EP1266730A1 - Method of manufacturing moisture resistant fibreboards - Google Patents

Method of manufacturing moisture resistant fibreboards Download PDF

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Publication number
EP1266730A1
EP1266730A1 EP01850102A EP01850102A EP1266730A1 EP 1266730 A1 EP1266730 A1 EP 1266730A1 EP 01850102 A EP01850102 A EP 01850102A EP 01850102 A EP01850102 A EP 01850102A EP 1266730 A1 EP1266730 A1 EP 1266730A1
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EP
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Prior art keywords
chips
formaldehyde
tannin
fibers
chipboard
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EP01850102A
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German (de)
French (fr)
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EP1266730B1 (en
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Edmone Roffael
Björn Mansson
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ROFFAEL, EDMONE
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Akzo Nobel NV
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Priority to EP01850102A priority Critical patent/EP1266730B1/en
Priority to DE50109378T priority patent/DE50109378D1/en
Priority to AT01850102T priority patent/ATE321636T1/en
Publication of EP1266730A1 publication Critical patent/EP1266730A1/en
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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

Definitions

  • the invention relates to a method for producing moisture-resistant Chipboard and fiberboard in the dry process, such as medium density fiberboard (MDF).
  • MDF medium density fiberboard
  • Wood chips and fiberboard are manufactured by using chips or Fibers glued with a binder, the glued chips or fibers to mats scatters and then at temperatures of 140 ° C to 220 ° C to chip or Fiberboard presses.
  • chipboard gluing is usually carried out afterwards Drying the chips can be used in the manufacture of medium density fiberboard (MDF) the fibers are glued before or after the fibers have dried.
  • MDF medium density fiberboard
  • the wood fibers are usually made in a so-called blow-line process first glued and then dried in one or two stages.
  • a binder for the production of chipboard and fiberboard mainly aminoplast resins, especially urea formaldehyde (UF resins) and urea-melamine formaldehyde resins (MUF resins) are used. It can too other binders such as alkaline curing phenol formaldehyde resins (PF resins), Tannin formaldehyde resins (TF resins) and adhesives based on polymers Diisocyanates (PMDI) can be used. So far, these binders have one comparatively minor importance. In multi-layer chipboard and fiberboard different binders can be used in the different layers come.
  • PF resins alkaline curing phenol formaldehyde resins
  • TF resins Tannin formaldehyde resins
  • PMDI polymers Diisocyanates
  • oriented beach boards frequently used PMDI in the middle layer and MUF resins in the outer layers.
  • So-called chipboard can also be produced, in which the Cover layers consist of fibers and the middle layers consist of chips.
  • binders in the chip and fiber layers be used.
  • UF resins The urea-formaldehyde resins adhere as two binders Disadvantages. These are the subsequent release of formaldehyde and the low Moisture resistance of wood-based materials made with UF resins. With UF resins can not produce chipboard or fiberboard that the Pass the cooking strength test according to DIN 68763. With UF resins are also Spanund Fiberboard with extremely low thickness swelling hardly or not producible. This is particularly true when the molar ratio of formaldehyde: urea in the UF resins is low. From a certain molar ratio (formaldehyde : Urea) increases with a decrease in the formaldehyde content in the resin Thickness swelling clearly.
  • the formaldehyde release from chipboard this will reduce if the chips have dried to a moisture content of a maximum of 12% can be treated with formaldehyde-active substances such as urea.
  • formaldehyde-active substances such as urea.
  • the chips before treatment with the formaldehyde scavenger or with the urea have a maximum moisture content of 12%, the urea penetrates deep into the Wood structure stays on during the hardening process of the binder spatially separated and unfolds its effect only after the hardening process and during the subsequent storage of the chipboard produced.
  • This The disadvantage of this method is that the moisture resistance is based on Formaldehyde used Binedffen reduced. Your commitment is with the Use of resins with a molar ratio of formaldehyde: urea of 1: 1 and among them very critical (DE 3222195).
  • melamine resin or Melamine urea resin with phenol in the presence of formaldehyde or one Melamine methylol compound.
  • MUPF resins Melamine urea phenol formaldehyde resins
  • MUPF and MUF resins are expensive.
  • the introduction of melamine in Urea-formaldehyde resins also reduce the curing speed of the Harzes and therefore leads, albeit slightly, to an extension of the required pressing times.
  • melamine as a formaldehyde scavenger in UF resins with a high molar ratio of formaldehyde: urea (1.5: 1) is also known (DE-OS 1653167).
  • the addition of melamine to urea formaldehyde resins with a low molar ratio of formaldehyde: urea (1: 1 to about 1.2: 1) is also known from EP 0062389.
  • the moisture resistance which is determined according to DIN 68763 as the V100 value, drops considerably if the amount of formaldehyde in the binder is reduced.
  • the V100 value decreases considerably when the ratio F / NH 2 (formaldehyde / NH 2 groups) in the resin drops below 0.65. This seems to be due to the fact that as the proportion of formaldehyde in the resin decreases, the crosslinking density of the cured resin decreases.
  • an increase in the proportion of formaldehyde has the disadvantage that the release of formaldehyde from the chipboard or fiberboard produced is increased.
  • EP-A-0013447 also proposes aminoplast resins in combination use with 2 to 20% soluble or dispersible protein as a binder.
  • PMDI diisocyanates
  • the object of this invention was therefore to find a new way to produce moisture-resistant chipboard and fiberboard without the Curing speed of the binders used, especially those Base of MUF resins, to reduce or the moisture resistance of the reduce manufactured plates or increase formaldehyde release. It is also the object of the invention, panels with high moisture resistance Manufactured using extremely low MUF resins Formaldehyde content.
  • the condensed tannin added to the fibers in a blow-line before gluing.
  • gluing in Glue mixers also use the tannin before the fibers dry added. This procedure has the advantage that the condensed tannins can also be applied in diluted form to the chips or to the fibers.
  • the teaching of the present invention also differs from the teaching of DE-OS 4402341, the treatment of chips with alkaline Tannin formaldehyde resins, preferably at a pH above 12 and subsequent drying of the glued chips before the pressing process.
  • the aim of DE-OS 4402341 is to self-condense the tannins without Addition of a crosslinking agent such as formaldehyde. Up to which Moisture content of the chips must be dried can be found in DE-OS 4402341 do not remove.
  • the example listed in DE-OS 4402341 does not contain any Information about the pressing temperature. With the procedure according to DE-OS 440234A1, boards with moisture-resistant gluing cannot be achieved. However, this is the object of the present invention.
  • the amount of Tannin solution, based on the weight of the chips, is 3.33% (or 1% Solid tannin based on dry chips).
  • the chips were removed immediately afterwards dried to a moisture of 1-2%.
  • the dried chips were with glued with a MUF resin.
  • the binder expenditure was 11% (based on the atro weight of the chips).
  • the glued chips then became mats sprinkled and hot pressed to 19 mm thick chipboard.
  • the pine wood chips were without Add condensed tannins to a moisture of 1-2% and dried with an MUF resin in quantities of 12% based on the atomic weight of the chips glued and then sprinkled into mats and hot pressed.
  • the chips are pre-condensed with tannins treated after drying and after drying - as usual - with a mixture glued with tannin formaldehyde resin and melamine urea formaldehyde resin Scattered mats and then pressed to chipboard.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Wood Science & Technology (AREA)
  • Forests & Forestry (AREA)
  • Dry Formation Of Fiberboard And The Like (AREA)
  • Inorganic Fibers (AREA)

Abstract

Production of moisture-resistant chip- or fiber-board by the dry process using phenol-formaldehyde, melamine-urea-formaldehyde, melamine-urea-phenol-formaldehyde, tannin-formaldehyde or PMDI resin binder comprises contacting the wet chips or fibers with condensed tannins, and drying the chips and fibers to a moisture content of ≤ 5% and ≤ 15% respectively prior to contacting with binder.

Description

Die Erfindung betrifft ein Verfahren zur Herstellung von feuchtebeständigen Spanplatten und Faserplatten im Trockenverfahren, wie mitteldichte Faserplatten (MDF). Holzspan- und Faserplatten werden hergestellt, indem man Späne bzw. Fasern mit einem Bindemittel beleimt, die beleimten Späne bzw. Fasern zu Matten streut und anschließend bei Temperaturen von 140°C bis 220°C zu Span- bzw. Faserplatten preßt. Im Falle der Spanplatten erfolgt die Beleimung in der Regel nach Trocknen der Späne, bei der Herstellung von mitteldichten Faserplatten (MDF) kann die Beleimung der Fasern vor oder auch nach dem Trocknen der Fasern stattfinden. Üblicherweise werden die Holzfasern in einem sogenannten Blow-line-Verfahren zuerst beleimt und anschließend ein- oder zweistufig getrocknet.The invention relates to a method for producing moisture-resistant Chipboard and fiberboard in the dry process, such as medium density fiberboard (MDF). Wood chips and fiberboard are manufactured by using chips or Fibers glued with a binder, the glued chips or fibers to mats scatters and then at temperatures of 140 ° C to 220 ° C to chip or Fiberboard presses. In the case of chipboard, gluing is usually carried out afterwards Drying the chips can be used in the manufacture of medium density fiberboard (MDF) the fibers are glued before or after the fibers have dried. The wood fibers are usually made in a so-called blow-line process first glued and then dried in one or two stages.

Als Bindemittel für die Herstellung von Span- und Faserplatten werden hauptsächlich Aminoplastharze, insbesondere Harnstoff-Formaldehyd (UF-Harze) und Harnstoff-Melaminformaldehydharze (MUF-Harze) eingesetzt. Es können auch andere Bindemittel wie alkalisch härtende Phenolformaldehydharze (PF-Harze), Tanninformaldehydharze (TF-Harze) und Klebstoffe auf Basis von polymeren Diisocyanaten (PMDI) verwendet werden. Diese Bindemittel haben bislang eine vergleichsweise geringe Bedeutung. In mehrschichtigen Span- und Faserplatten können in den verschiedenen Schichten unterschiedliche Bindemittel zum Einsatz kommen. So werden z.B. bei der Herstellung von Oriented Strandboards (OSB) häufig PMDI in der Mittelschicht und MUF-Harze in den Deckschichten eingesetzt. Es können auch sogenannte Span-Faserplatten hergestellt werden, bei denen die Deckschichten aus Fasern und die Mittelschichten aus Spänen bestehen. Hier können ebenfalls unterschiedliche Bindemittel in den Span- und Faserschichten verwendet werden.As a binder for the production of chipboard and fiberboard mainly aminoplast resins, especially urea formaldehyde (UF resins) and urea-melamine formaldehyde resins (MUF resins) are used. It can too other binders such as alkaline curing phenol formaldehyde resins (PF resins), Tannin formaldehyde resins (TF resins) and adhesives based on polymers Diisocyanates (PMDI) can be used. So far, these binders have one comparatively minor importance. In multi-layer chipboard and fiberboard different binders can be used in the different layers come. For example, in the production of oriented beach boards (OSB) frequently used PMDI in the middle layer and MUF resins in the outer layers. So-called chipboard can also be produced, in which the Cover layers consist of fibers and the middle layers consist of chips. Here can also different binders in the chip and fiber layers be used.

Den Harnstoff-Formaldehydharzen (UF-Harzen) haften als Bindemittel zwei Nachteile an. Diese sind die nachträgliche Formaldehydabgabe und die geringe Feuchtebeständigkeit der mit UF-Harzen hergestellten Holzwerkstoffe. Mit UF-Harzen lassen sich keine Span- oder Faserplatten herstellen, die den Kochfestigkeitstest gemäß DIN 68763 bestehen. Mit UF-Harzen sind ferner Spanund Faserplatten mit extrem niedriger Dickenqellung kaum oder nicht herstellbar. Dies trifft insbesondere zu, wenn das Molverhältnis von Formaldehyd : Harnstoff in den UF-Harzen niedrig liegt. Von einem bestimmten Molverhältnis an (Formaldehyd : Harnstoff) erhöht sich mit Verringerung des Formaldehydgehalts im Harz die Dickenquellung deutlich. Dies wirkt sich ebenfalls auf die Feuchtigkeitsbeständigkeit der Holz-zu-Holz-Bindung negativ aus. Es hat deshalb nicht an Versuchen gefehlt, die Feuchtebeständigkeit der mit UF-Harzen hergestellten Holzwerkstoffe, insbesondere Span- und Faserplatten, zu verbessern und ihre Formaldehydabgabe zu verringern (Roffael 1993: Formaldehyde Release from Particleboards and other Wood-Based Panels, Malaysian Forest Records No. 37).The urea-formaldehyde resins (UF resins) adhere as two binders Disadvantages. These are the subsequent release of formaldehyde and the low Moisture resistance of wood-based materials made with UF resins. With UF resins can not produce chipboard or fiberboard that the Pass the cooking strength test according to DIN 68763. With UF resins are also Spanund Fiberboard with extremely low thickness swelling hardly or not producible. This is particularly true when the molar ratio of formaldehyde: urea in the UF resins is low. From a certain molar ratio (formaldehyde : Urea) increases with a decrease in the formaldehyde content in the resin Thickness swelling clearly. This also affects moisture resistance the wood-to-wood bond is negative. There was therefore no lack of attempts the moisture resistance of the wood-based materials made with UF resins, especially chipboard and fiberboard, to improve their formaldehyde release (Roffael 1993: Formaldehyde Release from Particleboards and other Wood-Based Panels, Malaysian Forest Records No. 37).

Es sind verschiedene Methoden zur Verminderung der Formaldehydabgabe von Holzspanplatten vorgeschlagen worden. So ist z.B. bekannt, die Leimflotte mit einem enolisierbaren Aldehyd oder Keton zu versehen (EP-OS 002596). Ferner ist bekannt, die Spanplatten nach der Fertigstellung mit formaldehydaktiven Stoffen wie Harnstoff und/oder Ammoniak zu versehen (DE-PS 2829021). Ferner ist vorgeschlagen worden (DE-AS 2740207), die zu verleimenden Späne mit einer wässerigen Dispersion zu behandeln, die einen Formaldehydfänger wie Harnstoff enthält.. Nach der AT-PS 368766 läßt sich die Formaldehydabgabe von Spanplatten dadurch verringern, wenn die Späne nach dem Trocknen bis zu einer Feuchte von maximal 12 % mit formaldehydaktiven Stoffen wie Harnstoff behandelt werden. Da die Späne vor der Behandlung mit dem Formaldehydfänger bzw. mit dem Harnstoff eine Feuchte von maximal 12 % aufweisen, dringt der Harnstoff tief in die Holzstruktur ein, bleibt während des Härtungsprozesses von dem Bindemittel räumlich getrennt und entfaltet seine Wirkung erst nach dem Härtungsprozeß und während der nachträglichen Lagerung der hergestellten Holzspanplatten. Diese Methode hat den Nachteil, daß sie die Feuchtigkeitsbeständigkeit des auf Basis von Formaldehyd eingesetzten Binedmittels verringert. Ihr Einsatz ist bei der Verwendung von Harzen mit einem Molverhältnis Formaldehyd : Harnstoff von 1 : 1 und darunter sehr kritisch (DE 3222195). There are various methods for reducing formaldehyde release from Chipboard has been proposed. For example, known, the glue fleet with a to provide enolizable aldehyde or ketone (EP-OS 002596). Further is known, the chipboard after completion with formaldehyde-active substances such as To provide urea and / or ammonia (DE-PS 2829021). Further is have been proposed (DE-AS 2740207), the chips to be glued with a treat aqueous dispersion that is a formaldehyde scavenger such as urea contains .. According to AT-PS 368766 the formaldehyde release from chipboard this will reduce if the chips have dried to a moisture content of a maximum of 12% can be treated with formaldehyde-active substances such as urea. There the chips before treatment with the formaldehyde scavenger or with the urea have a maximum moisture content of 12%, the urea penetrates deep into the Wood structure stays on during the hardening process of the binder spatially separated and unfolds its effect only after the hardening process and during the subsequent storage of the chipboard produced. This The disadvantage of this method is that the moisture resistance is based on Formaldehyde used Binedmittel reduced. Your commitment is with the Use of resins with a molar ratio of formaldehyde: urea of 1: 1 and among them very critical (DE 3222195).

Als Methode für die Erhöhung der Feuchtebeständigkeit der UF-Harze ist die Abmischung der UF-Harze mit Melaminformaldehydharzen vorgeschlagen worden. Harnstoff-Formaldehydharze, die Anteile an Melaminformaldehydharzen enthalten, werden in der Spanplattenindustrie für die Herstellung von Span- und Faserplatten mit niedriger Dickenquellung und erhöhter Feuchtebeständigkeit eingesetzt. Den mit solchen Harzen erzeugten Bindungen fehlt es jedoch an der hohen Wetterfestigkeit (DE-PS 2020481). In der zitierten Patentschrift (DE-PS 2020481) wird deshalb vorgeschlagen, Wetterfestigkeit verleihende Holzleime auf Basis von Melamin und gegebenenfalls Harnstoff dadurch herzustellen, daß man einem wässerigen Melaminharz, das mit bis zu 600 Molprozent mit Harnstoff verschnitten sein kann, unter speziellen Bedingungen geringe Mengen an Phenol zusetzt. Zweckmäßigerweise erfolgt die Umsetzung des Melaminharzes bzw. des Melaminharnstoffharzes mit Phenol in Anwesenheit von Formaldehyd oder einer Methylolverbindung des Melamins. Auch solche Melaminharnstoffphenolformaldehydharze (MUPF-Harze), die als Mischkondensate von Melamin, Harnstoff und Phenol mit dem Formaldehyd angesehen werden, werden in der Holzwerkstoffindustrie für die Herstellung von Holzspanplatten eingesetzt. MUPF- und MUF-Harze sind kostspielig. Das Einbringen von Melamin in Harnstoff-Formaldehydharze verringert zudem die Härtungsgeschwindigkeit des Harzes und führt mithin, wenn auch geringfügig, teilweise zu einer Verlängerung der erforderlichen Presszeiten.As a method for increasing the moisture resistance of the UF resins is the Mixing of the UF resins with melamine formaldehyde resins has been proposed. Urea-formaldehyde resins containing proportions of melamine formaldehyde resins, are used in the chipboard industry for the production of chipboard and fiberboard with low thickness swelling and increased moisture resistance. The one with However, bonds produced by such resins lack high weather resistance (DE-PS 2020481). In the cited patent specification (DE-PS 2020481) is therefore proposed to provide weatherproof wood glue based on melamine and optionally produce urea by adding an aqueous Melamine resin, which can be blended with up to 600 mole percent with urea, adds small amounts of phenol under special conditions. Conveniently, the implementation of the melamine resin or Melamine urea resin with phenol in the presence of formaldehyde or one Melamine methylol compound. Even those Melamine urea phenol formaldehyde resins (MUPF resins) used as mixed condensates of melamine, urea and phenol with the formaldehyde, are used in the wood-based panel industry for the production of chipboard used. MUPF and MUF resins are expensive. The introduction of melamine in Urea-formaldehyde resins also reduce the curing speed of the Harzes and therefore leads, albeit slightly, to an extension of the required pressing times.

Auch der Einsatz von Melamin als Formaldehydfänger in UF-Harzen mit hohem Molverhältnis von Formaldehyd:Harnstoff (1,5:1) ist bekannt (DE-OS 1653167). Ebenfalls ist die Zugabe von Melamin zu Harnstofformaldehydharzen mit niedrigem Molverhältnis Formaldehyd:Harnstoff (1:1 bis etwa 1,2:1) aus EP 0062389 bekannt. Bei der Herstellung von Holzspanplatten mit MUF-Harzen geht die Feuchtebeständigkeit, die nach DIN 68763 als V100-Wert bestimmt wird, erheblich zurück, wenn die Menge an Formaldehyd im Bindemittel reduziert wird. Nach EP 0025245 nimmt der V100-Wert erheblich ab, wenn im Harz das Verhältnis F/NH2 (Formaldehyd/NH2-Gruppen) unter 0,65 absinkt. Dies scheint darauf zu beruhen, daß mit sinkendem Formaldehydanteil im Harz die Vernetzungsdichte des gehärteten Harzes zurückgeht. Eine Erhöhung des Formaldehydanteils hat jedoch den Nachteil, daß die Formaldehydabgabe der hergestellten Span- oder Faserplatten erhöht wird.The use of melamine as a formaldehyde scavenger in UF resins with a high molar ratio of formaldehyde: urea (1.5: 1) is also known (DE-OS 1653167). The addition of melamine to urea formaldehyde resins with a low molar ratio of formaldehyde: urea (1: 1 to about 1.2: 1) is also known from EP 0062389. When manufacturing chipboard with MUF resins, the moisture resistance, which is determined according to DIN 68763 as the V100 value, drops considerably if the amount of formaldehyde in the binder is reduced. According to EP 0025245, the V100 value decreases considerably when the ratio F / NH 2 (formaldehyde / NH 2 groups) in the resin drops below 0.65. This seems to be due to the fact that as the proportion of formaldehyde in the resin decreases, the crosslinking density of the cured resin decreases. However, an increase in the proportion of formaldehyde has the disadvantage that the release of formaldehyde from the chipboard or fiberboard produced is increased.

Um diese Nachteile abzustellen, ist vorgeschlagen worden, eine Mischung von Aminoplastharzen und Diisocyanaten (PMDI) als Bindemittel einzusetzen (FR-A-2.371.292). Auch die EP-A-0013447 schlägt vor, Aminoplastharze in Kombination mit 2 bis 20 % löslichem oder dispergierbarem Protein als Bindemittel einzusetzen. Die Verwendung von PMDI als Zusatzmittel für UF-Harze oder MUF-Harze führt zur Erhöhung der Bindemittelkosten und erfordert besondere Vorsichtsmaßnahmen im Betrieb. Die Aufgabe dieser Erfindung war es daher, einen neuen Weg zu finden, feuchtebeständige Holzspanplatten und Holzfaserplatten herzustellen ohne die Härtungsgeschwindigkeit der eingesetzten Bindemittel, insbesondere solcher auf Basis von MUF-Harzen, zu verringern oder die Feuchtebeständigkeit der hergestellten Platten herabzusetzen oder die Formaldehydabgabe zu erhöhen. Es ist ferner die Aufgabe der Erfindung, Platten mit hoher Feuchtigkeitsbeständigkeit herzustellen bei der Verwendung von MUF-Harzen mit extrem niedrigem Formaldehydgehalt.To overcome these drawbacks, it has been proposed to mix Use aminoplast resins and diisocyanates (PMDI) as binders (FR-A-2.371.292). EP-A-0013447 also proposes aminoplast resins in combination use with 2 to 20% soluble or dispersible protein as a binder. The use of PMDI as an additive for UF resins or MUF resins leads to Increase in binder costs and requires special precautions in Business. The object of this invention was therefore to find a new way to produce moisture-resistant chipboard and fiberboard without the Curing speed of the binders used, especially those Base of MUF resins, to reduce or the moisture resistance of the reduce manufactured plates or increase formaldehyde release. It is also the object of the invention, panels with high moisture resistance Manufactured using extremely low MUF resins Formaldehyde content.

Es wurde nun überraschend gefunden, daß sogar der Bindemittelaufwand bei der Herstellung von Span- oder Faserplatten mit Melaminharnstofformaldehydharzen als Bindemittel merklich verringert werden kann, wenn man die nassen Späne bzw. Fasern vor der Trocknung mit kondensierten Tanninen oder modifizierten Polymeren, basierend auf kondensierten Tanninen, nicht mit Tanninformaldehydharzen, wie Quebracho- und/oder Mimosatanninen behandelt, anschließend die Späne oder Fasern bis zu einer Feuchte von maximal ca. 5 % im Falle der Herstellung von Spanplatten bzw. 15 % im Falle von Faserplatten trocknet und darauffolgend die Späne bzw. die Fasern - wie üblich - mit MUF-Harzen beleimt, zu Matten streut und anschließend zu Span- oder Faserplatten preßt. Im Falle der nach dem Trockenprozeß hergestellten Faserplatten wird das kondensierte Tannin den Fasern vor dem Beleimen im Blow-line zugegeben. Beim Beleimen in Beleimungsmischern wird das Tannin ebenfalls vor dem Trocknen der Fasern zugegeben. Diese Vorgehensweise hat den Vorteil, daß die kondensierten Tannine auch in verdünnter Form auf die Späne bzw. auf die Fasern aufgebracht werden. It has now surprisingly been found that even the expenditure on binders in the Manufacture of chipboard or fiberboard with melamine urea formaldehyde resins as Binder can be significantly reduced if the wet chips or Fibers before drying with condensed tannins or modified Polymers based on condensed tannins, not with Tannin formaldehyde resins, such as quebracho- and / or mimosatannins, then the chips or fibers up to a maximum moisture of approx. 5% Dries in the case of the production of chipboard or 15% in the case of fiberboard and then the chips or the fibers - as usual - glued with MUF resins, Scatters to mats and then presses it to chipboard or fiberboard. In case of After the dry process produced fiberboard, the condensed tannin added to the fibers in a blow-line before gluing. When gluing in Glue mixers also use the tannin before the fibers dry added. This procedure has the advantage that the condensed tannins can also be applied in diluted form to the chips or to the fibers.

Dies gewährleistet eine weitgehend gleichmäßige Verteilung der Tannine auf die Späne bzw. Fasern. Ferner können die kondensierten Tannine mit dem während der Trocknung von Holzspänen bzw. -fasern gegebenenfalls frei werdenden Formaldehyd reagieren und ihn abfangen. Dadurch wird die Emission an Formaldehyd während der Trocknung der Späne und Fasern ebenfalls erheblich verrringert. Auch die Formaldehydabgabe der aus den Spänen und Fasern hergestellten Platten wird überraschenderweise auf diese Weise deutlich vermindert. Bei der Herstellung von sogenannten Faser-Spanplatten, bei denen die Deckschichten aus Fasern und die Mittelschichten aus Spänen bestehen, können die Tannine sowohl den Fasern als auch den Spänen in unterschiedlichen Mengen beigegeben werden. Diese Vorgehensweise unterscheidet sich grundsätzlich von der Lehre der DE-PS 1958492, nach der bei der Herstellung von Tanninformaldehydharz-gebundenen mitteldichten Faserplatten das Tannin zuerst den Fasern zugegeben und der Formaldehyd erst nach dem Trocknen der Fasern hinzugefügt wird. Hier wird lediglich einer gegebenenfalls eintretenden Vorhärtung des Tanninformaldehydharzes im Blow-line entgegen gewirkt. Somit handelt es sich hier um eine völlig andere Aufgabenstellung mit einer anderen Zielsetzung und Vorgehensweise.This ensures a largely even distribution of the tannins on the Chips or fibers. Furthermore, the condensed tannins with the during the Drying of wood shavings or fibers, if necessary, will be released React formaldehyde and intercept it. This will result in the emission Formaldehyde also significantly during the drying of the chips and fibers verrringert. Also the release of formaldehyde from the chips and fibers produced plates is surprisingly clear in this way reduced. In the production of so-called fiber chipboard, in which the Cover layers made of fibers and the middle layers made of chips the tannins in both the fibers and the chips in different amounts be added. This procedure differs fundamentally from the teaching of DE-PS 1958492, according to the in the manufacture of Tannin-formaldehyde resin-bound medium-density fiberboard the tannin first added to the fibers and the formaldehyde only after the fibers have dried will be added. Here is only a pre-hardening that may occur counteracted the tannin formaldehyde resin in the blow-line. So it is here is a completely different task with a different objective and Method.

Die Lehre der vorliegenden Erfindung unterscheidet sich ebenfalls von der Lehre der DE-OS 4402341, die eine Behandlung von Spänen mit alkalisch eingestellten Tanninformaldehydharzen, vorzugsweise bei einem pH-Wert von über 12 und darauffolgender Trocknung der beleimten Späne vor dem Preßvorgang vorsieht. Das Ziel bei der DE-OS 4402341 ist es, eine Selbstkondensation der Tannine ohne Zugabe von einem Vernetzer wie Formaldehyd hervorzurufen. Bis zu welchem Feuchtegehalt die Späne getrocknet werden müssen, läßt sich der DE-OS 4402341 nicht entnehmen. Das in der DE-OS 4402341 aufgeführte Beispiel enthält keine Angaben über die Preßtemperatur. Mit der Vorgehensweise gemäß DE-OS 440234A1 lassen sich keine Platten mit feuchtebeständiger Verleimung erzielen. Dies ist jedoch die Aufgabe der vorliegenden Erfindung. Gerade durch die Wechselwirkung zwischen den kondensierten Tanninen und dem nach der Trocknung einzusetzenden Bindemittel wird die Feuchtebeständigkeit hervorgerufen und die Formaldehydabgabe verringert. Außerdem führt die Trocknung der Späne nach der Zugabe des Tannins zu einer Verringerung der Preßzeit, da die gesamte Feuchte der beleimten Späne bzw. Fasern geringer ist.The teaching of the present invention also differs from the teaching of DE-OS 4402341, the treatment of chips with alkaline Tannin formaldehyde resins, preferably at a pH above 12 and subsequent drying of the glued chips before the pressing process. The aim of DE-OS 4402341 is to self-condense the tannins without Addition of a crosslinking agent such as formaldehyde. Up to which Moisture content of the chips must be dried can be found in DE-OS 4402341 do not remove. The example listed in DE-OS 4402341 does not contain any Information about the pressing temperature. With the procedure according to DE-OS 440234A1, boards with moisture-resistant gluing cannot be achieved. However, this is the object of the present invention. Just through that Interaction between the condensed tannins and that after the Binding agents to be used for drying will cause moisture resistance and reduces formaldehyde release. The chips also dry out after the addition of the tannin to a reduction in the pressing time as the whole Moisture of the glued chips or fibers is lower.

Die folgenden Beispiele sollen die Erfindung erläutern ohne sie einzuschränken:The following examples are intended to illustrate the invention without restricting it:

Beispiel 1:Example 1:

Kiefernholzspäne mit einer Feuchte von 50 % werden mit einer Tanninlösung mit einer Stoffkonsistenz von 30 % (=30 %ige Tanninlösung) besprüht. Die Menge an Tanninlösung, bezogen auf das Gewicht der Späne, beträgt 3,33 % (bzw. 1 % Feststoff Tannin bezogen auf atro Späne). Die Späne wurden unmittelbar danach bis zu einer Feuchte von 1-2 % getrocknet. Die getrockneten Späne wurden mit einem MUF-Harz beleimt. Dabei betrug der Bindemittelaufwand 11 % (bezogen auf das Atro-Gewicht der Späne). Die beleimten Späne wurden anschließend zu Matten gestreut und zu 19 mm dicken Spanplatten heiß gepreßt.Pine wood chips with a moisture content of 50% are mixed with a tannin solution sprayed with a consistency of 30% (= 30% tannin solution). The amount of Tannin solution, based on the weight of the chips, is 3.33% (or 1% Solid tannin based on dry chips). The chips were removed immediately afterwards dried to a moisture of 1-2%. The dried chips were with glued with a MUF resin. The binder expenditure was 11% (based on the atro weight of the chips). The glued chips then became mats sprinkled and hot pressed to 19 mm thick chipboard.

Vergleichsweise wurden in einem zweiten Versuch die Kiefernholzspäne ohne Zugabe von kondensierten Tanninen bis zu einer Feuchte von 1-2 % getrocknet und mit einem MUF-Harz in Mengen von 12 % bezogen auf das Atro-Gewicht der Späne beleimt und anschließend zu Matten gestreut und heiß gepreßt.By comparison, in a second experiment, the pine wood chips were without Add condensed tannins to a moisture of 1-2% and dried with an MUF resin in quantities of 12% based on the atomic weight of the chips glued and then sprinkled into mats and hot pressed.

Die Platten wurden nach der Herstellung bei 20°C und 65°C relativer Luftfeuchte vier Wochen klimatisiert und anschließend auf ihre physikalisch-technologischen Eigenschaften geprüft. Die Ergebnisse sind der nachstehend aufgeführten Tabelle zu entnehmen: Eigenschaft Versuch 1
Späne mit Tannin vor der Trocknung behandelt und an- schließend mit 11 % eines MUF-Harzes beleimt und zu Platten gepreßt Versuch 2
Späne ohne Tanninbehand lung getrocknet und an- schließend mit 12 % MUF-Harz beleimt und zu Platten gepreßt Biegefestigkeit (N/mm2) 18,7 18,0 Querzugfestigkeit (N/mm2) 0,8 0,7 Dickenquellung (2 h/24 h) 4,0%/8,7 % 4,7 %/8,9 % Formaldehydabgabe (mg/1 kg) 4,2 5,3 V 313-Test (N/mm2) 0,25 0,23 The plates were air-conditioned for four weeks after production at 20 ° C and 65 ° C relative air humidity and then tested for their physical and technological properties. The results are shown in the table below: property Trial 1
Chips were treated with tannin before drying and then glued with 11% of a MUF resin and pressed into plates Trial 2
Chips are dried without tannin treatment and then glued with 12% MUF resin and pressed into plates Flexural strength (N / mm 2 ) 18.7 18.0 Transverse tensile strength (N / mm 2 ) 0.8 0.7 Thickness swelling (2 h / 24 h) 4.0% / 8.7% 4.7% / 8.9% Formaldehyde release (mg / 1 kg) 4.2 5.3 V 313 test (N / mm 2 ) 0.25 0.23

Die Ergebnisse zeigen, dass die mechanisch-technologischen Eigenschaften der unter Verwendung von Tanninen vor dem Trocknen der Späne hergestellten Holzspanplatten, die 11 % Melaminharnstoffharz als Bindemittel enthalten, denen der Platten, die 12 % desselben Melaminharnstoffharzes (MUF-Harz) enthalten, ebenbürtig sind. Die Formaldehydabgabe der unter Einsatz von Tanninen hergestellten Spanplatten ist geringer als die der ohne Tannin hergestellten Spanplatten geblieben. Selbstverständlich kann anstelle des eingesetzten MUF-Harzes ein MUPF-Harz oder sogar ein PF-Harz für die Beleimung der Späne eingesetzt werden. Auch der Einsatz von MUF-/PMDI-Harzen ist möglich. Des Weiteren kann auch ein Tanninformaldehydharz oder eine Mischung aus Tanninformaldehydharz und Melaminharnstoffformaldehydharz als Bindemittel eingesetzt werden. Im letzten Fall werden die Späne mit kondensierten Tanninen vor dem Trocknen behandelt und nach dem Trocknen - wie üblich - mit einer Mischung von Tanninformaldehydharz und Melaminharnstofformaldehydharz beleimt, zu Matten gestreut und anschließend auch zu Spanplatten gepresst. The results show that the mechanical-technological properties of the using tannins before drying the chips Chipboard containing 11% melamine urea resin as a binder, to which panels containing 12% of the same melamine urea resin (MUF resin), are equal. The release of formaldehyde using tannins Particleboard produced is less than that produced without tannin Chipboard remained. Of course, instead of the MUF resin used a MUPF resin or even a PF resin for glueing the chips be used. The use of MUF / PMDI resins is also possible. Of Furthermore, a tannin formaldehyde resin or a mixture of Tannin formaldehyde resin and melamine urea formaldehyde resin as binders be used. In the latter case, the chips are pre-condensed with tannins treated after drying and after drying - as usual - with a mixture glued with tannin formaldehyde resin and melamine urea formaldehyde resin Scattered mats and then pressed to chipboard.

Beispiel 2:Example 2:

Industrieholzspäne mit einer Feuchte von etwa 50 % wurden in einem Trockner bei einer Heißlufttemperatur von etwa 130°C bis zu einer Feuchte von ca. 2 % getrocknet und anschließend mit einem MUF-Harz in Mengen von 12 % (Festharz/atro Späne) beleimt, zu Matten gestreut und anschließend bei einer Preßtemperatur von 200°C bei einem Preßfaktor von 8 s/mm zu Spanplatten gepreßt. An den hergestellten Platten wurden nach der Klimatisierung bei 20°C und 65 % rel. Luffeuchte die mechanisch-technologischen Eigenschaften ermittelt. Die Ergebnisse sind in Tabelle 2 zusammengestellt.Industrial wood chips with a moisture content of around 50% were placed in a dryer a hot air temperature of approx. 130 ° C up to a humidity of approx. 2% dried and then with an MUF resin in quantities of 12% (Solid resin / atro chips) glued, sprinkled into mats and then at one Press temperature of 200 ° C with a press factor of 8 s / mm pressed to chipboard. According to the Air conditioning at 20 ° C and 65% rel. Humidity the mechanical-technological Properties determined. The results are summarized in Table 2.

In einem zweiten Versuch wurden die Industriespäne mit einem handelsüblichen kondensierten Tannin, das durch Extraktion von Quebrachoholz gewonnen wurde, in Mengen von 1,2 % (Festtannin/Späne) besprüht und anschließend ebenso auf eine Feuchte von ca. 2 % heruntergetrocknet. Nach dem Trocknen wurden die Späne mit dem selben MUF-Harz wie im ersten Versuch in Mengen von 10,8 % (Festharz/Späne) beleimt und anschließend zu Matten gestreut. Die hergestellten Matten wurden zu Spanplatten gepreßt. Die hergestellten 16 mm dicken Spanplatten wurden nach der Klimatisierung bei 20 °C/65 % rel. Luftfeuchte bestimmt. Die Ergebnisse sind ebenfalls in Tabelle 2 zusammengestellt.In a second experiment, the industrial chips were used with a commercially available condensed tannin obtained by extraction of quebracho wood in Sprayed quantities of 1.2% (solid tannin / chips) and then also on one Dried down moisture of approx. 2%. After drying, the chips were removed the same MUF resin as in the first test in amounts of 10.8% (Solid resin / chips) glued and then scattered to mats. The manufactured Mats were pressed into chipboard. The 16 mm thick chipboard produced were after air conditioning at 20 ° C / 65% rel. Humidity determined. The Results are also summarized in Table 2.

Aus den Ergebnissen wird hier ebenfalls deutlich, daß die unter Einsatz von Tannin vor dem Trocknen der Späne hergestellten Spanplatten in ihren mechanisch-technologischen Eigenschaften weitgehend denen entsprechen, die allein mit MUF-Bindemitteln hergestellt sind. Des Weiteren lassen die Untersuchungsergebnisse deutlich werden, daß die Formaldehydabgabe der unter Einsatz von Tannin hergestellten Platten niedriger liegt als die der ohne Tannin hergestellten. Eigenschaft Versuch 1
Späne vor der Trocknung mit Tannin behandelt und an- schließend mit 10,8 % eines MUF-Harzes beleimt Versuch 2
Späne ohne Behandlung mit Tannin vor der Trocknung und mit 12 % eines MUF- Harzes beleimt Querzugfestigkeit N/mm2 1,45 1,49 Dickenquellung 24 h % 7,2 5,9 Kochquerzugfestigkeit N/mm2 (V100-Wert) 0,35 0,34 Formaldehydabgabe (Perforatorwert) mg/100 g 4,4 4,9 Flaschenwert mg/1000 g 7,3 8,0 Rohdichte der Platte g/cm3 719 738 Plattendicke mm 16 16 From the results it is also clear here that the mechanical and technological properties of the chipboard produced using tannin before the chips are dried largely correspond to those produced using only MUF binders. Furthermore, the results of the investigation make it clear that the formaldehyde release of the plates produced using tannin is lower than that of those produced without tannin. property Trial 1
Chips are treated with tannin before drying and then glued with 10.8% of an MUF resin Trial 2
Chips without treatment with tannin before drying and glued with 12% of a MUF resin Cross tensile strength N / mm 2 1.45 1.49 Thickness swelling 24 h% 7.2 5.9 Cooking cross tensile strength N / mm 2 (V100 value) 0.35 0.34 Formaldehyde release (perforator value) mg / 100 g 4.4 4.9 Bottle value mg / 1000 g 7.3 8.0 Gross density of the plate g / cm 3 719 738 Board thickness mm 16 16

Claims (14)

Verfahren zur Herstellung von feuchtebeständigen Span- oder Faserplatten nach dem Trockenprozeß mit Phenol-Formaldehydharzen oder Melamin-Harnstoff-Formaldehydharzen oder Melamin-Harnstoffphenolharzen oder Tanninformaldehydharzen oder PMDI als Bindemittel, dadurch gekennzeichnet, daß die nassen Späne oder Fasern vor dem Beleimen mit dem Bindemitel mit kondensierten Tanninen behandelt werden und anschließend die Späne bis zu einer Feuchte von höchstens 5 % und die Fasern bis zu einer Feuchte von maximal 15 % getrocknet werden.Process for the production of moisture-resistant chipboard or fiberboard after the drying process with phenol-formaldehyde resins or melamine-urea-formaldehyde resins or melamine-urea-phenol resins or tannin-formaldehyde resins or PMDI as a binder, characterized in that the wet chips or fibers are condensed with the binder before gluing Tannins are treated and then the chips are dried to a moisture of 5% or less and the fibers to a moisture of 15% or less. Verfahren nach Anspruch 1 dadurch gekennzeichnet, daß als Tannin Extrakte aus dem Quebrachoholz eingesetzt werden.A method according to claim 1, characterized in that extracts from quebracho wood are used as tannins. Verfahren gemäß Anspruch 1 und 2 dadurch gekennzeichnet, daß die Tanninlösung einen Stoffgehalt von 30 % hat.Method according to claims 1 and 2, characterized in that the tannin solution has a substance content of 30%. Verfahren nach Anspruch 1, 2 und 3 dadurch gekennzeichnet, daß der pH-Wert der Tanninlösung im sauren Bereich liegt.A method according to claim 1, 2 and 3, characterized in that the pH of the tannin solution is in the acidic range. Verfahren nach Anspruch 1 dadurch gekennzeichnet, daß der pH-Wert der Tanninlösung im alkalischen Bereich liegt.A method according to claim 1, characterized in that the pH of the tannin solution is in the alkaline range. Verfahren nach Anspruch 1 dadurch gekennzeichnet, daß die vor der Trocknung mit Tanninen behandelten Späne nur in den Deckschichten von dreischichtigen Holzspanplatten eingesetzt werden.A method according to claim 1, characterized in that the chips treated with tannins before drying are used only in the top layers of three-layer chipboard. Verfahren nach Anspruch 1 dadurch gekennzeichnet, daß die vor der Trocknung mit Tanninen behandelten Späne nur in der Mittelschicht von dreichschichtigen Spanplatten eingesetzt werden.A method according to claim 1, characterized in that the chips treated with tannins before drying are used only in the middle layer of three-layer chipboard. Verfahren nach Anspruch 1 dadurch gekennzeichnet, daß die vor der Trocknung mit Tanninen behandelten Fasern nur in der Mittelschicht von dreischichtigen Faserplatten eingesetzt werden.A method according to claim 1, characterized in that the fibers treated with tannins before drying are used only in the middle layer of three-layer fiberboard. Verfahren nach Anspruch 1 dadurch gekennzeichnet, daß die vor dem Trocknen mit Tannin behandelten Fasern in der Deckschicht von Span-Faserplatten eingesetzt werden.A method according to claim 1, characterized in that the fibers treated with tannin before drying are used in the top layer of chipboard. Verfahren nach Anspruch 1 dadurch gekennzeichnet, daß das als Bindemittel verwendete MUF-Harz ein Molverhältnis F/NH2 von unter 0,7 aufweist. A method according to claim 1, characterized in that the MUF resin used as a binder has a molar ratio F / NH 2 of less than 0.7. Verfahren nach Anspruch 1 dadurch gekennzeichnet, daß das als Bindemittel verwendete MUF-Harz ein Molverhältnis F/NH2 von unter 0,5 hat.A method according to claim 1, characterized in that the MUF resin used as a binder has a molar ratio F / NH 2 of less than 0.5. Verfahren nach Anspruch 1 dadurch gekennzeichnet, daß in den Schichten, deren Späne vor dem Trocknen nicht mit Tannin behandelt wurden, das verwendete Bindemittel für die Herstellung von Span- und Faserplatten eine Mischung aus Tanninformaldehyd- und Melamin-Harnstoff-Formaldehydharzen ist.A method according to claim 1, characterized in that in the layers, the chips of which have not been treated with tannin before drying, the binder used for the production of particle board and fiberboard is a mixture of tannin-formaldehyde and melamine-urea-formaldehyde resins. Verfahren nach Anspruch 1 dadurch gekennzeichnet, daß die Späne oder die Fasern vor der Behandlung mit Tannin eine Feuchte von über 12 % haben.Process according to Claim 1, characterized in that the chips or the fibers have a moisture content of more than 12% before the treatment with tannin. Verfahren nach Anspruch 1 dadurch gekennzeichnet, daß die Späne oder die Fasern vor dem Behandeln mit Tannin eine Feuchte von über 50 % haben.A method according to claim 1, characterized in that the chips or the fibers have a moisture of over 50% before treatment with tannin.
EP01850102A 2001-06-12 2001-06-12 Method of manufacturing moisture resistant fibreboards Expired - Lifetime EP1266730B1 (en)

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AT01850102T ATE321636T1 (en) 2001-06-12 2001-06-12 METHOD FOR PRODUCING MOISTURE-RESISTANT CHIPBOARD AND MEDIUM-DENSITY FIBERBOARD (MDF)

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WO2004058843A1 (en) * 2002-12-24 2004-07-15 Borden Chemical Australia Pty Ltd A tannin, aldehyde, amino compound- based resin composition and its use as a binding agent for composite wood products
FR2850414A1 (en) * 2003-01-24 2004-07-30 Espace Production Internationa Antistatic laminated floor covering comprises an overlay-forming resin containing a mixture of electrolytes
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WO2006114089A1 (en) * 2005-04-26 2006-11-02 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Method for producing reduced-emission, low-thickness swell medium density fiber boards and molded fiber parts
WO2009020438A1 (en) 2007-08-08 2009-02-12 Kronospan Sk S.R.O. Single - layer particle construction board
WO2017023218A1 (en) 2015-04-21 2017-02-09 Kastamonu Entegre Agac Sanayi Anonim Sirketi Production process of the resins containing polyflavonoid and derivatives and their application in the wood based composite board products
CN105583934A (en) * 2015-11-30 2016-05-18 万华生态板业股份有限公司 Application of ZB (Zinc Borate) which is used as mildew preventive in production of straw boards
WO2019117799A1 (en) * 2017-12-15 2019-06-20 Nsr Ab Hybrid resin particle-board

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ATE321636T1 (en) 2006-04-15
DE50109378D1 (en) 2006-05-18

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