EP3455042A1 - Panneau de fibres à résistance accrue contre toute attaque fongique et son procédé de fabrication - Google Patents

Panneau de fibres à résistance accrue contre toute attaque fongique et son procédé de fabrication

Info

Publication number
EP3455042A1
EP3455042A1 EP17721689.2A EP17721689A EP3455042A1 EP 3455042 A1 EP3455042 A1 EP 3455042A1 EP 17721689 A EP17721689 A EP 17721689A EP 3455042 A1 EP3455042 A1 EP 3455042A1
Authority
EP
European Patent Office
Prior art keywords
fiberboard
guanidine compound
polymeric
polymeric mono
mono
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
EP17721689.2A
Other languages
German (de)
English (en)
Other versions
EP3455042B1 (fr
Inventor
Thomas Kuncinger
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.)
Fritz Egger GmbH and Co OG
Original Assignee
Fritz Egger GmbH and Co OG
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 Fritz Egger GmbH and Co OG filed Critical Fritz Egger GmbH and Co OG
Priority to SI201730330T priority Critical patent/SI3455042T1/sl
Priority to PL17721689T priority patent/PL3455042T3/pl
Publication of EP3455042A1 publication Critical patent/EP3455042A1/fr
Application granted granted Critical
Publication of EP3455042B1 publication Critical patent/EP3455042B1/fr
Priority to HRP20201110TT priority patent/HRP20201110T1/hr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • 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
    • B27K2200/00—Wooden materials to be treated
    • B27K2200/15—Pretreated particles or fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
    • B27K3/02—Processes; Apparatus
    • B27K3/15—Impregnating involving polymerisation including use of polymer-containing impregnating agents
    • B27K3/153—Without in-situ polymerisation, condensation, or cross-linking reactions
    • 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
    • B27N3/06—Making particle boards or fibreboards, with preformed covering layers, the particles or fibres being compressed with the layers to a board in one single pressing operation
    • 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
    • B27N3/08—Moulding or pressing
    • B27N3/16—Transporting the material from mat moulding stations to presses; Apparatus specially adapted for transporting the material or component parts therefor, e.g. cauls
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04B—GENERAL BUILDING CONSTRUCTIONS; WALLS, e.g. PARTITIONS; ROOFS; FLOORS; CEILINGS; INSULATION OR OTHER PROTECTION OF BUILDINGS
    • E04B1/00—Constructions in general; Structures which are not restricted either to walls, e.g. partitions, or floors or ceilings or roofs
    • E04B1/62—Insulation or other protection; Elements or use of specified material therefor
    • E04B1/92—Protection against other undesired influences or dangers

Definitions

  • the invention relates to a fiberboard with increased resistance to
  • Another object of the invention is a roof or wall component, which consists of such a fiberboard or contains. Further, the invention relates to the use of a polymeric mono-guanidine compound in fiberboard manufacture to increase the resistance of the fiberboard to fungal attack.
  • Fiberboard is widely used in building construction, especially in interior and loft conversions, as well as in furniture, for example, as a wall element for exterior or interior use, as a support plate for laminate flooring, for front and rear fronts of furniture or Unterbeplankung and insulation of roof structures.
  • DHF plates vapor-permeable and vapor-permeable are preferably used
  • moisture-resistant fiberboard used as Unterdeckplatten for planking of roofs and walls.
  • a good moisture resistance or a good protection against microbial infestation is desired because DHF plates may be exposed to water or moisture for long periods of time. For example, this stress may be due to external weather conditions or evaporation of water in , -
  • Fiberboard manufacturing resins used and / or incompatible with them Fiberboard manufacturing resins used and / or incompatible with them.
  • biocide wood preservatives are coal tar oils (creosols),
  • water-soluble preservatives are in many cases combinations of inorganic salts with mostly water-insoluble organic active ingredients.
  • the latter are rendered water-emulsifiable / dispersible and thus water-dilutable with the aid of emulsifiers or dispersants (therefore "water-based").
  • EP 2 146 571 B1 describes a furniture and / or interior fitting which is antimicrobially treated by impregnation with a resin composition.
  • the resin composition contains a biocidal composition
  • emulsifying effect can additionally promote the swelling of the fiberboard.
  • EP 1 813 402 A2 describes a fiberboard for roofing and wall construction, which contains borates as mold fungus protection in its covering layer.
  • the boron compounds appear to be effective against fungi in principle, but these compounds are water-soluble and not fixed in the fiber material. As a result, they remain easily washable even with the addition of fixing agents and their effect is lost in the course of the application period.
  • Emission through evaporation, attrition, or other release may affect human health. Often biocides also lose their effect through gradual (natural) degradation.
  • water-based wood preservatives may be removed from time
  • Fiber board to be washed out on the one hand the antimicrobial
  • Processing temperatures for example when drying the pre- or
  • Biocides based on metals such as silver, copper or zinc therefore appear unsuitable. Their accumulation represents a serious problem in the treatment of waste water in municipal sewage treatment plants and the compliance with limit values after their thermal utilization.
  • the biocide will continue to be active for a long time. Sufficient fixation of the biocide in the surface of the fiberboard would therefore be desirable.
  • an object of the invention was to provide a fiberboard with increased
  • Another aspect of the object underlying the invention was to produce an environmentally friendly product, which is characterized by a long-lasting fungus resistance.
  • the invention relates to a fiberboard, which is obtainable by pressing adhesively bonded, lignocellulose-containing fibers, wherein at least one polymeric - -
  • Mono-guanidine compound is concentrated in the area of at least one of the two surfaces of the fiberboard.
  • Polymeric mono-guanidine compounds are mainly used as disinfectant auxiliary components for disinfecting the skin or mucous membrane, in wound antiseptics, in hand disinfectants, for pure surface disinfection, for example by applying and wiping a guanidine-containing solution, in the medical field for controlling bacteria or for water disinfection, for example in swimming pools known.
  • Polymeric mono-guanidine compounds can also be used as an additive in emulsion paint.
  • WO 2010/106002 A1 describes a polymer mixture containing a polymeric mono-guanidine compound.
  • the polymeric mono-guanidine compound is introduced into an already finished polymer and processed into a powder. This powder can be incorporated in commercial emulsion paint and applied as an antimicrobial paint on metal surfaces.
  • the application of polymeric mono-guanidine compounds in the field of fiberboard or their production is not yet known. In the
  • Microorganisms that typically infest wood or fiberboard are primarily fungi. Moreover, it was not foreseeable for the skilled person that the polymeric mono-guanidine compounds with those prevailing in the manufacture of fibreboard
  • polymeric mono-guanine-din compounds also has the advantage that they have a very low toxicity and in practical experiments, no formation of resistance to the wood-contaminating microorganisms has been shown. Furthermore, through the use of polymeric mono-guanidine compounds, such as
  • Fiber plate surface and the negatively charged cell walls of the microorganisms to be based Fiber plate surface and the negatively charged cell walls of the microorganisms to be based.
  • Polymeric mono-guanidine compounds which can be used according to the invention are composed of bridged mono-guanidine compounds.
  • Mono-guanidine compounds may also be referred to as imino ureas or as carbamidines.
  • An example of a mono-guanidine compound is guanidine, too
  • iminomethanediamine with the empirical formula CH5N3.
  • Mono-guanidine compounds can be the bridging of the mono-guanidine compounds, such as guanidine, for example, by alkylene chains.
  • Mono-guanidine compounds or polymeric mono-guanidine compounds are generally known to the person skilled in the art. The properties and preparation of monoguanidine compounds or polymeric mono-guanidine compounds are described, for example, in "Ulimanns Enzyklopadie der ischen Chemie - Volume 12", Verlag Chemie, GmbH, 1976, pages 411-419.
  • Guanidine compounds are guanidine and guanidine hydrochloride, a well-known example of a polymeric mono-guanidine compound
  • Polymeric mono-guanidine compounds have, as structural element, a guanidine group, which is shown by way of example below. This is in particular a mono-guanidine structural element.
  • R 1 and R 2 independently of one another are linear or branched
  • Hydrocarbon chain having 1 to 16 carbon atoms or a linear or branched substituted with at least one heteroatom
  • Hydrocarbon chain having 1 to 16 carbon atoms, wherein the at least one heteroatom is selected from oxygen and / or nitrogen; - - x 0, 1 or an integer between 2 and 10 can mean and
  • n is an integer greater than or equal to 2.
  • x is 0 and R 1 is an alkylene radical of the general formula (II)
  • m is an integer between 1 and 16, preferably between 1 and 12, particularly preferably between 1 and 8 and in particular equal to 6.
  • x 0 and R 1 is on
  • n is an integer between 1 and 10, in particular 1, 2 or 3, and R is hydrogen or a methyl radical.
  • Preferred alkylenediamines of the formula (III) which can be used according to the invention are selected from the group consisting of ethylenediamine, trimethylenediamine, propylenediamine, hexamethylenediamine and mixtures thereof.
  • x 0 and R 1 is an oxyalkylene, of the general formula (IV),
  • n 1, 2, 3, 4 or 5 and R is hydrogen or a methyl radical.
  • Preferred examples of the oxyalkylenes which can be used according to the invention are
  • Oxyalkylenediamines are oxyethylenediamine, in particular triethyleneglycol diamine and / or
  • guanidine groups contained in the polymeric mono-guanidine compounds can also be present in charged form, in particular as cations in a salt with Gegenanion.
  • polymeric mono-guanidine compounds which can be used according to the invention are preferably polymeric mono-guanidine compounds, their salts or a
  • Polymeric mono-guanidine compounds have as guanidine structural elements only mono-guanidine structural elements.
  • An example of a polymeric mono-guanidine compound which can be used according to the invention is polyhexamethyleneguanidine (PHMG), represented in formula (VI). - -
  • Well-suited polymeric monoguanidine compounds according to the invention are compounds from the group consisting of polyalkylene guanidines, in particular polyhexamethylene guanidine, polyalkylene diamine guanidines, polyoxyalkylene guanidines, polyoxyalkylene diamine guanidines and their salts.
  • Polyoxyalkyleneguanidines polyoxyalkylenediamine guanidines that R 1 and / or R 2 is an alkylene, alkylenediamine, oxyalkylene and / or oxyalkylenediamine.
  • polyhexamethyleneguanidine PHMG is used as the polymeric mono-guanidine compound.
  • the salt of the polymeric mono-guanidine compound may be selected from the group consisting of hydrochloride, chloride, hydroxide, phosphate, fluoride, bromide, iodide, formate, acetate, diphosphate, sulfate, sulfide, nitrate, thiocyanate, thiosulfate, carbonate, Maleate, fumarate, tartrate, mesylate, gluconate and toluenesulfonate, with hydrochloride, chloride, hydroxide, phosphate, diphosphate, acetate and carbonate being preferred. Particularly preferred is hydrochloride and / or chloride.
  • the salts of the polymeric mono-guanidine compounds show a lower corrosive effect, so that the metallic devices used in the production of fiberboard are spared and also improves the range of applications. Independently - From the lower corrosivity increased by the preferred ions, the environmental compatibility of the product or its degradation products.
  • the polymeric mono-guanidine compound which can be used according to the invention can be used together with or in a mixture with a further additive.
  • This additive may be selected from the group consisting of other biocides, quaternary ammonium compounds and mixtures thereof.
  • this additive is a quaternary ammonium compound.
  • the quaternary ammonium compound may be selected from the group consisting of didecyldimethylammonium chloride (DDAC),
  • ADBAC dimethylbenzylammonium chloride
  • ADBAC / BKC alkyl dimethylbenzyl ammonium chloride
  • the fiberboard according to the invention has at least one polymeric mono-guanidine compound which is concentrated in the region of at least one of the two surfaces of the fiberboard.
  • the polymeric mono-guanidine compound may be concentrated in the region of both surfaces of the fiberboard.
  • concentration concentration of the polymeric mono-guanidine compound In the region of the surface or on the surface of the fiberboard, in particular, in the region or on the surface of the fiberboard, the highest concentration of the polymeric mono-guanidine compound is present in the fiberboard according to the invention
  • Fiberboard core includes the center of the fiberboard resulting from the cuboid shape of the fiberboard as the intersection of the spatial diagonals.
  • fiberboard core means the middle layer around the center of the fiberboard, which layer is substantially parallel to the surface of the fiberboard and has a mean layer thickness of 1, 2, 3, 4, or 5 mm.
  • fiberboard core means the center of the fiberboard or a substantially spherical volume about the center of the fiberboard, the radius of which may be 1, 2, 3, 4, or 5 mm.
  • surface of the fiberboard refers to the entire surface layer in which the polymeric mono-guanidine compound is concentrated
  • the thickness of this treated surface layer is dependent upon the depth of penetration of the polymeric mono-guanidine compound in which the polymeric mono-guanidine compound is concentrated is from the - -
  • Central layer which forms or comprises the core of the fiberboard and which is preferably substantially free of polymeric mono-guanidine compounds.
  • the thickness of the surface layer in which the polymeric mono-guanidine compound is concentrated is at least 0.01, 0.05, 0.1, 0.5, 1, 2, 3 or 5 mm into the interior of the fiberboard.
  • the superficial layer in which the polymeric mono-guanidine compound is concentrated preferably runs essentially parallel to the surface of the fiberboard.
  • thickness e.g., layer thickness or plate thickness
  • mean thickness e.g. as an average of 5 thickness measurements at different positions of the fiberboard.
  • the core of the fiberboard is substantially free of polymeric monoguanidine compounds, that is, there is a region inside the fiberboard that is substantially free of the polymeric mono-guanidine compound.
  • the fiberboard there is a concentration gradient of polymeric mono-guanidine compound between at least one surface of the fiberboard and its center.
  • the fiberboard has, in particular in its core, a range of less than 0.3, 0.1, 0.05 or 0.01% by weight.
  • polymeric mono-guanidine compound based on the dry matter (atro) of the lignocellulosic material, and most preferably contains substantially no polymeric mono-guanidine compound in its core.
  • the amount of the polymeric mono-guanidine compound in the fiberboard of the present invention is also referred to as the surface area concentration, not the surface area
  • volume concentration based on the total volume of the fiberboard, defined.
  • the polymeric mono-guanidine compound concentrated in the region of at least one of the two surfaces of the fiberboard preferably has one
  • Area concentration of 2 to 200 g / m 2 more preferably from 4 to 80 g / m 2 and particularly preferably from 6 to 30 g / m 2 , based on the respective surface of the fiberboard on.
  • the fiberboards of the invention also showed in practical experiments no worse mechanical properties than conventional fiberboard. This was surprising because the skilled person due to the putative effect of the polymeric mono-guanidine compounds (cationic surface modification) a
  • the polymeric mono-guanidine compounds are concentrated only in the region of at least one of the two surfaces of the fiberboard and the core of the fiberboard can be substantially free of it, a possible fiber structure damage is avoided and the mechanical properties substantially by the
  • Disk core are determined, remain as far as possible unimpaired.
  • Another advantage that has been shown in practice is that the polymeric monoguanidine compounds are also suitable for a variety of fiber-binder combinations. The addition of additional substances can impair the properties of the binder and thus lead to insufficient binder effect and / or mechanical properties of the final product. Due to the fibreboard structure selected according to the invention, the concentration of the polymeric monoguanidine compounds is only in the range of at least one of the two surfaces - Provides the fiberboard, such problems can be largely avoided.
  • Wood preservatives can be avoided. Thus, no harmful or environmentally harmful residues or emissions could be detected in the fiberboard of the invention.
  • the incorporation of the polymeric monoguanidine compounds onto the fiber mat appears to fix the polymeric mono-guanidine compounds during the compression to the fiber plate.
  • the fiberboard according to the invention may be a single-layer or multilayer fiberboard.
  • the fiberboard according to the invention is in
  • lignocellulosic fibers Essentially from lignocellulosic fibers.
  • essential here means up to 80, 85, 90, 95, 98 or 99 wt .-%, based on the total weight of the fiberboard.
  • the fiberboard may contain other additives such as fire retardants,
  • Solvents such as butyl alcohols, ethylene glycol dimethacrylate, ethylene glycol dimethacrylate, ethylene glycol dimethacrylate, ethylene glycol dimethacrylate, ethylene glycol dimethacrylate, ethylene glycol dimethacrylate, ethylene glycol dimethacrylate, ethylene glycol dimethacrylate, ethylene glycol dimethacrylate, ethylene glycol dimethacrylate, sulfate, sorbitol, sorbitol, sorbitol, sorbitol, ether glycol dimethoxysulfate, ethylene glycol dimethoxysulfate, ethylene glycol dimethoxylate, ethylene glycol dimethoxylate, ethylene glycol dimethacrylate, ethylene glycol dimethacrylate, ethylene glycol dimethacrylate, ethylene glycol dimethacrylate, ethylene glycol dimethacrylate, ethylene glycol dimethacrylate, ethylene glycol dimeth
  • Lignocellulose in the context of the invention contains lignin as well as cellulose and / or hemicellulose.
  • 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 which have a ⁇ -l , 4-glycosidic linkage.
  • Hemicellulose is a collective name for
  • 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 six-carbon sugar monomers (hexoses).
  • Ligans are amorphous, irregularly branched aromatic macromolecules that occur naturally in cell walls and cause the lignification of the cell composed of substituted phenylpropanol units, have a lipophilic character and are insoluble in neutral solvents, such as water, at room temperature
  • 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.
  • the lignocellulosic fibers are preferably wood fibers. These wood fibers can be produced by defibering of wood particles, wood fibers, wood chips or finely divided wood material. Preferred woods for the
  • Production of a fiberboard obtainable by the process according to the invention are, for example, softwoods, in particular pine and / or spruce wood. , ,
  • the fiberboard is a DHF, UDF, LDF, MDF, or HDF board.
  • the fiberboard is a DHF board.
  • the DHF plate according to the invention corresponds to the standard EN
  • the apparent density of the fiberboard is 500 to 700 kg / m 3 , preferably 550 to 650 kg / m 3, and particularly preferably 580 to 625 kg / m 3 .
  • the density can be determined according to EN 323: 93-08.
  • the fiberboard has a thickness of 8 to 30 mm, preferably 10 to 22 mm and particularly preferably 12 to 20 mm.
  • the fiberboard on at least one positive or non-positive connection element in particular a groove and / or spring.
  • at least one of the edge surfaces of the fibreboard can be designed such that it can be connected to another edge surface of another fiberboard.
  • the connection is a tongue and groove connection or bung. It is particularly preferred if the groove, spring and / or bouncing is round, oval, conical or angular.
  • the connection between the fiberboard is form-fitting. Particularly preferred is the compound
  • the fiber plate on at least one edge surface a groove and at least one other edge surface on a spring.
  • a spring When bunging a spring can be incorporated in half the width of the edge of one of the two components to be connected.
  • Processes according to the invention are obtainable, advantageous in that, in addition to the increased fungal resistance, they can also be used to achieve a sufficiently secured outer skin in roof structures. Moreover, by the tongue and groove-form-fitting or the bung, but also the hydrophobized surface an improved
  • the fiberboard according to the invention can be produced in a particularly practical manner by a process which comprises the following steps: a) provision of a fiber mat containing glued, lignocellulose-containing fibers b) treatment of at least one of the two surfaces of the fiber mat from step a) with a polymeric mono-guanidine Connection,
  • step c) pressing the surface-treated fiber mat obtained from step b) into a fiberboard.
  • the inventive method is based on known from the prior art process for fiber board production, in addition to the usual
  • Fibers in particular to DHF, HDF or MDF boards, known. Due to the advantages described above, the treatment with the polymeric mono-guanidine compound can be easily applied to a variety of production processes, such as
  • the usual methods for producing a single-layer or multi-layer fiberboard have the following steps in common: First, the wood material is treated in a digester and then defibered. The comminution or defibration of the wood material is often done in a refiner. Typical process conditions used in industry for comminution or defibration are process temperatures of 160 to 200 ° C and pressures up to 10 bar. Thereafter, the fibers are optionally dried and then glued. The Beieimen the fibers can be done in a Beleimtrommel by spraying. In the production of
  • Fiber boards can be used a variety of binders. Usually, no hardeners are added to the binder in fiberboard manufacture. The glued fibers are finally scattered into a fiber mat, which the person skilled in the art also calls “fiber cake”, optionally preformed and pressed into a fiberboard.
  • step b Process the treatment of the fibers only after their gluing at the stage of the fiber mat, i. in step b). Since, by this procedure, the treated fibers are subjected to only one thermal step, namely compression to a fiberboard, the process according to the invention is particularly gentle on the fibers and the polymeric mono-guanidine compounds used in the process.
  • a further advantage of the treatment according to the invention with the polymeric monoguanidine compound is that its use can be easily integrated into conventional processes of the wood industry for the production of fiberboard.
  • inventive method is used, is of particular advantage.
  • Aqueous solutions or suspensions can be well integrated into the usual process steps and equipment used in fiber board production. There are no time-consuming intermediate steps or process interruptions required.
  • the polymeric mono-guanidine compound can be applied for example via a blowline. Due to the water solubility of the polymeric mono-guanidine compound no organic solvents need to be introduced, which on the one hand a fire hazard and on the other an additional, potentially
  • Wood preservatives is that no other additives, such as - -
  • Emulsifiers are required to dissolve the polymeric mono-guanidine compound and can apply to the fiber mat can. As a result, an additional swelling of the fiber board can be avoided.
  • the inventive method is particularly well suited for the production of fiberboard and is not limited to any specific fiber plate type.
  • the fiberboards obtainable by the process may be single-layered or multi-layered.
  • the embodiments described here allow the uncomplicated increase in the fungal resistance of at least one surface or main side of the DHF plate, which is particularly advantageous because it produces a DHF plate with increased resistance to fungal attack without elaborate intermediate steps, following production,
  • the method according to the invention initially provides that in step a) a fiber mat which contains glued, lignocellulose-containing fibers is provided.
  • the provision is made in conventional processes for making fiberboard, e.g. by spreading lignocellulosic, glued fibers into a fiber mat.
  • the fibers are first glued and then sprinkled onto a forming belt to form a fiber mat.
  • the fiber mat can be additionally formed in a further step and / or smoothed on its upwardly facing surface.
  • the fiber mat preferably consists essentially of lignocellulose-containing
  • Fibers In the "essential” here means up to 80, 85, 90, 95, 98 or 99 wt .-%, based on the total weight of the fiber mat
  • Fiberboard other additives such as fire retardants, solvents, - -
  • Solubilizers Solubilizers, viscosity adjusting agents, wetting agents, emulsifiers, pH-adjusting agents, fats, fatty acids or stabilizers.
  • the lignocellulosic fibers are glued with a binder before, during and / or after they are scattered into a fiber mat.
  • a binder it may be understood as meaning wholly or partially wetting with a composition containing a binder, and such compositions will be referred to by those skilled in the art as a "sizing liquor”.
  • Bury can in particular also mean the uniform distribution of the binder-containing composition on the lignocellulose-containing fibers.
  • the application of the binder-containing composition can
  • blowline can in addition to the added binders and
  • surface-modifying agents which neutralize the surface and / or encapsulate the fiber may also be sprayed onto the water-repellent agents.
  • the lining of the lignocellulose-containing fibers can also be done in a drum or by spraying on the assembly line.
  • the amount of binder used in gluing or gluing is
  • the binder in an amount of 0.1 to 15 wt .-% based on the
  • Wood dry weight (solid resin / atro) is used.
  • the application of the binder can be carried out, for example, in the blowline known to the person skilled in the art.
  • the method according to the invention is suitable for a large number of binder-wood fiber combinations.
  • binders which can be used according to the invention are aminoplasts, phenoplasts, vinyl acetates, isocyanates, epoxy resins and / or acrylic resins, in particular also urea-formaldehyde resin (UF), melamine - -
  • Formaldehyde resin phenol-formaldehyde resin (PF), polyvinyl acetate and / or
  • a system based on urea-formaldehyde resins (UF) is used as binder for the gluing
  • the binder is preferably an isocyanate-based binder, more preferably the binder contains an isocyanate or consists of 80, 90, 95, 99 or 100% by weight thereof, and particularly good results are obtained when the isocyanate is present Polyisocyanate, in particular polymeric diisocyanate (PMDI) is.
  • polymeric diphenylmethane diisocyanate can be used as the polymeric diisocyanate.
  • the fibers of the fiberboard are glued with an isocyanate-based binder, preferably a PMDI based. With these binders can be dispensed with the addition of a curing agent.
  • the inventive method further provides that in step b) at least one of the two surfaces of the fiber mat from step a) is treated with a polymeric monoguanidine compound.
  • surface of the fiber mat means the surface of one of the two main sides of the fiber mat or the later surfaces (or main sides) of the fiberboard as defined above
  • surface of the fiber mat as used herein means the so-called “cover layer” of the fiber mat or fiberboard, which is the most superficial fibrous layer of the fiber mat or fiberboard
  • the cover layer can be the - - most superficial layer of a single-layer or multi-layer fiberboard obtained therefrom.
  • surface of the fiber mat means the entire surface layer which has been treated with a monomeric guanidine compound or in which the polymeric monoguanidine compound is concentrated, which has already been defined above for the fiberboard
  • the thickness of this treated surface layer is dependent on the depth of penetration of the polymeric mono-guanidine compound
  • the treated surface layer is to be distinguished from the middle layer which forms the core of the fiber mat and which does not interfere with
  • the thickness of the treated surface layer (and thus also the depth of penetration of the polymeric mono-guanidine compound into the fiber mat) is at least 0.01, 0.05, 0.1, 0 , 5, 1, 2, 3 or 5 mm into the interior of the fiber mat or the later fiberboard considered from the surface of the fiber mat or the later fiberboard.
  • the fiber mat used in the method according to the invention is the same as that already mentioned above for the fiberboard according to the invention.
  • only one of the two surfaces of the fiber mat is treated. This is preferably the top of the fiber mat. This is to be distinguished from the underside on which the fiber mat rests.
  • Treated surfaces i.e., top and bottom
  • Guanidine compound in the region of at least one of the two surfaces of the fiber mat automatically achieved because the polymeric mono-guanidine compound does not distribute evenly within the fiber mat.
  • the penetration depth and thus the thickness of the region in which the polymeric mono-guanidine compound is concentrated can be determined by the person skilled in the art, for example, by varying the amount of the polymeric mono-guanidine compound used for the treatment or by varying the exposure time, i. the time that elapses between the treatment with the polymeric mono-guanidine compound in step b) and the pressing to the fiberboard in step c).
  • polymeric mono-guanidine compound in the singular, this includes the plural, in particular several identical polymeric monoguanidine compounds and several different polymeric mono-guanidine compounds and mixtures thereof.
  • the polymeric mono-guanidine compound can be sprinkled as a solid or as part of a solid composition.
  • the polymeric mono-guanidine compound is employed in the form of or as part of a liquid.
  • Liquid as used herein may mean a dilute solution of the polymeric monoguanidine compound (ie, the liquid then comprises the polymeric monoguanidine compound as well as a diluent.)
  • composition which contains the polymeric mono-guanidine compound, and optionally other components.
  • This liquid can also have more
  • Additives in particular a quaternary ammonium compound.
  • a polymeric mono-guanidine compound is used in step b) of the process according to the invention.
  • the polymeric mono-guanidine compound the above already applies.
  • the polymer is - -
  • Mono-guanidine compound thereby as (possibly diluted) liquid i. in liquid form, before.
  • the polymeric mono-guanidine compound is preferably present in the liquid in a concentration of 10, 15, 20, 25, 35, 40, 50, 60, 70, 75, 80, 85, 90, 95, 98 or 99% by weight. %, based on the total weight of the liquid.
  • Concentration of 10 wt .-% means that 10 g of the pure polymeric monoguanidine compound are weighed and supplemented with the liquid to 100 g.
  • Particularly preferred as the treatment liquid in step b) is an aqueous solution of the polymeric mono-guanidine compound.
  • the liquid may also contain further additives, for example release agents and / or quaternaries
  • Ammonium compounds included.
  • the polymeric mono-guanidine compound in step b) of the process according to the invention as part of a liquid composition and / or in a liquid in a concentration of 10 to 85 wt .-%, particularly preferably from 20 to 70 wt .-% and more preferably from 25 to 55 wt .-%, based on the total weight of the liquid used, in particular the liquid is an aqueous solution of the polymeric mono-guanidine compound, which may also contain other additives.
  • concentrations of the polymeric mono-guanidine compound in "% by weight” or "% by weight” given here are understood as meaning the proportion by mass. That is, it means the mass of the polymeric mono-guanidine compound based on the total mass of the liquid.
  • the polymeric mono-guanidine compound can be used as such, as a salt or as a mixture thereof.
  • the polymeric mono-guanidine compound and its salts the above applies.
  • the preferred amount of the polymeric mono-guanidine compound which is applied in step b) is 2 to 200 g / m 2 , particularly preferably 4 to 80 g / m 2 and particularly preferably 6 to 30 g / m 2 , based on the surface of the fiber mat treated in step b).
  • Treated surface means, for example, the _ - entire surface of the upper side, even if parts of it are left out, but not the sum total of all surfaces of the fiber mat, ie the upper side, the lower side and the edge surfaces.
  • the polymeric mono-guanidine compound is uniformly distributed over the surface of the top and / or bottom.
  • the above g / m 2 data refer to g of pure polymeric mono-guanidine compound per m 2 treated surface. If, for example, 50 g of a 50% strength by weight solution of the polymeric mono-guanidine compound are sprayed onto 1 m 2 surface in step b), the amount of polymeric mono-guanidine compound used here is 25 g / m 2 .
  • the polymeric monoguanidine compound, PHMG is its salt and / or a mixture thereof.
  • PHMG in particular PHMG * HC1.
  • PHMG is used as 10 to 85% by weight, in particular 20 to 70% by weight, solution in water. Particularly good results have been found in the treatment with a 25 to 55 wt .-% PHMG solution in water. These solutions may optionally contain further additives.
  • Integrate fiber board production The provision of the fiber mat can be done by sprinkling glued fibers on a forming belt.
  • one of the two surfaces of the fiber mat usually lies on the forming belt (referred to herein as the "underside"), while the other of the two surfaces of the fiber mat points upwards Top and / or carried on the resting on the form of the bottom. , ,
  • the treatment in step b) with the polymeric mono-guanidine compound or the polymeric mono-guanidine compound-containing liquid can be carried out, for example, by brushing or spraying.
  • the treatment is by spraying, e.g. by means of a blowline.
  • the treatment can be carried out in such a way that only the polymeric mono-guanidine compound from step b) is initially charged and then the fiber mat from step a) is provided and applied thereto.
  • the presentation may e.g. done by spraying. But it is also possible that only the fiber mat from step a) provided and then at least one of the two
  • Forming tape provided and then treated the upwardly facing surface of the fiber mat with the polymeric mono-guanidine compound of step b).
  • the polymeric mono-guanidine compound or the liquid containing it is preferably sprayed on.
  • the polymeric mono-guanidine compound or the liquid containing it is introduced onto the forming belt and then the fiber mat is provided.
  • the presentation of the polymeric mono-guanidine compound or the liquid containing them is preferably carried out by
  • the upwardly facing surface is additionally treated with the polymeric mono-guanidine compound or the liquid containing it. Thereby, a fiber mat which has been treated on both surfaces can be obtained.
  • Bottom is treated first.
  • the treatment time of the bottom 1 - - to 40 seconds preferably 2 to 30 seconds and especially 2 to 20 before the treatment of the top of the fiber mat done.
  • Fiber mat scattering and / or fiber mat shaping The treatment preferably takes place after the fiber mat formation and / or shortly before the pressing of the fiber mat into a fiber board.
  • the exposure time or the time between the treatment with the polymeric monoguanidine compound in step b) and the compression in step cj can
  • the time between the treatment with the polymeric mono-guanidine compound in step b) and the compression in step c) is at least 1, 2, 5, 10 or 15 seconds.
  • the upper limit for the time between the treatment with the polymeric mono-guanidine compound in step b) and the compression in step c) may be 5 minutes, 2 minutes, 40 seconds, 30 seconds or 20 seconds, wherein said lower and lower
  • the time between the treatment with the polymeric mono-guanidine compound in step b) and the compression in step c) is 1 to 40 seconds, more preferably 2 to 30 seconds, and most preferably 2 to 20 seconds.
  • step c) the surface-treated fiber mat obtained from step b) is pressed into a fiberboard.
  • step c) is a hot pressing. Suitable temperatures for the compression in step c) of the method according to the invention or one of its
  • Embodiments are temperatures of 150 ° C to 250 ° C, preferably from 160 ° C to 240 ° C, more preferably from 180 ° C to 230 ° C. At temperatures in these - -
  • Pressing temperature of at least about 150 ° C is performed.
  • the pressing factor in hot pressing is preferably 2 to 15 s / mm, preferably 2 to 12 s / mm, and particularly preferably 4 to 12 s / mm.
  • the residence time of the lignocellulose-containing fiberboard in seconds per millimeter thickness or thickness of the finished pressed lignocellulose-containing material is referred to as press factor
  • Fiber board understood in the press.
  • Lignocellulosic fiberboard be achieved.
  • the invention also provides fiberboard obtainable by the method described above.
  • Another object of the invention is a roof or wall component, in particular such a house-building.
  • This roof or wall component contains or consists of at least one fiberboard according to the invention.
  • the at least one polymeric mono-guanidine compound is preferably concentrated in the region of the surface, which, based on the house construction, points inwards.
  • Fiberboard is thus preferably oriented within the roof or wall component that the relative to the house construction interior surface to the
  • the fiberboard may, for example, have been produced by the method according to the invention or one of its embodiments.
  • the fiberboard is a DHF board having two different surfaces.
  • this was the, based on the house construction, internal
  • the polymeric mono-guanidine compound as described above, is compatible with the manufacturing process and fiberboard manufacturing conditions. In particular, it does not appear to react with components of the fiberboard which could result in undesirable discoloration of the product. By using the polymeric mono-guanidine compound thus unwanted discoloration of the product are largely avoided.
  • both surfaces of the fiberboard or the roof or wall component can be marked to distinguish the treated from the non-treated surface of the fiberboard or the roof or Wandbaüteils, one of the sides, especially the treated surface.
  • the fiberboard or roof or wall components according to the invention can therefore contain such a marking.
  • the invention also generally relates to the use of a polymeric monoguanidine compound in fiberboard manufacture to increase the resistance of the fiberboard to fungal attack.
  • a polymeric monoguanidine compound in fiberboard manufacture to increase the resistance of the fiberboard to fungal attack.
  • Fiber board production was surprising to the skilled person. This is especially true in view of the fact that wood or fiberboards are attacked by a different spectrum of microorganisms, in particular fungi, whereas the polymeric mono-guanidine compounds have been used in their previous use primarily against bacteria.
  • muscle means the broad definition for the realm of "fungi” from biological taxonomy.
  • unicellulars such as baker's yeast, this also includes multicellulars such as
  • fungus wood-destroying and / or wood-discolouring fungi are or are meant by infestation by these wood-destroying and / or wood-discolouring fungi typically damage the wood by, for example, brown rot, white rot, soft rot, mold, blue streaks or red streaks
  • the fungi are molds and / or blue fungi
  • the fungi may be further selected from the Basomycetes, Ascomycetes and Deutomycetes.
  • "Increasing resistance” as used herein is a reduction in fungal attack as compared to a non-biocidal , fungicidal and / or fungistatic reference. This resistance of the fibreboards to fungal attack can be determined, for example, by reference to the standard EN ISO 846: 1997 "Determination of the effect of
  • the invention also provides, in particular, for the use of a polymeric monoguanidine compound in the surface treatment of a fiber mat in the US Pat
  • Fiberboard production for increasing the resistance of the fiberboard to fungal attack in particular the use in the above-described
  • FIGS. 2a and 2b One by the method according to the invention - 3 - available fiberboard is shown for example in Figure 1.
  • Figure 1 shows a fiberboard 1, which was prepared by the process according to the invention.
  • the fiberboard 1 has two main sides 2 and 3, one the top 2 and the other the bottom 3 of
  • Fibrous plate 1 which were each treated with a polymeric mono-guanidine compound in step b) of the method according to the invention.
  • Areas 2 'and 3' outline the superficial layers of the two major sites whose resistance to fungal attack was enhanced by treatment with the polymeric mono-guanidine compound.
  • the at least one polymeric mono-guanidine compound is concentrated.
  • the core of the fiberboard remains free of the polymeric mono-guanidine compound.
  • the remaining surfaces 4 represent the edges of the fiberboard 1.
  • Figure 2a shows schematically the production of a fiberboard 1 'after a
  • Step b) is treated.
  • a fiber mat 5 which consists essentially of binder-coated lignocellulosic fibers, a liquid 6 containing a polymeric mono-guanidine compound is sprayed from above. Thereafter, the treated
  • Figure 2b shows schematically the production of a fiberboard 1 "after a
  • Embodiment of the method according to the invention in which both main sides, i. the top 2 and the bottom 3 were treated with a polymeric mono-guanidine compound in step b).
  • a liquid 6 containing a polymeric mono-guanidine compound is introduced by spraying on a forming belt 8. Thereafter, a fiber mat 5, which consists essentially of lignocellulose-containing fibers glued with binders, is provided on this introduced liquid 6. Subsequently, the liquid 6 is sprayed onto the upward-facing surface of the fiber mat 5 from above.
  • the fiber mat 5 treated from both main sides is pressed into the fiber plate 1 "in a hot press 7 under the action of elevated pressure and elevated temperature the top layer 2 "), which has been treated with the polymeric monoguanidine compound, is oriented upwards and the bottom 3 [or the top layer 3") oriented downwards. In the region 2 "and 3" at least one polymeric mono-guanidine compound is concentrated.
  • a reference plate was made according to an MDF process commonly used in the wood industry.
  • the experimental panels 1 and 2 were prepared according to an embodiment of the invention, ie, with treatment of both surfaces of the fiber mat with a polymeric mono-guanidine compound. - -
  • Binder emulsifiable PMDI (eMDI) type (IBOND MDF EN 4330 / Huntsman) 3% paraffin emulsion (w / w) - Type Pro A18 (Sasol)
  • Raw material fiber material as softwood (pine and spruce wood)
  • the reference plate was produced in duplicate according to the MDF process commonly used in the wood industry.
  • the reference plate was without
  • the experimental plates 1 and 2 were in duplicate after a
  • the glued fiber mats were additionally surface treated with PHMG (25% solution of PHMG * HCl in water) as part of the fiber mat molding and shortly before press entry.
  • PHMG 25% solution of PHMG * HCl in water
  • the amount of PHMG in step 1) and 3) per surface was 48 g / m 2 for the test panel 1 and 24 g / m 2 for the test panel 2 per surface
  • the results show that treatment with PHMG did not adversely affect the swelling.
  • the experimental plate 2 showed the same swelling as the
  • Experimental plate 2 0.48 N / m 2
  • the results show that the good mechanical properties were maintained despite the additional treatment with PHMG.
  • the experimental plates 1 and 2 even showed a slightly higher strength than the reference plate.
  • the experimental panel 2 showed approximately the same mechanical properties as the experimental panel 1. This was surprising since the experimental panel 1 had a slightly higher swelling, which is why the skilled person would have expected a decrease in the tensile strength.
  • Test specimen After one-week conditioning (20 ° C, 65% RH) of the
  • Test organism Penicillum sp.
  • Tween 80 About 0.1 g Tween 80 was added to 1 L stock mineral salt solution and the solution was subsequently sterilized.
  • test organism was first precultivated on malt extract agar plates.
  • the fungal spores were harvested by means of the mineral salt solution with the aid of a Drigalskispatels.
  • This solution was then filtered through an extraction tube with cotton wool (sterile). The germ count was determined with the Thomasch. The final bacterial count was a CFU of 4 ⁇ 10 7 / ml. This solution was diluted with mineral salt solution to a density of 10 6 CFU / ml, thus obtaining the spore suspension for the experiments.
  • the incomplete agar from 3.1.1. with glucose, so that a glucose concentration of 30 g / 1 was obtained. Then glasses with a volume of 750 ml were filled with 150 ml of agar and sealed with a lid, which was provided centrally with a cotton plug, and steam sterilized.
  • test bodies were applied to the incomplete agar (see point 3.1.1.), which was previously inoculated with a spore suspension of the test organism. If the test body contains no components that can be used for the fungi, the fungi can not develop any mycelium and can overgrow the test specimen or attack the test specimens through their metabolic products.
  • the - - To assess basic resistance of the test body against fungal attack in the absence of organic contaminants.
  • Example 1 used. For this purpose, the incomplete agar from point 3.1.1. with 200 ⁇ of the spore suspension from point 2 inoculated. The respective test piece was applied directly to the agar and incubated at 24 ° C / 90% RH for 4 weeks.
  • test bodies were applied to the complete agar (see point 3.1.2.), which was previously inoculated with a spore suspension of the test organism.
  • Experiments B and B ' are suitable for assessing the principal fungistatic action or property of the test bodies against fungal attack in the presence of organic contaminants. Even if the test bodies do not contain any nutrients, the fungi can overgrow the test bodies and attack the test bodies through their metabolic products. Growth inhibition on the test piece or on the growth medium (inhibition zone) indicates fungicidal or fungistatic activity or equipment of the test piece.
  • test specimens of the reference plate and the test plate 1 from example 1 were used in experiments B and experiment B '. This was the
  • experiment B the respective test body was applied directly to the complete agar and incubated at 24 ° C / 90% RH for 4 weeks. - -
  • experiment B the complete agar was first incubated until its surface was completely overgrown with the test organism. Thereafter, the respective test piece was applied to the complete agar and incubated at 24 ° C / 90% RH for 4 weeks.
  • test specimens of the reference plate showed predominantly a strong to medium fungal growth.
  • test specimens which were rated "medium” the fungal growth spread to the surface of the main side pointing upwards as well as to the edges of the respective test specimen.
  • test specimens of the test plate showed in all experiments mainly no to medium fungal growth.
  • the fungal growth only extended to the edges of each specimen The area of the upwardly facing main face treated with PHMG was not overgrown.

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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)
  • Multicomponent Fibers (AREA)

Abstract

L'invention concerne un panneau de fibres pouvant être obtenu par compression de fibres contenant de la lignocellulose encollées par un liant, au moins un composé polymère de mono-guanidine étant concentré dans la zone d'au moins une des deux surfaces du panneau de fibres. L'invention concerne en outre un procédé de fabrication d'un panneau de fibres selon l'invention, comprenant les étapes consistant à : a) fournir un mat de fibres contenant des fibres encollées contenant de la lignocellulose ; b) traiter au moins l'une des deux surfaces du mat de fibres de l'étape a) au moyen d'un composé polymère de mono-guanidine ; et c) comprimer le mat de fibres traité en surface obtenu à l'étape b) pour obtenir un panneau de fibres. L'invention concerne également un élément de toiture ou de mur, contenant le panneau de fibres selon l'invention ou constitué de celui-ci, le panneau de fibres étant un panneau DHF pourvu de deux surfaces différentes et la surface située à l'intérieur par rapport à la construction de la maison du panneau DHF étant traitée avec un composé polymère de mono-guanidine selon un procédé selon les revendications. En outre, l'invention concerne également l'utilisation d'un composé polymère de mono-guanidine dans la fabrication d'un panneau de fibres pour augmenter la résistance du panneau de fibres à une attaque fongique.
EP17721689.2A 2016-05-09 2017-05-05 Panneau de fibres à résistance accrue contre toute attaque fongique et son procédé de fabrication Active EP3455042B1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
SI201730330T SI3455042T1 (sl) 2016-05-09 2017-05-05 Vlaknena plošča z boljšo odpornostjo proti plesnobi in postopek za izdelavo le-te
PL17721689T PL3455042T3 (pl) 2016-05-09 2017-05-05 Płyta pilśniowa o podwyższonej odporności na atak grzybów oraz sposób jej wytwarzania
HRP20201110TT HRP20201110T1 (hr) 2016-05-09 2020-07-15 Vlaknasta ploča s povećanom otpornošću na gljivičnu infestaciju

Applications Claiming Priority (2)

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DE102016108551.0A DE102016108551B3 (de) 2016-05-09 2016-05-09 Faserplatte mit erhöhter Beständigkeit gegen Pilzbefall sowie Verfahren zu deren Herstellung
PCT/EP2017/060813 WO2017194420A1 (fr) 2016-05-09 2017-05-05 Panneau de fibres à résistance accrue contre toute attaque fongique et son procédé de fabrication

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EP3455042A1 true EP3455042A1 (fr) 2019-03-20
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EP (1) EP3455042B1 (fr)
DE (1) DE102016108551B3 (fr)
HR (1) HRP20201110T1 (fr)
PL (1) PL3455042T3 (fr)
SI (1) SI3455042T1 (fr)
WO (1) WO2017194420A1 (fr)

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Publication number Priority date Publication date Assignee Title
US11186993B2 (en) * 2017-10-24 2021-11-30 Thomas L. Kelly Enhanced roofing cover board
DE102017010366A1 (de) * 2017-11-09 2019-05-09 Fritz Egger Gmbh & Co. Og Harz-Zusammensetzung, Harzbeschichtung, diese enthaltende Laminate und Imprägnate sowie Verfahren zu deren Herstellung

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Publication number Priority date Publication date Assignee Title
DE3726108A1 (de) * 1986-08-07 1988-02-11 Homanit Gmbh & Co Kg Verfahren zur herstellung von hartfaserplatten
DE19800400A1 (de) * 1998-01-08 1999-07-15 Bayer Ag Substituierte Guanidin-Derivate
GB0010187D0 (en) * 2000-04-26 2000-06-14 Forbes Douglas C Improvements relating to construction
UA55660C2 (en) * 2002-04-05 2007-12-25 Method for treatment of packaging or storage of foodstuffs, mainly, liquid, and packaging treated by this method
DE102005051716A1 (de) * 2005-10-27 2007-05-03 Fritz Egger Gmbh & Co. Bindemittelzusammensetzung für Holzwerkstoffe
DE102006003699B3 (de) * 2006-01-26 2007-10-11 Glunz Ag Holzfaserplatte mit Schimmelschutz für den Dach- und Wandbau und Verfahren zu deren Herstellung
DE102007020390A1 (de) * 2007-04-30 2008-11-06 Pfleiderer Holzwerkstoffe Gmbh & Co. Kg Biozide Zusammensetzung, sowie Harzzusammensetzungen, Kompositmaterialien und Laminate, die diese enthalten
FI122723B (fi) * 2007-12-03 2012-06-15 Kemira Oyj Koostumus ja menetelmä puun käsittelemiseksi
FI121917B (fi) * 2008-11-25 2011-06-15 Bt Wood Oy Koostumus ja menetelmä puupohjaisen materiaalin käsittelemiseksi ja koostumuksella käsitelty puupohjainen materiaali
EP2230258A1 (fr) 2009-03-18 2010-09-22 Mindinvest Holdings Ltd. Médicament microbiocide
CA2768388C (fr) * 2009-07-14 2016-08-30 Kemira Oyj Composition biocide pour bois, procede de traitement du bois, et bois produit par ce dernier

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Publication number Publication date
WO2017194420A1 (fr) 2017-11-16
SI3455042T1 (sl) 2020-09-30
HRP20201110T1 (hr) 2020-10-30
DE102016108551B3 (de) 2017-11-02
PL3455042T3 (pl) 2020-11-02
EP3455042B1 (fr) 2020-06-24

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