioned at the end of the paper machine and as far as possible by high surface quality, good printability and higher splitting strength than known formaldehyde-free or prepregs, good paintability (high paint level) , good flatness and bondability with conventional adhesives in the Distinguish subsequent processing steps and thus are almost equivalent in off-line impregnated papers in their properties.
- the prepreg according to the invention is obtainable by impregnating a base paper with an impregnating combination which contains a thermally curable, formaldehyde-free resin solution and a thermally crosslinkable polymer dispersion.
- the impregnated base paper is dried and smoothed. The smoothing is expediently carried out within the paper machine used to produce the prepreg.
- the degree of crosslinking of the prepreg is at least 10% and at most 85%.
- the impregnated base paper has a residual moisture of 2 to 3 wt .-%.
- the invention also provides a process for producing thermally partially crosslinked, formaldehyde-free prepregs within the paper machine and their use as decorative coating materials.
- the proportion of the impregnating components is from 5 to 35% by weight, preferably from 10 to 30% by weight, based on the weight of the raw paper.
- a resin for impregnating the base paper, a resin can be used which contains the aforementioned components B) and C), but not the component A).
- Such resins are in the DE 197 35 959 A1 disclosed.
- the inventive water-dilutable impregnating mixture of the above-mentioned formaldehyde-free resin solutions A) + B) + C) or B) + C) and usually used polymer dispersions is applied to at least one side of the paper web, then dried to a residual moisture content of 2 to 3% by weight and then smoothed.
- the impregnated base paper is thereby partially crosslinked, the degree of crosslinking depending on the mixing ratio of the impregnating combination between at least 10% and max. 85%.
- this is only partially crosslinked prepreg sufficiently flexible. It is particularly advantageous for the quality of the prepreg if the residual moisture is already set in the paper machine ("on-line"). Under a paper machine is understood in accordance with the general use of the word, the plant for papermaking, starting from the screening of the pulp suspension to the rolling up of the base paper.
- the mixing ratio between formaldehyde-free resin solution (I) and polymer dispersion (II) may be 49:51 to 10:90 (solid: solid), preferably 45:55 to 20:80. Mixture ratios of 35:65 to 30:70 are particularly preferred, since prepregs which have been produced with impregnation combinations having these mixing ratios are particularly easy to print and are sufficiently flexible.
- the concentration of the impregnating mixture according to the invention, which contains further additives if required, can be up to 50% by weight.
- the impregnating combination according to the invention can be applied online to the paper web in an amount of between 5 and 35% by weight, preferably between 10 and 30% by weight, based on the basis weight of the base paper.
- application devices all commonly used within the paper machine units can be used, preferably roller application devices, such as size press or film press.
- the raw papers to be impregnated according to the invention are those which are described, inter alia, in the patents EP 0223 922 A1 .
- EP 0870 872 A1 and DE 101 34 302 A1 are described.
- the impregnation, drying and smoothing methods used in the documents cited and in the trade journal " Kliblatt für Textilfabrikation "No. 6 (2000), pp. 350 to 355 described in detail and known prior art.
- a raw paper of 20% pine sulfate pulp and 80% eucalyptus pulp was produced.
- the freeness was 30 ° SR (Schopper-Riegler).
- 25% titanium dioxide and 4% formaldehyde-free wet strength agent were used on atro pulp.
- This raw paper without engine sizing and with a basis weight of 48 g / m 2 was impregnated on both sides in a laboratory size press with a formaldehyde-free resin solution of about 30% solids content of modified polyacrylic acid and a polyhydric alcohol (Acrodur 950 L Fa. BASF) and then at dried at different temperatures within about 18 seconds to a residual moisture content of about 2%.
- the amount applied after drying was 10 g / m 2 .
- Table 1 shows the degrees of crosslinking of the prepregs dried at different temperatures. This is followed by partial cross-linking of the prepregs up to about 30%, with drying conditions customary in the paper machine (up to 110 ° C., drying time about 300 seconds).
- the order amount was about 12 g / m 2 .
- the degree of crosslinking of the prepreg according to the invention was about 70%.
- the addition of polymer dispersion to the resin solution significantly increases the degree of crosslinking.
- the degree of crosslinking of the classical prepreg was 76% (A) or 84% (B) and is thus significantly higher than that of prepregs according to the invention with proportions of formaldehyde-free resin solutions according to Examples 1 and 2
Landscapes
- Reinforced Plastic Materials (AREA)
- Paper (AREA)
- Glass Compositions (AREA)
- Laminated Bodies (AREA)
Abstract
Description
Die Erfindung betrifft Vorimprägnate, ein Verfahren zu deren Herstellung sowie daraus erhältliche dekorative Beschichtungswerkstoffe.The invention relates to prepregs, a process for their preparation and decorative coating materials obtainable therefrom.
Dekorative Beschichtungswerkstoffe, sogenannte Dekorpapiere oder Dekorfolien, werden vorzugsweise zur Oberflächenbeschichtung bei der Möbelherstellung und im Innenausbau, insbesondere für Laminatböden, eingesetzt. Diese Dekorfolien sind kunstharzgetränkte und gegebenenfalls nachträglich oberflärhenbehandelte Papierbahnen, die dekorativ bedruckt oder unbedruckt und in einem unter Druck und Wärme nicht mehr reaktivierbaren Zustand sind. Je nach Art des Tränkverfahrens wird zwischen duroplastischen Dekorfolien mit durchimprägniertem Kern (offline-Verfahren) und Dekorfolien auf der Basis von Vorimprägnaten (online-Verfahren) unterschieden, auf denen anschließend eine Finish-Beschichtung vorgenommen werden kann. Somit entsteht eine Dekorfolie, die eine fertige Oberfläche besitzt.Decorative coating materials, so-called decor papers or decorative films, are preferably used for surface coating in furniture production and interior design, especially for laminate flooring. These decorative films are resin-impregnated and optionally subsequently surface treated paper webs that are decoratively printed or unprinted and in a no longer reactivated under pressure and heat condition. Depending on the type of impregnation process, a distinction is made between thermosetting decorative films with impregnated core (offline process) and decorative films based on prepregs (on-line process), on which subsequently a finish coating can be carried out. This creates a decorative film that has a finished surface.
Dekorfolien auf der Basis von Vorimprägnaten werden bereits innerhalb der Papiermaschine, unmittelbar nach der Blattbildung und Trocknung, mit einem Harzgemisch in Abhängigkeit von der flächenbezogenen Masse des Basispapiers mehr oder weniger tief getränkt. Nach der Trocknung und Glättung, meist ebenfalls innerhalb der Papiermaschine, muss das Papier oder die Folie vernetzt und damit spaltfest sein, damit bei den nachfolgenden Verarbeitungsschritten der Finish-Beschichtung und Kaschierung auf entsprechende Träger keine Fasertrennung innerhalb der Dekorfolie eintritt. Außerdem wird von den Vorimprägnaten für die weitere Verarbeitung eine hohe Deckkraft und Oberflächengüte, gute Bedruckbarkeit im Rotationstiefdruck, gute Lackierbarkeit (hoher Lackstand), gute Planlage und Verklebbarkeit mit Span- und MDF-Platten (mitteldichte Faserplatten) verlangt.Decorative films based on prepregs are already more or less deeply soaked within the paper machine, immediately after sheet formation and drying, with a resin mixture, depending on the basis weight of the base paper. After drying and smoothing, usually also within the paper machine, the paper or the film must be crosslinked and thus be gap-resistant, so that during the subsequent processing steps of the finish coating and lamination on corresponding carrier no fiber separation occurs within the decorative film. In addition, the prepregs for further processing high coverage and surface quality, good printability in rotogravure, good paintability (high paint level), good flatness and bondability with chip and MDF boards (medium-density fiberboard) required.
Die für die Herstellung von Vorimprägnaten üblicherweise eingesetzten thermisch vernetzbaren Imprägnierharze sind wasserverdünnbare, formaldehydhaltige Harzlösungen auf der Basis von Harnstoff-, Melamin- oder Phenolharzen. Da ihre alleinige Verwendung zu relativ spröden Produkten führt, werden diese Harzlösungen im allgemeinen in Kombination mit wasserverdünnbaren, thermisch vernetzbaren Polymerdispersionen auf der Basis von Acrylsäure, Acrylsäureester, Styrol, Butadien, Vinylacetat oder Acrylnitril eingesetzt.The thermally crosslinkable impregnating resins commonly used for the preparation of prepregs are water-dilutable, formaldehyde-containing resin solutions based on urea, melamine or phenolic resins. Since their sole use leads to relatively brittle products, these resin solutions are generally used in combination with water-dilutable, thermally crosslinkable polymer dispersions based on acrylic acid, acrylic acid ester, styrene, butadiene, vinyl acetate or acrylonitrile.
Bei Vorimprägnaten kann die Harzaufnahme zwischen 5 und 35 Gew.-% betragen, wobei im allgemeinen der Anteil an Harzlösungen tiefer in das Rohpapier penetriert als der Anteil an Polymerdispersionen. Letztere reichern sich mehr oder weniger an der Ober- und Unterseite des Papiers an und gewährleisten eine gute Glättbarkeit und damit Bedruckbarkeit sowie Oberflächendichtigkeit und damit Lackierbarkeit (Lackstand) der Papiere. Die Harzlösungen dagegen sollen die gute Spaltfestigkeit und Planlage des Vorimprägnats durch Vernetzung des Faser-Harz-Verbundes während der weiteren Verarbeitungsprozesse gewährleisten.In the case of prepregs, the resin absorption can be between 5 and 35% by weight, with the proportion of resin solutions generally penetrating deeper into the base paper than the proportion of polymer dispersions. The latter accumulate more or less on the top and bottom of the paper and ensure good smoothability and thus printability and surface impermeability and thus paintability (paint level) of the papers. In contrast, the resin solutions are intended to ensure the good gap strength and flatness of the prepreg by crosslinking the fiber-resin composite during further processing.
Die Penetrationstiefe von Polymerdispersionen kann durch verschiedene Additive erhöht werden, wie z.B. durch wasserlösliche Polymere auf der Basis von Polyvinylalkoholen, Gelatine, Stärken, Cellulosederivaten, Alginaten und deren Mischungen (
Teilweise wird bei der Herstellung der Vorimprägnate unter Verwendung o.g. Additive gänzlich auf den Einsatz von klassischen formaldehydhaltigen Harzlösungen verzichtet. Diese dann formaldehydfreien Vorimprägnate sind jedoch in ihrer Spaltfestigkeit, Planlage und Bedruckbarkeit begrenzt.Partially used in the preparation of the prepregs using o.g. Additives completely dispensed with the use of classical formaldehyde-containing resin solutions. These then formaldehyde-free prepregs, however, are limited in their gap strength, flatness and printability.
Durch die Verwendung einer thermisch härtbaren, formaldehydfreien Harzlösung, die erst bei einer Wärmebehandlung des Vorimprägnats über einen Zeitraum von etwa 40 Sekunden bei etwa 132 °C gemäß
Der Erfindung liegt daher die Aufgabe zugrunde, teilvernetzte Vorimprägnate bereitzustellen, die bereits am Ende der Papiermaschine die genannten Nachteile weitgehend vermeiden und sich nach Möglichkeit durch hohe Oberflächengüte, gute Bedruckbarkeit und höhere Spaltfestigkeit als bekannte formaldehydfreie oder -haltige Vorimprägnate, gute Lackierbarkeit (hoher Lackstand), gute Planlage und Verklebbarkeit mit üblichen Klebstoffen in den nachfolgenden Verarbeitungsstufen auszeichnen und damit off line imprägnierten Papieren in ihren Eigenschaften nahezu gleichwertig sind.The invention is therefore based on the object to provide partially crosslinked prepregs that already largely avoid the disadvantages mentioned at the end of the paper machine and as far as possible by high surface quality, good printability and higher splitting strength than known formaldehyde-free or prepregs, good paintability (high paint level) , good flatness and bondability with conventional adhesives in the Distinguish subsequent processing steps and thus are almost equivalent in off-line impregnated papers in their properties.
Gelöst wird diese Aufgabe durch ein formaldehydfreies Vorimprägnat mit den Merkmalen gemäß Patentanspruch 1. Weitere vorteilhafte Ausführungsformen ergeben sich aus den Unteransprüchen.This object is achieved by a formaldehyde-free prepreg having the features of claim 1. Further advantageous embodiments will become apparent from the dependent claims.
In verfahrensmäßiger Hinsicht wird die Aufgabe gelöst durch ein Verfahren gemäß Patentanspruch 8, wobei vorteilhafte weitere Ausführungsformen in den entsprechenden Unteransprüchen angegeben sind.In procedural terms, the object is achieved by a method according to claim 8, wherein advantageous further embodiments are specified in the corresponding subclaims.
Das erfindungsgemäße Vorimprägnat ist erhältlich durch Imprägnieren eines Rohpapiers mit einer Imprägnier-Kombination, die eine thermisch härtbare, formaldehydfreie Harzlösungen und eine thermisch vernetzbare Polymerdispersion enthält. Das imprägnierte Rohpapier wird getrocknet und geglättet. Das Glätten erfolgt zweckmäßigerweise innerhalb der zur Herstellung des Vorimprägnats verwendeten Papiermaschine. Der Vernetzungsgrad des Vorimprägnats beträgt mindestens 10 % und höchstens 85 %. Das imprägnierte Rohpapier hat eine Restfeuchte von 2 bis 3 Gew.-%.The prepreg according to the invention is obtainable by impregnating a base paper with an impregnating combination which contains a thermally curable, formaldehyde-free resin solution and a thermally crosslinkable polymer dispersion. The impregnated base paper is dried and smoothed. The smoothing is expediently carried out within the paper machine used to produce the prepreg. The degree of crosslinking of the prepreg is at least 10% and at most 85%. The impregnated base paper has a residual moisture of 2 to 3 wt .-%.
Der Vernetzungsgrad wird analog der in der
Gegenstand der Erfindung ist auch ein Verfahren zur Herstellung thermisch teilvernetzter, formaldehydfreier Vorimprägnate innerhalb der Papiermaschine und deren Verwendung als dekorative Beschichtungswerkstoffe. Unter Vorimprägnaten werden erfindungsgemäß mit formaldehydfreien Harzlösungen in Kombination mit Polymerdispersionen teilimprägnierte Papiere verstanden. Der Anteil der lmprägnierkomponenten beträgt 5 bis 35 Gew.-%, vorzugsweise 10 bis 30 Gew.-%, bezogen auf das Rohpapiergewicht.The invention also provides a process for producing thermally partially crosslinked, formaldehyde-free prepregs within the paper machine and their use as decorative coating materials. Preimpregnates according to the invention with partially formaldehyde-free resin solutions in combination with polymer dispersions partially impregnated papers Understood. The proportion of the impregnating components is from 5 to 35% by weight, preferably from 10 to 30% by weight, based on the weight of the raw paper.
Die Restfeuchte des Vorimprägnats beträgt zwischen 1,5 bis 3 Gew.-%. Bei Restfeuchten von mehr als 3,5 Gew.-% kann das Vorimprägnat an Maschinenteilen anhaften, beispielsweise an den Glättwerkswalzen der Papiermaschine.The residual moisture content of the prepreg is between 1.5 and 3% by weight. At residual moisture contents of more than 3.5% by weight, the prepreg can adhere to machine parts, for example to the calender rolls of the paper machine.
Zum Imprägnieren geeignete formaldehydfreie Harzlösungen sind die in der
- A) mindestens ein durch radikalische Polymerisation erhältliches Polymerisat, das weniger als 5 Gew.-% einer α, β-ethylenisch ungesättigten Mono- oder Dicarbonsäure einpolymerisiert enthält,
- B) mindestens ein durch radikalische Polymerisation erhältliches Polymerisat, das mehr als 15 Gew.-% einer α, β-ethylenisch ungesättigten Mono- oder Dicarbonsäure einpolymerisiert enthält, und
- C) mindestens ein Alkanolamin mit mindestens zwei Hydroxylgruppen.
- A) at least one polymer obtainable by free-radical polymerization and containing less than 5% by weight of an α, β-ethylenically unsaturated mono- or dicarboxylic acid in copolymerized form,
- B) at least one polymer obtainable by free-radical polymerization which contains more than 15% by weight of an α, β-ethylenically unsaturated mono- or dicarboxylic acid in copolymerized form, and
- C) at least one alkanolamine having at least two hydroxyl groups.
Gemäß einer besonders bevorzugten Ausführungsform kann zum Imprägnieren des Rohpapiers ein Harz eingesetzt werden, das die zuvor genannten Komponenten B) und C), nicht aber die Komponente A) enthält. Solche Harze sind in der
Die erfindungsgemäße wasserverdünnbare Imprägniermischung aus o.g. formaldehydfreien Harzlösungen A) + B) + C) oder B) + C) und üblicherweise verwendeten Polymerdispersionen wird auf mindestens eine Seite der Papierbahn aufgebracht, anschließend bis zu einer Restfeuchte von 2 bis 3 Gew.-% getrocknet und danach geglättet. Das imprägnierte Rohpapier ist dadurch teilvernetzt, wobei der Vernetzungsgrad je nach Mischungsverhältnis der Imprägnier-Kombination zwischen mindestens 10 % und max. 85 % beträgt. In den nachfolgenden Verarbeitungsschritten, wie Bedrucken, Lackieren und KaschierenNerkleben ist dieses nur teilvernetzte Vorimprägnat ausreichend flexibel. Besonders vorteilhaft für die Qualität des Vorimprägnats ist es, wenn die Restfeuchte bereits in der Papiermaschine ("on-line") eingestellt wird. Unter eine Papiermaschine wird dabei in Übereinstimmung mit dem allgemeinen Gebrauch des Wortes die Anlage zur Papierherstellung, angefangen vom Sieben der Faserstoffsuspension bis zum Aufrollen des Rohpapiers verstanden.The inventive water-dilutable impregnating mixture of the above-mentioned formaldehyde-free resin solutions A) + B) + C) or B) + C) and usually used polymer dispersions is applied to at least one side of the paper web, then dried to a residual moisture content of 2 to 3% by weight and then smoothed. The impregnated base paper is thereby partially crosslinked, the degree of crosslinking depending on the mixing ratio of the impregnating combination between at least 10% and max. 85%. In the subsequent processing steps, such as printing, varnishing and laminating, this is only partially crosslinked prepreg sufficiently flexible. It is particularly advantageous for the quality of the prepreg if the residual moisture is already set in the paper machine ("on-line"). Under a paper machine is understood in accordance with the general use of the word, the plant for papermaking, starting from the screening of the pulp suspension to the rolling up of the base paper.
Das Mischungsverhältnis zwischen formaldehydfreier Harzlösung (I) und Polymerdispersion (II) kann 49:51 bis 10:90 (fest:fest), vorzugsweise 45:55 bis 20:80 betragen. Besonders bevorzugt sind Mischungsverhältnisse von 35:65 bis 30:70, da Vorimprägnate, die mit Imprägnier-Kombinationen mit diesen Mischungsverhältnissen hergestellt wurden, besonders gut bedruckbar und ausreichend flexibel sind.The mixing ratio between formaldehyde-free resin solution (I) and polymer dispersion (II) may be 49:51 to 10:90 (solid: solid), preferably 45:55 to 20:80. Mixture ratios of 35:65 to 30:70 are particularly preferred, since prepregs which have been produced with impregnation combinations having these mixing ratios are particularly easy to print and are sufficiently flexible.
Die Konzentration der erfindungsgemäßen Imprägniermischung, die bei Bedarf weitere Additive enthält, kann bis zu 50 Gew.-% betragen. Die erfindungsgemäße Imprägnier-Kombination kann online auf die Papierbahn in einer Menge zwischen 5 und 35 Gew.-%, vorzugsweise zwischen 10 und 30 Gew.-%, bezogen auf das Flächengewicht des Rohpapiers, aufgetragen werden. Als Auftragsvorrichtungen können alle üblicherweise innerhalb der Papiermaschine angewendeten Aggregate eingesetzt werden, vorzugsweise Walzenauftragsvorrichtungen, wie Leimpresse oder Filmpresse.The concentration of the impregnating mixture according to the invention, which contains further additives if required, can be up to 50% by weight. The impregnating combination according to the invention can be applied online to the paper web in an amount of between 5 and 35% by weight, preferably between 10 and 30% by weight, based on the basis weight of the base paper. As application devices, all commonly used within the paper machine units can be used, preferably roller application devices, such as size press or film press.
Überraschend wurde festgestellt, dass die erfindungsgemäßen Vorimprägnate bereits unmittelbar nach der Papiermaschine bessere Eigenschaften als bisher bekannte formaldehydhaltige und formaldehydfreie Vorimprägnate bezüglich Bedruckbarkeit und Oberflächenfestigkeit (Tesafestigkeit) aufweisen. Gleichzeitig behalten sie aber eine hohe Obertlächendichtigkeit (hoher Lackstand) sowie Dimensionsstabilität/Planlage, die formaldehydfreie unvernetzte Vorimprägnate gemäß
Erreicht werden diese hervorragenden Eigenschaften des erfindungsgemäßen Vorimprägnats durch die Kombination von Harzlösungen und Polymerdispersionen in einem bestimmten Abmischungsverhältnis, bei dem sich ein Optimum zwischen penetrierenden und filmbildenden Eigenschaften der Einzelkomponenten beim Imprägnieren des Rohpapiers einstellt und das bereits innerhalb der Papiermaschine, vermutlich durch Synergieeffekte und Temperatureinfluß, weitgehend seinen endgültigen Zustand erreicht hat.These outstanding properties of the prepreg according to the invention are achieved by the combination of resin solutions and polymer dispersions in a certain mixing ratio, in which an optimum between penetrating and film-forming properties of the individual components in the impregnation of the base paper and the already within the paper machine, probably by synergy effects and temperature influence, has largely reached its final state.
Das erfindungsgemäße Vorimprägnat ist dadurch bedeutend universeller in den Weiterverarbeitungsschritten einsetzbar und unterliegt keinen technologischen Einschränkungen bezüglich verschiedener Prozessparameter, wie Geschwindigkeit, Temperatur und Druck. Insbesondere können die erfindungsgemäßen Vorimprägnate so hergestellt werden, dass sie eine hoher Flexibilität, Dimensionsstabilität und gute Sperreigenschaften gegen Wasser und Lösungsmittel besitzen und insbesondere als Basismaterial für hochwertige Spezialpapiere, wie Druck- und Werbeträger, dekorative Wandmaterialien, Schleifpapiere, Klebebänder oder Fußbodenbeläge einsetzbar sind.The prepreg according to the invention is thus significantly more universally applicable in the further processing steps and is not subject to any technological limitations with respect to various process parameters, such as speed, temperature and pressure. In particular, the prepregs according to the invention can be prepared so that they have high flexibility, dimensional stability and good barrier properties against water and solvents and can be used in particular as a base material for high-quality specialty papers, such as printing and advertising media, decorative wall materials, abrasive papers, adhesive tapes or floor coverings.
Besonders gute Vorimprägnat-Qualitäten konnten erreicht werden, wenn der Vernetzungsgrad des Vorimprägnats mehr als 50 %, vorzugsweise 70 % und mehr beträgt.Particularly good pre-impregnate qualities could be achieved if the degree of crosslinking of the prepreg is more than 50%, preferably 70% or more.
Die erfindungsgemäß zu imprägnierenden Rohpapiere sind solche, die u.a. in den Patentschriften
Die folgenden Beispiele erläutern die Erfindung. Alle Mengenangaben beziehen sich auf den Feststoff oder Feststoffgehalt, sofern nichts anderes angegeben ist.The following examples illustrate the invention. All quantities are based on the solids or solids content, unless stated otherwise.
Erfindungsgemäß wurde ein Rohpapier aus 20 % Kiefernsulfat-Zellstoff und 80 % EukalyptusZellstoff hergestellt. Der Mahlgrad betrug 30 °SR (Schopper-Riegler). Als Zusätze wurden auf atro Zellstoff 25 % Titandioxid und 4 % formaldehydfreies Nassfestmittel eingesetzt. Dieses Rohpapier ohne Masseleimung und mit einer flächenbezogenen Masse von 48 g/m2 wurde in einer Laborleimpresse mit einer formaldehydfreien Harzlösung von ca. 30 % Feststoffgehalt aus modifizierter Polyacrylsäure und einem mehrwertigen Alkohol (Acrodur 950 L der Fa. BASF) beidseitig imprägniert und anschließend bei unterschiedlichen Temperaturen innerhalb von ca. 18 Sekunden bis zu einer Restfeuchte von ca. 2 % getrocknet.According to the invention, a raw paper of 20% pine sulfate pulp and 80% eucalyptus pulp was produced. The freeness was 30 ° SR (Schopper-Riegler). As additives, 25% titanium dioxide and 4% formaldehyde-free wet strength agent were used on atro pulp. This raw paper without engine sizing and with a basis weight of 48 g / m 2 was impregnated on both sides in a laboratory size press with a formaldehyde-free resin solution of about 30% solids content of modified polyacrylic acid and a polyhydric alcohol (Acrodur 950 L Fa. BASF) and then at dried at different temperatures within about 18 seconds to a residual moisture content of about 2%.
Die Auftragsmenge nach der Trocknung betrug 10 g/m2.The amount applied after drying was 10 g / m 2 .
In der Tabelle 1 sind die Vernetzungsgrade der bei unterschiedlichen Temperaturen getrockneten Vorimprägnate zusammengestellt. Danach erfolgt bei in der Papiermaschine üblichen Trocknungsbedingungen (bis 110 °C, Trocknungsdauer ca. 14 Sekunden bei 300 m/min) eine Teilvernetzung der Vorimprägnate bis zu etwa 30 %.Table 1 shows the degrees of crosslinking of the prepregs dried at different temperatures. This is followed by partial cross-linking of the prepregs up to about 30%, with drying conditions customary in the paper machine (up to 110 ° C., drying time about 300 seconds).
Das Rohpapier aus Beispiel 1 wurde mittels einer Laborleimpresse mit der erfindungsgemäßen Imprägniermischung aus einer formaldehydfreien Harzlösung (Acrodur 950 L) und einer Styrol-Acrylat-Dispersion (Acronal 305 D der Fa. BASF) im Verhältnis 35:65 (fest:fest) imprägniert und bei Temperaturen von etwa 110 °C bis zu einer Restfeuchte von ca. 2 % innerhalb von ca. 18 Sekunden getrocknet.The base paper from Example 1 was impregnated by means of a laboratory size press with the impregnating mixture according to the invention from a formaldehyde-free resin solution (Acrodur 950 L) and a styrene-acrylate dispersion (Acronal 305 D from BASF) in a ratio of 35:65 (solid: solid) and dried at temperatures of about 110 ° C to a residual moisture content of about 2% within about 18 seconds.
Die Auftragsmenge betrug etwa 12 g/m2. Der Vernetzungsgrad des erfindungsgemäßen Vorimprägnats betrug ca. 70 %. Demnach erhöht der Zusatz an Polymerdispersion zur Harzlösung den Vernetzungsgrad signifikant.The order amount was about 12 g / m 2 . The degree of crosslinking of the prepreg according to the invention was about 70%. Thus, the addition of polymer dispersion to the resin solution significantly increases the degree of crosslinking.
Das Rohpapier aus Beispiel 1 wurde mittels Laborleimpresse mit einer üblicherweise eingesetzten Imprägniermischung für klassische Vorimprägnate aus formaldehydfreier Styrol-Acrylat-Dispersion (Acronal 305) und formaldehydhaltiger Harzlösung (Urecoll TS) im Verhältnis 70:30 (A) und 90:10 (B) (fest gerechnet) imprägniert und danach analog Beispiel 2 getrocknet. Die Auftragsmenge betrug jeweils ca. 13 g/m2.The base paper from Example 1 was produced by means of a laboratory size press with a typically used impregnation mixture for classic prepregs of formaldehyde-free styrene-acrylate dispersion (Acronal 305) and formaldehyde-containing resin solution (Urecoll TS) in the ratios 70:30 (A) and 90:10 (B) ( solid calculated) and then dried analogously to Example 2. The order amount was in each case about 13 g / m 2 .
Der Vernetzungsgrad des klassischen Vorimprägnats betrug 76 % (A) bzw. 84 % (B) und liegt damit signifikant höher als der von erfindungsgemäßen Vorimprägnaten mit Anteilen an formaldehydfreien Harzlösungen gemäß Beispiel 1 und 2The degree of crosslinking of the classical prepreg was 76% (A) or 84% (B) and is thus significantly higher than that of prepregs according to the invention with proportions of formaldehyde-free resin solutions according to Examples 1 and 2
Die gemäß Beispiel 1 bis 3 hergestellten Vorimprägnate wurden unter konstanten Bedingungen in einem Laborkalander geglättet. Die erreichten Papiereigenschaften sind in der Tabelle 2 zusammengestellt.The prepregs prepared according to Examples 1 to 3 were smoothed under constant conditions in a laboratory calender. The paper properties achieved are summarized in Table 2.
Im Vergleich zu üblicherweise eingesetzten formaldehydhaltigen bzw. formaldehydarmen Vorimprägnaten (Vergleichsbeispiele 3 A und 3 B) weist das erfindungsgemäße formaldehydfreie Vorimprägnat (Beispiel 2) eine bedeutend bessere Spaltfestigkeit und Bedruckbarkeit auf. Der Lackstand bleibt auf hohem Qualitätsniveau, während die Planlage etwas schlechter wird.In comparison to conventionally used formaldehyde-containing or low-formaldehyde prepregs (Comparative Examples 3 A and 3 B), the formaldehyde-free prepreg according to the invention (Example 2) has a significantly better nip strength and printability. The paint level remains at a high level of quality, while the flatness gets a little worse.
Im Gegensatz zum formaldehydfreien Vorimprägnat gemäß Beispiel 1 zeichnet sich das erfindungsgemäße Vorimprägnat (Beispiel 2) durch eine verbesserte Oberflächendichtigkeit und damit bedeutend höheren Lackstand, geringeren Farbdurchschlag (Pinhole-Test) und bessere Bedruckbarkeit sowie höhere Planlage aus.In contrast to the formaldehyde-free prepreg according to Example 1, the prepreg of the invention (Example 2) is characterized by improved surface impermeability and thus significantly higher paint level, lower color penetration (pinhole test) and better printability and higher flatness.
Die signifikant besseren Eigenschaften des erfindungsgemäßen thermisch teilvernetzten Vorimprägnats sind verursacht durch die Kombination von Harzlösung und Polymerdispersion in einem bestimmten Bereich der Mischungsverhältnisse sowie der sich dadurch einstellenden höheren Vernetzungsgrade als mit der Harzlösung allein.
Acrodur 350 L, 30 %ig)
Auftrag ca. 10 g/m2
Note 5 = sehr schlecht
Acrodur 350 L, 30%)
Order about 10 g / m 2
Grade 5 = very bad
Claims (14)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10307966A DE10307966C5 (en) | 2003-02-24 | 2003-02-24 | Preimpregnate and process for its preparation |
EP04710840.2A EP1518024B2 (en) | 2003-02-24 | 2004-02-13 | Prepreg |
Related Parent Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP04710840.2A Division EP1518024B2 (en) | 2003-02-24 | 2004-02-13 | Prepreg |
EP04710840.2 Division | 2004-02-13 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1757731A2 true EP1757731A2 (en) | 2007-02-28 |
EP1757731A3 EP1757731A3 (en) | 2012-12-05 |
Family
ID=32841851
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP04710840.2A Expired - Lifetime EP1518024B2 (en) | 2003-02-24 | 2004-02-13 | Prepreg |
EP06119238A Withdrawn EP1757731A3 (en) | 2003-02-24 | 2004-02-13 | Prepreg |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP04710840.2A Expired - Lifetime EP1518024B2 (en) | 2003-02-24 | 2004-02-13 | Prepreg |
Country Status (7)
Country | Link |
---|---|
EP (2) | EP1518024B2 (en) |
AT (1) | ATE338167T1 (en) |
BR (1) | BRPI0407760B1 (en) |
CA (1) | CA2518942C (en) |
DE (2) | DE10307966C5 (en) |
ES (1) | ES2271845T5 (en) |
WO (1) | WO2004074577A1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2009077561A1 (en) * | 2007-12-17 | 2009-06-25 | Technocell Dekor Gmbh & Co. Kg | Compressible decorative paper impregnating agent which can be printed by the inkjet method |
DE102013114420A1 (en) | 2012-12-23 | 2014-06-26 | Michael Jokiel | Impregnated paper comprises base paper which is impregnated on one side with water-based impregnating solution comprising e.g. aqueous dispersion of styrene-ethyl-butyl acrylate copolymer and aqueous dispersion of styrene-acrylate copolymer |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7909397B2 (en) | 2003-05-15 | 2011-03-22 | Audiovox Corporation | In-vehicle docking station for a portable media player |
EP1942141A1 (en) | 2006-12-22 | 2008-07-09 | Rohm and Haas France SAS | Curable composition |
DE102008014558A1 (en) | 2008-03-15 | 2009-09-17 | Dracowo Forschungs- Und Entwicklungs Gmbh | Polycarboxylic acid modified native epoxides with a specific ratio of epoxide-polycarboxylic acid in glycidyl ester epoxide, useful for preparing polyether and polyester |
EP2695745B1 (en) | 2012-08-06 | 2015-08-26 | Unilin BVBA | Method for manufacturing panels having a decorative surface |
EP2894047B1 (en) | 2014-01-10 | 2019-08-14 | Unilin, BVBA | Method for manufacturing panels having a decorative surface |
EP2905145B1 (en) | 2014-02-06 | 2019-10-23 | Unilin, BVBA | Method for manufacturing floor panels having a decorative surface |
BE1025875B1 (en) | 2018-01-04 | 2019-08-06 | Unilin Bvba | Methods for manufacturing panels |
CA3180920A1 (en) | 2020-06-23 | 2021-12-30 | Gustavo DUARTE | Barrier paper or board |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1994000523A1 (en) * | 1992-06-22 | 1994-01-06 | Gebrueder Buhl Papierfabriken Gmbh | Aqueous impregnating composition |
WO1995017551A1 (en) * | 1993-12-21 | 1995-06-29 | Arjo Wiggins S.A. | Impregnated sheet used as a basis for a decorative coating |
DE19728250A1 (en) * | 1997-07-02 | 1999-01-07 | Koehler Decor Gmbh & Co Kg | Production of preimpregnate for making decorative laminate |
DE10134302C1 (en) * | 2001-07-14 | 2002-12-12 | Technocell Dekor Gmbh & Co Kg | Pre-impregnate obtained by impregnation of crude paper with a thermally hardenable formaldehyde-free resin useful in the production of decorative impregnates or coatings, and surface treatment of printed and unprinted papers |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2949306A1 (en) † | 1979-12-07 | 1981-06-11 | Letron GmbH, 8750 Aschaffenburg | Synthetic veneer of paper fibre compsn. impregnated with resin - contg. equal wt. of long and short fibres, can be made on paper machine |
DE19735959A1 (en) † | 1997-08-19 | 1999-02-25 | Basf Ag | Thermally curable, aqueous binding agent composition |
US20040039098A1 (en) * | 2002-08-22 | 2004-02-26 | Hector Belmares | Formaldehyde-free coatings and acoustical panel |
-
2003
- 2003-02-24 DE DE10307966A patent/DE10307966C5/en not_active Expired - Fee Related
-
2004
- 2004-02-13 AT AT04710840T patent/ATE338167T1/en not_active IP Right Cessation
- 2004-02-13 EP EP04710840.2A patent/EP1518024B2/en not_active Expired - Lifetime
- 2004-02-13 ES ES04710840T patent/ES2271845T5/en not_active Expired - Lifetime
- 2004-02-13 EP EP06119238A patent/EP1757731A3/en not_active Withdrawn
- 2004-02-13 DE DE502004001322T patent/DE502004001322D1/en not_active Expired - Lifetime
- 2004-02-13 BR BRPI0407760-1A patent/BRPI0407760B1/en not_active IP Right Cessation
- 2004-02-13 WO PCT/EP2004/001393 patent/WO2004074577A1/en active IP Right Grant
- 2004-02-13 CA CA2518942A patent/CA2518942C/en not_active Expired - Fee Related
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1994000523A1 (en) * | 1992-06-22 | 1994-01-06 | Gebrueder Buhl Papierfabriken Gmbh | Aqueous impregnating composition |
WO1995017551A1 (en) * | 1993-12-21 | 1995-06-29 | Arjo Wiggins S.A. | Impregnated sheet used as a basis for a decorative coating |
DE19728250A1 (en) * | 1997-07-02 | 1999-01-07 | Koehler Decor Gmbh & Co Kg | Production of preimpregnate for making decorative laminate |
DE10134302C1 (en) * | 2001-07-14 | 2002-12-12 | Technocell Dekor Gmbh & Co Kg | Pre-impregnate obtained by impregnation of crude paper with a thermally hardenable formaldehyde-free resin useful in the production of decorative impregnates or coatings, and surface treatment of printed and unprinted papers |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2009077561A1 (en) * | 2007-12-17 | 2009-06-25 | Technocell Dekor Gmbh & Co. Kg | Compressible decorative paper impregnating agent which can be printed by the inkjet method |
DE102013114420A1 (en) | 2012-12-23 | 2014-06-26 | Michael Jokiel | Impregnated paper comprises base paper which is impregnated on one side with water-based impregnating solution comprising e.g. aqueous dispersion of styrene-ethyl-butyl acrylate copolymer and aqueous dispersion of styrene-acrylate copolymer |
Also Published As
Publication number | Publication date |
---|---|
BRPI0407760A (en) | 2006-10-03 |
ES2271845T5 (en) | 2013-11-22 |
EP1757731A3 (en) | 2012-12-05 |
DE10307966C5 (en) | 2009-05-28 |
DE502004001322D1 (en) | 2006-10-12 |
BRPI0407760B1 (en) | 2014-04-22 |
EP1518024B2 (en) | 2013-08-07 |
CA2518942C (en) | 2014-08-05 |
EP1518024B1 (en) | 2006-08-30 |
EP1518024A1 (en) | 2005-03-30 |
CA2518942A1 (en) | 2004-09-02 |
DE10307966A1 (en) | 2004-09-09 |
WO2004074577A1 (en) | 2004-09-02 |
ES2271845T3 (en) | 2007-04-16 |
ATE338167T1 (en) | 2006-09-15 |
DE10307966B4 (en) | 2005-08-11 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP1407079B1 (en) | Prepreg | |
DE102007030102B4 (en) | prepreg | |
EP2222922B1 (en) | Compressible decorative paper impregnating agent which can be printed by the inkjet method | |
DE3541187C2 (en) | Process for producing a paper web impregnated with synthetic resins and their use | |
EP1518024B2 (en) | Prepreg | |
WO2005118718A1 (en) | Method for producing coated substrates | |
EP2537682B1 (en) | Prepreg | |
EP2045393B1 (en) | Method for manufacturing an abrasion resistant film and abrasion resistant film | |
EP0870872B1 (en) | One-side impregnated printing paper support | |
DE19758479C2 (en) | impregnating | |
EP3754109B1 (en) | Pre-impregnate with improved flatness | |
DE19728250A1 (en) | Production of preimpregnate for making decorative laminate | |
EP0022153B1 (en) | Process for producing a decorative finished effect sheet | |
DE2727312B2 (en) | ||
DE19715268A1 (en) | Laminating sheet, e.g. for chipboard laminates | |
WO2007012617A1 (en) | Aminoplast resin film for coating substrates | |
DE2232847A1 (en) | PROCESS FOR THE MANUFACTURING OF CARRIER SHEETS IMPROVED WITH AMINOPLASTIC RESIN AND DECORATED WITH LACQUERED RESIN | |
DE2228936A1 (en) | COATING FOR WOOD-BASED MATERIALS | |
DE102013114420A1 (en) | Impregnated paper comprises base paper which is impregnated on one side with water-based impregnating solution comprising e.g. aqueous dispersion of styrene-ethyl-butyl acrylate copolymer and aqueous dispersion of styrene-acrylate copolymer | |
DE2500164A1 (en) | USE OF CARRIERS WITH A TOP LAYER FOR THE MANUFACTURING OF PRODUCTS IMPROVED WITH HARDABLE CONDENSATION RESINS |
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 |
|
AC | Divisional application: reference to earlier application |
Ref document number: 1518024 Country of ref document: EP Kind code of ref document: P |
|
AK | Designated contracting states |
Kind code of ref document: A2 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT RO SE SI SK TR |
|
PUAL | Search report despatched |
Free format text: ORIGINAL CODE: 0009013 |
|
AK | Designated contracting states |
Kind code of ref document: A3 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT RO SE SI SK TR |
|
RIC1 | Information provided on ipc code assigned before grant |
Ipc: D21H 27/26 20060101AFI20121026BHEP |
|
17P | Request for examination filed |
Effective date: 20130605 |
|
RBV | Designated contracting states (corrected) |
Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT RO SE SI SK TR |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
RIC1 | Information provided on ipc code assigned before grant |
Ipc: D21H 27/26 20060101ALI20130620BHEP Ipc: D21H 17/70 20060101AFI20130620BHEP |
|
AKX | Designation fees paid |
Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT RO SE SI SK TR |
|
INTG | Intention to grant announced |
Effective date: 20130719 |
|
17Q | First examination report despatched |
Effective date: 20140220 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN |
|
18D | Application deemed to be withdrawn |
Effective date: 20140503 |