[go: up one dir, main page]

EP1716995A2 - Produit à base d'acides gras et de dérivés paraffiniques pour la protection de matériaux lignocellulosiques - Google Patents

Produit à base d'acides gras et de dérivés paraffiniques pour la protection de matériaux lignocellulosiques Download PDF

Info

Publication number
EP1716995A2
EP1716995A2 EP06112951A EP06112951A EP1716995A2 EP 1716995 A2 EP1716995 A2 EP 1716995A2 EP 06112951 A EP06112951 A EP 06112951A EP 06112951 A EP06112951 A EP 06112951A EP 1716995 A2 EP1716995 A2 EP 1716995A2
Authority
EP
European Patent Office
Prior art keywords
wood
fatty acid
mixture
paraffin
protective agent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP06112951A
Other languages
German (de)
English (en)
Other versions
EP1716995A3 (fr
EP1716995B1 (fr
Inventor
Holger Prof. Dr. Militz
Carsten Dr. Mai
Hong Minh Nguyen
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Georg August Universitaet Goettingen
Original Assignee
Georg August Universitaet Goettingen
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Georg August Universitaet Goettingen filed Critical Georg August Universitaet Goettingen
Priority to EP20060112951 priority Critical patent/EP1716995B1/fr
Publication of EP1716995A2 publication Critical patent/EP1716995A2/fr
Publication of EP1716995A3 publication Critical patent/EP1716995A3/fr
Application granted granted Critical
Publication of EP1716995B1 publication Critical patent/EP1716995B1/fr
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K5/00—Treating of wood not provided for in groups B27K1/00, B27K3/00
    • B27K5/007—Treating of wood not provided for in groups B27K1/00, B27K3/00 using pressure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
    • B27K3/16—Inorganic impregnating agents
    • B27K3/26—Compounds of iron, aluminium, or chromium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
    • B27K3/34—Organic impregnating agents
    • B27K3/36—Aliphatic compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
    • B27K3/52—Impregnating agents containing mixtures of inorganic and organic compounds
    • 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
    • B27N1/006—Pretreatment of moulding material for increasing resistance to swelling by humidity

Definitions

  • the present invention relates to protective agents based on fatty acid derivatives and paraffin for lignocellulosic materials, in particular for wood and wood-based materials, and lignocellulosic materials treated with these protective agents. Furthermore, the invention relates to a method for the treatment of wood and other lignocellulosic materials with new preservatives.
  • the protective agents according to the invention have hydrocarbons as base in the form of fatty acid derivatives and paraffin and are used for application to the lignocellulosic material in organic solvent, in supercritical CO 2 and / or in aqueous dispersion or emulsion.
  • lignocellulosic materials in particular wood and wood-based materials absorb ambient moisture and are subject to dimensional changes in the case of fluctuations in the moisture content. This leads in particular to wood for swelling and shrinking, as a result to cracking and plating applied to their chipping.
  • lignocellulosic materials, in particular wood the infestation by fungi, on the one hand by wood-destroying fungi such as Basidiomycetes, on the other hand by discolouring fungi, such as blue fungus and mold.
  • Known wood preservatives on an organic basis are used to prevent fungal attack. These are generally used for wood in hazard classes 2 and 3 according to DIN 68800/3 and EN 335, have a relatively low molecular weight and are monomeric. They are absorbed by the microorganisms and have a biocidal effect. These are, for example, 3-iodo-2-propynyl-butyl-carbamate (IPBC), triazoles (propiconazole, tebuconazole) or copper salts.
  • IPBC 3-iodo-2-propynyl-butyl-carbamate
  • IPBC 3-iodo-2-propynyl-butyl-carbamate
  • triazoles propiconazole, tebuconazole
  • copper salts for example, 3-iodo-2-propynyl-butyl-carbamate (IPBC), triazoles (propiconazole, tebuconazole) or copper salts.
  • a disadvantage of these biocidal wood preservatives is that the dimensional stability of wood is not improved in the event of moisture fluctuations.
  • the WO 03/024680 describes a wood preservative comprising a mixture of tall oil with at least 10% by weight of rosin acids, in particular for pressure impregnation of wood, followed by a heating step to at least 100 ° C.
  • the DE 198 29 037 discloses preservatives for wood from montan wax, terpene-containing montan wax fractions, paraffin, optionally hydrocarbon wax, optionally carboxylic acids (stearic acid) and optionally other water-repellent substances with the example of coffee wax.
  • biocidal active ingredient furthermore, copper, chromium and arsenic compounds, aroma, bitter and / or other pest repellents, for example essential oils, may be present as customary.
  • the DE 40 36 508 discloses active ingredients for oily wood preservative formulations directed against wood destroying and wood discoloring fungi.
  • the DE 39 27 108 A1 discloses a microbicidal wood preservative with water-soluble cationic or cationizable microbicidal compounds which are water-insoluble by binding to a rosin acid or its derivative.
  • a microbicidal compound coupled to rosin acid there are mentioned chloroacetamide, quaternary ammonium compounds such as substituted dimethylbenzylammonium salt, eg, alkyldimethylbenzylammonium chloride.
  • the WO 98/24603 relates to the use of boric acid triesters of hydrophobic hydrocarbon acids having from 5 to 60 carbon atoms, which may optionally be hydroxy-, carboxy- and / or amino-functionalized, for the hydrophobization of wood.
  • the DE 40 20 495 A1 uses isocyanate-modified linseed oil mixed with a siccative in a solvent of aliphatic, hydrocarbon-free liquids in admixture with a finely divided paraffin, wax or polyolefin dispersion.
  • N, N-diaryl-N'-aryl-N '- (trihalomethylthio) sulfamide may be added as biocide.
  • the US 4,360,385 discloses wood treatment compositions comprising a hydrophobic substance from the group of ⁇ -olefins or paraffin fractions, as well as a preservative from the group of wood preservatives, alkyd resins, quaternary ammonium halides, sulfates and hydroxides, as well as alkyl and aryl esters of phosphorus-containing and sulfur-containing acids in mixture with organic solvent.
  • JP 01174404 A describes an agent for treating wood with epoxidized higher fatty acid esters obtainable by reacting epoxidized linseed oil with PT-octylphenol and formalin in acid. By impregnating wood and drying at 140 ° C, the wood is first modified by the epoxidized fatty acid ester, which then polymerize and cure epoxidized fatty acid esters and novolac resin.
  • the WO 03/024681 A1 relates to a wood preservative based on fatty acids and / or resin acids which are at least partially saponified, with the counterion being calcium and / or aluminum.
  • compositions according to the invention for the treatment of lignocellulosic materials should have a reduced toxic effect on the environment, i. e.g. a lower ecotoxicity outside the treated lignocellulosic material.
  • a further object of the invention is to provide chipboard and other wood-based materials, including, for the purposes of the invention, also wood-plastic composites which have better resistance to moisture variations, in particular reduced swellability, preferably with substantially constant or improved strength properties in comparison with conventional chipboard
  • Another object of the present invention is wood - plastic -.
  • WPCs composite materials
  • Such composite materials contain, in addition to wood particles, a synthetic polymer, for example a thermoplastic such as polyethylene, polypropylene, other polyolefins, polystyrene, polyvinyl, polyvinyl chloride or copolymers thereof, alternatively thermosets, for example polyamides, alkyd or phenolic resins.
  • the invention provides protective agents for the treatment of lignocellulosic materials, in particular wood, based on hydrocarbons in the form of functionalized reactive fatty acid derivatives and / or paraffin, which is dispersed by protective colloids as a dispersion or emulsion and in admixture with zirconium and / or or aluminum salt in aqueous mixture. Furthermore, the present invention provides the use of the protective agents according to the invention for the treatment of wood and wood-based materials.
  • lignocellulosic materials are, for example, solid wood and wood-based materials, such as chipboard, medium-density fiberboard, Oriented Strand Boards (OSB), paper, cardboard, lignocellulose-based insulation boards, plywood, veneers and packaging material containing biodegradable compounds, especially wood.
  • solid wood and wood-based materials such as chipboard, medium-density fiberboard, Oriented Strand Boards (OSB), paper, cardboard, lignocellulose-based insulation boards, plywood, veneers and packaging material containing biodegradable compounds, especially wood.
  • OSB Oriented Strand Boards
  • the protective agent for lignocellulosic materials according to the invention can be applied to the lignocellulosic material by impregnation, for example under applied vacuum or pressure, dipping or brushing.
  • the present invention provides protective agents based on fatty acid derivatives and paraffin, which are particularly suitable for protecting lignocellulosic materials, since they can be applied or impregnated in aqueous and / or solvent-containing composition or from supercritical CO 2 on the lignocellulosic material On the other hand, they bind with the lignocellulosic material, which can be attributed to physical interactions and, as the inventors believe, to chemical interactions.
  • the lignocellulosic materials according to the invention a durable protection against attack by microorganisms, especially against molds, and in combination with the fungicidal effect increased dimensional stability in the event of moisture fluctuations.
  • the protective agents of the invention may be used as aqueous preparations, i. aqueous mixtures, or dispersion / emulsion of hydrocarbons, which are reinforced by derivatization or by mixing with metal cations for the treatment of wood and wood-based materials in their hydrophobizing and fungi-action against conventional water repellents.
  • the hydrocarbon portion of the protecting agent i. the fatty acid residue or the paraffin, is preferably straight-chain with 8 to 50, preferably up to 40 or up to 20 carbon atoms and unsaturated, preferably saturated.
  • the hydrocarbon moiety may be substituted, preferably derivatized with branched, preferably straight-chain, saturated or unsaturated hydrocarbon chains.
  • the derivatization of the hydrocarbon moiety takes place in such a way that the protective agent has groups which can react with lignocellulose, in particular reactive groups which can react with hydroxyl groups.
  • reactive groups include, for example, organic acid, N-methylol, ketene, ketene dimer, (cyclic or non-cyclic) anhydride and / or isocyanate groups, the latter preferably being blocked by blocking groups, e.g. oximblockiert.
  • the protective agents therefore contain catalysts which promote the reaction of the derivatized hydrocarbon moiety with lignocellulosic hydroxyl groups.
  • Catalysts in particular for protective agents which contain reactive N-methylol groups, are metal salts from the group of metal halides, metal sulfates, metal nitrates, metal tetrafluoroborates, metal phosphates or mixtures thereof. Examples are Magnesium chloride, zinc chloride, lithium chloride, lithium bromide, boron trifluoride, aluminum chloride, aluminum sulfate, zinc nitrate, sodium tetrafluoroborate or mixtures thereof.
  • Suitable catalysts are also ammonium salts from the group of ammonium chloride, ammonium sulfate, ammonium oxalate, diammonium phosphate or mixtures thereof.
  • Other suitable catalysts are organic or inorganic acids, for example maleic acid, formic acid, citric acid, tartaric acid, oxalic acid, p-toluenesulfonic acid, hydrochloric acid, sulfuric acid, boric acid or mixtures thereof.
  • Magnesium chloride, zinc chloride, magnesium sulfate, magnesium nitrate and / or aluminum sulfate are preferably used, particularly preferably magnesium chloride.
  • This catalyst is used in a concentration of 0.1 to 10 wt .-%, preferably 0.2 to 8 wt .-%, particularly preferably 0.3 to 5 wt .-%, based on the protective agent.
  • paraffins are used in admixture with zirconium and / or aluminum salt in an aqueous mixture.
  • the aqueous mixture of paraffin is a finely divided suspension or a colloidal mixture of paraffin in water.
  • emulsion emulsifiers or detergents can be used, but preferably protective colloids. Because protective colloids make it possible to break the emulsion or the colloidal fine distribution on the wood or wood-based material and to deposit the paraffin.
  • the protective colloids In contrast to emulsifiers or detergents, the protective colloids have a lower tendency to leach, so that the hydrophobing and antiperspirant effect of the paraffin is more stable or durable.
  • the addition of zirconium or aluminum salts to the aqueous paraffin mixture leads, compared to the use of paraffin alone, to an increase in the hydrophobing effect.
  • the content of the aqueous paraffin mixture of aluminum and / or zirconium salt also leads to an increase in the fixation of the hydrocarbon and thus to increase the resistance to leaching of hydrocarbons, e.g. Paraffin in wood and wood-based material.
  • this effect of aluminum and / or zirconium salt is attributed to the formation of hydrogen bonds between hydrocarbon and wood or wood content in the wood material.
  • aluminum and / or zirconium salts in proportions of 0.01 to 3 wt .-%, preferably 0.1 to 1 wt .-%, more preferably used to 0.3 wt .-% of the emulsion.
  • Preferred salts are aluminum hydroxide, aluminum phosphate, aluminum acetate and formate, Al 2 O 3 in formic or acetic acid or aluminum chloride, alum, zirconium chloride, oxychloride, acetate and zirconium sulfate.
  • the protective agents according to the invention are obtainable inter alia by reaction of fatty acids with melamine, which is at least partially reacted with formaldehyde, wherein the reaction product can optionally be reacted with methanol.
  • fatty acids with melamine, which is at least partially reacted with formaldehyde, wherein the reaction product can optionally be reacted with methanol.
  • formaldehyde formaldehyde
  • fatty acid amides and / or fatty alcohols instead of fatty acids.
  • protecting agents of the invention are obtainable by reacting fatty acid amides with formaldehyde or by reacting fatty acid-urea compounds with formaldehyde.
  • protecting agents according to the invention are alkyl ketene dimers, which are shown below by the example of a compound having two saturated hydrocarbon chains, but which can also have other chain lengths, for example C 12 to C 18.
  • protective agents according to the invention are alkenylsuccinic anhydrides, an example of which is shown below with a saturated C 13 alkyl radical.
  • This protecting agent may be replaced by formal replacement of the saturated H 27 C 13 hydrocarbon chain with a saturated or partially unsaturated hydrocarbon chain of 4 to 18 carbon atoms.
  • ASA Alkenyl succinic anhydride
  • protecting agents according to the invention of N-methylol compounds can be formed, which are accessible for example by reaction of fatty acid amides with formaldehyde, hereinafter exemplified for stearamide and formaldehyde.
  • Fatty acid amides e.g. stearamide:
  • Fatty acid e.g. stearylurea:
  • the protective agent contains hydrocarbons which are obtainable by reacting fatty acids and / or fatty acid amides and / or fatty alcohols with N-methylolated amino compounds, preferably melamine which is at least partially reacted with formaldehyde, in accordance with the reaction scheme shown by way of example below:
  • reaction products with N-methylolated amino compounds e.g. Melamine, oligomeric or polymerize to form oligomers or polymers.
  • the formation of these oligomers or polymers preferably proceeds autocatalytically and can be enhanced by the addition of bifunctionalized compounds which act as crosslinkers, e.g. C1 to C8 diaminoalkanes and / or urea.
  • reaction products with N-methylolated amino compounds e.g. Melamine
  • N-methylolated amino compounds e.g. Melamine
  • formaldehyde is substoichiometrically added to the free amino groups formaldehyde, so that the reaction products still have at least one free amino group, which react with the added fatty acids and / or fatty acid anhydrides or chlorides.
  • amide bonds are also formed between N-methylolated amino compound and fatty acid residue.
  • lignocellulosic material is treated with the reaction components of the protective agent, eg mixtures of the fatty acid reacted hydrocarbon with the derivatizing component of the fatty acid, for example melamine, which is at least partially N-methylolated by reaction with formaldehyde, or fatty acid amide or Fatty acid urea with formaldehyde as derivatizing ingredient.
  • the mixtures of the reaction components of the protective agent are used to treat the lignocellulosic material in combination with a catalyst which catalyzes the reaction with the lignocellulosic hydroxyl groups.
  • metal salts from the group of metal halides, metal sulfates, metal nitrates, metal tetrafluoroborates, metal phosphates or mixtures thereof.
  • metal halides metal sulfates, metal nitrates, metal tetrafluoroborates, metal phosphates or mixtures thereof.
  • examples are magnesium chloride, zinc chloride, lithium chloride, lithium bromide, boron trifluoride, aluminum chloride, aluminum sulfate, zinc nitrate, sodium tetrafluoroborate or mixtures thereof.
  • Suitable catalysts are also ammonium salts from the group of ammonium chloride, ammonium sulfate, ammonium oxalate, diammonium phosphate or mixtures thereof.
  • Suitable catalysts are organic or inorganic acids, for example maleic acid, formic acid, citric acid, tartaric acid, oxalic acid, p-toluenesulfonic acid, hydrochloric acid, sulfuric acid, boric acid or mixtures thereof.
  • organic or inorganic acids for example maleic acid, formic acid, citric acid, tartaric acid, oxalic acid, p-toluenesulfonic acid, hydrochloric acid, sulfuric acid, boric acid or mixtures thereof.
  • magnesium chloride, zinc chloride, magnesium sulfate, aluminum sulfate are used, more preferably magnesium chloride.
  • a first variant of the treatment of lignocellulosic material this is treated with a mixture of a fatty acid amide with formaldehyde and catalyst, in a second variant with a mixture of a fatty acid urea compound with formaldehyde and in a third variant with a mixture of melamine, formaldehyde, catalyst and fatty acid, fatty amine, fatty amide and / or fatty alcohol.
  • an aqueous emulsion of a non-derivatized hydrocarbon with zirconium salt is used, which as a particularly preferred hydrocarbon is a paraffin fraction having a melting point from 50 to 60 ° C, a minor proportion of liquid at room temperature paraffin fraction, zirconium and / or aluminum salt and effective as emulsifiers protective colloids.
  • an aqueous formulation containing a basic aluminum salt in aqueous emulsion besides paraffin having a melting point of 40 to 80 ° C and a lower proportion of a liquid paraffin fraction at room temperature can be used.
  • paraffin which may generally have a melting point of about 40-80 ° C, especially 50-60 ° C
  • wax, ceresin, lanolin, Japan wax, Vaselineöle, artificial or natural resins and latex can be used, likewise in aqueous emulsion in combination with a zirconium and / or aluminum salt.
  • mixtures according to the invention can be used instead of the aqueous mixture in a mixture with water or completely in organic solvent or supercritical CO 2 for the treatment of lignocellulosic materials.
  • the lignocellulosic material in particular wood, treated with the protective agent and / or its reaction components and then dried at temperatures up to 200 ° C.
  • the protective agent in addition to fatty acid derivative as a reactive hydrocarbon derivative additionally contains unfunctionalized hydrocarbons in Mixture with aluminum and / or zirconium salts, for example paraffin, waxes or other hydrophobing agents.
  • the wood particles of these materials are likewise treated with the protective agent according to the invention and then bonded in a known manner or introduced into a mixture with synthetic polymers.
  • a coupling component may be added to the mixture with adhesive or synthetic polymer, preferably maleic anhydride, more preferably by reaction with maleic anhydride modified polypropylene (MAPP).
  • Particleboard produced with wood particles treated with a preservative according to the invention shows a higher resistance to moisture or a lower water absorption and swelling, while the strength properties, in particular the tensile strength, are only insignificantly influenced. Also in comparison with chipboard whose wood particles were treated before bonding with paraffin alone instead of the protective agent according to the invention, the particle board or WPCs according to the invention have a higher resistance to moisture fluctuations, improved resistance to fungal attack and improved strength properties, in particular tensile strength.
  • Suitable protective colloids are, for example, glues, gelatin, cellulose ethers, e.g. Tylose, Cellapret, gums, mucilages, starch and dextrin, but preferably glue.
  • Suitable emulsifiers include, inter alia, methoxylated or ethoxylated C 12 -C 20 -hydrocarbons, for example methoxylated or ethoxylated fatty acids, in particular ethoxylated stearic acid.
  • protective colloids or substances used as emulsifier do not form precipitates with the aluminum or zirconium salts.
  • Further compounds which can be used as emulsifier are monoesters of higher molecular weight fatty acids with polyvalent alcohols, for example polyethoxylated vegetable oil (available under the name Emulphor), alkylphenol ethoxylates (available under the name Igepal), diglycol stearate or higher aliphatic or hydroaromatic alcohols.
  • emulsifier salts of higher molecular weight aliphatic and aromatic sulfonic acids for example Suitable alkylnaphthalenesulfonic acids, as well as known under the name Lamepon A fatty acid (eg oleic acid) protein (eg collagen or oligopeptides from collagen) condensation product or the collagen surfactant Lamepon F.
  • Example 1 Preparation of a protective agent for lignocellulosic materials of fatty acid-substituted cationic N-methylol compounds
  • a fatty acid-substituted cationic N-methylol compound (melamine stearyl ether) having an addition of the Lewis acid aluminum sulfate of 0.3% by weight was used as a catalyst to obtain an aqueous composition having a concentration of 5% by weight.
  • lignocellulosic material wood samples are dipped in the aqueous emulsion, with times of 1 to 48 hours producing satisfactory results. It is then dried and fixed at a temperature of 120 ° C in a drying oven. It can be shown that the protective agent according to the invention leads to a reduction in water absorption in the subsequent dip test and a superficial hydrophobing is achieved.
  • Example 2 Preparation of a protective agent for lignocellulosic materials based on an alkyldiketene dimer
  • the alkyl (C 16 H 33 ) diketendimer is mixed into 5% by weight in water.
  • Wood samples can be treated by immersion in the emulsion for 1 to 48 h in this emulsion, then dried and fixed at 120 ° C in a drying oven.
  • Example 1 can be a reduction in water absorption in the immersion test, as well as a superficial hydrophobing achieve.
  • Example 3 Preparation of a protective agent for lignocellulosic material based on an alkenyl succinic anhydride
  • alkenyl succinic anhydride Alkenylsuccinic anhydride added to 5 wt .-% in water.
  • Examples 1 and 2 can be shown that a dip treatment of wood and subsequent fixation at about 120 ° C to reduce water absorption in the subsequent immersion test and surface hydrophobization leads.
  • catalysts are added to the aqueous mixture of the alkyl diketene dimer, which may for example be selected from Lewis acids, preferably aluminum sulfate, trichloride and magnesium chloride.
  • Example 4 Reduction of water absorption of wood by impregnation with protective agent according to the invention
  • Beech wood samples measuring 5 ⁇ 10 ⁇ 30 mm were fully saturated in conventional vacuum pressure impregnation (120 mbar, 12 bar) with emulsions according to Examples 1 to 3 within three hours.
  • conventional vacuum pressure impregnation 120 mbar, 12 bar
  • the preservatives are hardened and fixed in the wood.
  • the reduction in water uptake was determined by immersing the impregnated beech wood samples in the immersion test for 96 hours followed by vacuum for the alkyl diketendimer protectant of Example 2, each with different concentrations of the protectant in the impregnation solution shown in FIG.
  • the water absorption in percent of the total weight is shown in Figure 1, which treated with water instead of protective agent suspension treated beech wood sample shows the highest water absorption as a comparison.
  • the water absorption was determined by weight determination of the beech wood samples.
  • N-methylolated fatty acid here exemplified stearic acid
  • stearic acid a derivatized hydrocarbon N-methylolated fatty acid
  • impregnation of beech wood samples with a fatty acid substituted (stearic) cationic N-methylol compound water-based in the specified in Figure 2 wt .-% in aqueous composition was followed by heat treatment at 40 ° C to 120 ° C for 4 days in the oven also a reduction the water absorption capacity of the beech wood samples.
  • the measurement results for 96 hours immersion test with subsequent vacuum are shown in FIG. 2 and show that the water absorption increases with increasing content of the Impregnating solution of inventive protective agent, the water absorption capacity of the lignocellulosic material decreases.
  • Example 5 Increasing the resistance of lignocellulosic material to wood-degrading fungi
  • Wood samples with the dimensions 5 ⁇ 10 ⁇ 30 mm were treated in an aqueous protective agent suspension according to Example 1, namely in vacuum pressure impregnation (120 mbar, 12 bar) for 3 hours with a 9 wt. % suspension saturated, then treated with increasing temperature of 40 ° C to 120 ° C for 4 days in a drying oven.
  • FIG. 3 clearly show, with the example of beech wood pine wood, that degradation of the lignocellulosic material by wood-destroying fungi is greatly reduced when impregnated with the protective agent.
  • Example 6 Increasing the resistance to fungal fungi by preservatives
  • Platelets of various types of wood were treated by vacuum pressure impregnation (120 mbar, 12 bar) with an aqueous emulsion according to Example 1 with a content of 3 or 9% by weight of the protective agent. Subsequently, the plates were heat-treated at 40 ° C for 72 hours and at 120 ° C for 16 hours. In this heat treatment, water was first dried and carried out at higher temperatures, a reaction of the protective agent with the lignocellulosic material. Subsequently, the samples were conditioned after sterilization for about 2 weeks at 20 ° C and 65% relative humidity.
  • the platelets were placed in agar dishes colonized with Aureobasidium pullulans .
  • a second inoculation of the platelets was done by placing a small round slice of agar, also colonized with Aureobasidium pullulans , on the top surface of the wood sample.
  • Each agar dish contained two treated wood samples as well as two control samples which had been treated in parallel with water instead of the preservative.
  • the infestation of the wood samples was evaluated on an arbitrary scale from 0 (no infestation) to 4 (heavily stained).
  • FIG. 5 shows photographs of the wood chips which had been treated with a 9% strength by weight suspension of the protective agent according to Example 1 after the subsequent incubation with Aureobasidium pullulans over 6 weeks.
  • Example 7 Increase of the weathering resistance of lignocellulosic material
  • lignocellulosic material pine wood samples were treated by vacuum pressure impregnation (120 mbar, 12 bar) with an aqueous emulsion according to Example 1 with 9 wt.% Protective agent. Thereafter, the samples were thermally treated at 40 ° C for 72 hours and at 120 ° C for 16 hours, whereby water was dried off and the protective agent reacted with the lignocellulosic material.
  • FIG. 6 are photographs of wood samples before and after accelerated weathering, namely wood samples treated in the first line with control samples, in the second row with water treated control samples, where column A the surfaces before weathering shows column B after 24 hours condensation with 24 subcycles (2.5 h QUV + 0.5 h spray), column C after 24 hours condensation + 30 subcycles (2.5 h QUV + 0.5 h spray), and Column D after 24 h condensation + 48 subcycles (2.5 h QUV + 0.5 h spray).
  • FIG. 6 clearly show that lignocellulosic material obtains a higher weathering resistance by treatment with a protective agent according to the invention, which is manifested inter alia in the reduced cracking and the less graying (without added microorganisms).
  • Example 8 Reduction of the water absorption of wood by impregnation with protective agent according to the invention based on an emulsion of paraffin with aluminum salt
  • Example 4 beech wood samples were fully soaked with an emulsion protection agent according to the invention, using as protective agent an aqueous emulsion of paraffin (melting point 50-60 ° C.) with aluminum salt (available under the name Hydrophobol APK from CIBA).
  • an aqueous emulsion of paraffin melting point 50-60 ° C.
  • aluminum salt available under the name Hydrophobol APK from CIBA.
  • Example 9 Increasing resistance to wood-degrading fungi
  • Example 5 wood samples were treated with an emulsion of 9 wt .-% paraffin (melting point 50 - 60 ° C) with aluminum salt in aqueous emulsion (Hydrophobol APK).
  • the uptake of the protective agent after drying and the loss of mass of wood samples after 16 weeks in contact Coniophora souna (pine) and Trametes versicolor (beech) are shown in Figure 8 under A) for pine wood and B) for beech wood.
  • As a control wood was used in each case, which had been treated only with water instead of the protective agent.
  • Example 10 Increase of resistance to fungal fungi by paraffin and aluminum salt protectants
  • Example 6 platelets of various types of wood were treated with an aqueous paraffin emulsion of 9 and 3 wt .-% paraffin, melting point 50 - 60 ° C, 1 wt .-% aluminum hydroxide (hydrophobol APK) in aqueous emulsion.
  • the heat treatment was carried out according to Example 6.
  • the score on the arbitrary scale from 1 (low infestation) to 4 (maximum faded) are shown in Figure 9 for the different species of wood.
  • this protection agent according to the invention drastically reduces the infestation by fading fungi.
  • top layer and middle layer chips consisting of a mixture of 85% spruce wood and 15% beech wood were mixed with 1) paraffin (melting point 50-60 ° C.) with aluminum salt addition (hydrophobol APK), 2) fatty acid-modified melamine according to Example 1 in admixture with paraffin (1: 1) and 3) Alkyldiketendimer according to Example 2 each suspended to 3 wt .-% in aqueous emulsion.
  • the chips were kept in the emulsion in a vacuum oven for about one hour at a vacuum of about 40 mbar, then the impregnating emulsion was filtered under light vacuum and the chips in the oven for 12 hours at 60 ° C predryed, finally at 110 ° C dried for 2 hours. Reference plates were made from untreated chips for comparison.
  • the chips were made into V20-type chipboards having a desired thickness of 20 mm and a bulk density of 0.7 g / cm 3 .
  • the glue used was urea-formaldehyde resin (UF resin Kaurit 350, BASF, Ludwigshafen), which has a dry matter content of 66.5 ⁇ 1%, a pH of 7.5-9.5 at 20 ° C., a density of 1.28-1.3 g / cm 3 (20 ° C) and an ex works viscosity of 350 to 600 mPas.
  • a motorized gluing drum with a volume of approx. 0.154 m 3 with belt drive was used for the gluing of the surface layer and middle layer chips.
  • the gluing was carried out with a loading gun (Walter Pilot) with a 1.0 mm nozzle.
  • a one-level bottom piston press (Si Zikamp) with a maximum hydraulic working pressure of 283 bar was used.
  • the plate-shaped press punches had a format of 600 x 800 x 80 mm and could be heated to 250 ° C.
  • the chip moisture of the chips used for plate production was below 5%, the desired moisture after gluing 12% for the top layer and 9% for the middle layer.
  • the initial weight was about 850 g for the cover layer and 1300 g for the middle layer for the desired bulk density of 0.7 g / cm 3 .
  • Leim fleets were prepared by stirring with a stirrer (Jahnke and Kunkel, type RE162).
  • the gluing in the gluing drum after the circulation process was carried out by spraying the glue through a nozzle projecting into the drum.
  • the scattering was carried out by means of a scattering mold (300 x 500 mm) on a press plate, which was provided with non-stick paper. After sprinkling the top layer chips on the press plate, the middle layer chips were sprinkled, then the top layer of cover shavings. Before machine pressing, the chip cake had to be precompressed manually.
  • the sizing liquor had the following composition: Kaurit 350 to 10% by weight for top layer, 8.5% by weight for middle layer, ammonium sulfate to 0.5% by weight for top layer, to 1% by weight for middle layer.
  • Kaurit 350 to 10% by weight for top layer 8.5% by weight for middle layer
  • ammonium sulfate 0.5% by weight for top layer
  • 1% by weight for middle layer For pressing, a pressure of 220 bar at 195 ° C over 4 min was used.
  • Composite materials according to the invention which are characterized by the content of the wood component in a protective agent according to the invention, were prepared from spruce wood chips treated according to the invention and polypropylene.
  • 500 g spruce wood chips (Lignocell P super, Rettenmaier company) were in each 5 L of a 0.3 wt .-%, 0.75 wt .-% or 1.5 wt .-% emulsion of a paraffin (melting point 52 to 54 ° C) with aluminum salt (series P), alternatively with a fatty acid-modified melamine (series F) and shaken horizontally for 2 hours at room temperature, then filtered off.
  • a paraffin melting point 52 to 54 ° C
  • aluminum salt series P
  • series F a fatty acid-modified melamine
  • the impregnated chips were dried for 72 hours at 25 ° C, 60 ° C and 103 ° C. Subsequently, the chips were conditioned at 20 ° C and 65% relative humidity to constant weight and then determined the weight. An aliquot was dried at 103 ° C and weighed to determine dry weight or moisture. For comparison, chips were treated only in water (control) instead of the protective agent.
  • the composite had a chip content of 60% with 40% polypropylene.
  • a mechanical mixture of the treated (P or F) and untreated (control) spruce wood chips with polypropylene was obtained by mechanical mixing with granulated polypropylene (polypropylene-polyethylene copolymer, randomly distributed, melt flow index to ISO 1133 1.8 ⁇ 0.4 g / 10 min at 230 ° C / 2.16 kg) in the rolling mill or roll mill and then pressed.
  • the mechanical properties were determined according to ISO 180 (notched impact strength), ISO 527-2 (tensile strength) and ISO 1183-1 (density).
  • the water retention of the composite was determined by dipping the WPCs over 1 to 14 d compared to the control. The measured values are shown in Table 2 below.
  • the measured strength values show only insignificant changes compared to the control with untreated chips for both preservatives according to the invention, while the values of water retention show that this is markedly reduced by the protective agents according to the invention.
  • the composite materials whose wood content has been treated with protective agent according to the invention an improved resistance to moisture, especially against liquid water.

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Forests & Forestry (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical And Physical Treatments For Wood And The Like (AREA)
EP20060112951 2005-04-22 2006-04-24 Produit à base d'acides gras et de dérivés paraffiniques pour la protection des matériaux lignocellulosiques Not-in-force EP1716995B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP20060112951 EP1716995B1 (fr) 2005-04-22 2006-04-24 Produit à base d'acides gras et de dérivés paraffiniques pour la protection des matériaux lignocellulosiques

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP05103311 2005-04-22
EP20060112951 EP1716995B1 (fr) 2005-04-22 2006-04-24 Produit à base d'acides gras et de dérivés paraffiniques pour la protection des matériaux lignocellulosiques

Publications (3)

Publication Number Publication Date
EP1716995A2 true EP1716995A2 (fr) 2006-11-02
EP1716995A3 EP1716995A3 (fr) 2007-07-04
EP1716995B1 EP1716995B1 (fr) 2009-02-25

Family

ID=36758634

Family Applications (1)

Application Number Title Priority Date Filing Date
EP20060112951 Not-in-force EP1716995B1 (fr) 2005-04-22 2006-04-24 Produit à base d'acides gras et de dérivés paraffiniques pour la protection des matériaux lignocellulosiques

Country Status (1)

Country Link
EP (1) EP1716995B1 (fr)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008028183A1 (fr) * 2006-09-01 2008-03-06 Wisconsin Alumni Research Foundation Procédé de production d'un panneau de fibres de moyenne densité
WO2009004110A1 (fr) * 2007-07-05 2009-01-08 Bio-Teho Oy Composition pour traiter des matériaux, procédé de traitement des matériaux et matériaux traités avec la composition
WO2009156594A1 (fr) * 2008-06-27 2009-12-30 Dynea Oy Procédé de traitement d’un panneau de bois
WO2013083110A1 (fr) * 2011-12-05 2013-06-13 Guido Radde Liquide d'imprégnation pour rendre déperlant du matériau de type papier et des surfaces textiles et utilisation associée
US8771551B2 (en) 2008-06-06 2014-07-08 Metsäliitto Osuuskunta Method of treating wood
DE102014009884A1 (de) * 2014-07-04 2016-01-07 Fritz Egger Gmbh & Co. Og Verfahren zur Herstellung einer Faserplatte
CN111037700A (zh) * 2014-11-06 2020-04-21 地板技术有限公司 地板嵌板、地板嵌板的应用和制造本质材料板的方法
WO2020151104A1 (fr) * 2019-01-23 2020-07-30 湖南桃花江竹材科技股份有限公司 Traverse de bambou assemblée et procédé de préparation associé
CN114786897A (zh) * 2019-12-13 2022-07-22 有机木材公司 新型木材保护方法和用该方法生产的木材产品

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102008032274B4 (de) * 2008-07-09 2013-01-03 Witex Flooring Products Gmbh Verfahren zur Herstellung von Bauplatten
DE102011018213A1 (de) 2011-04-20 2012-10-25 Svt Gmbh Rohrkupplung in Form eines Drehgelenks eines Verladearms

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE921051C (de) 1952-01-18 1954-12-06 Basf Ag Verfahren zur Herstellung von Formkoerpern aus zerkleinertem Holz
DE1492507A1 (de) 1965-11-19 1969-05-22 Novopan Gmbh Verfahren zur Verminderung der Quellung bei Holzwerkstoffen
JPS63176101A (ja) 1987-01-17 1988-07-20 トキワ木材工業株式会社 木材の処理方法
GB2200917A (en) 1987-01-26 1988-08-17 Okura Industrial Co Ltd Process for producing wood-based mouldings of plastic character
DE4036508A1 (de) 1990-01-02 1991-07-04 Bitterfeld Wolfen Chemie Neue oelige holzschutzmittel
JPH0470302A (ja) 1990-06-30 1992-03-05 Arakawa Chem Ind Co Ltd 改質木材の製造方法
DE19829037A1 (de) 1998-06-30 2000-01-05 Romonta Gmbh Konservierungsmittel für Holz
WO2001023154A1 (fr) 1999-09-30 2001-04-05 Valtion Teknillinen Tutkimuskeskus Procede de protection du bois
DE10048197A1 (de) 1999-09-30 2001-07-19 Yamaha Corp Modifizierungverfahren für Holzelemente
WO2003024680A1 (fr) 2001-09-14 2003-03-27 Bengt Carlsson Agent de preservation du bois contenant du tall-oil brut
WO2005009700A1 (fr) 2003-07-25 2005-02-03 Stora Enso Oyj Traitement de bois thermo-modifie

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE921051C (de) 1952-01-18 1954-12-06 Basf Ag Verfahren zur Herstellung von Formkoerpern aus zerkleinertem Holz
DE1492507A1 (de) 1965-11-19 1969-05-22 Novopan Gmbh Verfahren zur Verminderung der Quellung bei Holzwerkstoffen
JPS63176101A (ja) 1987-01-17 1988-07-20 トキワ木材工業株式会社 木材の処理方法
GB2200917A (en) 1987-01-26 1988-08-17 Okura Industrial Co Ltd Process for producing wood-based mouldings of plastic character
DE4036508A1 (de) 1990-01-02 1991-07-04 Bitterfeld Wolfen Chemie Neue oelige holzschutzmittel
JPH0470302A (ja) 1990-06-30 1992-03-05 Arakawa Chem Ind Co Ltd 改質木材の製造方法
DE19829037A1 (de) 1998-06-30 2000-01-05 Romonta Gmbh Konservierungsmittel für Holz
WO2001023154A1 (fr) 1999-09-30 2001-04-05 Valtion Teknillinen Tutkimuskeskus Procede de protection du bois
DE10048197A1 (de) 1999-09-30 2001-07-19 Yamaha Corp Modifizierungverfahren für Holzelemente
WO2003024680A1 (fr) 2001-09-14 2003-03-27 Bengt Carlsson Agent de preservation du bois contenant du tall-oil brut
WO2005009700A1 (fr) 2003-07-25 2005-02-03 Stora Enso Oyj Traitement de bois thermo-modifie

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8123904B2 (en) 2006-09-01 2012-02-28 Wisconsin Alumni Research Foundation Method of making medium density fiberboard
WO2008028183A1 (fr) * 2006-09-01 2008-03-06 Wisconsin Alumni Research Foundation Procédé de production d'un panneau de fibres de moyenne densité
WO2009004110A1 (fr) * 2007-07-05 2009-01-08 Bio-Teho Oy Composition pour traiter des matériaux, procédé de traitement des matériaux et matériaux traités avec la composition
US8771551B2 (en) 2008-06-06 2014-07-08 Metsäliitto Osuuskunta Method of treating wood
EA024957B1 (ru) * 2008-06-27 2016-11-30 Серфактор Джермани Гмбх Способ обработки древесной плиты
WO2009156594A1 (fr) * 2008-06-27 2009-12-30 Dynea Oy Procédé de traitement d’un panneau de bois
US10335977B2 (en) 2008-06-27 2019-07-02 Surfactor Germany Gmbh Method for treating a wood board
WO2013083110A1 (fr) * 2011-12-05 2013-06-13 Guido Radde Liquide d'imprégnation pour rendre déperlant du matériau de type papier et des surfaces textiles et utilisation associée
DE102014009884A1 (de) * 2014-07-04 2016-01-07 Fritz Egger Gmbh & Co. Og Verfahren zur Herstellung einer Faserplatte
CN111037700A (zh) * 2014-11-06 2020-04-21 地板技术有限公司 地板嵌板、地板嵌板的应用和制造本质材料板的方法
US11072087B2 (en) 2014-11-06 2021-07-27 Flooring Technologies Ltd. Wooden material panel, in particular in the form of a wood-plastic composite material, and a method for producing the same
CN111037700B (zh) * 2014-11-06 2022-04-15 地板技术有限公司 地板嵌板、地板嵌板的应用和制造本质材料板的方法
WO2020151104A1 (fr) * 2019-01-23 2020-07-30 湖南桃花江竹材科技股份有限公司 Traverse de bambou assemblée et procédé de préparation associé
US12203224B2 (en) 2019-01-23 2025-01-21 Hunan Taohuajiang Bamboo Science & Technology Co., Ltd. Assembled bamboo sleeper and preparation method thereof
CN114786897A (zh) * 2019-12-13 2022-07-22 有机木材公司 新型木材保护方法和用该方法生产的木材产品
CN114786897B (zh) * 2019-12-13 2024-03-12 有机木材公司 木材保护方法和用该方法生产的木材产品

Also Published As

Publication number Publication date
EP1716995A3 (fr) 2007-07-04
EP1716995B1 (fr) 2009-02-25

Similar Documents

Publication Publication Date Title
DE69813010T2 (de) Verfahren zur herstellung von verbundwerkstoff-gegenständen aus zellulose
US6569540B1 (en) Dimensionally stable wood composites and methods for making them
EP2637829B1 (fr) Navires comprenant du bois imprégné et modofié thermiquement ous des matériaux dérivés de tel bois
WO2007082837A1 (fr) Procédé pour réduire l'émission de formaldéhyde de matériaux dérivés du bois
EP1858677A1 (fr) Production de corps moules en materiaux finements divises a base de lignocellulose
AU2001251468A1 (en) Dimensionally stable wood composites and methods for making them
EP1716995B1 (fr) Produit à base d'acides gras et de dérivés paraffiniques pour la protection des matériaux lignocellulosiques
US6811731B2 (en) Methods of incorporating phosphate/borate fire retardant formulations into wood based composite products
DE102008023085A1 (de) Verfahren zur Herstellung von Holzwerkstoffen
US7371787B2 (en) Methods of incorporating treatment agents into wood based composite products
WO2018096074A1 (fr) Procédé pour modifier des produits contenant de la lignocellulose et production de matériaux à base de bois à partir de ceux-ci ainsi que produits contenant de la lignocellulose pouvant ainsi être obtenus
DE1492513A1 (de) Holzbehandlungsmittel
EP0648807B1 (fr) Liant à base de tannin
US4643860A (en) Preservative treated composite wood product
DE3536417C2 (fr)
DE602005004221T2 (de) Verfahren zur Herstellung von Faserformkörpern
CH642907A5 (de) Verfahren zur herstellung einer holzspanplatte sowie die hergestellte holzspanplatte.
WO2006013146A1 (fr) Produit de protection et de traitement du bois
EP1780243B2 (fr) Composition de liant pour matériaux à base de bois
EP3778160B1 (fr) Composition de résine, revêtement de résine, stratifiés et impregnés les contenant, ainsi que leur procédé de fabrication
DE4406825A1 (de) Bindemittel auf der Basis von Tannin
EP1806213B1 (fr) Procédé d'imprégnation de copeaux de bois
DE102005061998A1 (de) Verfahren zur Herstellung modifizierter Furnierwerkstoffe
EP3581629A1 (fr) Résines modifiées à base de formaldéhyde
CH443535A (de) Bindemittelgemisch zum Leimen von Schichtholzmaterial

Legal Events

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

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL BA HR MK YU

RTI1 Title (correction)

Free format text: COMPOSITION BASED ON FATTY ACIDS AND PARAFFIN DERIVATIVES FOR PROTECTING LIGNOCELLULOSIC MATERIALS,

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL BA HR MK YU

17P Request for examination filed

Effective date: 20071206

AKX Designation fees paid

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

RTI1 Title (correction)

Free format text: COMPOSITION BASED ON FATTY ACIDS AND PARAFFIN DERIVATIVES FOR PROTECTING LIGNOCELLULOSIC MATERIALS

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: GERMAN

REF Corresponds to:

Ref document number: 502006002920

Country of ref document: DE

Date of ref document: 20090409

Kind code of ref document: P

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

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090225

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090225

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090225

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090225

NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090225

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090525

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090225

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090625

REG Reference to a national code

Ref country code: IE

Ref legal event code: FD4D

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

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090812

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090225

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090225

Ref country code: IE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090225

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090605

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090225

BERE Be: lapsed

Owner name: GEORG-AUGUST-UNIVERSITAT GOTTINGEN

Effective date: 20090430

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

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090225

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090225

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

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

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

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

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090525

26N No opposition filed

Effective date: 20091126

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

Ref country code: MC

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

Effective date: 20090430

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

Ref country code: BE

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

Effective date: 20090430

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

Ref country code: GB

Payment date: 20100324

Year of fee payment: 5

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

Ref country code: FR

Payment date: 20100506

Year of fee payment: 5

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

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090526

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

Ref country code: CH

Payment date: 20100426

Year of fee payment: 5

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

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090225

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

Ref country code: LU

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

Effective date: 20090424

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

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090826

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

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090225

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

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090225

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

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

Effective date: 20110424

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20111230

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

Ref country code: LI

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

Effective date: 20110430

Ref country code: CH

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

Effective date: 20110430

Ref country code: FR

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

Effective date: 20110502

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

Ref country code: GB

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

Effective date: 20110424

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

Ref country code: AT

Payment date: 20120420

Year of fee payment: 7

REG Reference to a national code

Ref country code: AT

Ref legal event code: MM01

Ref document number: 423661

Country of ref document: AT

Kind code of ref document: T

Effective date: 20130430

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

Ref country code: AT

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

Effective date: 20130430

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

Ref country code: DE

Payment date: 20140616

Year of fee payment: 9

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 502006002920

Country of ref document: DE

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

Ref country code: DE

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

Effective date: 20151103