EP3268190B1 - Procédé de fabrication d'un matériau à base de particules de bois et durcisseur employé dans ledit matériau pour aminoplaste - Google Patents

Procédé de fabrication d'un matériau à base de particules de bois et durcisseur employé dans ledit matériau pour aminoplaste Download PDF

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Publication number
EP3268190B1
EP3268190B1 EP16712254.8A EP16712254A EP3268190B1 EP 3268190 B1 EP3268190 B1 EP 3268190B1 EP 16712254 A EP16712254 A EP 16712254A EP 3268190 B1 EP3268190 B1 EP 3268190B1
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Prior art keywords
wood
acid
hardener
hydrothermal
lignocellulosic material
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German (de)
English (en)
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EP3268190A1 (fr
Inventor
Thomas Kuncinger
Jürgen GIESSWEIN
Theresa KAISERGRUBER
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Fritz Egger GmbH and Co OG
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Fritz Egger GmbH and Co OG
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Priority to PL16712254T priority Critical patent/PL3268190T3/pl
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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
    • 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
    • B27N3/00—Manufacture of substantially flat articles, e.g. boards, from particles or fibres
    • B27N3/002—Manufacture of substantially flat articles, e.g. boards, from particles or fibres characterised by the type of binder
    • 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
    • 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
    • B27N3/00—Manufacture of substantially flat articles, e.g. boards, from particles or fibres
    • B27N3/02—Manufacture of substantially flat articles, e.g. boards, from particles or fibres from particles

Definitions

  • the present invention relates to a process for the production of wood chipboard materials according to claim 1 and the use of a hydrothermally and mechanically digested lignocellulosic material as a hardener for an aminoplast resin according to claim 20.
  • Chip-based materials so-called chipboard materials, consist of shredded wood material that can be pressed into single or multilayer boards.
  • the classification of wood-based panels is usually according to EN 309. Important classification criteria are the production process (extruded or flat pressed), the surface finish (rough, ground, press-coated), the shape and size of the wood materials used (wood chips, wood flakes, wood wafers, wood strands), the panel structure (single-layered or multi-layered) and the intended use.
  • Wood chipboard materials are used, for example, in the construction industry as an insulating, constructive or cladding element, in the furniture industry and as a floor covering.
  • Chipboard materials are produced from finely divided wood material of various types of wood with the addition of natural and / or synthetic binders as well as other substances.
  • cutting processes are used to recover wood particles. Examples of wood particles are wood flakes, wood strands, wood wafers, wood chips and wood chips.
  • the wood particles are usually dried, glued with a composition (glue liquor) containing a binder and arranged in one or different layers (scattering). Finally, the scattered wood material is pressed under pressure and temperature to the respective desired wood chip material.
  • Wood chipboard materials and wood fiber materials as well as their production processes differ fundamentally from each other.
  • Wood fiber materials contain as the main component derived from wood fiber material. This fibrous material is obtained by steaming or cooking (e.g., in a precooker or digester) wood material and by chemical or mechanical disruption (e.g., in a refiner) to single fiber, fiber bundles, or fiber debris.
  • wood chip materials as the main component contain chip material, i. Pieces of wood. The chip material is obtained by merely crushing wood material. A treatment by steaming, cooking or by chemical or mechanical disruption as in the defibering is just not.
  • Binders for the production of wood chip materials may have one or more constituents. Usually consist or contain binders for the production of wood chipboard resins.
  • Synthetic resins are known to those skilled in principle. Synthetic resins are for example in Rompps Chemie-Lexikon, 7th edition, Frankh'sche Verlags Stuttgart, 1973, page 1893 described. An important group of synthetic resins are condensate resins. These harden by condensation reactions, which often Water is split off. Condensate resins include, for example, phenol-formaldehyde resins and aminoplast resins.
  • Aminoplast resins have proved to be particularly practical in connection with the production of wood chip materials.
  • a wood chip material contains at least one aminoplast resin as a binder.
  • Aminoplast resins are typically used in wood chipboard to bond the lignocellulosic parts or wood particles together. In this case, a single aminoplast resin or mixture of different aminoplast resins can be used.
  • Aminoplast resins are known to the person skilled in the art and are described, for example, in US Pat. Ullmanns Enzyklopadie der ischen Chemie ", 4th Edition, Volume 7, p. 403ff , described.
  • Aminoplast resins can be obtained by condensing an amino, imino or amide group-containing component with a carbonyl compound.
  • Common starting materials for aminoplast resins are, for example, urea and / or melamine (as the amino-containing component) and formaldehyde (as the carbonyl compound). In the latter case, the amino-containing component is usually precondensed in a first step with the carbonyl compound to a certain degree.
  • melamine resin or a urea resin may in particular form the main constituents of aminoplast resins.
  • the aminoplast resin can then be crosslinked throughout. Resins formed from urea and formaldehyde are also referred to as urea-formaldehyde resins. Resins formed from melamine and formaldehyde are referred to as melamine-formaldehyde resin.
  • aminoplast resins are mentioned here or elsewhere, they are meant to include aminoplast resin compositions. Aminoplast resins and / or aminoplast resin compositions may also contain water.
  • the curing of synthetic resins, in particular of aminoplast resins, can be carried out, for example, by addition of acidic catalysts.
  • acidic catalysts usually conventional hardeners come into consideration. Hardeners and their reaction to initiate the curing reaction are, for example, in " Wood Materials and Glues: Technology and Influencing Factors "by M. Dunky and P. Niemz, Springer-Verlag, 2013, pages 265-270 described.
  • the typical curing agents for aminoplast resins have in common that they can contain, consist of, or release acid. This acid catalyzes or initiates the curing reaction.
  • Examples of conventional hardeners are strong organic acids, inorganic acids such as sulfuric acid and phosphoric acid, salts which are acidic in water, such as aluminum chloride and aluminum nitrate (also referred to as acid salts), salts formed by reaction with components of the synthetic resin, preferably with formaldehyde to generate an acid (also referred to as acid-generating salts) such as ammonium phosphate, ammonium nitrate, ammonium sulfate and ammonium chloride, and mixtures of the aforementioned substances.
  • inorganic acids such as sulfuric acid and phosphoric acid
  • salts which are acidic in water such as aluminum chloride and aluminum nitrate (also referred to as acid salts)
  • salts formed by reaction with components of the synthetic resin preferably with formaldehyde to generate an acid (also referred to as acid-generating salts) such as ammonium phosphate, ammonium nitrate, ammonium sulfate and ammonium chloride, and mixtures of
  • Formaldehyde may be harmful to human or animal health and may cause allergies, skin, respiratory or eye irritation. In chronic exposure, it may even be carcinogenic. Therefore, it is desirable to produce wood chip materials with a reduced formaldehyde content. This is particularly important with regard to the use of wood chipboard materials for the production of furniture or flooring.
  • JP S60 210406 A describes a process for producing a lignocellulosic floor covering using mixed, dry cellulose fine aggregates, powdered cork material and urea resin.
  • DE 10 2004 010796 A1 relates to a process for reducing formaldehyde release and other organic volatile compounds from lignocellulosic material sheets, in which the material is fiberized into particles and / or fibers by thermo-mechanical pulping, glued, formed into mats, and pressed into a finished sheet, which is characterized by The digestion products of the lignocellulosic material are partially or completely removed by washing.
  • the WO 02/068178 A2 describes a method for bonding laminated products with an aminoplast resin using a curing agent containing acid, an acid salt, and / or an acid-generating salt, as well as a polymer dispersion.
  • the WO 2005/030895 A1 describes binder systems which, besides aminoplast resins and N-functionalized copolymers, also contain at least one acid, an acid salt and / or an acid-generating salt.
  • the WO 2007/012615 A1 describes a curing agent composition for aminoplast resins which comprises an acid, an acidic salt and / or an acid-generating salt and an aminoplast resin dispersion having a residual activity of less than or equal to 100 J / g.
  • a disadvantage of the hardener compositions listed in the prior art is that the curing of the resin is difficult to control when using strong acids as a hardener, since the curing can begin even on addition of the acid.
  • ammonium salts can also be problematic for environmental, economic and safety aspects.
  • ammonium compounds represent a potential emission source for ammonia before, during and after production, and on the other hand, the use of ammonium chloride with regard to recycling and thermal end use must also be critically assessed.
  • ammonium nitrate poses a risk during storage because it is fire-promoting and explosive.
  • further method steps may be carried out before, after and / or between the steps a) to c).
  • Optional steps may be, for example, heating in a preheat container, crushing, storing, mixing, adding further substances, spreading or drying the material used or obtained in steps a) to c).
  • the aminoplast resin used in the process according to the invention may also contain other hardeners
  • the hardener obtained by hydrothermal and mechanical pulping of lignocellulose-containing material is referred to herein as the "first hardener”.
  • the use of the first hardener can be integrated in a simple manner into conventional processes of the wood industry for the production of wood chip materials. No complicated intermediate steps or process interruptions are required.
  • the first hardener used in the invention is available inexpensively and readily available. It is available by hydrothermal and mechanical digestion of lignocellulosic material.
  • the first hardener is obtained from biomass containing lignocellulose. If biomass is mentioned here, then it means a wide variety of plants, plant parts, fruits and mixtures thereof, in particular plant waste from agriculture or the wood industry. The utilization of this biomass for the production of the first hardener is thus an ecologically very relevant advantage, since biomass is a renewable raw material.
  • a particular embodiment of the invention makes it possible to produce plant waste, which is only or no longer suitable for final use, for the production of the first Hardener to use. Overall, an improved cascade use of vegetable raw materials can be achieved by the method according to the invention.
  • the first hardener can be produced in a particularly simple and cost-effective manner.
  • Process for the hydrothermal and mechanical digestion of lignocellulosic Material are known to those skilled in the art, for example from the manufacture of fibreboard.
  • the first hardener can be particularly easily added to the binder composition (glue liquor) and is compatible with it. This is not possible, for example, in the case of the use of strong acids which is sometimes practiced in the prior art, as are used, for example, in the hardening precoating method.
  • the inventive method allows a reduced use of the above-mentioned chemicals.
  • the use according to the invention of the first claim 20 according to claim 20 the demand for free formaldehyde and / or the amount of conventional hardeners, such as. As acid-generating salts are significantly reduced.
  • the first hardener is an environmentally friendly alternative and / or supplement to the conventional hardeners explained above.
  • this surprising effect of the first hardener appears to be explained by one or more acids being released during the hydrothermal and mechanical digestion. This at least one acid seems to contribute to the curing of the resin.
  • the at least one acid released during the hydrothermal and mechanical digestion also appears to be a volatile acid.
  • this acid does not remain or only for a short time in the glue joint of the finished wood chip material. This short residence time of the acid hydrolysis of the glue joint can be largely avoided by this acid.
  • acid may mean a single acid or mixtures of different acids.
  • Important parameters for wood chip materials are swelling, transverse tensile strength and water absorption. Surprisingly, it has been found in practical experiments that these parameters in wood chip materials, which by the Processes according to the invention have been improved.
  • the first hardener according to the invention which is obtainable by hydrothermal and mechanical pulping, reduces the amount of conventional hardener and sometimes even be dispensed with, without causing a deterioration of these parameters
  • the transverse tensile strength of the wood chipboard materials produced can be improved
  • the swelling and / or water absorption of the wood chipboard materials produced can be significantly reduced.
  • Lignocellulose when referring to "lignocellulosic material”, it refers to vegetable matter containing lignocellulose.
  • Lignocellulose according to the invention contains cellulose and / or hemicellulose and lignin.
  • Cellulose is an unbranched polysaccharide consisting of several hundred to ten thousand cellobiose units. These cellobiose units, in turn, consist of two molecules of glucose linked by a 6-1,4-glucosidic bond.
  • Hemicellulose is a collective name for various components of plant cell walls.
  • the hemicelluloses are branched polysaccharides with a lower chain length - usually less than 500 sugar units - which are composed of different sugar monomers.
  • Hemicellulose is composed essentially of various sugar monomers such as glucose, xylose, arabinose, galactose and mannose, which sugars may have acetyl and methyl substituted groups. They have a random, amorphous structure and are readily hydrolyzable.
  • Xylose and arabinose consist for the most part of sugar monomers with five carbon atoms (pentoses).
  • Mannose or galactose consist mainly of sugar monomers with six carbon atoms (hexoses).
  • Ligans are amorphous, irregularly branched aromatic macromolecules, which occur in nature as part of cell walls and there cause the lignification (lignification) of the cell. They are composed of substituted phenylpropanol units, have a lipophilic character and are insoluble in room temperature in neutral solvents such as water. Precursors of lignin are, for example, p-coumaryl alcohol, coniferyl alcohol and sinapyl alcohol. The molecular weights of lignin are usually between 10,000 and 20,000 g / mol.
  • Hydrolysis in the sense of the disclosure may in particular mean the cleavage of a (bio) chemical compound by reaction with water.
  • Wood chip material refers to a variety of materials based on chip, which consist of wood or contain wood.
  • Wood chipboard refers to a product group in the field of wood materials, which are made of wood particles and at least one binder by means of heat and pressure.
  • the latter includes fiberboard such as the medium density (MDF) and high density (HDF) fiberboard
  • Wood chip materials wood used for the manufacture of the fiberboard, wood fibers, fiber bundles or fiber fragments are digested in.
  • MDF medium density
  • HDF high density
  • wood chip materials examples include particleboard, flat-plate, single-layer, multi-layer, lightweight flat, extruded, extruded (ET - Extruded Tubular), Extruded Solid (ES), Plastic-coated Melanin Faced Board (MFB), Chipboard Moldings or Oriented Strand Board (OSB).
  • the division of the chipboard can be done according to DIN EN 312, whereby the chipboard can differ in strength and moisture resistance.
  • OSB boards can be classified according to their use according to EN 300.
  • Such wood chip materials can be further processed, for example, into laminates, floor coverings, countertops, table tops, pallets and / or wooden moldings. Wood chip materials, their manufacture and requirements for these are also in " Taschenbuch der Holztechnik ", A. Wagendies, F. Scholz, Carl Hanser Verlag, 2nd edition, 2012 on pages 143 to 146 described.
  • the wood chip material is a wood chipboard.
  • the wood chip material is a chipboard or OSB board.
  • Practical experiments have shown that the method according to the invention and the described embodiments are particularly suitable for the production of pressed wood chip materials, in particular for the production of chipboard and OSB boards.
  • the wood-chip material or its intermediate or intermediate product, consists essentially of lignocellulose-containing material and binders. "Substantially” here means to 90 wt .-%, 95 wt .-%, 99 wt .-% or 99.9 wt .-%, each based on the total weight of the wood chip material.
  • the wood chip material or its intermediate or intermediate, contains other substances.
  • wetting and / or separating agents can be added for an improved pressing process.
  • antifungal agents or fire retardants may be added.
  • the finished lignocellulosic wood chip materials can meet special requirements. Such requirements have already been mentioned above and are known to the person skilled in the art.
  • such further substances in the inventive method before, during and / or after one of the steps a) to c) are added.
  • Step a) of the method according to the invention provides for the provision of wood particles. If wood particles are mentioned here, this means any wood particles that can be used for the production of wood chip materials. Wood particles may be any size reduction products of lignocellulose-containing materials. Wood particles, as used herein, are not wood fibers.
  • first lignocellulose-containing material Since the hardener used according to the invention also contains lignocellulose, the wood particles used in step a) are referred to herein as "first lignocellulose-containing material".
  • the material used to produce the hardener is referred to as a "second lignocellulose-containing material”.
  • the first lignocellulosic material differs from the second lignocellulosic material as explained below.
  • a first lignocellulose-containing material which is in the form of wood particles is used in step a).
  • the first lignocellulose-containing material can be produced by comminuting lignocellulose-containing materials.
  • the first lignocellulose-containing material is provided in the form of wood particles, ie it may contain or consist of wood particles.
  • Wood particles as used herein, may contain wood or be made of wood. Examples of wood particles are finely divided wood material, wood chips, wood strands, wood wafers, wood flakes and wood chips.
  • the wood particles for wood chip materials are obtained by cutting processes.
  • the wood particles can be dried or stored before further processing. It is also possible to admix further substances to the first and / or second lignocellulose-containing material.
  • step c) is a hot pressing.
  • the press factor during hot pressing is from 2 to 10 s / mm, preferably from 3 to 6 s / mm.
  • Press factor is understood to mean in particular the residence time of the lignocellulose-containing wood chip material in seconds per millimeter thickness or thickness of the finished pressed lignocellulose-containing wood chip material in the press.
  • Suitable temperatures for the compression in step c) of the process according to the invention or one of its embodiments are temperatures of 150 ° C to 250 ° C, preferably from 160 ° C to 240 ° C, particularly preferably from 180 ° C to 230 ° C. At temperatures in these ranges, the process can be carried out particularly economically.
  • first lignocellulosic material Since the process according to the invention is a process for producing wood chips from the wood particles used in step a) (referred to herein as "first lignocellulosic material"), this process does not involve defibration, steaming, cooking or chemical and / or mechanical pulping (For example, in a refiner) of the first lignocellulosic material, as practiced for example in the production of wood fiber boards.
  • the first lignocellulose-containing material is glued with a composition which comprises at least one aminoplast resin and at least one first hardener. If this is referred to as "gluing”, then it can be understood as wholly or partially wetting with a composition containing a binder ("binder-containing composition"). Such compositions are also referred to by the person skilled in the art as "glue liquor”.
  • the binder is an aminoplast resin. Gluing can in particular also mean the uniform distribution of the binder-containing composition on the wood particles.
  • the application of the binder-containing composition can be carried out, for example, by impregnation or spraying.
  • the process according to the invention comprises in step b) the gluing of wood particles with a composition comprising at least one aminoplast resin and at least one first hardener.
  • the hardener can be added to the aminoplast resin before and / or during gluing to produce the composition.
  • a previously prepared mixture of aminoplast resin and first hardener is used as the composition for gluing the wood particles and applied to the wood particles.
  • the wood particles are glued with a composition containing an aminoplast resin and a first hardener by applying a previously prepared mixture of aminoplast resin and first hardener to the wood particles.
  • the method according to the invention likewise encompasses those embodiments in which the hardener is added to the aminoplast resin only during gluing and the composition is first formed in situ during gluing. This can be achieved, in particular, by separating the aminoplast resin and the first hardener during gluing of the wood particles from each other, if necessary with other additives or binders are applied to the wood particles.
  • the aminoplast resin and the hardener mix to form a composition that "contains" an aminoplast resin and a first hardener.
  • the aminoplast resin and in a second step the first hardener may be applied to the wood particles.
  • first step first apply the first curing agent and then in a second step, the aminoplast resin on the wood particles.
  • a simultaneous application of aminoplast resin and first curing agent by two separate application devices, such as nozzles, on the wood particles is possible.
  • another embodiment of the method provides for the wood particles to be glued with a composition containing an aminoplast resin and a first hardener by separately applying the aminoplast resin and the first hardener to the wood particles.
  • the amount of binder used in gluing is preferably 0.1 to 20 wt .-%, in particular 1 to 16 wt .-%, more preferably 4 to 14 wt .-%, based on the dry weight of wood (solid resin / atro). For many applications, it is particularly practical if the binder in an amount of 0.1 to 15 wt .-% based on the dry weight of wood (solid resin / atro) is used.
  • the method according to the invention or one of its embodiments is suitable for a multiplicity of binder-wood particle combinations.
  • at least one aminoplast resin is used as the binder.
  • other synthetic resins in particular phenolic resins, vinyl acetates, isocyanates, epoxy resins and / or acrylic resins can also be used in the process according to the invention.
  • the binder consists of an aminoplast resin and one or more hardeners.
  • aminoplast resins are urea-formaldehyde resins (UF), melamine-reinforced urea-formaldehyde resins (MUF), melamine-urea-phenol-formaldehyde resins (MUPF), or mixtures thereof.
  • UF urea-formaldehyde resin
  • UMF melamine-reinforced urea-formaldehyde resins
  • MUPF melamine-urea-phenol-formaldehyde resins
  • particularly good results can be achieved with urea-formaldehyde resins (UF), melamine-reinforced urea-formaldehyde resins (MUF) or mixtures thereof.
  • the aminoplast resin is obtainable by condensation of an amino group-containing component with a carbonyl compound.
  • the carbonyl compound is preferably formaldehyde.
  • the amino group-containing component is preferably melamine and / or urea. More preferably, the aminoplast resin is a melamine resin or a urea resin, especially a melamine-formaldehyde resin or a urea-formaldehyde resin.
  • the composition (glue liquor) used in the process according to the invention also contains at least one first hardener.
  • the binder contains 0.1 to 15 wt .-% of the first hardener, in particular 0.5 to 10 wt .-%, based on the solid resin content of the aminoplast resin.
  • Hardener as used herein is a term known to those skilled in the art of making chipboard material.
  • Hardeners are catalysts which catalyze a curing or crosslinking reaction, ie promote or initiate without being consumed itself.
  • catalysts are substances that increase the rate of reaction by lowering the activation energy of a chemical reaction without being self-consumed.
  • the curing of aminoplast resins is carried out by acid catalysis.
  • the acid which acts as a hardener, initiates or drives the curing or crosslinking reaction without being consumed.
  • Hardeners are therefore to be distinguished from the starting materials of the aminoplast resin crosslinking reaction, which react with each other during the aminoplast resin curing and are therefore consumed.
  • hardeners are also to be distinguished from additives, for example diluents such as lignin, which are able to polymerize via functional groups into the aminoplast resin.
  • additives for example diluents such as lignin, which are able to polymerize via functional groups into the aminoplast resin.
  • Such additives which during the Aminoplastharz curing polymerize and thereby abreact and can be consumed are not covered by the term "hardener" as used herein.
  • the first hardener used according to the invention is based on lignocellulose-containing material. It is obtained by hydrothermal and mechanical digestion of such a lignocellulose-containing material. According to one embodiment, the first hardener used according to the invention therefore contains or consists of hydrothermally and mechanically digested lignocellulose-containing material.
  • the curing used according to the invention is obtained from a second lignocellulose-containing material which differs from the first lignocellulose-containing material described above used in step a).
  • This difference consists in particular of the origin and / or the underlying raw materials.
  • provision is made in particular for the second lignocellulose-containing material to originate from a different raw material than the first lignocellulose-containing material.
  • the first and second lignocellulose-containing material may represent different raw materials or be made or obtained from different raw materials.
  • the difference in the raw materials in the genus or the compilation of plant species from which the two lignocellulose-containing materials are obtained are obtained.
  • plant species and plant genus are to be understood according to the usual botanical definition (taxon and genus).
  • the first lignocellulose-containing material is provided in the form of wood particles, that is to say that at least one raw material from which the first lignocellulose-containing material originates is wood.
  • the second lignocellulose-containing material can be obtained from a different type of wood than that used as raw material was used for the first lignocellulosic material.
  • the raw materials for the first and second lignocellulose-containing material preferably differ in that the second lignocellulose-containing material originates from a raw material that is different from wood, in particular from tree wood.
  • the second lignocellulosic material is selected from the group consisting of annuals, crops, grasses, foliage, cereals, their constituents and waste, or mixtures thereof.
  • Crop is in particular straw, wheat, rye, barley, oats, millet, corn, miscanthus, rice, their constituents, their waste and / or mixtures thereof understood.
  • the term "annual plants” refers to plants and / or their constituents containing lignocellulose, which require a period of vegetation from the germination of their seed to the fertilization of their flower and the maturity of the new seed, and to the maturity of the new one Seeds die off.
  • one or more of these selected second lignocellulose-containing materials are hydrothermally and mechanically digested. This hydrothermally and mechanically digested material can then be used as the first hardener.
  • This hydrothermally and mechanically digested material can then be used as the first hardener.
  • the use of the above-described lignocellulose-containing materials for the preparation of the first hardener has proven to be economically advantageous.
  • the plants mentioned are easy to cultivate and can be processed easily and in a few process steps. For example, the processing of plant waste not only ensures a low-cost raw material, but also an improved cascade use of plant raw materials.
  • the use of wood, especially tree wood, as a raw material for the production of the first hardener the much longer cultivation times, the significantly increased workload and the cost of processing the wood would be disadvantageous.
  • the second lignocellulosic material contains no wood, especially no tree wood, and also does not come from such raw materials.
  • the raw materials enumerated above for the second lignocellulose-containing material do not fall under the generic term wood.
  • the second lignocellulosic material can be used uncut for hydrothermal and mechanical digestion.
  • the second lignocellulosic material may also be pre-shredded for hydrothermal and mechanical digestion. Preferably, this is dry pre-crushed.
  • the comminuted second lignocellulosic material may have an average particle size - determined by the mesh size of the screen - of 20 ⁇ m to 20 mm, 0.05 ⁇ m to 1 mm or 0.4 ⁇ m to 0.4 mm.
  • the "average particle sizes” stated here are average sieve diameters which are determined by the particles passing through a defined mesh size of a sieve.
  • methods for the determination of particle sizes are known to the person skilled in the art, for example the sieve analysis according to DIN 66165.
  • the average sieve diameter it is possible, for example, to choose a sieve system with mesh sizes decreasing from top to bottom.
  • the individual proportions can be weighed and represented as a percentage in the form of a particle distribution. From this, the mean sieve diameter can be determined according to DIN 66165. For small particle sizes or particle fractions, microscopic methods can be used to determine the particle size.
  • the comminuted second lignocellulosic material has a particle size distribution at least 70, 80, 90 or 95% by weight of the material having a screen diameter of 20 ⁇ m to 20 mm, 0.05 ⁇ m to 1 mm, or 0.1 ⁇ m to 0, 4 mm, determined by the mesh size of the screen.
  • This particle size distribution can be present before or after mechanical pulping.
  • this particle size distribution refers to the material that has already been mechanically comminuted and is subjected only to a hydrothermal and mechanical pulping.
  • the particle size or average particle size can be determined such that the particles of the second lignocellulose-containing material, a sieve with a mesh size of 20 mm, preferably of 1 mm, more preferably of 0.4 mm and particularly preferably of 0.2 mm happen.
  • particle fractions can be used which result from particles that pass through these mesh sizes.
  • the mean particle size is determined in this embodiment by a "maximum size" of the particles through the mesh sizes defined above.
  • These particle sizes can be present before or after the hydrothermal and mechanical disruption.
  • these particle sizes relate to the material that has already been mechanically comminuted and is subjected only to a hydrothermal and mechanical pulping.
  • the comminuted second lignocellulose-containing material has a particle size distribution in which at least 70, 80, 90 or 95% by weight of the material has a screen diameter of less than 20 mm, preferably less than 1 mm, less than 0.4 mm or less than 0, 2 mm, each determined by passing a sieve with a corresponding mesh size.
  • the first hardener may have a dry weight of from 5 to 25% by weight, in particular from 10 to 20% by weight, based on the total weight of the material.
  • the first hardener in step b) contains an acid which has been released by the hydrothermal and mechanical digestion of the second lignocellulose-containing material.
  • the hydrothermally and mechanically digested second lignocellulosic material directly contains the acid that can act as a catalyst in the curing reaction (as described above) and does not need to be released.
  • the second lignocellulosic material releases at least one acid during the hydrothermal and mechanical digestion in the presence of water and / or heat.
  • “Hydrothermal” as used herein means that the digestion occurs under the action of water and elevated temperature.
  • the water can come from the materials used or added.
  • Preferably Water is added, especially in the form of water vapor.
  • the digestion mentioned in step b) is a simultaneous hydrothermal and mechanical digestion.
  • the release of the acid seems to be due to the good hydrolyzability of the hemicellulose.
  • the ⁇ -1,4-glucosidic bonds of the glucose molecules are very stable.
  • the hydrolysis of the cellulose requires drastic conditions, such as strongly acidic or strongly alkaline conditions or more specific enzymes.
  • One reason why the microcrystalline cellulose does not release acid during the hydrothermal and mechanical digestion could thus be that this digestion is not sufficiently acidic or alkaline.
  • the second lignocellulosic material described above is much better suited than, for example, tree wood.
  • the second lignocellulose-containing material used according to the invention in particular the abovementioned plants, have a higher average hemicellulose proportion than, for example, tree wood, in particular softwood.
  • the release of the acid contributes to the curing of the resin. This is especially the case when the resin can be cured by acid catalysis.
  • the acid catalysis curable resins include, in particular, aminoplast resins.
  • the acid released during the hydrothermal and mechanical digestion contributes to the curing of the aminoplast resin contained in the binder-containing composition.
  • the acid released during the hydrothermal and mechanical digestion has a molecular weight of from 40 g / mol to 500 g / mol, in particular from 40 g / mol to 250 g / mol.
  • the acid is a Brönsted acid having a pK a of 2 to 8, especially 3 to 6.
  • the acid is a carboxylic acid having a chain length of 1 to 5 carbon atoms. Examples of carboxylic acids are formic acid, acetic acid, propionic acid, butanoic acid, pentanoic acid and derivatives thereof. Examples and properties of Bronsted acids are, for example, in " Basic Knowledge of Chemistry ", C.
  • PK a is the negative decadic logarithm of the acid constant K a under standard conditions (see also " Organic Chemistry, "Jonathan Clayden, Nick Greeves, Stuart Warren, OUP Oxford, 2012, pages 163-181 ). The smaller the pK a value, the stronger the acidity. If an acid has several dissociation stages (eg H 2 SO 4 : pK a 1st stage: -3, 2nd stage: 1.92), the pK a value of the 1st dissociation stage is here with the pK a value The pK a values of some important Bronsted acids can be found in the following table.
  • the carboxylic acid is a weak acid. If here or elsewhere weak acids are mentioned, then it is meant that the pK a is equal to or greater than 3. For a pK a of Brönsted acid of less than 3, the binder may be attacked by the acid and at least partially hydrolyzed ,
  • the carboxylic acid is a volatile acid.
  • volatile acids are formic acid or acetic acid.
  • the volatility of the acid can further contribute to the better stability of the glue joint. One reason for this could be that a volatile acid remains in the glue joint for a shorter time than acids from conventional hardeners. This shorter retention time can reduce or even prevent unwanted hydrolysis of the glue joint.
  • the first hardener is available by hydrothermal and mechanical pulping.
  • Suitable temperatures for the hydrothermal and mechanical digestion of the second lignocellulose-containing material are temperatures of 120 to 180 ° C, preferably 130 to 170 ° C and particularly preferably 140 to 160 ° C.
  • the duration of the hydrothermal and mechanical digestion is 2 seconds to 40 minutes, in particular 5 seconds to 30 minutes.
  • cooker pressure reactor and refiner are known to those skilled in the wood industry.
  • cooker is meant in particular a device which is suitable for hydrothermal digestion of the second lignocellulose-containing material.
  • Pressure reactor is any reaction vessel which constitutes a sealed, delimited space in which pressure can be built up and which is suitable for carrying out the hydrothermal digestion of the second lignocellulosic material.
  • reffiner the expert understands a device for comminution or defibration of wood, especially under pressure. Examples of refiner in use in practice are Southerland refiner with hollow axle and a movable grinding disc, Fritz refiner with 10 grinding discs, Calfin refiner or hydrorefiner.
  • the hydrothermal digestion in step (i) can be carried out at a temperature of 120 to 180 ° C, in particular at 140 to 160 ° C. Suitable pressures for the hydrothermal digestion are between 3 to 8 bar, in particular at 4 to 6 bar. The duration of the digestion can be between 5 and 40 minutes. An opening time of 30 minutes has proved to be advantageous. Good results can be achieved if step (i) is carried out in the presence of water. The use of water vapor has proved to be particularly practical.
  • step (ii) takes place in a refiner.
  • Particularly suitable process temperatures are in a range of 140 to 180 ° C, in particular from 150 to 160 ° C and at a pressure of 1 to 8 bar, in particular at 4 to 6 bar.
  • the duration of the mechanical digestion can be 2 seconds to 5 minutes, in particular 5 seconds to 3 minutes.
  • step (ii) can be carried out in the presence of water, in particular water vapor.
  • optionally further method steps may be carried out before, after or between steps (i) and (ii).
  • Optional steps may be heating in a preheat container, crushing, storing, mixing, spreading, adding further substances, or drying the lignocellulosic material or a mixture containing the lignocellulosic material of step (i) and / or (ii).
  • the binder-containing composition also contains a second hardener in addition to the first hardener used according to the invention.
  • the second hardener may be a conventional hardener described above, in particular an ammonium salt.
  • suitable ammonium salts are ammonium nitrate, ammonium phosphate, ammonium chloride and Ammonium sulfate.
  • these ammonium salts form their corresponding acid which acts as an acid catalyst to cure the resin. Examples of these are nitric acid, phosphoric acid, hydrochloric acid, sulfuric acid.
  • first hardener used according to the invention is particularly compatible with aminoplast resins and the conventional hardeners conventionally used there. Furthermore, binder compositions containing an aminoplast resin, a first hardener according to the invention and a second hardener have proven to be stable.
  • the binder-containing composition contains 0.1 to 4 wt .-% ammonium salt, in particular 0.5 to 3.0 wt .-%, based on the solid resin content of the resin.
  • the ammonium salt is ammonium nitrate and the resin is an aminoplast resin. It is particularly advantageous that the proportion of the conventional second hardener can be reduced by using the first hardener. In a particularly preferred embodiment of the invention, the second hardener can be saved up to half or more if the second hardener is used in combination with the first hardener used according to the invention.
  • this also means that, for example, in comparison with the sole use of ammonium salts as curing agents for amino resins, significantly less ammonium salt has to be added to the process. As a result of the reduced ammonium salt content, the process also requires less formaldehyde. As a result, wood chip materials can be obtained with reduced formaldehyde content. The same applies to other, explained in the beginning conventional hardener.
  • the disclosure further relates to lignocellulose-containing wood chip materials which have been produced or obtainable by the method according to the invention or its embodiments described above.
  • a wood chip material can be used particularly well for the production of a laminate, flooring, a worktop, table top, a piece of furniture or a pallet.
  • the invention also relates to the use of the first hardener according to the invention according to claim 20, which was obtained by hydrothermal and mechanical pulping of a second lignocellulose-containing material, in a method according to the invention for the production of wood chip materials described above.
  • the first hardener releases an acid.
  • the first hardener releases acetic acid and / or formic acid.
  • the above-mentioned advantages of the method according to the invention also apply to the inventive use of the first hardener.
  • the strength of conventional wood chip materials can be maintained or even improved even while reducing the amount of conventional hardeners.
  • an improvement in swelling behavior and / or water absorption can be achieved.
  • One reason for this could be that the acid released during the hydrothermal and mechanical digestion is free and volatilises more rapidly than conventional hardeners. This creates a neutral glue joint, which positively influences the characteristics of the wood chip material described above.
  • Version 1 In the first variant, the digestion of the lignocellulose-containing material was carried out in a discontinuous single-disc refiner (Sprout Waldron). The refiner was filled with the material and steam (160 ° C) was introduced into the cyclone. The material remained at 160 ° C and 6 bar for about 2 minutes in the refiner, then the cyclone was opened and the material was transported out via the screw and a 2.5 mm valve within about 5 minutes.
  • Variant 2 In the second variant, the lignocellulose-containing material was pre-shredded dry in an Ecopulser (Krause Maschinenbau GmbH) and screened (Retsch AS 200). The particle fraction smaller than 0.6 mm was then boiled in a pressure reactor (Büchiglasuster Cyclon 300) at 160 ° C and 5 to 6 bar under an approximately 1: 5 dilution with water for about 30 min.
  • the first hardener used was the lignocellulose-containing material prepared according to Example 1 in dosages of 1, 3, 6 and 10% by weight of the solid, based on the solid resin fraction (hereinafter% solid / FH) Quantities of 1, 1.5, 2 and 3% fixed / FH.
  • the treated lignocellulosic material was added to the size liquor containing an aminoplast resin. Following the plate pressing, the transverse tensile strength, swelling and water absorption were determined. For this purpose, specimens of geometry 50 ⁇ 50 ⁇ 14 mm were first cut to size. Each test specimen was measured by means of a digital thickness probe before the test, and the mass determined and used to calculate the density.
  • the transverse tensile strength was determined according to EN 319. To this end, each test specimen was bonded by means of a hot melt adhesive with two aluminum yokes on the top and bottom and then pulled apart after cooling on the testing machine (Zwick Zmart.Pro) at a constant test speed of 1 mm / min. The force leading to the break in the middle of the specimen was recorded and the resulting transverse tensile strength over the specimen area was calculated [N / mm 2 ].
  • the determination of the thickness swelling after 24 hours of water storage was carried out according to DIN EN 317.
  • the test specimens were stored for this purpose at a water temperature of 20 ° C for 24 h under water. Subsequently, the increase in thickness was determined relative to the starting thickness and the percentage thickness swelling was calculated.
  • the reference plates 1 and 2 were made without the addition of the first hardener.
  • the test plates 1 to 3 were produced with the first hardener of variant 1 from example 1 and the test plates 4 and 5 were produced with the first hardener of variant 2 from example 1.
  • test panels were each made at least twice and determines the transverse tensile strength, the swelling and the water absorption.
  • the measurements below are averages of at least two plates.
  • the transverse tensile strength was determined for reference plates 1 and 2 and experimental plates 1 to 3. The results are shown in Diagram 1.
  • the measurement showed a reduced swelling for the experimental plates 4 and 5 despite reduced content of ammonium nitrate.

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

Claims (20)

  1. Procédé de fabrication d'un matériau à base de particules de bois, qui comprend les étapes
    a) mise à disposition d'un premier matériau contenant de la lignocellulose sous la forme de particules de bois,
    b) encollage du premier matériau contenant de la lignocellulose avec une composition qui comprend au moins une résine aminoplaste et au moins un premier durcisseur et un deuxième durcisseur, sachant que le premier durcisseur a été obtenu par la décomposition hydrothermique et / ou mécanique d'un deuxième matériau contenant de la lignocellulose, sachant que le deuxième durcisseur provient d'une matière brute autre que celle du premier durcisseur, et sachant que le deuxième durcisseur est un sel d'ammonium,
    c) compression pour l'obtention d'un matériau à base de particules de bois.
  2. Procédé selon la revendication 1, caractérisé en ce que, pendant la décomposition hydrothermique et / ou mécanique, un acide est libéré à partir du deuxième matériau contenant de la lignocellulose.
  3. Procédé selon la revendication 2, caractérisé en ce que l'acide contribue au durcissement de la résine aminoplaste.
  4. Procédé selon revendication 2 ou 3, caractérisé en ce que l'acide présente un poids moléculaire de 40 g / mol à 500 g / mol, en particulier de 40 g / mol à 250 g / mol.
  5. Procédé selon l'une des revendications 2 à 4, caractérisé en ce que l'acide est un acide selon Brönsted, dont le pKa est de 2 à 8, en particulier de 3 à 6.
  6. Procédé selon l'une des revendications 2 à 5, caractérisé en ce que l'acide est un acide carboxylique, choisi, en particulier, à partir du groupe qui comprend l'acide formique, l'acide acétique, l'acide propionique, l'acide butylique, l'acide valérique et des dérivés de ceux-ci.
  7. Procédé selon l'une des revendications précédentes, caractérisé en ce que la décomposition hydrothermique et / ou mécanique du deuxième matériau contenant de la lignocellulose est exécutée à une température de 120 à 180 °C, en particulier de 140 à 160 °C.
  8. Procédé selon l'une des revendications précédentes, caractérisé en ce que la décomposition hydrothermique et / ou mécanique du deuxième matériau contenant de la lignocellulose est exécutée à une pression de 3 à 10 bar, en particulier de 4 à 8 bar.
  9. Procédé selon l'une des revendications précédentes, caractérisé en ce que la durée de la décomposition hydrothermique et / ou mécanique est de 2 secondes à 40 minutes, en particulier de 5 secondes à 30 minutes.
  10. Procédé selon l'une des revendications précédentes, caractérisé en ce que la décomposition hydrothermique et / ou mécanique est exécutée dans un conteneur de préchauffage, un appareil de cuisson et / ou un raffineur.
  11. Procédé selon l'une des revendications précédentes, caractérisé en ce que la composition contient 0,1 à 15 % en poids du premier durcisseur, en particulier 0,5 à 10 % en poids, en référence respective à la part de résine solide de la résine aminoplaste.
  12. Procédé de fabrication d'un matériau à base de particules de bois selon l'une des revendications précédentes, sachant que la décomposition hydrothermique et / ou mécanique, mentionnée dans l'étape b), comprend les étapes suivantes :
    (i) décomposition hydrothermique du deuxième matériau contenant de la lignocellulose dans un appareil de cuisson et / ou dans un réacteur sous pression,
    (ii) décomposition mécanique par broyage du deuxième matériau contenant de la lignocellulose en provenance de l'étape (i) dans un raffineur.
  13. Procédé selon l'une des revendications précédentes, caractérisé en ce que les particules de bois de l'étape a) sont choisies à partir du groupe qui comprend des matières à base de bois à fines particules, des flocons de bois, des tranches de bois, du bois d'épaves, des copeaux de bois et des rognures de bois.
  14. Procédé selon l'une des revendications précédentes, caractérisé en ce que le deuxième matériau contenant de la lignocellulose est choisi à partir du groupe qui comprend des plantes annuelles, des plantes de culture, des herbes, des feuilles, des céréales, ainsi que des composants, déchets et mélanges de celles-ci.
  15. Procédé selon la revendication 14, caractérisé en ce que les plantes de culture sont choisies à partir du groupe qui comprend la paille, le blé, le seigle, le sarrasin, l'avoine, le millet, le maïs, le miscanthus, le riz, ainsi que des composants, déchets et mélanges de ceux-ci.
  16. Procédé selon l'une des revendications précédentes, caractérisé en ce que la résine aminoplaste est une résine de mélamine ou d'urée.
  17. Procédé selon l'une des revendications précédentes, caractérisé en ce que le sel d'ammonium est choisi à partir du groupe qui comprend le nitrate d'ammonium, le chlorure d'ammonium et le sulfate d'ammonium.
  18. Procédé selon l'une des revendications précédentes, caractérisé en ce que la composition contient 0,1 à 4 % en poids du deuxième durcisseur, en particulier 0,5 à 3,0 % en poids, en référence respective à la part de résine solide de la résine aminoplaste.
  19. Procédé selon l'une des revendications précédentes, caractérisé en ce que le matériau à base de particules de bois est une plaque de copeaux ou une plaque OSB.
  20. Utilisation d'un matériau contenant de la lignocellulose décomposé par traitement hydrothermique et / ou mécanique en tant que durcisseur pour une résine aminoplaste dans un procédé de fabrication d'un matériau à base de particules de bois selon l'une des revendications 1 à 19.
EP16712254.8A 2015-03-10 2016-03-10 Procédé de fabrication d'un matériau à base de particules de bois et durcisseur employé dans ledit matériau pour aminoplaste Active EP3268190B1 (fr)

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DE102015103511.1A DE102015103511B4 (de) 2015-03-10 2015-03-10 Verfahren zur Herstellung eines Holzspanwerkstoffs und darin verwendete Härter für Aminoplaste
PCT/EP2016/055171 WO2016142483A1 (fr) 2015-03-10 2016-03-10 Procédé de fabrication d'un matériau à base de particules de bois et durcisseur employé dans ledit matériau pour aminoplaste

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WO2020226600A2 (fr) 2019-05-06 2020-11-12 Alpay Aytekin Composition utilisée pour le revêtement de composés inorganiques utilisés dans la production de revêtement de plancher lamellé
DE102020128378A1 (de) 2020-10-28 2022-04-28 Ava Biochem Ag Verfahren zur herstellung eines verbundwerkstoffs

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US4414361A (en) 1981-08-17 1983-11-08 Atlantic Richfield Company Organic polyisocyanate-cyclic alkylene carbonate adhesive binder compositions
JPS60210406A (ja) * 1984-04-03 1985-10-22 Sadao Nishibori 木質床材
NO324322B1 (no) 2001-02-26 2007-09-24 Dynea Oy Anvendelse av herder samt fremgangsmate ved liming
EP1670870B1 (fr) 2003-09-26 2008-07-23 Basf Se Systeme de liant contenant des resines aminoplastes, des copolymeres formes a partir de monomeres ethyleniquement insatures a fonction n, et eventuellement du vinyl alcool et des acides
DE102004010796A1 (de) * 2004-03-05 2005-09-22 Roffael, Edmone, Prof. Dr.-Ing. Verfahren zur Verminderung der Formaldehydabgabe von Lignocellulose haltigen Holzwerkstoffen, insbesondere von mitteldichten Faserplatten (MDF)
DE102005019627B3 (de) 2005-04-26 2006-10-26 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Verfahren zur Herstellung von mitteldichten Faserplatten und Faserformteilen mit verringerter Emission und niedriger Dickenquellung
DE102005035693A1 (de) 2005-07-27 2007-02-01 Basf Ag Härtezusammensetzung für Aminoplastharz

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TR201904393T4 (tr) 2019-05-21
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WO2016142483A1 (fr) 2016-09-15
HUE042217T2 (hu) 2019-06-28
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EP3268190A1 (fr) 2018-01-17
LT3268190T (lt) 2019-04-10

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