EP2546038B1 - Method of reducing the emissions of fleeting organic compounds in wooden materials - Google Patents

Method of reducing the emissions of fleeting organic compounds in wooden materials Download PDF

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Publication number
EP2546038B1
EP2546038B1 EP11005690.0A EP11005690A EP2546038B1 EP 2546038 B1 EP2546038 B1 EP 2546038B1 EP 11005690 A EP11005690 A EP 11005690A EP 2546038 B1 EP2546038 B1 EP 2546038B1
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Prior art keywords
wood
additive
process according
organic compounds
volatile organic
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German (de)
French (fr)
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EP2546038A1 (en
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Joachim Prof.Dr. Hasch
Julia Dr. Borowka
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Kronotec AG
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Kronotec AG
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Priority to PL11005690T priority Critical patent/PL2546038T3/en
Priority to EP11005690.0A priority patent/EP2546038B1/en
Priority to ES11005690.0T priority patent/ES2537642T3/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
    • B27N1/003—Pretreatment of moulding material for reducing formaldehyde gas emission

Definitions

  • the present application relates to a method according to claim 1 for the production of coated wood materials from lignocellulose, in particular chipboard, fiberboard or OSB boards but also plywood and solid wood, these wood materials in the production of reducing the emission of volatile organic compounds but also very volatile organic Compounds, such as unsaturated or saturated aldehydes, with at least one additive is treated. More specifically, these additives are alcohols, which are optionally introduced in combination with catalytically effective amounts of acid. Alternatively or additionally, a treatment with suitable antioxidants can take place.
  • the present application is directed to the use according to claim 11 of alcohols, optionally in combination with catalytically effective amounts of acid and / or antioxidant as additives for reducing the emission of VOC, in particular of unsaturated and saturated aldehydes, in the preparation and the use of lignocellulosic wood materials.
  • the application is directed to obtainable by the process according to the invention wood materials according to claim 14 or by using the additives produced wood materials with reduced emission of volatile organic compounds.
  • volatile organic compounds include all volatile organic compounds, their retention time in the gas chromatograph between C6 (hexane) and C16 (hexadecane).
  • VOCs are not a homogeneous class of substances but a smorgasbord of compounds. These include organic acids, saturated and unsaturated aldehydes, alcohols, carboxylic acids, terpenes, aliphatic and aromatic hydrocarbons and many more.
  • VVOC very volatile organic compounds
  • Formaldehyde or formic acid which also occur in the production of wood-based materials.
  • aldehydes as used herein includes saturated and unsaturated aldehydes as falling within the classes of volatile organic compounds or very volatile organic compounds.
  • VOCs and also of WOCs does not occur during the manufacturing process, but also during use by decomposition of wood constituents, as a result of the chemical degradation of the adhesives used.
  • VOC emissions are mainly due to wood-related releases of so-called primary emissions of volatile wood constituents, such as terpenes, or chemical degradation products, such as acetic acid, and so-called secondary or tertiary emissions, e.g. higher aldehydes, such as pentanal or higher carboxylic acids.
  • primary emissions of volatile wood constituents such as terpenes
  • chemical degradation products such as acetic acid
  • secondary or tertiary emissions e.g. higher aldehydes, such as pentanal or higher carboxylic acids.
  • Typical conversion products that occur inter alia during storage and processing of the wood or crushed products include pentanal and hexanal.
  • Particularly critical compounds in the heterogeneous group of VOC and WOC are the saturated and unsaturated aldehydes. These are not only toxic, but also carcinogenic in part. Furthermore, they are classified as critical by the olfactory aspect.
  • the aldehydes are formed, inter alia, in the production of wood-based materials, as shown above, and are released in particular by OSB plates delayed by fragmentation of unsaturated fatty acids and due to the use of aldehyde-containing adhesives.
  • OSB panels in the structural area this is a great disadvantage, since in this application, the OSB panels have no emission-reducing coating and in large quantities, especially as the area of the plate based on the total cubic meters of the room or building is installed.
  • Adhesives such as those currently being used in the manufacture of wood-based materials such as OSB boards, dense fiberboard, etc. include aminoplast adhesives such as urea-formaldehyde (UF) adhesives, melamine-urea-phenol-formaldehyde adhesives (MUPF adhesives) or melamine-urea-formaldehyde adhesives (MUF adhesives).
  • UF urea-formaldehyde
  • MUPF adhesives melamine-urea-phenol-formaldehyde adhesives
  • UMF adhesives melamine-urea-formaldehyde adhesives
  • Suitable adhesives typically used in wood-based materials include diisocyanate-based adhesives (PMDI), polyurethane adhesives, phenol-formaldehyde (PF) adhesives, and / or tannin-formaldehyde (TF) adhesives, or mixtures thereof.
  • PMDI diisocyanate-based adhesives
  • PF phenol-formaldehyde
  • TF tannin-formaldehyde
  • the resulting volatile organic compounds and very volatile organic compounds such as aldehydes and acids, then emit during the later manufacturing process or later use of the wood-based materials produced. They can also have a negative influence on the bond strength and thus adversely affect the properties of the produced wood materials.
  • the WO 2010/144969 A1 describes the production of perlite and fiber-based composite plates.
  • the use of various additives has been proposed, including the use of maleic anhydride or similar compounds.
  • the use of reducing or oxidizing agents is also known.
  • an increase in the pH is proposed, for example by addition of alkali metal hydroxides.
  • VOC volatile organic compounds
  • VVOC highly volatile organic compounds
  • the odor nuisance resulting from these volatile or very volatile organic compounds should also be reduced.
  • an important aspect is that the manufacturing cost of wood-based materials is not significantly increased.
  • the agents used themselves must not be toxic or carcinogenic, but should as far as possible either react with the heterogeneous classes of volatile organic substances or very volatile organic compounds or prevent their formation from constituents of the wood-based materials.
  • the object of the present invention is achieved in that certain additives are added at certain times in the inventive method for producing or processing the wood materials from lignocellulose.
  • These additives are alcohols, optionally in combination with a catalytically effective amount of acid and / or certain antioxidants.
  • the present application is directed to a process for the production of coated wood materials from lignocellulose, in particular chipboard, fiberboard, OSB boards or plywood according to claim 1.
  • the additives used according to the invention prevent degradation of the fatty acids or fatty acid esters.
  • aldehydes optionally formed by conversion reactions are converted to corresponding non-emitting compounds.
  • the compounds obtained by the reaction are such that they are no longer volatile and thus no longer contribute to the VOC and VVOC emissions or aldehyde emissions or the toxicity of the resulting compounds is significantly reduced.
  • the emission is also after production, i. in daily use, significantly reduced.
  • the additives are applied to a carrier material.
  • Such application may be by known means and methods. These methods include application by spraying, impregnation, dipping or painting onto the substrate.
  • the additive may be present on one side or both sides of the carrier material.
  • the additive is preferably present on the side facing the wood-based material.
  • the carrier material may e.g. a cellulose layer, paper or the like. According to the invention, the carrier material can be applied to the wood material prior to pressing the mixture or after pressing. For solid wood as a cervical spine, the carrier material containing the additive is applied to the solid wood accordingly.
  • the carrier material may be transparent or formed with a decor.
  • the support materials may be conventional, so-called overlay products or, for example, 100% cellulose paper, as used in the field of the production of wood-based materials, such as panels.
  • the carrier material may be soaked, sprayed or otherwise impregnated with the additive. This carrier material is then applied before spreading on the conveyor belt and scrape after scattering but before pressing.
  • the support material is applied to the wood material, e.g. rooted or otherwise connected to the wood material. It is preferred that in wood-based panels, such as OSB boards, fiberboard, plywood or chipboard but also solid wood, the support material is applied on both sides of the cervical spine. It is preferred that the additive is present at least on the HWS side facing.
  • the additive is introduced onto the lignocellulose-containing comminuted product before compression and after spreading or laying.
  • the additive is preferably added before compression but after defibering or machining and in particular after drying.
  • the additive may be in the form of an aqueous solution or as a powder mixture directly after the pressing operation, e.g. be applied by spraying by means of nozzles on one or both sides of the produced wood material.
  • an entry can be made by rolling.
  • the additive can be dosed as a solution or as a powder to the lignocellulose-containing comminution products or the mixture of lignocellulose-containing comminution products and adhesive.
  • a metered addition can also take place before the dryer but after defibering or cutting.
  • the time of metering depends on the form of the additive, for example as an aqueous solution or as a powder.
  • the additive may be incorporated only in portions of the board.
  • the additive is preferably introduced at least into the regions of the wood-based panel that form the covering layer, such as an OSB board.
  • the additive can be applied both partially before compression and after compression with a carrier material.
  • the wood-based materials are those made of wood chips, wood strands or wood fibers as lignocellulose-containing crushed products.
  • the wood material is an OSB board.
  • the wood-based materials may be further coated with known layers, such as a lacquer layer, decorative layer or wearing layer.
  • the additives may also or only be present in these layers. That is, the carrier material may be formed as a decorative layer, lacquer layer, wear layer or according to sub-layers.
  • the cervical spine is solid wood and the additives are applied to the cervical spine by known methods.
  • the additives to be used according to the invention are alcohols, in particular polyhydric alcohols. It is particularly preferred that these alcohols be added together with a catalytically effective amount of acid to allow for acid-catalyzed reaction of the alcohols. The alcohols may then be e.g. react with resulting aldehydes to form acetals.
  • Fats and oils are esters of polyhydric alcohols, usually glycerol, with saturated and unsaturated fatty acids. Due to the oxidative degradation of these fats and fatty acids in the pressing process at high temperatures arise z.
  • Another reaction pathway in addition to the acetal formation is the esterification with fatty acids from the wood. This is also usually acid-catalyzed. The fatty acids are esterified, thus counteracting a degradation of the fatty acids to VOC and WOC.
  • Preferred alcohols are polyhydric alcohols, in particular glycerol or alkylene glycols, such as ethylene glycol, propanediol, butanediol, etc.
  • an antioxidant can be used.
  • Antioxidants allow trapping of radicals that z. B. at high temperatures or light. At high temperatures or light z.
  • hydroxyl radicals that have the ability to rapidly oxidize other substances. This easily forms VOCs and VVOCs from the natural components in the wood.
  • the antioxidants especially the antioxidants selected from ascorbic acid, vitamin E or butylhydroxytoluene (BHT), have the ability to trap such radicals and thus prevent the formation of VOCs or VVOCs from the constituents of the wood. According to the invention, these antioxidants are incorporated or applied in or on the carrier material.
  • the additives are added in an amount of 0.5 to 5% by weight of solid solid in terms of dry wood.
  • the lignocelluloses such as the wood-based materials or the comminuted products thereof, may be both conifers and hardwoods. Even mixtures of these two types of wood are possible.
  • the wood chips, strands or wood fibers come from conifers.
  • the wood materials which can be produced by the production method according to the invention are produced according to claim 14.
  • the process can be supplemented by other processes known to the person skilled in the art for reducing the emission of volatile organic compounds or very volatile organic compounds, such as aldehydes.
  • the wood-based materials may preferably be chipboard wood made of wood chips, OSB strands of wood strands, plywood boards of wood veneer and wood fiber boards, in particular MDF boards, of wood fibers.
  • wood-based materials also includes plywood and, in particular, solid wood.
  • the wood materials OSB boards and lightweight and super light MDF boards.
  • Lignocelluloses are understood to mean lignocellulose-containing materials, such as wood.
  • the resulting comminution products of lignocellulose include, in particular, wood strands, wood chips, wood fibers as well as wood veneers.
  • the adhesives used in the process according to the invention comprise, as adhesives, phenol-formaldehyde adhesive, isocyanate-based adhesive, urea-formaldehyde adhesive, melamine-urea-formaldehyde adhesive, melamine-urea-phenol-formaldehyde adhesive, tannin-formaldehyde adhesive or a mixture thereof.
  • the present application is directed to the use of a composition containing an alcohol as defined herein optionally in combination with catalytically effective amounts of an acid and / or an antioxidant as defined herein for reducing the emission of VOC and VVOC, respectively , in particular saturated and unsaturated aldehydes, in the production and use of wood materials of lignocellulose.
  • This use is characterized in that the additive during the manufacturing process of the wood material is registered or applied. The additive is applied or applied, as stated above, with the aid of a carrier material.
  • the use is particularly advantageous for adhesives selected from phenol-formaldehyde adhesive, isocyanate-based adhesive, urea-formaldehyde adhesive, melamine-urea-formaldehyde adhesive, melamine-urea-phenol-formaldehyde adhesive, tannin-formaldehyde adhesive or a mixture thereof is used.
  • the additives are particularly suitable for use at least in the top layer of OSB boards or wood fiber boards.
  • the use of the additives preferably takes place in an amount of from 0.5% by weight to 5% by weight of solids, based on atro-wood.
  • wood materials obtainable by the process according to the invention.
  • wood-based materials are, in particular, fibreboards, in particular lightweight and superlight MDF boards or OSB boards, but also solid wood.
  • the additives used according to the invention are particularly advantageous in terms of a longer-term effect for suppressing the emissions of VOC or VVOC, since the additives present in the carrier material or in the outer layer also avoid the formation and emission of VOC or VVOC in the longer term.
  • a reference plate and two plates were made using glued strands from current production (12% MUPF as adhesive) using the additive glycerin and ascorbic acid. These plates were then pressed into a format of 10mm x 300mm x 300mm and a bulk density of 530kg / m 3 . Parameters for pressing are shown below Table to find. Before pressing, the glued strands were mixed with the respective additive. Furthermore, a part of the additive was sprayed on the surface of the plate after pressing. Sample A contains the additive glycerol in a dosage of 5 wt .-%. Addition of Additive A further added a few drops of hydrochloric acid for catalysis. Sample B contains the additive ascorbic acid in an amount of 1% by weight on atro wood. Table 1 Press diagram pressing stage Pressure [N / mm 2 ] Time T [° C] 1 2 60 200 2 1 60 200 3 0.2 10 200
  • Samples were prepared from the above-obtained OSB plates measuring 210 ⁇ 210 ⁇ thickness mm 3 . From the edge of these samples a 7mm wide strip was taken. This was then separated into two samples with a length of 95mm. One sample each was placed with the top side and the other with bottom side oriented towards the air flow in the topo-extractor. The results are expressed as the mean of these two measurements.
  • thermo-extraction method For a qualitative and comparative study of the emission potential of structurally similar materials, the thermo-extraction method is suitable.
  • thermo-extractor TE1, Gerstel, Mülheim ad Ruhr, Germany. It is a glass tube with a relatively small volume of about 25.9 cm 3 , which is located in the thermo-extractor. Throughout the system, a continuous nitrogen flow (100ml / min-1) is passed, which - as in the conventional test chamber tests - is passed over an adsorbent at regular times. According to DIN ISO 16000-6: 2004, these were analyzed in a GC-MS with thermosorption and cold trap. The whole system was operated at room temperature (23 ° C). Described was the method of Scherer et al. (Dangerous substances - clean air, 2006, 66 (3), 87-93 ).
  • thermo-extraction In order to achieve always the same and thus reproducible conditions, a steel sample holder was used which leaves a potentially emitting sample surface of about 7.1 cm 2 .
  • Thermo-extractor sample holder and the sample dimensions are shown.
  • the conditions for the thermo-extraction are summarized in Table 2. 11 air volumes were sampled 10 minutes after the samples were placed in the thermo-extractor. The results are expressed as the substance quantity in relation to the air sampling volume ( ⁇ g m -3 ).
  • Table 2 Conditions for thermo-extraction parameter property Temperature in ° C RT Mass flow in ml min -1 100 Room volume in m 3 0.00002586 Air change rate in h -1 232.0 Sample surface in m 2 0.00075 Room load in m 2 m -3 29.1 Area-specific ventilation rate in m 3 - 2 h -1 8.0 carrier gas nitrogen
  • Table 3 Results ⁇ g / m 3 Sample 0 Sample A Sample B aldehydes 681 153 42 Saturated aldehydes 651 140 31 Unsaturated aldehydes 18 3 1 hexanal 577 124 26 2-heptenal 12 3 1 2-octenal 6 0 0

Description

Die vorliegende Anmeldung betrifft ein Verfahren gemäß Anspruch 1 zur Herstellung von beschichteten Holzwerkstoffen aus Lignozellulose, insbesondere Spanplatten, Faserplatten oder OSB-Platten aber auch Sperrholz und Vollholz, wobei diese Holzwerkstoffe bei der Herstellung zur Verminderung der Emission von flüchtigen organischen Verbindungen aber auch sehr flüchtiger organischer Verbindungen, wie ungesättigte oder gesättigte Aldehyde, mit mindestens einem Additiv behandelt wird. Genauer handelt es sich bei diesen Additiven um Alkohole, die gegebenenfalls in Kombination mit katalytisch wirksamen Mengen an Säure eingetragen wird. Alternativ oder zusätzlich kann eine Behandlung mit geeigneten Antioxidationsmitteln erfolgen. In einem weiteren Aspekt richtet sich die vorliegende Anmeldung auf die Verwendung gemäß Anspruch 11 von Alkoholen, gegebenenfalls in Kombination mit katalytisch wirksamen Mengen an Säure und/oder Antioxidationsmittel als Additive zur Verminderung der Emission von VOC, insbesondere von ungesättigten und gesättigten Aldehyden, bei der Herstellung und dem Gebrauch von Holzwerkstoffen aus Lignozellulose. Schließlich richtet sich die Anmeldung auf mit dem erfindungsgemäßen Verfahren erhältliche Holzwerkstoffe gemäß Anspruch 14 bzw. durch Verwendung der Additive hergestellte Holzwerkstoffe mit verringerter Emission von flüchtigen organischen Verbindungen.The present application relates to a method according to claim 1 for the production of coated wood materials from lignocellulose, in particular chipboard, fiberboard or OSB boards but also plywood and solid wood, these wood materials in the production of reducing the emission of volatile organic compounds but also very volatile organic Compounds, such as unsaturated or saturated aldehydes, with at least one additive is treated. More specifically, these additives are alcohols, which are optionally introduced in combination with catalytically effective amounts of acid. Alternatively or additionally, a treatment with suitable antioxidants can take place. In a further aspect, the present application is directed to the use according to claim 11 of alcohols, optionally in combination with catalytically effective amounts of acid and / or antioxidant as additives for reducing the emission of VOC, in particular of unsaturated and saturated aldehydes, in the preparation and the use of lignocellulosic wood materials. Finally, the application is directed to obtainable by the process according to the invention wood materials according to claim 14 or by using the additives produced wood materials with reduced emission of volatile organic compounds.

Stand der TechnikState of the art

Die Emission von flüchtigen organischen Verbindungen (VOC) aus Holzwerkstoffen (HWS) stellt unter dem Aspekt der zunehmenden Nutzung von holzartigen Produkten in den Räumen ein gravierendes Problem dar. Zu den flüchtigen organischen Verbindungen zählen neben gesättigten und ungesättigten Aldehyden alle flüchtigen organischen Stoffe, deren Retentionszeit im Gaschromatograph zwischen C6 (Hexan) und C16 (Hexadecan) liegt. Die VOC sind keine homogene Substanzklasse, sondern ein Sammelsurium von Verbindungen. Unter anderem sind diese organischen Säuren, gesättigte und ungesättigte Aldehyde, Alkohole, Carbonsäuren, Terpene, aliphatisch und aromatische Kohlenwasserstoffe und vieles mehr. Weiterhin gibt es die sehr flüchtigen organischen Verbindungen (VVOC), unter die z.B. Formaldehyd oder Ameisensäure fällt, die ebenfalls bei der Herstellung von Holzwerkstoffen auftreten. Die Emission dieser flüchtigen und sehr flüchtigen Holzinhaltsstoffen oder Bestandteilen der Klebstoffe aus Holzprodukten einschließlich Vollholz und Holzwerkstoffplatten stellt aufgrund verschärfter Grenzwerte bzw. einer größeren Sensibilisierung der Endverbraucher mehr und mehr ein Problem dar.The emission of volatile organic compounds (VOC) from wood-based materials (HWS) represents a serious problem in terms of the increasing use of woody products in the rooms. In addition to saturated and unsaturated aldehydes, volatile organic compounds include all volatile organic compounds, their retention time in the gas chromatograph between C6 (hexane) and C16 (hexadecane). VOCs are not a homogeneous class of substances but a smorgasbord of compounds. These include organic acids, saturated and unsaturated aldehydes, alcohols, carboxylic acids, terpenes, aliphatic and aromatic hydrocarbons and many more. Furthermore, there are the very volatile organic compounds (VVOC), under which e.g. Formaldehyde or formic acid, which also occur in the production of wood-based materials. The emission of these volatile and highly volatile wood constituents or components of wood product adhesives, including solid wood and wood-based panels, is becoming more and more of a problem due to tightening limits or increasing end-user awareness.

Der Ausdruck Aldehyde, wie er vorliegend verwendet wird, umfasst gesättigte und ungesättigte Aldehyde soweit sie in die Klassen der flüchtigen organischen Verbindungen oder sehr flüchtigen organischen Verbindungen fallen.The term aldehydes as used herein includes saturated and unsaturated aldehydes as falling within the classes of volatile organic compounds or very volatile organic compounds.

Zur Vermeidung der Emission dieser flüchtigen organischen Verbindungen wurden bisher verschiedene Vorschläge gemacht. So wird in der EP 185 231 beschrieben, dass Oxidationsmittel zur Verringerung der Emissionen eingesetzt werden. Weiterhin wurden verschiedene Vorschläge zur Verringerung der Emission von Formaldehyd vorgeschlagen. Aufgrund der Heterogenität der flüchtigen organischen Verbindungen ist aber eine insbesondere dauerhafte Vermeidung bzw. Verringerung der Emission dieser Verbindungen gewünscht. Eine Umwandlung der heterogenen Klasse der VOC, die teilweise toxisch sind, durch eine einzige chemische Reaktion ist allerdings schwierig.To avoid the emission of these volatile organic compounds, various proposals have hitherto been made. So will in the EP 185 231 described that oxidizing agents are used to reduce emissions. Furthermore, various proposals have been proposed to reduce the emission of formaldehyde. Due to the heterogeneity of the volatile organic compounds, however, a particularly permanent avoidance or reduction of the emission of these compounds is desired. A transformation of the heterogeneous class of VOCs, which are partially toxic, however, a single chemical reaction is difficult.

Eine Verringerung von flüchtigen organischen Verbindungen und sehr flüchtigen organischen Verbindungen aus dem Holz, insbesondere von flüchtigen Holzinhaltsstoffen während der Herstellung aber auch im Gebrauch, ist daher nach wie vor erwünscht. Zu beachten ist dabei, dass die Emission der VOC aber auch der WOC nicht im Herstellungsprozess, sondern auch bei Nutzung durch Abbau von Holzinhaltsstoffen auch durch den chemischen Abbau der verwendeten Klebstoffe auftritt. VOC-Emissionen beruhen allerdings hauptsächlich auf holzbedingte Freisetzungen von sogenannte Primäremission von flüchtigen Holzinhaltsstoffen, wie Terpenen, oder chemischen Abbauprodukten, wie Essigsäure, und sogenannte Sekundär- bzw. Tertiäremissionen, z.B. höhere Aldehyde, wie Pentanal oder höhere Carbonsäuren. Diese Abbauprodukte entstehen durch lang andauernde Oxidationsprozesse von Holzinhaltsstoffen, wie Fettsäuren, aber auch Lignin, Zellulose und Hemizellulose.A reduction of volatile organic compounds and very volatile organic compounds from the wood, in particular volatile wood constituents during production but also in use, is therefore still desirable. It should be noted that the emission of VOCs and also of WOCs does not occur during the manufacturing process, but also during use by decomposition of wood constituents, as a result of the chemical degradation of the adhesives used. However, VOC emissions are mainly due to wood-related releases of so-called primary emissions of volatile wood constituents, such as terpenes, or chemical degradation products, such as acetic acid, and so-called secondary or tertiary emissions, e.g. higher aldehydes, such as pentanal or higher carboxylic acids. These decomposition products are caused by long-lasting oxidation processes of wood constituents, such as fatty acids, but also lignin, cellulose and hemicellulose.

Typische Umwandlungsprodukte, die unter anderem während der Lagerung und der Bearbeitung des Holzes oder der Zerkleinerungsprodukte auftreten, sind z.B. Pentanal und Hexanal. Als besonders kritische Verbindungen sind in der heterogenen Gruppe der VOC und der WOC die gesättigten und ungesättigten Aldehyde einzustufen. Diese sind nicht nur toxisch, sondern zum Teil auch karzinogen. Weiterhin sind sie vom olfaktorischen Aspekt als kritisch einzustufen. Die Aldehyde entstehen unter anderem bei der Herstellung von Holzwerkstoffen, wie oben dargestellt, und werden insbesondere von OSB-Platten zeitverzögert durch Fragmentierung von ungesättigten Fettsäuren und aufgrund der Verwendung von Aldehyd-haltigen Klebstoffen freigesetzt. Gerade für OSB-Platten im konstruktiven Bereich ist dieses von großem Nachteil, da bei dieser Anwendung die OSB-Platten keine emissionsmindernde Beschichtung aufweisen und in großen Mengen, insbesondere als Fläche der Platte bezogen auf die Gesamtkubikmeterzahl des Raumes oder des Gebäudes, verbaut wird.Typical conversion products that occur inter alia during storage and processing of the wood or crushed products include pentanal and hexanal. Particularly critical compounds in the heterogeneous group of VOC and WOC are the saturated and unsaturated aldehydes. These are not only toxic, but also carcinogenic in part. Furthermore, they are classified as critical by the olfactory aspect. The aldehydes are formed, inter alia, in the production of wood-based materials, as shown above, and are released in particular by OSB plates delayed by fragmentation of unsaturated fatty acids and due to the use of aldehyde-containing adhesives. Especially for OSB panels in the structural area this is a great disadvantage, since in this application, the OSB panels have no emission-reducing coating and in large quantities, especially as the area of the plate based on the total cubic meters of the room or building is installed.

Ähnliche Probleme mit einer Aldehydemission können bei dem Einsatz von leichten Holzwerkstoffen, wie leichten und superleichten MDF zur Wärmedämmung, auftreten. Diese emittieren verstärkt Aldehyde, z.B. zyklische Aldehyde. Probleme ergeben sich dabei sowohl durch die Emissionsmenge als auch durch die Toxizität der Verbindungen.Similar problems with aldehyde emission can occur with the use of light wood materials, such as lightweight and superlight MDF for thermal insulation. These emit more aldehydes, e.g. cyclic aldehydes. Problems arise both by the amount of emission and by the toxicity of the compounds.

Wie bereits ausgeführt, werden auch durch die verwendeten Klebstoffe während der Herstellung oder anschließend während der Verwendung flüchtige organische Verbindungen, wie Aldehyde, freigesetzt. Zu den Klebstoffen, wie sie derzeit in der Herstellung von Holzwerkstoffen, wie OSB-Platten, mit dichte Faserplatten usw. behandelt werden, zählen Aminoplastklebstoffe, wie Harnstoff-Formaldehyd-Klebstoffe (UF-Klebstoffe), Melamin-Harnstoff-Phenol-Formaldehyd-Klebstoffe (MUPF-Klebstoffe) oder Melamin-Harnstoff-Formaldehyd-Klebstoffe (MUF-Klebstoffe). Weitere Klebstoffe, wie sie typischerweise bei Holzwerkstoffen eingesetzt werden, umfassen Klebstoffe auf Basis von Diisocyanaten (PMDI), Polyurethanklebstoffe, Phenol-Formaldehyd-Klebstoffe (PF-Klebstoffe) und/oder Tannin-Formaldehyd-Klebstoffe (TF-Klebstoffe) oder Gemische hiervon. Dabei finden im Faserplattenbereich hauptsächlich Aminoplastklebstoffe Verwendung. Hier tritt eine Freisetzung der Aldehyde und anderer VOCs und VVOCs sowohl während der Herstellung bei Holzwerkstoffen als auch nach deren Herstellung oder bei ihrer Anwendung statt. Bei der Faserplattenherstellung kann es z.B. bei der thermomechanischen Behandlung der Lignozellulose-haltigen Materialien zu einem chemischen Teilabbau des Holzes kommen. Die dabei entstehenden, flüchtigen organischen Verbindungen und sehr flüchtigen organischen Verbindungen, wie Aldehyde und Säuren, emittieren dann während des späteren Herstellungsverfahrens oder bei späterer Nutzung der hergestellten Holzwerkstoffe. Sie können ebenfalls einen negativen Einfluss auf die Verklebungsfestigkeit haben und somit die Eigenschaften der hergestellten Holzwerkstoffe negativ beeinflussen.As already stated, volatile organic compounds, such as aldehydes, are also released by the adhesives used during production or subsequently during use. Adhesives such as those currently being used in the manufacture of wood-based materials such as OSB boards, dense fiberboard, etc. include aminoplast adhesives such as urea-formaldehyde (UF) adhesives, melamine-urea-phenol-formaldehyde adhesives (MUPF adhesives) or melamine-urea-formaldehyde adhesives (MUF adhesives). Other adhesives typically used in wood-based materials include diisocyanate-based adhesives (PMDI), polyurethane adhesives, phenol-formaldehyde (PF) adhesives, and / or tannin-formaldehyde (TF) adhesives, or mixtures thereof. In the field of fibreboard mainly aminoplast adhesives are used. Here a release of the aldehydes and other VOCs and VVOCs takes place both during the production of wood-based materials as well as after their production or in their application. In fiberboard production, e.g. in the thermomechanical treatment of the lignocellulosic materials to a partial chemical degradation of the wood come. The resulting volatile organic compounds and very volatile organic compounds, such as aldehydes and acids, then emit during the later manufacturing process or later use of the wood-based materials produced. They can also have a negative influence on the bond strength and thus adversely affect the properties of the produced wood materials.

Es wurden bereits vielfältige Ansätze unternommen, diese Probleme der Emission von flüchtigen organischen Verbindungen, einschließlich der Aldehyde, zu begrenzen. Die WO 2010/144969 A1 beschreibt die Herstellung von Perlit und faserbasierten Kompositplatten. In der EP 1 852 231 die Verwendung von verschiedenen Additiven vorgeschlagen, so wird unter anderem die Verwendung von Maleinsäureanhydrid oder ähnlichen Verbindungen vorgesehen. Der Einsatz von Reduktions- bzw. Oxidationsmitteln ist ebenfalls bekannt. Des Weiteren wird eine Erhöhung des pH-Wertes vorgeschlagen, z.B. durch Zusatz von Alkalihydroxyden.Many approaches have already been taken, these emissions issues of volatile organic compounds, including aldehydes. The WO 2010/144969 A1 describes the production of perlite and fiber-based composite plates. In the EP 1 852 231 The use of various additives has been proposed, including the use of maleic anhydride or similar compounds. The use of reducing or oxidizing agents is also known. Furthermore, an increase in the pH is proposed, for example by addition of alkali metal hydroxides.

Aus der WO 2006/032267 sind Verfahren zur Reduktion von ungesättigten Aldehyden in Fettsäure-haltigen Hölzern bekannt. Dabei wird der im Holz enthaltene Fettsäureester gespalten, inhibiert oder oxidiert. Dazu wird allgemein die Verwendung von Antioxidantien, alkalischen Verbindungen oder Oxidationsmitteln vorgeschlagen. Hier werden allerdings diese Additive vor dem Trocknen des sägefrischen Massivholzes bzw. vor oder während der Herstellung der Holzpartikel behandelt. Ein Zufügen dieser nach oder während des Inkontaktbringens der Zerkleinerungsprodukte mit Klebstoffen und insbesondere nach Verpressen der Holzwerkstoffe ist nicht vorgesehen bzw. wird als nachteilig angesehen.From the WO 2006/032267 are known methods for the reduction of unsaturated aldehydes in fatty acid-containing woods. The fatty acid ester contained in the wood is split, inhibited or oxidized. For this purpose, the use of antioxidants, alkaline compounds or oxidizing agents is generally proposed. However, these additives are treated before drying the freshly cut solid wood or before or during the production of the wood particles. Adding this after or during the contacting of the comminution products with adhesives and in particular after pressing the wood-based materials is not provided or is considered to be disadvantageous.

Es besteht daher nach wie vor ein Bedarf nach Verfahren, die Emission von flüchtigen organischen Verbindungen aber auch sehr flüchtigen organischen Verbindungen, insbesondere auch von Aldehyden sowie organischen Säuren, insbesondere von Abbauprodukten von Fettsäuren aus den Holzwerkstoffen, zu verringern.There is therefore still a need for methods to reduce the emission of volatile organic compounds but also very volatile organic compounds, especially of aldehydes and organic acids, in particular of degradation products of fatty acids from the wood materials.

Der vorliegenden Erfindung liegt nunmehr die Aufgabe zugrunde, beschichtete Holzwerkstoffe aus Lignozellulose, insbesondere Spanplatten, Faserplatten oder OSB-Platten aber auch Sperrholz und Vollholz bereitzustellen, die eine verbesserte Verringerung bzw. Vermeidung von Emissionen von flüchtigen organischen Verbindungen (VOC) und sehr flüchtigen organischen Verbindungen (VVOC) aufweisen. Dabei soll die Emission dieser flüchtigen oder sehr flüchtigen oder sehr flüchtigen organischen Verbindungen einschließlich gesättigten und ungesättigten Aldehyden sowohl bei der Herstellung als auch im späteren Gebrauch deutlich heruntergesetzt werden. Weiterhin soll auch die durch diese flüchtigen bzw. sehr flüchtigen organischen Verbindungen ergebene Geruchsbelästigung verringert werden. Insbesondere ist dabei zu berücksichtigen, dass keine den Herstellungsprozess dieser Holzwerkstoffe störenden Substanzen verwendet oder generiert werden. Ebenfalls stellt ein wichtiger Aspekt dar, dass die Herstellungskosten der Holzwerkstoffe nicht signifikant erhöht werden. Dabei dürfen die eingesetzten Mittel selbst nicht toxisch oder karzinogen wirken, sollten aber möglichst umfangreich entweder mit den heterogenen Klassen der flüchtigen organischen Substanzen oder sehr flüchtigen organischen Verbindungen reagieren bzw. eine Bildung dieser aus Bestandteilen der Holzwerkstoffe verhindern.It is an object of the present invention to provide coated wood-based materials of lignocellulose, in particular chipboard, fiberboard or OSB boards, but also plywood and solid wood, which provide improved reduction or avoidance of emissions of volatile organic compounds (VOC) and highly volatile organic compounds (VVOC). It is said that the emission of this volatile or very volatile or volatile organic compounds, including saturated and unsaturated aldehydes, are significantly reduced both in production and in later use. Furthermore, the odor nuisance resulting from these volatile or very volatile organic compounds should also be reduced. In particular, it should be taken into account that no substances which disturb the production process of these wood-based materials are used or generated. Also, an important aspect is that the manufacturing cost of wood-based materials is not significantly increased. In this case, the agents used themselves must not be toxic or carcinogenic, but should as far as possible either react with the heterogeneous classes of volatile organic substances or very volatile organic compounds or prevent their formation from constituents of the wood-based materials.

Beschreibung der ErfindungDescription of the invention

Die Aufgabe der vorliegenden Erfindung wird dadurch gelöst, dass bei dem erfindungsgemäßen Verfahren zum Herstellen oder Bearbeiten der Holzwerkstoffe aus Lignozellulose zu bestimmten Zeitpunkten bestimmte Additive zugesetzt werden. Bei diesen Additiven handelt es sich um Alkohole, gegebenenfalls in Kombination mit einer katalytisch wirksamen Menge an Säure und/oder bestimmten Antioxidationsmitteln.The object of the present invention is achieved in that certain additives are added at certain times in the inventive method for producing or processing the wood materials from lignocellulose. These additives are alcohols, optionally in combination with a catalytically effective amount of acid and / or certain antioxidants.

D.h., in einem ersten Aspekt richtet sich die vorliegende Anmeldung auf ein Verfahren zur Herstellung von beschichteten Holzwerkstoffen aus Lignozellulose, insbesondere Spanplatten, Faserplatten, OSB-Platten oder Sperrholz gemäß Anspruch 1.That is, in a first aspect, the present application is directed to a process for the production of coated wood materials from lignocellulose, in particular chipboard, fiberboard, OSB boards or plywood according to claim 1.

Im Gegensatz zu den meisten bisher eingesetzten Verfahren werden dabei nicht nur chemische Modifikationen der emittierenden VOCs und VVOCs angestrebt, sondern vor allem an eine Umsetzung bzw. ein Abbau der Ausgangsstoffe im Holz verhindert. D.h., die erfindungsgemäß verwendeten Additive verhindern einen Abbau der Fettsäuren bzw. Fettsäureester. Des Weiteren werden gegebenenfalls durch Umwandlungsreaktionen gebildete Aldehyde in entsprechende nicht-emittierende Verbindungen umgewandelt.In contrast to most of the processes used so far, not only are chemical modifications of the emitting VOCs and VVOCs aimed for, but above all they prevent conversion or degradation of the starting materials in the wood. In other words, the additives used according to the invention prevent degradation of the fatty acids or fatty acid esters. Furthermore, aldehydes optionally formed by conversion reactions are converted to corresponding non-emitting compounds.

Die durch die Umsetzung erhaltenen Verbindungen sind derart, dass sie nicht mehr flüchtig sind und somit nicht mehr zu den VOC- und VVOC-Emissionen bzw. Aldehydemissionen beitragen bzw. die Toxizität der entstehenden Verbindungen ist deutlich reduziert. Dabei ist insbesondere die Emission auch nach der Herstellung, d.h. im täglichen Gebrauch, deutlich verringert.The compounds obtained by the reaction are such that they are no longer volatile and thus no longer contribute to the VOC and VVOC emissions or aldehyde emissions or the toxicity of the resulting compounds is significantly reduced. In particular, the emission is also after production, i. in daily use, significantly reduced.

Das erfindungsgemäße Verfahren umfasst die Schritte

  1. a) Inkontaktbringen von Lignozellulose-haltigen Zerkleinerungsprodukten mit Klebstoffen;
  2. b) Verpressen der Mischung aus a) unter Wärmebehandlung,
dadurch gekennzeichnet, dass die Additive auf einem Trägermaterial vorliegen und dieses Additiv-aufweisende Trägermaterial zwischen Schritt a) und b) und/oder nach Schritt b) auf die Lignozellulose-haltigen Zerkleinerungsprodukte oder auf den verpressten Holzwerkstoff aufgebracht wird.The method according to the invention comprises the steps
  1. a) contacting lignocellulose-containing comminution products with adhesives;
  2. b) pressing the mixture from a) under heat treatment,
characterized in that the additives are present on a carrier material and this additive-containing carrier material between step a) and b) and / or after step b) is applied to the lignocellulose-containing crushed products or to the compressed wood material.

D.h., erfindungsgemäß werden die Additive auf ein Trägermaterial aufgebracht. Dieser gilt insbesondere für die Antioxidantien als erfindungsgemäße Additive. Ein solches Aufbringen kann durch bekannte Maßnahmen und Verfahren erfolgen. Diese Verfahren schließen ein Aufbringen durch Sprühen, Imprägnieren, Eintauchen oder Aufstreichen auf das Trägermaterial ein.That is, according to the invention, the additives are applied to a carrier material. This applies in particular to the antioxidants as additives according to the invention. Such application may be by known means and methods. These methods include application by spraying, impregnation, dipping or painting onto the substrate.

Dabei kann das Additiv auf einer Seite oder beiden Seiten des Trägermaterials vorliegen. Bevorzugt liegt dabei das Additiv auf der dem Holzwerkstoff zugewandten Seite vor. Das Trägermaterial kann z.B. eine Zelluloselage, Papier oder ähnliches sein. Das Trägermaterial kann dabei erfindungsgemäß vor dem Verpressen der Mischung oder nach dem Verpressen auf den Holzwerkstoff aufgebracht werden. Bei Vollholz als HWS wird das Additiv aufweisende Trägermaterial entsprechend auf das Vollholz aufgebracht.In this case, the additive may be present on one side or both sides of the carrier material. The additive is preferably present on the side facing the wood-based material. The carrier material may e.g. a cellulose layer, paper or the like. According to the invention, the carrier material can be applied to the wood material prior to pressing the mixture or after pressing. For solid wood as a cervical spine, the carrier material containing the additive is applied to the solid wood accordingly.

Zusätzlich kann durch das Trägermaterial eine Abdeckung des Holzwerkstoffes erfolgen und somit die Emission der VOC und VVOC zusätzlich verhindert werden.In addition, by the carrier material, a covering of the wood material and thus the emission of VOC and VVOC be additionally prevented.

Das Trägermaterial kann dabei transparent oder mit einem Dekor ausgebildet sein. Die Trägermaterialien können übliche, sogenannte Overlay-Produkte sein oder z.B. 100% Zellulosepapier, wie sie im Bereich der Herstellung von Holzwerkstoffen, z.B. Paneelen eingesetzt werden. Gegebenenfalls kann nach Aufbringen des Additivs auf das Trägermaterial eine Trocknung des Additivs bei Raumtemperatur erfolgen, bevor das Additiv-aufweisende Trägermaterial mit den Holzwerkstoffen oder den Lignozellulose-haltigen Zerkleinerungsprodukten mit Klebstoffen in Verbindung gebracht wird.The carrier material may be transparent or formed with a decor. The support materials may be conventional, so-called overlay products or, for example, 100% cellulose paper, as used in the field of the production of wood-based materials, such as panels. Optionally, after application of the additive to the carrier material, a drying of the additive at room temperature, before the additive-containing carrier material with the wood materials or the lignocellulose-containing crushing products is associated with adhesives.

Zum Beispiel kann das Trägermaterial mit dem Additiv getränkt, besprüht oder in anderer Weise imprägniert werden. Dieses Trägermaterial wird dann vor dem Streuen auf dem Förderband aufgetragen und nach der Streuung aber vor dem Pressen aufgerakelt. In einer alternativen Form wird das Trägermaterial nach dem Pressen auf den Holzwerkstoff aufgebracht und z.B. aufgerakelt oder in anderer Art und Weise mit dem Holzwerkstoff verbunden. Es ist dabei bevorzugt, dass bei Holzwerkstoffplatten, wie OSB-Platten, Faserplatten, Sperrholz oder Spanplatten aber auch Vollholz das Trägermaterial auf beiden Seiten des HWS aufgebracht ist. Dabei ist bevorzugt, dass das Additiv zumindest auf der dem HWS zugewandten Seite vorliegt.For example, the carrier material may be soaked, sprayed or otherwise impregnated with the additive. This carrier material is then applied before spreading on the conveyor belt and scrape after scattering but before pressing. In an alternative form, after pressing, the support material is applied to the wood material, e.g. rooted or otherwise connected to the wood material. It is preferred that in wood-based panels, such as OSB boards, fiberboard, plywood or chipboard but also solid wood, the support material is applied on both sides of the cervical spine. It is preferred that the additive is present at least on the HWS side facing.

In einer weiteren Ausführungsform wird das Additiv auf das Lignozellulose-haltige Zerkleinerungsprodukt vor dem Verpressen und nach dem Streuen oder Legen eingebracht. Bevorzugt wird dabei das Additiv vor dem Verpressen aber nach dem Zerfasern oder Zerspanen und insbesondere nach dem Trocknen hinzugefügt.In a further embodiment, the additive is introduced onto the lignocellulose-containing comminuted product before compression and after spreading or laying. In this case, the additive is preferably added before compression but after defibering or machining and in particular after drying.

Das Additiv kann dabei in Form einer wässrigen Lösung oder als Pulvermischung direkt nach dem Pressvorgang z.B. durch Besprühen mittels Düsen auf einer oder beiden Seiten des hergestellten Holzwerkstoffes aufgebracht werden. Alternativ kann ein Eintragen durch Walzen erfolgen.The additive may be in the form of an aqueous solution or as a powder mixture directly after the pressing operation, e.g. be applied by spraying by means of nozzles on one or both sides of the produced wood material. Alternatively, an entry can be made by rolling.

In einer anderen Ausführungsform kann das Additiv als Lösung oder als Pulver zu den Lignozellulose-haltigen Zerkleinerungsprodukten bzw. der Mischung aus Lignozellulose-haltigen Zerkleinerungsprodukten und Klebstoff, dosiert werden. Hierbei kann ein Zudosieren auch vor dem Trockner aber nach dem Zerfasern oder Zerspanen erfolgen. Der Zeitpunkt der Zudosierung hängt dabei von der Form des Additivs z.B. als wässrige Lösung oder als Pulver ab.In another embodiment, the additive can be dosed as a solution or as a powder to the lignocellulose-containing comminution products or the mixture of lignocellulose-containing comminution products and adhesive. In this case, a metered addition can also take place before the dryer but after defibering or cutting. The time of metering depends on the form of the additive, for example as an aqueous solution or as a powder.

Zum Beispiel kann bei der Herstellung von OSB-Platten das Additiv nur in Teilbereichen der Platte eingebracht werden. Bevorzugt wird dabei das Additiv zumindest in den die Deckschicht ausbildenden Bereichen der Holzwerkstoffplatte, wie einer OSB-Platte, eingebracht. Weiterhin kann das Additiv sowohl teilweise vor dem Verpressen als auch nach dem Verpressen mit einem Trägermaterial aufgebracht werden.For example, in the manufacture of OSB boards, the additive may be incorporated only in portions of the board. In this case, the additive is preferably introduced at least into the regions of the wood-based panel that form the covering layer, such as an OSB board. Furthermore, the additive can be applied both partially before compression and after compression with a carrier material.

Es ist besonders bevorzugt, dass die Holzwerkstoffe solche sind, hergestellt aus Holzspäne, Holzstrands oder Holzfasern als Lignozellulose-haltige Zerkleinerungsprodukte.It is particularly preferred that the wood-based materials are those made of wood chips, wood strands or wood fibers as lignocellulose-containing crushed products.

Insbesondere ist es bevorzugt, dass der Holzwerkstoff eine OSB-Platte ist. Die Holzwerkstoffe können gegebenenfalls weiter mit bekannten Schichten, wie einer Lackschicht, Dekorschicht oder Verschleißschicht beschichtet sein. Die Additive können dabei auch oder nur in diesen Schichten vorliegen. D.h., das Trägermaterial kann als Dekorschicht, Lackschicht, Verschleißschicht oder entsprechend Unterschichten ausgebildet sein.In particular, it is preferred that the wood material is an OSB board. If appropriate, the wood-based materials may be further coated with known layers, such as a lacquer layer, decorative layer or wearing layer. The additives may also or only be present in these layers. That is, the carrier material may be formed as a decorative layer, lacquer layer, wear layer or according to sub-layers.

In einer alternativen Ausführungsform ist der HWS Vollholz und die Additive werden mit bekannten Verfahren auf den HWS aufgebracht beziehungsweise eingebracht.In an alternative embodiment, the cervical spine is solid wood and the additives are applied to the cervical spine by known methods.

Bei den erfindungsgemäß zu verwendenen Additiven handelt es sich einerseits um Alkohole, insbesondere mehrwertige Alkohole. Es ist insbesondere bevorzugt, dass diese Alkohole zusammen mit einer katalytisch wirksamen Menge an Säure eingetragen werden, um eine Säure-katalysierte Umsetzung der Alkohole zu ermöglichen. Die Alkohole können dann z.B. mit entstehenden Aldehyden zu Acetalen reagieren.On the one hand, the additives to be used according to the invention are alcohols, in particular polyhydric alcohols. It is particularly preferred that these alcohols be added together with a catalytically effective amount of acid to allow for acid-catalyzed reaction of the alcohols. The alcohols may then be e.g. react with resulting aldehydes to form acetals.

Fette und Öle sind Ester von mehrwertigen Alkoholen, üblicherweise Glycerin, mit gesättigten und ungesättigten Fettsäuren. Durch den oxidativen Abbau dieser Fette und Fettsäuren im Pressvorgang unter hohen Temperaturen entstehen z. B. Aldehyde. Bei der Zugabe von Glycerin oder anderen, insbesdonere mehrwertigen Alkoholen mit einer geringen Menge einer Säure zur säurekatalytischen Umsetzung reagieren die Aldehyde zu Acetalen. Dabei stehen bei Glycerin z. B. drei Hydroxygruppen zur Verfügung. Es ist daher bevorzugt, dass mehrwertige Alkohole als Additive zugesetzt werden.Fats and oils are esters of polyhydric alcohols, usually glycerol, with saturated and unsaturated fatty acids. Due to the oxidative degradation of these fats and fatty acids in the pressing process at high temperatures arise z. B. aldehydes. Upon addition of glycerine or other, especially polyhydric, alcohols with a small amount of acid for acid catalytic conversion, the aldehydes react to form acetals. In this case, for glycerol z. B. three hydroxy groups available. It is therefore preferred that polyhydric alcohols are added as additives.

Ein weiterer Reaktionsweg neben der acetalen Bildung ist die Veresterung mit Fettsäuren aus dem Holz. Dieses ist ebenfalls üblicherweise säurekatalysiert. Dabei werden die Fettsäuren verestert und somit einer Degradation der Fettsäuren zu VOC und WOC entgegenwirkt.Another reaction pathway in addition to the acetal formation is the esterification with fatty acids from the wood. This is also usually acid-catalyzed. The fatty acids are esterified, thus counteracting a degradation of the fatty acids to VOC and WOC.

Es ist daher besonders bevorzugt, dass bei Verwendung von Alkohol als Additiv Säure zur säurekatalytischen Umsetzung der Alkohole hinzugefügt werden. Hierbei reichen geringe Mengen an Säure aus, das diese katalytisch wirkt.It is therefore particularly preferred that, when alcohol is used as an additive, acid is added to the acid-catalytic conversion of the alcohols. In this case, small amounts of acid are sufficient, which catalyzes this.

Bevorzugte Alkohole sind mehrwertige Alkohole, insbesondere Glycerin oder Alkylenglykole, wie Ethylenglykol, Propandiol, Butandiol usw.Preferred alcohols are polyhydric alcohols, in particular glycerol or alkylene glycols, such as ethylene glycol, propanediol, butanediol, etc.

Als weiteres Additiv kann ein Antioxidationsmittel eingesetzt werden. Antioxidationsmittel erlauben ein Abfangen von Radikalen, die z. B. bei hohen Temperaturen oder Licht entstehen. Bei hohen Temperaturen oder Licht entstehen z. B. Hydroxylradikale, die die Fähigkeit haben, andere Substanzen schnell zu oxidieren. Hierdurch werden leicht VOCs und VVOCs aus den natürlichen Bestandteilen im Holz gebildet. Die Antioxidationsmittel, insbesondere die Antioxidationsmittel ausgewählt aus Ascorbinsäure, Vitamin E oder Butylhydroxytoluol (BHT), haben die Fähigkeit, solche Radikale abzufangen und somit die Bildung von VOCs oder VVOCs aus den Bestandteilen des Holzes zu verhindern. Diese Antioxidationsmittel werden erfindungsgemäß in oder auf das Trägermaterial ein- bzw. aufgebracht.As another additive, an antioxidant can be used. Antioxidants allow trapping of radicals that z. B. at high temperatures or light. At high temperatures or light z. For example, hydroxyl radicals that have the ability to rapidly oxidize other substances. This easily forms VOCs and VVOCs from the natural components in the wood. The antioxidants, especially the antioxidants selected from ascorbic acid, vitamin E or butylhydroxytoluene (BHT), have the ability to trap such radicals and thus prevent the formation of VOCs or VVOCs from the constituents of the wood. According to the invention, these antioxidants are incorporated or applied in or on the carrier material.

Es ist bevorzugt, dass die Additive in einer Menge von 0,5 bis 5 Gew.-% fester Feststoff bezogen auf atro Holz hinzugefügt werden.It is preferable that the additives are added in an amount of 0.5 to 5% by weight of solid solid in terms of dry wood.

Beim Einsatz der erfindungsgemäßen Additive bei der Herstellung oder Bearbeitung der Holzwerkstoffe, wie z. B. OSB-Platten oder MDF-Platten aber auch Sperrholz und Vollholz, wurde überraschend eine deutliche Reduzierung der VOC bzw. VVOC einschließlich der Aldehyde beobachtet. Zusätzlich war auch eine deutlich geringere Emission von anderen flüchtigen organischen Verbindungen zu beobachten. Eine Verringerung der Emission wird sowohl während der Herstellung als auch bei der späteren Verwendung erreicht. Dies ist umso überraschender, als nicht davon ausgegangen werden konnte, dass aufgrund der Vielzahl von reaktiven Verbindungen, die im Holz vorhanden sind, diese Additiv VOC bzw. VVOC und insbesondere die Aldehyde wirksam in ihrer Emission verringern können.When using the additives according to the invention in the manufacture or processing of wood materials, such. As OSB boards or MDF boards but also plywood and solid wood, a significant reduction of VOC or VVOC including the aldehydes was surprisingly observed. In addition, a significantly lower emission of other volatile organic compounds was observed. Emission reduction is achieved both during manufacture and during later use. This is all the more surprising, since it could not be assumed that due to the large number of reactive compounds that are present in the wood, this additive VOC or VVOC and in particular the aldehydes can effectively reduce their emission.

Bei den Lignozellulosen, wie den Holzwerkstoffen oder den Zerkleinerungsprodukten hiervon, kann es sich sowohl um Nadelhölzer als auch um Laubhölzer handeln. Auch Mischungen dieser beiden Holzarten sind möglich. Bevorzugt stammen die Holzspäne, Strands oder Holzfasern von Nadelhölzern. Die mit dem erfindungsgemäßen Herstellungsverfahren herstellbaren Holzwerkstoffe werden gemäß Anspruch 14 hergestellt. Dabei kann das Verfahren zusätzlich durch andere, dem Fachmann bekannte Verfahren, zur Verminderung der Emission von flüchtigen organischen Verbindungen oder sehr flüchtigen organischen Verbindungen, wie Aldehyde, ergänzt werden.The lignocelluloses, such as the wood-based materials or the comminuted products thereof, may be both conifers and hardwoods. Even mixtures of these two types of wood are possible. Preferably, the wood chips, strands or wood fibers come from conifers. The wood materials which can be produced by the production method according to the invention are produced according to claim 14. In addition, the process can be supplemented by other processes known to the person skilled in the art for reducing the emission of volatile organic compounds or very volatile organic compounds, such as aldehydes.

Bei den Holzwerkstoffen (HWS) kann es sich bevorzugt um Spanplattenholz aus Holzspänen, OSB-Strands aus Holzstrands, Sperrholzplatten aus Holzfurnier und Holzfaserplatten, insbesondere MDF-Platten, aus Holzfasern handeln. Unter den Ausdruck "Holzwerkstoffe" fallen aber auch Sperrholz und insbesondere auch Vollholz. Bevorzugt sind die Holzwerkstoffe OSB-Platten und leichte und superleichte MDF-Platten.The wood-based materials (HWS) may preferably be chipboard wood made of wood chips, OSB strands of wood strands, plywood boards of wood veneer and wood fiber boards, in particular MDF boards, of wood fibers. However, the term "wood-based materials" also includes plywood and, in particular, solid wood. Preferably, the wood materials OSB boards and lightweight and super light MDF boards.

Unter Lignozellulosen werden Lignozellulose-haltige Materialien, wie Holz, verstanden. Daraus erhaltene Zerkleinerungsprodukte von Lignozellulose umfassen insbesondere Holzstrands, Holzspäne, Holzfasern als auch Holzfurnier.Lignocelluloses are understood to mean lignocellulose-containing materials, such as wood. The resulting comminution products of lignocellulose include, in particular, wood strands, wood chips, wood fibers as well as wood veneers.

Die verwendeten Klebstoffe im erfindungsgemäßen Verfahren umfassen als Klebstoffe Phenol-Formaldehyd-Klebstoff, Klebstoff auf Basis von Isocyanaten, Harnstoff-Formaldehyd-Klebstoff, Melamin-Harnstoff-Formaldehyd-Klebstoff, Melamin-Harnstoff-Phenol-Formaldehyd-Klebstoff, Tannin-Formaldehyd-Klebstoff oder ein Gemisch hiervon.The adhesives used in the process according to the invention comprise, as adhesives, phenol-formaldehyde adhesive, isocyanate-based adhesive, urea-formaldehyde adhesive, melamine-urea-formaldehyde adhesive, melamine-urea-phenol-formaldehyde adhesive, tannin-formaldehyde adhesive or a mixture thereof.

In einem weiteren Aspekt richtet sich die vorliegende Anmeldung auf die Verwendung einer Zusammensetzung enthaltend einen Alkohol, wie hierin definiert, gegebenenfalls in Kombination mit katalytisch wirksamen Mengen einer Säure und/oder einem Antioxidationsmittel, wie hier definiert, zur Verminderung der Emission von VOC bzw. VVOC, insbesondere gesättigten und ungesättigten Aldehyden, bei der Herstellung und bei Nutzung von Holzwerkstoffen aus Lignozellulose. Diese Verwendung zeichnet sich dadurch aus, dass das Additiv während des Herstellungsprozesses des Holzwerkstoffes eintragbar oder auftragbar ist. Das Additiv wird dabei ein- oder aufgetragen, wie oben ausgeführt, mit Hilfe eines Trägermaterials.In a further aspect, the present application is directed to the use of a composition containing an alcohol as defined herein optionally in combination with catalytically effective amounts of an acid and / or an antioxidant as defined herein for reducing the emission of VOC and VVOC, respectively , in particular saturated and unsaturated aldehydes, in the production and use of wood materials of lignocellulose. This use is characterized in that the additive during the manufacturing process of the wood material is registered or applied. The additive is applied or applied, as stated above, with the aid of a carrier material.

Die Verwendung ist insbesondere vorteilhaft bei Klebstoffen ausgewählt aus Phenol-Formaldehyd-Klebstoff, Klebstoff auf Basis von Isocyanaten, Harnstoff-Formaldehyd-Klebstoff, Melamin-Harnstoff-Formaldehyd-Klebstoff, Melamin-Harnstoff-Phenol-Formaldehyd-Klebstoff, Tannin-Formaldehyd-Klebstoff oder ein Gemisch hiervon verwendet wird.The use is particularly advantageous for adhesives selected from phenol-formaldehyde adhesive, isocyanate-based adhesive, urea-formaldehyde adhesive, melamine-urea-formaldehyde adhesive, melamine-urea-phenol-formaldehyde adhesive, tannin-formaldehyde adhesive or a mixture thereof is used.

Die Additive sind insbesondere geeignet zur Verwendung zumindest in der Deckschicht von OSB-Platten oder Holzfaserplatten.The additives are particularly suitable for use at least in the top layer of OSB boards or wood fiber boards.

Bevorzugt findet die Verwendung der Additive dabei in einer Menge von 0,5 Gew.-% bis 5 Gew.-% Feststoff bezogen auf atro Holz statt.The use of the additives preferably takes place in an amount of from 0.5% by weight to 5% by weight of solids, based on atro-wood.

Schließlich richtet sich in einem weiteren Aspekt die vorliegende Anmeldung auf mit dem erfindungsgemäßen Verfahren erhältliche Holzwerkstoffe. Bei diesen Holzwerkstoffen handelt es sich insbesondere um Faserplatten, insbesondere leichte und superleichte MDF-Platten oder um OSB-Platten, aber auch um Vollholz.Finally, in a further aspect, the present application is directed to wood materials obtainable by the process according to the invention. These wood-based materials are, in particular, fibreboards, in particular lightweight and superlight MDF boards or OSB boards, but also solid wood.

Mit Hilfe des erfindungsgemäßen Verfahrens ist es möglich unter geringer Dosierung der Additive eine Emission von VOC bzw. VVOC aus Holzwerkstoffen bei der Herstellung aber auch im Gebrauch zu verringern. Bei Einsatz von Trägermaterialien ist es zusätzlich möglich die Emission von VOC bzw. VVOC durch Abdeckung zu unterdrücken.With the aid of the method according to the invention, it is possible with low dosage of the additives to reduce an emission of VOC or VVOC from wood-based materials during production but also during use. When using carrier materials, it is additionally possible to suppress the emission of VOC or VVOC by covering.

Außerdem sind die erfindungsgemäß verwendeten Additive insbesondere vorteilhaft in Bezug auf eine längerfristige Wirkung zur Unterdrückung der Emissionen von VOC oder VVOC, da die im Trägermaterial oder in der Deckschicht vorhandenen Additive auch längerfristig die Bildung und Emission von VOC oder VVOC vermeiden.In addition, the additives used according to the invention are particularly advantageous in terms of a longer-term effect for suppressing the emissions of VOC or VVOC, since the additives present in the carrier material or in the outer layer also avoid the formation and emission of VOC or VVOC in the longer term.

Im Folgenden wird die Erfindung mit Hilfe von Beispielen näher erläutert, ohne dass sie auf diese beschränkt ist.In the following, the invention will be explained in more detail by means of examples, without being limited to these.

Beispiel 1: Herstellung von emissionsarmen OSBExample 1: Production of low emission OSB

Es wurde unter Verwendung beleimter Strands aus der laufenden Produktion (12% MUPF als Klebstoff) eine Referenzplatte und zwei Platten unter Verwendung des Additivs Glycerin und Ascorbinsäure hergestellt. Diese Platten wurden dann verpresst zu einem Format von 10mm x 300mm x 300mm und einer Rohdichte von 530kg/m3. Parameter zur Pressung sind in der unten dargestellten Tabelle zu finden. Vor dem Pressen wurden die beleimten Strands mit dem jeweiligen Additiv vermischt. Weiterhin wurde ein Teil des Additivs nach dem Pressen auf der Oberfläche der Platte aufgespritzt. Probe A enthält das Additiv Glycerin in einer Dosierung von 5 Gew.-%. Bei Zugabe des Additivs A wurden weiterhin einige Tropfen Salzsäure zur Katalyse hinzugefügt. Die Probe B enthält das Additiv Ascorbinsäure mit einem Anteil von 1 Gew.-% auf Atroholz. Tabelle 1 Pressdiagramm Pressstufe Druck [N/mm2] Zeit [s] T [°C] 1 2 60 200 2 1 60 200 3 0,2 10 200 A reference plate and two plates were made using glued strands from current production (12% MUPF as adhesive) using the additive glycerin and ascorbic acid. These plates were then pressed into a format of 10mm x 300mm x 300mm and a bulk density of 530kg / m 3 . Parameters for pressing are shown below Table to find. Before pressing, the glued strands were mixed with the respective additive. Furthermore, a part of the additive was sprayed on the surface of the plate after pressing. Sample A contains the additive glycerol in a dosage of 5 wt .-%. Addition of Additive A further added a few drops of hydrochloric acid for catalysis. Sample B contains the additive ascorbic acid in an amount of 1% by weight on atro wood. Table 1 Press diagram pressing stage Pressure [N / mm 2 ] Time T [° C] 1 2 60 200 2 1 60 200 3 0.2 10 200

Nach Abkühlen der Platte wurde diese luftdicht verschlossen und zur Analyse aufbewahrt.After cooling the plate, it was sealed airtight and stored for analysis.

Beispiel 2: Bestimmung der Emission von VOC aus OSBExample 2: Determination of the emission of VOC from OSB Material und Methodenmaterial and methods Materialmaterial

Es wurden Proben aus den oben erhaltenen OSB-Platten mit den Abmessungen 210 x 210 x Dicke mm3 hergestellt. Vom Rand dieser Proben wurde jeweils ein 7mm breiter Streifen entnommen. Dieser wurde dann in zwei Proben mit einer Länge von 95mm aufgetrennt. Je eine Probe wurde mit der Oberseite und die andere mit Unterseite zum Luftstrom im Themoextraktor orientiert eingebracht. Die Ergebnisse werden als Mittelwert dieser beiden Messungen ausgedrückt.Samples were prepared from the above-obtained OSB plates measuring 210 × 210 × thickness mm 3 . From the edge of these samples a 7mm wide strip was taken. This was then separated into two samples with a length of 95mm. One sample each was placed with the top side and the other with bottom side oriented towards the air flow in the topo-extractor. The results are expressed as the mean of these two measurements.

Methode: ThermoextraktionMethod: Thermo-extraction

Für eine qualitative und vergleichende Untersuchung des Emissionspotenzials strukturell ähnlicher Materialien eignet sich die Thermoextraktionsmethode.For a qualitative and comparative study of the emission potential of structurally similar materials, the thermo-extraction method is suitable.

Die unterschiedlichen Proben wurden mit einem sogenannten Thermoextraktor (TE1, Gerstel, Mülheim a.d. Ruhr, Deutschland) charakterisiert. Dabei handelt es sich um ein Glasröhrchen mit verhältnismäßig kleinen Raumvolumen von ca. 25,9cm3, das sich in dem Thermoextraktor befindet. Durch das gesamte System wird ein kontinuierlicher Stickstofffluss (100ml/min-1) geleitet, der - wie bei den konventionellen Prüfkammertests - zu regelmäßigen Zeitpunkten über ein Adsorbens geleitet wird. Gemäß DIN ISO 16000-6:2004 wurden diese in einem GC-MS mit Thermosdesorption und Kühlfalle analysiert. Das ganze System wurde bei Raumtemperatur (23°C) betrieben. Beschrieben wurde die Methode von Scherer et.al. (Gefahrstoffe-Reinhaltung der Luft, 2006, 66(3), 87-93 ). Um immer gleiche und damit reproduzierbare Bedingungen zu erreichen, wurde ein Probenhalter aus Stahl verwendet, der eine potenziell emittierende Probenoberfläche von etwa 7,1 cm2 freilässt. In Abbildung 1 sind Thermoextraktor, Probenhalter und die Probendimensionen dargestellt. Die Bedingungen bei der Thermoextraktion sind in Tabelle 2 zusammengefasst. Die Probenahme von 11 Luftvolumen erfolgte 10 Minuten nachdem die Proben in den Thermoextraktor eingebracht wurden. Die Ergebnisse werden als Substanzmenge bezogen auf das Luftprobenahmevolumen (µg m-3) ausgedrückt. Tabelle 2: Bedingungen bei der Thermoextraktion Parameter Eigenschaft Temperatur in °C RT Massenfluss in ml min-1 100 Raumvolumen in m3 0,00002586 Luftwechselrate in h-1 232,0 Probenoberfläche in m2 0,00075 Raumbeladung in m2 m-3 29,1 Flächenspezifische Lüftungsrate in m3 -2 h-1 8,0 Trägergas Stickstoff The different samples were characterized with a so-called thermo-extractor (TE1, Gerstel, Mülheim ad Ruhr, Germany). It is a glass tube with a relatively small volume of about 25.9 cm 3 , which is located in the thermo-extractor. Throughout the system, a continuous nitrogen flow (100ml / min-1) is passed, which - as in the conventional test chamber tests - is passed over an adsorbent at regular times. According to DIN ISO 16000-6: 2004, these were analyzed in a GC-MS with thermosorption and cold trap. The whole system was operated at room temperature (23 ° C). Described was the method of Scherer et al. (Dangerous substances - clean air, 2006, 66 (3), 87-93 ). In order to achieve always the same and thus reproducible conditions, a steel sample holder was used which leaves a potentially emitting sample surface of about 7.1 cm 2 . In illustration 1 Thermo-extractor, sample holder and the sample dimensions are shown. The conditions for the thermo-extraction are summarized in Table 2. 11 air volumes were sampled 10 minutes after the samples were placed in the thermo-extractor. The results are expressed as the substance quantity in relation to the air sampling volume (μg m -3 ). Table 2: Conditions for thermo-extraction parameter property Temperature in ° C RT Mass flow in ml min -1 100 Room volume in m 3 0.00002586 Air change rate in h -1 232.0 Sample surface in m 2 0.00075 Room load in m 2 m -3 29.1 Area-specific ventilation rate in m 3 - 2 h -1 8.0 carrier gas nitrogen

Die Ergebnisse der Untersuchung sind in der Tabelle 3 dargestellt. Tabelle 3: Ergebnisse µg/m3 Probe 0 Probe A Probe B Aldehyde 681 153 42 Gesättigte Aldehyde 651 140 31 Ungesättigte Aldehyde 18 3 1 Hexanal 577 124 26 2-Heptenal 12 3 1 2-Octenal 6 0 0 The results of the study are shown in Table 3. Table 3: Results μg / m 3 Sample 0 Sample A Sample B aldehydes 681 153 42 Saturated aldehydes 651 140 31 Unsaturated aldehydes 18 3 1 hexanal 577 124 26 2-heptenal 12 3 1 2-octenal 6 0 0

Wie deutlich zu erkennen ist, ist in den Proben A und B mit dem jeweiligen Additiv eine deutliche Vermeidung der Aldehyde zu beobachten. Insbesondere die gesättigten aber auch die ungesättigten Aldehyde sind deutlich reduziert.As can be clearly seen, a clear avoidance of aldehydes is observed in samples A and B with the respective additive. In particular, the saturated but also the unsaturated aldehydes are significantly reduced.

Die Ergebnisse sind noch einmal graphisch in der Figur 1 dargestellt.The results are again graphically in the FIG. 1 shown.

Claims (15)

  1. Process for production of coated wood-base materials from lignocellulose, in particular flakeboard panels, fibreboard panels or OSB panels, comprising the steps of
    a) contacting lignocellulosic comminution products with adhesives;
    b) compression moulding the mixture from a) under heat treatment, wherein
    further at least one additive selected from alcohols, optionally in combination with a catalytically effective amount of an acid, and/or an antioxidant is introduced as additive between the contacting as per step a) and the compression moulding as per step b) and/or after the compression moulding as per step b) to reduce the emission of volatile organic compounds or very volatile organic compounds, in particular saturated or unsaturated aldehydes, characterized in that the additives are present on a carrier material and this additive-displaying carrier material is applied atop the lignocellulosic comminution products or atop the compression-moulded wood-base material between steps a) and b) and/or after step b).
  2. Process according to Claim 1, characterized in that the additive is a polyhydric alcohol, in particular glycerol, ethylene glycol or propanediol.
  3. Process according to either of Claims 1 and 2, further comprising introducing an acid for the acid-catalysed reaction of alcohols with aldehydes or fatty acids.
  4. Process according to Claim 1, characterized in that the antioxidant is ascorbic acid, vitamin E or butylhydroxytoluene.
  5. Process according to any of Claims 1 to 4, characterized in that the carrier is a cellulosic material, such as paper, one- or both-sidedly coated or impregnated with the additive.
  6. Process according to Claim 5, characterized in that the carrier material is blade coated onto the lignocellulosic comminution product before compression moulding and after forming or laying and/or onto the compression-moulded wood-base material after compression moulding.
  7. Process according to any of Claims 1 to 4, characterized in that the additive is applied one- or both-sidedly atop the compression-moulded wood-base material after step b) and/or introduced into at least the lignocellulosic comminution products which form the outer layer.
  8. Process according to any preceding claim, characterized in that the comminution products are admixed with the additive before compression moulding but after defiberization or flaking.
  9. Process according to any preceding claim, characterized in that the wood-base materials are wood-base materials formed from wood flakes, wood strands or wood fibres as lignocellulosic comminution products.
  10. Process according to any preceding claim, characterized in that the amount of additive added is between 0.5 to 5 wt% of solids based on absolutely dry wood.
  11. Use of an additive containing alcohol optionally in combination with catalytically effective amounts of an acid and/or an antioxidant to reduce the emission of volatile organic compounds or very volatile organic compounds, in particular saturated and unsaturated aldehydes, in the production and the use of wood-base materials from lignocellulose, characterized in that the additive is introducable or coatable via an additive-displaying carrier material during the operation to produce the wood-base material.
  12. Use according to Claim 11, characterized in that the additive is used at least in the outer layer of OSB panels or wood fibreboard panels.
  13. Use according to either of Claims 11 and 12, characterized in that the additive is applied in an amount of 0.5 wt% to 5 wt% of solids based on absolutely dry wood.
  14. Wood-base material obtainable with a process according to any of Claims 1 to 10.
  15. Wood-base material according to Claim 14, wherein the wood-base material comprises fibreboard panels, in particular light and superlight MDF panels or OSB panels.
EP11005690.0A 2011-07-12 2011-07-12 Method of reducing the emissions of fleeting organic compounds in wooden materials Active EP2546038B1 (en)

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DE1619244A1 (en) * 1966-05-27 1971-02-11 Goldschmidt Ag Th Barrier or primer film
US5160503A (en) * 1989-11-13 1992-11-03 West Point Pepperell Water-soluble blends of active methylene compounds and polyhydric alcohols as formaldehyde scavengers
EP1793972A1 (en) * 2004-09-21 2007-06-13 Institut für Holztechnologie Dresden gGmbH Timber or derived timber product, method for producing the same
AR054353A1 (en) * 2005-05-02 2007-06-20 Basf Ag METHOD FOR TREATMENT OF WOOD SURFACES
DE102006020612B4 (en) * 2006-05-02 2019-03-14 SWISS KRONO Tec AG Process for the production of wood-based materials with reduced emission of volatile organic compounds, wood-based materials obtainable therewith and the use of certain additives for reducing the release of volatile organic compounds from wood-based materials and wood-pulp products of lignocelluloses
DE102009046127A1 (en) * 2008-10-28 2010-04-29 Institut Für Holztechnologie Dresden Gemeinnützige Gmbh Process for the production of wood fiber materials and wood fiber materials with reduced emission of volatile VOCs
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