EP1808278A1 - Process for Reducing the Formaldehyde Emission of Wood Materials - Google Patents
Process for Reducing the Formaldehyde Emission of Wood Materials Download PDFInfo
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- EP1808278A1 EP1808278A1 EP06100479A EP06100479A EP1808278A1 EP 1808278 A1 EP1808278 A1 EP 1808278A1 EP 06100479 A EP06100479 A EP 06100479A EP 06100479 A EP06100479 A EP 06100479A EP 1808278 A1 EP1808278 A1 EP 1808278A1
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- wood
- polyamine
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27N—MANUFACTURE BY DRY PROCESSES OF ARTICLES, WITH OR WITHOUT ORGANIC BINDING AGENTS, MADE FROM PARTICLES OR FIBRES CONSISTING OF WOOD OR OTHER LIGNOCELLULOSIC OR LIKE ORGANIC MATERIAL
- B27N1/00—Pretreatment of moulding material
- B27N1/003—Pretreatment of moulding material for reducing formaldehyde gas emission
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/02—Processes; Apparatus
- B27K3/15—Impregnating involving polymerisation including use of polymer-containing impregnating agents
Definitions
- the present invention relates to a process for formaldehyde emission reduction in wood-based materials by treatment with polyamines.
- Wood-based materials are a cost-effective and resource-saving alternative to solid wood, and have gained great importance especially in furniture construction and as building materials.
- starting materials serve wood layers of different thickness, wood strips, wood chips or wood fibers from different woods.
- wood parts or wood particles are usually pressed with natural and / or synthetic binders and optionally with the addition of further additives to plate or strand-shaped wood materials.
- Formaldehyde-containing resins or adhesives are often used as binders, for example UF resins (urea-formaldehyde resins) or melamine-containing urea-formaldehyde resins.
- the resins are produced by polycondensation of formaldehyde with urea or melamine. In order to obtain good adhesive properties, an excess of formaldehyde is generally added in this case. This means that there is free formaldehyde in the finished wood material that is released into the environment. Since the polycondensation proceeds slightly backwards, the back reaction is also a source of formaldehyde release.
- Formaldehyde may cause allergies, skin, respiratory or eye irritation above certain limits in humans.
- the reduction of formaldehyde emission in interior components is therefore an important concern.
- the formaldehyde emission can also be reduced by aftertreatment of the wood-based materials.
- the JP 2002-273145 A describes a method for reducing the formaldehyde release of wood composites, wherein several, each individually for Reduction of formaldehyde emission suitable measures can be combined.
- the described aqueous formaldehyde scavenger is composed of 20 to 50% by weight of urea, and a balance of a non-volatile amine, a means of increasing the permeability of the wood so that the urea and non-volatile amine can penetrate the composite, and a film-forming Solid which, upon drying, becomes a physical barrier to the formaldehyde on the wood composite. This film can affect the coatability of wood composites.
- the solution of the problem is based on the known methods for reducing the formaldehyde emission in wood materials by applying nitrogen-containing compounds.
- the process according to the invention is then characterized in that a mixture is applied to the wood material which contains at least one polyamine and optionally up to 20% by weight, based on the mixture, of urea.
- the mixture may be in aqueous form or without the addition of solvents.
- the aqueous polyamine solution contains preferably 10 to 50 wt .-% polyamine, in particular 15 to 45 wt .-% polyamine, particularly preferably 25 to 40 wt .-% polyamine, each based on the polymer solution.
- Polyamine (a) is understood as meaning compounds which have a molecular weight of at least 500 g / mol and at least 6 primary or secondary amino groups. Preference is given to using polyamines which have a molecular weight of at least 800 g / mol and at least 10 primary or secondary amino groups. As polyamines, preference is given to polyethyleneimine and polyvinylamine.
- the weight-average molecular weight of the polyvinylamine is preferably 5,000 to 350,000 g / mol, more preferably 5,000 to 100,000 g / mol, that of the polyethyleneimine is preferably 800 to 100,000 g / mol, more preferably 800 to 70,000 g / mol, most preferably 2,000 to 50,000 g / mol.
- Polyethyleneimine can be prepared by acid catalyzed polymerization of ethyleneimine and is obtained as an aqueous solution at levels of from 20 to 100% by weight, more preferably between 40 and 70% by weight of polyethylenimine.
- Polyvinylamine is prepared by polymerization of vinylformamide and subsequent hydrolysis and is obtained as an aqueous solution of 2 to 50 wt .-%, particularly preferably from 5 to 25 wt .-% of.
- the degree of hydrolysis can be adjusted by the reaction conditions and determines the ratio of amine groups to formamide groups.
- these solutions can be used directly as a basis for the polyamine solutions according to the invention.
- ionic and nonionic surfactants as used, for example, in US Pat H. Stache, "Tensid-Taschenbuch", Carl Hanser Verlag, Kunststoff, Vienna, 1981 . are used, in concentration of 0 to 5 wt .-%, preferably from 0 to 2 wt .-% are used.
- the pH can be adjusted by the following additives as optional component (c): mineral or organic acids such as sulfuric acid or formic acid.
- Component (c) may be added to the aqueous polymer solution from 0 to 30% by weight, preferably from 0 to 20% by weight.
- additives can be added to the aqueous polymer solution, for example, additives from the group of water repellents, e.g. Paraffin emulsions and waxes, fungicides, organic solvents or dyes.
- group of water repellents e.g. Paraffin emulsions and waxes, fungicides, organic solvents or dyes.
- the aqueous polyamine solution may contain up to 20% by weight of urea based on the polymer solution.
- the aqueous polymer solution contains less than 15% by weight of urea, preferably less than 10% by weight of urea and in particular less than 5% by weight of urea, in each case based on the polymer solution.
- the polymer solution is free of urea.
- a sufficient amount of polyamine solution is applied so that the amount of polyamine per m 2 surface of the wood material is between 1 g and 200 g, preferably between 2 g and 50 g, more preferably between 3 g and 30 g.
- the aqueous polymer solution can be applied to the wood material by various measures known to those skilled in the art. These include, for example, spraying, rolling, dipping, knife coating, brushing, curtain coating, preferably the amine solution is applied by spraying.
- Wood-based materials are all materials which are made of wood strips, such as, for example, fun board or plywood boards, wood-based materials produced from wood chips, for example chipboard or OSB boards, and wood-fiber materials such as LDF, MDF and HDF boards. These wood-based materials are produced from the corresponding wood particles with the addition of natural and / or synthetic binders by hot pressing.
- wood materials containing formaldehyde-containing binders are treated by the process according to the invention.
- OSB, wood fiber and chipboard Preference is given to OSB, wood fiber and chipboard.
- the wood-based materials can be surface-treated after pressing by grinding.
- the application of the polyamines according to the invention can be carried out before or after the grinding, preferably after grinding.
- the wood-based material may have an elevated temperature during application or at room temperature are located.
- the wood-based material can also be heat-treated after application, for example by infrared radiation, heated rollers or in a heat channel.
- the polyamines can be applied on one side or on both sides, preferably on both sides.
- the polyamine solution is preferably applied at a pH of from 3 to 12, preferably from 7 to 11, particularly preferably at a pH of from 9 to 11, it also being possible for protonation of the polyamines to occur in the less preferred acidic range.
- the invention also relates to the wood materials produced by the process according to the invention, in particular wood-containing materials containing formaldehyde-containing binders. Particular preference is given to particleboards and fibreboards treated according to the invention.
- the wood-based materials obtained by the process can then be surface-finished.
- the surface finishing can be done by coating with different materials. For example, a painting, funcing, lamination or lamination can be performed.
- Such surface-treated wood materials are also the subject of the invention.
- the wood-based materials according to the invention can be used for the production of furniture, packaging materials, in building construction, in dry construction or in interior work, for example as a laminate, insulation or support.
- a 30% aqueous solution of a polyethyleneimine having an average molecular weight of 5,000 g / mol was sprayed on the chipboard so that 40 g / m 2 of polyethylenimine was applied to the chipboard. Subsequently, the surface was heated to 60 ° C within 150 sec and then stored for 1 day at 20 ° C / 65% humidity.
- Formaldehyde emission with or without aftertreatment was determined in accordance with the DIN standard DIN EN717-2 (Determination of Formaldehyde Release Part 2: Formaldehyde Release by the Gas Analysis Method) from 1994 and DIN Standard DIN EN717-1 (Determination of Formaldehyde Release Part 1 : Formaldehyde release according to the test chamber method) from the year 2004 in a 1 m 3 chamber.
- the air flow is set to 60 1 / h.
- the escaping air is collected in a gas wash bottle containing an aqueous solution of acetylacetone and ammonium acetate.
- Formaldehyde reacts in aqueous solution with ammonium ions and acetylacetone to diacetyldihydrolutidine (DDL). This reaction is highly specific for formaldehyde.
- the DDL has an absorption maximum at 412 nm and can be quantitatively detected by spectroscopy. To determine the formaldehyde concentration, the values for the last 3 hours are averaged.
- test specimens with the dimensions 0.5 x 0.5 x thickness xm 3 with 0.75 m open edge are placed in a test chamber with a volume of 1 m 3 .
- the measurement is carried out for at least 10 to a maximum of 28 days at 23 ° C and a relative humidity of 45 +/- 3%.
- the air intake and exhaust is chosen so that the entire air is replaced once within 1 hour.
- 120 l of air are passed at a rate of 2 l / min into a gas scrubber bottle filled with aqueous ammonium acetate and acetylacetone solution.
- the formaldehyde concentration is also determined spectroscopically.
- the formaldehyde emission results from this method from a compensation curve, while 4 consecutive values may vary by no more than 5%. If this condition is not fulfilled after 28 days, the last 4 values are used for averaging.
- the chipboards A-C were coated after 24 h in standard atmosphere (20 ° C / 65% humidity) as follows:
- a white decorative paper (80 g / m 2 ) was impregnated with 100 g / m 2 of a resin liquor of Kauramin impregnating resin 792 and hardener 529 (100: 0.3) and dried in the oven at 160 ° C. The resulting film is placed on the surface of the chipboard and pressed (190 ° C, 25 bar, 35 s). To stabilize the test piece, a counter pull film is simultaneously pressed on the back side.
- a lattice test is carried out. For this purpose, two times four parallel line-shaped cuts (distance 0.5 cm) are made through the surface with a razor blade so that a diamond-shaped pattern is created. In the corners of the diamonds, there is a partial flaking of the coating. The percentage of destroyed surface is determined. The smaller the value, the better the coatability of the chipboard.
Abstract
Description
Die vorliegende Erfindung betrifft ein Verfahren zur Formaldehydemissionsreduktion bei Holzwerkstoffen durch Behandlung mit Polyaminen.The present invention relates to a process for formaldehyde emission reduction in wood-based materials by treatment with polyamines.
Holzwerkstoffe sind eine kostengünstige und Ressourcen schonende Alternative zu Massivholz, und haben große Bedeutung insbesondere im Möbelbau und als Baumaterialien erlangt. Als Ausgangsstoffe dienen Holzlagen unterschiedlicher Stärke, Holzstreifen, Holzspäne oder Holzfasern aus verschiedenen Hölzern. Solche Holzteile oder Holzpartikel werden üblicherweise mit natürlichen und/oder synthetischen Bindemitteln und gegebenenfalls unter Zugabe weiterer Additive zu platten- oder strangförmigen Holzwerkstoffen verpresst.Wood-based materials are a cost-effective and resource-saving alternative to solid wood, and have gained great importance especially in furniture construction and as building materials. As starting materials serve wood layers of different thickness, wood strips, wood chips or wood fibers from different woods. Such wood parts or wood particles are usually pressed with natural and / or synthetic binders and optionally with the addition of further additives to plate or strand-shaped wood materials.
Als Bindemittel werden häufig formaldehydhaltige Harze oder Kleber eingesetzt, beispielsweise UF-Harze (Harnstoff-Formaldehydharze) oder Melamin-haltige Harnstoff-Formaldehydharze. Die Harze werden durch Polykondensation von Formaldehyd mit Harnstoff bzw. Melamin hergestellt. Um gute Klebereigenschaften zu erhalten, wird hierbei in der Regel ein Überschuss an Formaldehyd zugegeben. Dies bedeutet, dass im fertigen Holzwerkstoff freier Formaldehyd vorliegt, der an die Umgebung abgegeben wird. Da die Polykondensation geringfügig rückwärts verläuft, ist die Rückreaktion ebenfalls eine Quelle zur Formaldehydfreisetzung.Formaldehyde-containing resins or adhesives are often used as binders, for example UF resins (urea-formaldehyde resins) or melamine-containing urea-formaldehyde resins. The resins are produced by polycondensation of formaldehyde with urea or melamine. In order to obtain good adhesive properties, an excess of formaldehyde is generally added in this case. This means that there is free formaldehyde in the finished wood material that is released into the environment. Since the polycondensation proceeds slightly backwards, the back reaction is also a source of formaldehyde release.
Auch Holz selbst kann Formaldehyd an die Umgebung abgeben, insbesondere nach einer Wärmebehandlung.Even wood itself can release formaldehyde to the environment, especially after a heat treatment.
Formaldehyd kann oberhalb bestimmter Grenzwerte beim Menschen Allergien, Haut-, Atemwegs- oder Augenreizungen verursachen. Die Reduzierung der Formaldehydemission in Bauteilen im Innenbereich ist daher ein wichtiges Anliegen.Formaldehyde may cause allergies, skin, respiratory or eye irritation above certain limits in humans. The reduction of formaldehyde emission in interior components is therefore an important concern.
Eine Erniedrigung der Formaldehydemission durch verringerte Zugabe von Formaldehyd bei der Herstellung führt nur bedingt zum Erfolg, da sich die Klebereigenschaften des Bindemittels mit abnehmender Formaldehydkonzentration verschlechtern, sowie das Abbinden des Klebers deutlich verlangsamt wird. Dies führt zu verlängerten Produktionszyklen (beschrieben in "
Eine weitere Möglichkeit zur Reduktion der Formaldehydemission besteht in der Zugabe von Formaldehydfängern wie Ammoniumsalzen oder Harnstoff zu den Holzpartikeln oder dem Formaldehydharz. Nachteilig an diesem Verfahren ist jedoch die verlangsamte Abbindegeschwindigkeit des Harzes, zudem werden die mechanischen Eigenschaften der Produkte nachteilig beeinflusst.Another way to reduce the formaldehyde emission is the addition of formaldehyde scavengers such as ammonium salts or urea to the wood particles or the formaldehyde resin. A disadvantage of this method, however, is the slower setting rate of the resin, in addition, the mechanical properties of the products are adversely affected.
Die Formaldehydemission lässt sich auch durch Nachbehandlung der Holzwerkstoffe reduzieren.The formaldehyde emission can also be reduced by aftertreatment of the wood-based materials.
Technische Bedeutung haben die Begasung von Holzwerkstoffen, insbesondere Spanplatten mit Ammoniak (RY AB-Verfahren, Verko-Verfahren) sowie das Besprühen der Spanplatten mit Formaldehydfängern (Swedspan-Verfahren) erhalten (
In der
Die
Trotz vieler Maßnahmen, wie der Anpassung der Stöchiometrie der formaldehydhaltigen Bindemittel beziehungsweise des Zusatzes von Formaldehydfängern, sowie unterschiedlicher Verfahren zur Nachbehandlung von Holzwerkstoffen sind weitere Maßnahmen nötig, um die Emission von Formaldehyd aus Holzwerkstoffen zu senken.Despite many measures, such as the adaptation of the stoichiometry of the formaldehyde-containing binder or the addition of formaldehyde scavengers, as well as different methods for the aftertreatment of wood-based materials, further measures are necessary to reduce the emission of formaldehyde from wood-based materials.
Es ist Aufgabe der Erfindung, die Formaldehydemission von Holzwerkstoffen zu verringern, wobei weder die mechanischen Eigenschaften noch die Beschichtbarkeit der Holzwerkstoffe oder die Quellwerte negativ beeinflusst werden sollen, wie sie beispielsweise durch zu hohe Konzentrationen an Harnstoff in Formaldehydfängern oder durch Auftragung von Ammoniumsalzen verursacht werden kann.It is the object of the invention to reduce the formaldehyde emission of wood-based materials, wherein neither the mechanical properties nor the coatability of the wood-based materials or the swelling values should be adversely affected, as may be caused for example by excessively high concentrations of urea in formaldehyde scavengers or by application of ammonium salts ,
Die Lösung der Aufgabe geht aus von den bekannten Verfahren zur Reduktion der Formaldehydemission bei Holzwerkstoffen durch Aufbringen stickstoffhaltiger Verbindungen. Das erfindungsgemäße Verfahren ist dann dadurch gekennzeichnet, dass auf den Holzwerkstoff eine Mischung aufgebracht wird, die mindestens ein Polyamin und gegebenenfalls bis zu 20 Gew.-%, bezogen auf die Mischung, Harnstoff enthält.The solution of the problem is based on the known methods for reducing the formaldehyde emission in wood materials by applying nitrogen-containing compounds. The process according to the invention is then characterized in that a mixture is applied to the wood material which contains at least one polyamine and optionally up to 20% by weight, based on the mixture, of urea.
Die Mischung kann in wässriger Form oder ohne Zusatz von Lösemitteln vorliegen.The mixture may be in aqueous form or without the addition of solvents.
Die Polyamine können auf den Holzwerkstoff insbesondere als wässrige Polymerlösung aufgebracht werden. Die wässrige Polymerlösung ist insbesondere erhältlich durch Mischen von -jeweils bezogen auf die Polymerlösung-
- (a) 1 bis 99 Gew.-% Polyamin
- (b) 0 bis 5 Gew.-% Additiven zur Verbesserung der Benetzbarkeit
- (c) 0 bis 30 Gew.-% Additiven zur Einstellung des pH-Wertes
- (d) 0 bis 30 Gew.-% anderen Additiven wie Fungiziden, Hydrophobierungsmitteln, Farbstoffen, organischen Lösungsmitteln
- (e) 0 bis 20 Gew.-% Harnstoff
- (a) 1 to 99% by weight of polyamine
- (b) 0 to 5% by weight of additives for improving wettability
- (C) 0 to 30 wt .-% additives for adjusting the pH
- (D) 0 to 30 wt .-% of other additives such as fungicides, water repellents, dyes, organic solvents
- (e) 0 to 20% by weight of urea
Die wässrige Polyaminlösung enthält bevorzugt 10 bis 50 Gew.-% Polyamin, insbesondere 15 bis 45 Gew.-% Polyamin, besonders bevorzugt 25 bis 40 Gew.-% Polyamin, jeweils bezogen auf die Polymerlösung.The aqueous polyamine solution contains preferably 10 to 50 wt .-% polyamine, in particular 15 to 45 wt .-% polyamine, particularly preferably 25 to 40 wt .-% polyamine, each based on the polymer solution.
Unter Polyamin (a) werden Verbindungen verstanden, die ein Molekulargewicht von mindestens 500 g/mol und mindestens 6 primäre oder sekundäre Aminogruppen aufweisen. Bevorzugt werden Polyamine eingesetzt, die ein Molekulargewicht von mindestens 800 g/mol und mindestens 10 primäre oder sekundäre Aminogruppen aufweisen. Als Polyamine werden bevorzugt Polyethylenimin und Polyvinylamin gewählt.Polyamine (a) is understood as meaning compounds which have a molecular weight of at least 500 g / mol and at least 6 primary or secondary amino groups. Preference is given to using polyamines which have a molecular weight of at least 800 g / mol and at least 10 primary or secondary amino groups. As polyamines, preference is given to polyethyleneimine and polyvinylamine.
Das gewichtsmittlere Molekulargewicht des Polyvinylamins beträgt bevorzugt 5.000 bis 350.000 g/mol, besonders bevorzugt 5.000 bis 100.000 g/mol, das des Polyethylenimins beträgt bevorzugt 800 bis 100.000 g/mol, besonders bevorzugt 800 bis 70.000 g/mol, ganz besonders bevorzugt 2.000 bis 50.000 g/mol.The weight-average molecular weight of the polyvinylamine is preferably 5,000 to 350,000 g / mol, more preferably 5,000 to 100,000 g / mol, that of the polyethyleneimine is preferably 800 to 100,000 g / mol, more preferably 800 to 70,000 g / mol, most preferably 2,000 to 50,000 g / mol.
Polyethylenimin kann durch sauer katalysierte Polymerisation von Ethylenimin hergestellt werden und fällt als wässrige Lösung mit Gehalten von 20 bis 100 Gew.-%, besonders bevorzugt zwischen 40 und 70 Gew.% Polyethylenimin an. Polyvinylamin wird durch Polymerisation von Vinylformamid und anschließender Hydrolyse hergestellt und fällt als wässrige Lösung von 2 bis 50 Gew.-%, besonders bevorzugt von 5 bis 25 Gew.-% an. Der Hydrolysegrad kann durch die Reaktionsbedingungen eingestellt werden und bestimmt das Verhältnis von Amingruppen zu Formamidgruppen. Vorteilhaft können diese Lösungen direkt als Basis für die erfindungsgemäßen Polyaminlösungen verwendet werden.Polyethyleneimine can be prepared by acid catalyzed polymerization of ethyleneimine and is obtained as an aqueous solution at levels of from 20 to 100% by weight, more preferably between 40 and 70% by weight of polyethylenimine. Polyvinylamine is prepared by polymerization of vinylformamide and subsequent hydrolysis and is obtained as an aqueous solution of 2 to 50 wt .-%, particularly preferably from 5 to 25 wt .-% of. The degree of hydrolysis can be adjusted by the reaction conditions and determines the ratio of amine groups to formamide groups. Advantageously, these solutions can be used directly as a basis for the polyamine solutions according to the invention.
Es können nur ein bestimmtes Polyamin oder Mischungen aus mehreren Polyaminen verwendet werden.Only one particular polyamine or mixtures of several polyamines can be used.
Als fakultative Komponente (b) der wässrigen Polymerlösung können zur Verbesserung der Benetzbarkeit ionische und nichtionische Tenside, wie sie beispielsweise in
Der pH-Wert lässt sich durch die folgenden Additive als fakultative Komponente (c) einstellen: Mineralische oder organische Säuren wie Schwefelsäure oder Ameisensäure. Komponente (c) kann der wässrigen Polymerlösung von 0 bis 30 Gew.-%, bevorzugt von 0 bis 20 Gew.-% zugegeben werden.The pH can be adjusted by the following additives as optional component (c): mineral or organic acids such as sulfuric acid or formic acid. Component (c) may be added to the aqueous polymer solution from 0 to 30% by weight, preferably from 0 to 20% by weight.
Als fakultative Komponente (d) können weitere Additive der wässrigen Polymerlösung hinzugefügt werden, beispielsweise Additive aus der Gruppe Hydrophobierungsmittel, z.B. Paraffinemulsionen und Wachse, Fungizide, organische Lösungsmittel oder Farbstoffe.As optional component (d), further additives can be added to the aqueous polymer solution, for example, additives from the group of water repellents, e.g. Paraffin emulsions and waxes, fungicides, organic solvents or dyes.
Als fakultative Komponente (e) kann die wässrige Polyaminlösung bis zu 20 Gew.-% Harnstoff, bezogen auf die Polymerlösung, enthalten. Vorteilhaft enthält die wässrige Polymerlösung weniger als 15 Gew.-% Harnstoff, bevorzugt weniger als 10 Gew.-% Harnstoff und insbesondere weniger als 5 Gew.-% Harnstoff, jeweils bezogen auf die Polymerlösung. Besonders bevorzugt ist die Polymerlösung frei von Harnstoff.As optional component (e), the aqueous polyamine solution may contain up to 20% by weight of urea based on the polymer solution. Advantageously, the aqueous polymer solution contains less than 15% by weight of urea, preferably less than 10% by weight of urea and in particular less than 5% by weight of urea, in each case based on the polymer solution. Most preferably, the polymer solution is free of urea.
Es wird eine ausreichende Menge an Polyaminlösung aufgebracht, so dass die Menge an Polyamin pro m2 Oberfläche des Holzwerkstoffs zwischen 1 g und 200 g, bevorzugt zwischen 2 g und 50 g, besonders bevorzugt zwischen 3 g und 30 g beträgt.A sufficient amount of polyamine solution is applied so that the amount of polyamine per m 2 surface of the wood material is between 1 g and 200 g, preferably between 2 g and 50 g, more preferably between 3 g and 30 g.
Die wässrige Polymerlösung kann durch verschiedene, dem Fachmann bekannte Maßnahmen auf den Holzwerkstoff aufgebracht werden. Dazu zählen beispielsweise Aufsprühen, Walzen, Tauchen, Rakeln, Streichen, Curtain Coating, bevorzugt wird die Aminlösung durch Aufsprühen aufgebracht.The aqueous polymer solution can be applied to the wood material by various measures known to those skilled in the art. These include, for example, spraying, rolling, dipping, knife coating, brushing, curtain coating, preferably the amine solution is applied by spraying.
Als Holzwerkstoffe kommen alle Werkstoffe in Betracht, die aus Holzstreifen gefertigt sind wie beispielsweise Funierplatten oder Sperrholzplatten, aus Holzspänen hergestellte Holzwerkstoffe, beispielsweise Spanplatten oder OSB-Platten, sowie Holzfaserwerkstoffe wie LDF-, MDF- und HDF-Platten. Diese Holzwerkstoffe werden aus den entsprechenden Holzpartikeln unter Zugabe von natürlichen und/oder synthetischen Bindemitteln durch Heißverpressung hergestellt. Bevorzugt werden nach dem erfindungsgemäßen Verfahren formaldehydhaltige Bindemittel enthaltende Holzwerkstoffe behandelt. Bevorzugt sind OSB-, Holzfaser- und Spanplatten. Die Holzwerkstoffe können nach dem Pressen durch Schleifen oberflächenbehandelt werden. Das Aufbringen der erfindungsgemäßen Polyamine kann vor oder nach dem Schleifen erfolgen, bevorzugt nach dem Schleifen. Der Holzwerkstoff kann beim Aufbringen eine erhöhte Temperatur aufweisen oder sich bei Raumtemperatur befinden. Der Holzwerkstoff kann nach dem Auftragen auch wärmebehandelt werden, beispielsweise durch Infrarotstrahlung, beheizte Walzen oder in einem Wärmekanal. Die Polyamine können einseitig oder beidseitig aufgebracht werden, bevorzugt beidseitig.Wood-based materials are all materials which are made of wood strips, such as, for example, fun board or plywood boards, wood-based materials produced from wood chips, for example chipboard or OSB boards, and wood-fiber materials such as LDF, MDF and HDF boards. These wood-based materials are produced from the corresponding wood particles with the addition of natural and / or synthetic binders by hot pressing. Preferably, wood materials containing formaldehyde-containing binders are treated by the process according to the invention. Preference is given to OSB, wood fiber and chipboard. The wood-based materials can be surface-treated after pressing by grinding. The application of the polyamines according to the invention can be carried out before or after the grinding, preferably after grinding. The wood-based material may have an elevated temperature during application or at room temperature are located. The wood-based material can also be heat-treated after application, for example by infrared radiation, heated rollers or in a heat channel. The polyamines can be applied on one side or on both sides, preferably on both sides.
Die Polyaminlösung wird bevorzugt mit einem pH-Wert von 3 bis 12, bevorzugt von 7 bis 11, besonders bevorzugt mit einem pH-Wert von 9 bis 11 aufgebracht, wobei im weniger bevorzugten sauren Bereich auch Protonierung der Polyamine auftreten kann.The polyamine solution is preferably applied at a pH of from 3 to 12, preferably from 7 to 11, particularly preferably at a pH of from 9 to 11, it also being possible for protonation of the polyamines to occur in the less preferred acidic range.
Gegenstand der Erfindung sind auch die nach dem erfindungsgemäßen Verfahren hergestellten Holzwerkstoffe, insbesondere formaldehydhaltige Bindemittel enthaltende Holzwerkstoffe. Besonders bevorzugt sind erfindungsgemäß behandelte Spanplatten und Holzfaserplatten.The invention also relates to the wood materials produced by the process according to the invention, in particular wood-containing materials containing formaldehyde-containing binders. Particular preference is given to particleboards and fibreboards treated according to the invention.
Die nach dem Verfahren erhaltenen Holzwerkstoffe können anschließend oberflächenveredelt werden. Die Oberflächenveredlung kann durch Beschichtung mit verschiedenen Materialien erfolgen. Beispielsweise kann eine Lackierung, Funierung, Kaschierung oder Laminierung durchgeführt werden. Auch solche oberflächenveredelten Holzwerkstoffe sind Gegenstand der Erfindung.The wood-based materials obtained by the process can then be surface-finished. The surface finishing can be done by coating with different materials. For example, a painting, funcing, lamination or lamination can be performed. Such surface-treated wood materials are also the subject of the invention.
Die erfindungsgemäßen Holzwerkstoffe können zur Herstellung von Möbeln, von Verpackungsmaterialien, im Hausbau, im Trockenausbau oder im Innenausbau beispielsweise als Laminat, Dämmstoff oder Träger eingesetzt werden.The wood-based materials according to the invention can be used for the production of furniture, packaging materials, in building construction, in dry construction or in interior work, for example as a laminate, insulation or support.
Die Untersuchungen wurden mit geschliffenen Harnstoff-Formaldehyd-Leimgebundenen Spanlatten mit einer Dicke von 16 mm und einer Dichte von 650 kg/m3 durchgeführt.The tests were carried out with ground urea-formaldehyde glue-bonded chip slabs having a thickness of 16 mm and a density of 650 kg / m 3 .
- A keine (nicht erfindungsgemäß)A no (not according to the invention)
- B reine Harnstofflösung (nicht erfindungsgemäß)B pure urea solution (not according to the invention)
Eine 30%ige Harnstofflösung wurde in einer Menge, die zu einer Harnstoffmenge von 40 g/m2 führt, auf die Spanplatte aufgebracht, 150 sec auf 60 °C erwärmt und anschließend 1 Tag bei 20 °C/65 % Luftfeuchte gelagert.
- C Polyethyleniminlösung (erfindungsgemäß)
- C Polyethyleneimine solution (according to the invention)
Eine 30%ige wässrige Lösung eines Polyethylenimins mit einem mittleren Molekulargewicht von 5.000 g/mol wurde auf die Spanplatte gesprüht, so dass auf die Spanplatte 40 g/m2 Polyethylenimin aufgebracht wurden. Im Anschluss wurde die Oberfläche innerhalb von 150 sec auf 60°C erwärmt und anschließend 1 Tag bei 20 °C/65 % Luftfeuchte gelagert.A 30% aqueous solution of a polyethyleneimine having an average molecular weight of 5,000 g / mol was sprayed on the chipboard so that 40 g / m 2 of polyethylenimine was applied to the chipboard. Subsequently, the surface was heated to 60 ° C within 150 sec and then stored for 1 day at 20 ° C / 65% humidity.
Die Formaldehydemission mit oder ohne Nachbehandlung wurde nach der DIN-Norm DIN EN717-2 (Bestimmung der Formaldehydabgabe Teil 2: Formaldehydabgabe nach der Gasanalyse-Methode) aus dem Jahr 1994 und der DIN-Norm DIN-EN717-1 (Bestimmung der Formaldehydabgabe Teil 1: Formaldehydabgabe nach der Prüfkammer-Methode) aus dem Jahr 2004 in einer 1 m3-Kammer bestimmt.Formaldehyde emission with or without aftertreatment was determined in accordance with the DIN standard DIN EN717-2 (Determination of Formaldehyde Release Part 2: Formaldehyde Release by the Gas Analysis Method) from 1994 and DIN Standard DIN EN717-1 (Determination of Formaldehyde Release Part 1 : Formaldehyde release according to the test chamber method) from the year 2004 in a 1 m 3 chamber.
Bei der EN717-2 wird ein Prüfkörper mit den Abmessungen 0,4m x 0,05m x (Dicke des Prüfkörpers in m), mit verschlossenen Schmalflächen in einer Kammer mit einem Volumen von 0,004 m3 bei 60 °C und 2 +/- 1 % relativer Luftfeuchte 4 Stunden lang untersucht. Der Luftstrom wird auf 60 1/h eingestellt. Jeweils 1 h lang wird die austretende Luft in einer Gaswaschflasche gesammelt, die eine wässrige Lösung von Acetylaceton und Ammoniumacetat enthält. Formaldehyd reagiert in wässriger Lösung mit Ammoniumionen und Acetylaceton zu Diacetyldihydrolutidin (DDL). Diese Reaktion ist hoch spezifisch für Formaldehyd. Das DDL hat ein Absorptionsmaximum bei 412 nm und lässt sich quantitativ spektroskopisch nachweisen. Zur Ermittlung der Formaldehydkonzentration werden die Werte für die letzten 3 Stunden gemittelt.For the EN717-2, a test specimen with the dimensions 0.4m x 0.05m x (thickness of the specimen in m), with closed narrow surfaces in a chamber with a volume of 0.004 m 3 at 60 ° C and 2 +/- 1 % relative humidity examined for 4 hours. The air flow is set to 60 1 / h. For 1 hour each, the escaping air is collected in a gas wash bottle containing an aqueous solution of acetylacetone and ammonium acetate. Formaldehyde reacts in aqueous solution with ammonium ions and acetylacetone to diacetyldihydrolutidine (DDL). This reaction is highly specific for formaldehyde. The DDL has an absorption maximum at 412 nm and can be quantitatively detected by spectroscopy. To determine the formaldehyde concentration, the values for the last 3 hours are averaged.
Nach der EN717-1 werden zwei Prüfkörper mit den Abmessungen 0,5 x 0,5 x Dicke x m3 mit 0,75 m offener Kante in eine Prüfkammer mit dem Volumen 1 m3 gestellt. Die Messung wird mindestens 10 bis maximal 28 Tage lang bei 23 °C und einer relativen Luftfeuchte von 45 +/- 3 % durchgeführt. Die Luftzu- und abfuhr wird so gewählt, dass innerhalb von 1 Stunde die gesamte Luft einmal ausgewechselt wird. Zur Probenentnahme werden 120 l Luft mit einer Geschwindigkeit von 2 l/min in eine Gaswaschflasche geleitet, die mit wässriger Ammoniumacetat- und Acetylacetonlösung gefüllt ist. Die Formaldehydkonzentration wird ebenfalls spektroskopisch bestimmt. Die Formaldehydemission ergibt sich nach diesem Verfahren aus einer Ausgleichskurve, dabei dürfen 4 aufeinander folgende Werte höchstens um 5 % variieren. Ist nach 28 Tagen diese Bedingung noch nicht erfüllt, werden die letzten 4 Werte zur Mittelwertbildung herangezogen.According to the EN717-1, two test specimens with the dimensions 0.5 x 0.5 x thickness xm 3 with 0.75 m open edge are placed in a test chamber with a volume of 1 m 3 . The measurement is carried out for at least 10 to a maximum of 28 days at 23 ° C and a relative humidity of 45 +/- 3%. The air intake and exhaust is chosen so that the entire air is replaced once within 1 hour. For sampling, 120 l of air are passed at a rate of 2 l / min into a gas scrubber bottle filled with aqueous ammonium acetate and acetylacetone solution. The formaldehyde concentration is also determined spectroscopically. The formaldehyde emission results from this method from a compensation curve, while 4 consecutive values may vary by no more than 5%. If this condition is not fulfilled after 28 days, the last 4 values are used for averaging.
Die Spanplatten A-C wurden nach 24 h im Normklima (20 °C/65 % Luftfeuchte) wie folgt beschichtet:The chipboards A-C were coated after 24 h in standard atmosphere (20 ° C / 65% humidity) as follows:
Ein weißes Dekorpapier (80 g/m2) wurde mit 100 g/m2 einer Harzflotte aus Kauramin Tränkharz 792 und Härter 529 (100 : 0,3) getränkt und im Ofen bei 160 °C getrocknet. Der so erhaltene Film wird auf die Oberfläche der Spanplatte gelegt und verpresst (190 °C, 25 bar, 35 s). Zur Stabilisierung des Prüfkörpers wird gleichzeitig auf der Rückseite ein Gegenzugfilm aufgepresst.A white decorative paper (80 g / m 2 ) was impregnated with 100 g / m 2 of a resin liquor of Kauramin impregnating resin 792 and hardener 529 (100: 0.3) and dried in the oven at 160 ° C. The resulting film is placed on the surface of the chipboard and pressed (190 ° C, 25 bar, 35 s). To stabilize the test piece, a counter pull film is simultaneously pressed on the back side.
Zur Bewertung der Beschichtbarkeit wird ein Gittertest durchgeführt. Dazu werden mit einer Rasierklinge zwei mal vier parallele linienförmige Schnitte (Abstand 0,5 cm) durch die Oberfläche gemacht, so dass ein rautenförmiges Muster entsteht. In den Ecken der Rauten kommt es zu einem teilweisen Abplatzen der Beschichtung. Der Prozentsatz an zerstörter Oberfläche wird bestimmt. Je kleiner der Wert, desto besser ist die Beschichtbarkeit der Spanplatte.To evaluate the coatability, a lattice test is carried out. For this purpose, two times four parallel line-shaped cuts (distance 0.5 cm) are made through the surface with a razor blade so that a diamond-shaped pattern is created. In the corners of the diamonds, there is a partial flaking of the coating. The percentage of destroyed surface is determined. The smaller the value, the better the coatability of the chipboard.
Claims (11)
Priority Applications (14)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP06100479A EP1808278A1 (en) | 2006-01-17 | 2006-01-17 | Process for Reducing the Formaldehyde Emission of Wood Materials |
UAA200810446A UA95792C2 (en) | 2006-01-17 | 2007-01-12 | Method for treatment of wood materials |
NZ569380A NZ569380A (en) | 2006-01-17 | 2007-01-12 | Method for the reduction of formaldehyde emissions in wood materials |
CN200780002439.6A CN101370626B (en) | 2006-01-17 | 2007-01-12 | Method for the reduction of formaldehyde emissions in wood materials |
MYPI20082648A MY146656A (en) | 2006-01-17 | 2007-01-12 | Method for the reduction of formaldehyde emissions in wood materials |
AU2007206994A AU2007206994B2 (en) | 2006-01-17 | 2007-01-12 | Method for the reduction of formaldehyde emissions in wood materials |
PCT/EP2007/050272 WO2007082837A1 (en) | 2006-01-17 | 2007-01-12 | Method for the reduction of formaldehyde emissions in wood materials |
US12/161,276 US8460761B2 (en) | 2006-01-17 | 2007-01-12 | Method for reduction of formaldehyde emissions in wood materials |
RU2008133385/05A RU2437755C2 (en) | 2006-01-17 | 2007-01-12 | Method to reduce release of formaldehyde in wood materials |
BRPI0706437-3A BRPI0706437A2 (en) | 2006-01-17 | 2007-01-12 | process for reducing formaldehyde emission from wood-based material, wood-based material, laminate, and, use of wood-based material |
CA 2631869 CA2631869C (en) | 2006-01-17 | 2007-01-12 | Method for the reduction of formaldehyde emissions in wood materials |
JP2008550726A JP5328370B2 (en) | 2006-01-17 | 2007-01-12 | Method for reducing formaldehyde emissions in woody materials |
EP07703814A EP1979139A1 (en) | 2006-01-17 | 2007-01-12 | Method for the reduction of formaldehyde emissions in wood materials |
NO20082648A NO20082648L (en) | 2006-01-17 | 2008-06-05 | Process for reducing formaldehyde emissions in wood materials |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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EP06100479A EP1808278A1 (en) | 2006-01-17 | 2006-01-17 | Process for Reducing the Formaldehyde Emission of Wood Materials |
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EP1808278A1 true EP1808278A1 (en) | 2007-07-18 |
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EP06100479A Withdrawn EP1808278A1 (en) | 2006-01-17 | 2006-01-17 | Process for Reducing the Formaldehyde Emission of Wood Materials |
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EP (1) | EP1808278A1 (en) |
CN (1) | CN101370626B (en) |
UA (1) | UA95792C2 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102008005875A1 (en) * | 2008-01-24 | 2009-07-30 | Georg-August-Universität Göttingen Stiftung Öffentlichen Rechts | Use of polymers with amino or ammonium groups to increase the durability of wood over woody fungi |
DE102008049941B3 (en) * | 2008-10-02 | 2010-04-29 | Fritz Egger Gmbh & Co. | Panel, in particular floor panel |
CN102398295A (en) * | 2011-11-29 | 2012-04-04 | 宁波蓝鼎电子科技有限公司 | Method for preparing fiber board with low-content formaldehyde |
Families Citing this family (5)
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MY158695A (en) * | 2011-10-05 | 2016-11-15 | Malaysian Palm Oil Board | Method for producing fibreboards utilizing palm biomass |
WO2017058797A1 (en) * | 2015-09-28 | 2017-04-06 | Milliken & Company | Composition and method for reducing residual aldehyde content and foul odors of polyols |
CN110964434B (en) * | 2019-11-28 | 2021-05-11 | 西南林业大学 | Aldehyde-free green environment-friendly adhesive and preparation method thereof |
CN113750768A (en) * | 2021-09-28 | 2021-12-07 | 绍兴道普新材料科技有限公司 | Epsilon-polylysine formaldehyde scavenger |
CN114685933B (en) * | 2021-12-15 | 2024-01-02 | 江苏金发科技新材料有限公司 | Polyformaldehyde composite material and preparation method and application thereof |
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UA95792C2 (en) | 2011-09-12 |
CN101370626B (en) | 2013-05-01 |
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