WO2006013146A1 - Produit de protection et de traitement du bois - Google Patents

Produit de protection et de traitement du bois Download PDF

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Publication number
WO2006013146A1
WO2006013146A1 PCT/EP2005/053399 EP2005053399W WO2006013146A1 WO 2006013146 A1 WO2006013146 A1 WO 2006013146A1 EP 2005053399 W EP2005053399 W EP 2005053399W WO 2006013146 A1 WO2006013146 A1 WO 2006013146A1
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WO
WIPO (PCT)
Prior art keywords
wood
use according
protective agent
amino
amine
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PCT/EP2005/053399
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German (de)
English (en)
Inventor
Prof. Dr. Holger Militz
Dr. Carsten Mai
Oliver Weigenand
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Georg-August Universität Göttingen
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Publication of WO2006013146A1 publication Critical patent/WO2006013146A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C08L83/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • 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
    • B27K3/0278—Processes; Apparatus involving an additional treatment during or after impregnation
    • B27K3/0292—Processes; Apparatus involving an additional treatment during or after impregnation for improving fixation
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/10—Metal compounds
    • C08K3/11—Compounds containing metals of Groups 4 to 10 or of Groups 14 to 16 of the Periodic Table
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/38—Boron-containing compounds

Definitions

  • the present invention relates to wood preservatives, and the use of wood preservatives, which is suitable to make wood and other substances based on cellulose and / or lignin preserved, especially against weathering and microorganisms. Furthermore, this invention relates to methods for the compensation of lignocellulosic materials by using the wood preservatives, as well as with the Holztikmittehi invention treated lignocellulosic materials, especially wood.
  • At this wood preservative is disadvantageous that at least chromium and arsenic are harmful to health and the environment.
  • water-soluble wood preservatives consist of a quaternary ammonium, for example Didecylpolyoxethylammoniumborat (benzalkonium chloride).
  • Didecylpolyoxethylammoniumborat benzalkonium chloride
  • On these wood preservatives is disadvantageous that they can be deposited only superficially on this due to their immediate binding to wood.
  • biocidal active ingredients are 3-iodo-2-propynyl butylcarbamate (EPBC) or triazoles (propiconnazole, tebuconnazole).
  • the known organic wood preservatives are used for the use classes 1, 2 and 3 according to DIN EN 351 and do not lead to a water repellency of the wood, so that the tendency of the wood to absorb water and thus the dimensional stability remains unchanged.
  • JP 2002348567A describes wood preservatives which consist of a mixture of different alkoxysilanes, including amino-containing alkoxysilanes.
  • No. 6,294,608 discloses aqueous emulsions for treating mineral building materials and wood with a mixture of silanes which are provided with alkyl and alkoxy groups or aminoalkyl groups. Polysiloxane compounds having at least one amino group are not disclosed.
  • EP 0716127 discloses organopolysiloxanes and their aqueous mixtures which can be used inter alia for the hydrophobization of cellulose products or as additives for paints and coatings. As the nitrogen-containing radical, a ureido-alkyl group may be contained on the organopolysiloxane.
  • EP 0716128 discloses aminoalkyl-alkoxysilanes which can be used inter alia for the hydrophobization of cellulose products or as additives for paints and varnishes. Polysiloxanes are not disclosed here.
  • the known organic wood preservatives are used for the use classes 1 to 3 according to DIN EN 351 and give the wood no or an improvement in need of hydrophobing.
  • a desired hydrophobization with the present invention results in that the tendency of the wood to water absorption is reduced and thus the dimensional stability is maintained even when changing the water content of the environment.
  • the agents used hitherto for hydrophobing do not provide effective protection against degradation of wood by fungi.
  • the combination of these properties can be achieved so far only by a two-stage treatment of the wood.
  • the present invention relates to protectants that can be used for wood and other lignocellulosic materials to increase their resistance, for example, to microbial degradation and / or weathering, such as sunlight (UV), rain, and other variations in humidity.
  • the agent according to the invention is used as a protective agent for lignocellulosic materials.
  • the present invention relates to a process for improving the properties of wood or lignocellulosic materials by treatment with a preservative of the invention.
  • the present invention relates to wood or other lignocellulosic materials which have been treated with preservatives of the invention.
  • the protective agent to be used according to the invention for wood and wood-based materials, chipboard, medium-density fiberboard, Oriented Strand boards (OSB), paper, cardboard, lignocellulose-based insulation boards, plywood, veneers and packaging material containing biodegradable compounds, hereinafter referred to as lignocellulosic materials contains an amino-modified silicone.
  • the protective agent to be used in the present invention has an amino-modified silicone, which is also referred to as an aminosilicone, and improves after application to the Surface of the lignocellulosic material and / or in its volume, for example by impregnation, its weather resistance and resistance to microbial attack.
  • amino silicone to be used according to the invention has a high resistance to washing out.
  • the protective agent to be used according to the invention enables a method for applying, for. As an impregnation, in a single process step.
  • the protective agent to be used according to the invention has a backbone of straight-chain, optionally branched structural units of silicon dioxide whose free side chains have substituents selected from the group consisting of alkyl, alkoxy and amine, wherein at least one amine substituent on the amino-modified silicone is available.
  • the amine substituent may be a primary, secondary, tertiary or quaternary amine, in the case of several amine substituents also identical or different of the amine substituents.
  • aminoalkyl radicals are mentioned by way of example: H 2 N (CH 2 ) 2 -; H 2 N (CH 2 ) 2 NH (CH 2 ) 3 -; (CH 2 ) 2 N (CH 2 ) -; H 2 N (CH 2 ) 5 -; H (NHCH 2 CH 2 ) 3 -; n- C 4 H 9 NHCH 2 CH 2 NHCH 2 CH 2 -.
  • the number of siloxane units having a SiC-donated radical having a primary, secondary, tertiary or quaternary amino group is up to 50% of the siloxane units, preferably 0.1 to 20%, more preferably 0.2 to 10%.
  • the molecular weight of the aminosilicones for protecting agents according to the invention is for example between about 500 and about 500,000, preferably between about 2,000 and about 200,000.
  • the substituents R 1 to R 4 are each independently selected for each structural unit from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, iso-butyl and amine, at least one radical being an amine substituent which is a primary, secondary, tertiary or quaternary amine; the substituents R 1 to R 4 may also be saturated or unsaturated, straight-chain, cyclic or branched hydrocarbons having up to 20 carbon atoms. It is preferred that three of the hydrocarbon radicals are at least monounsaturated, such as, for example, vinyl, allyl or butadienyl radicals.
  • three of the hydrocarbon radicals may be cycloaliphatic, for example a cyclohexyl radical, or aromatic, such as, for example, a phenyl, naphthyl or an alkylaryl radical, such as tosyl radicals, or aralkyl radicals, such as a benzyl radical.
  • the hydrocarbon radicals can also have further functional groups, such as an alkoxy or hydroxyl group corresponding to R5 or R6, a carboxylic acid group or epoxy group. As an example, Lauryl is called.
  • R5 and R6 are selected from hydroxyl, alkyl or alkoxy groups, in particular from
  • R 1 to R 4 may also have substituents corresponding to R 5 and R 6.
  • the structural elements A and B can be arranged in a straight-chain or branched manner, wherein the order or arrangement of the structural elements can also be freely selected. Exemplary are: R5 -A n -B m -A m -B n -A n -R 6, R 5 - (AB) n - A m - B n - and R6 R5 - A n - B m - A n - R 6.
  • R1 to R3 are alkyl, more preferably methyl and / or ethyl, most preferably methyl, and R4 is an amine, most preferably a quaternary amine.
  • the protective agent according to the invention contains a mixture of different amino-modified silicones of the general formula I.
  • the aminosilicone to be used as protectants according to the invention contains condensable groups bonded directly to silicon, it may be used in admixture with an organopolysiloxane or a mixture thereof, the organopolysiloxane having at least three Si-bonded hydrogen atoms per molecule.
  • a catalyst it is possible to add a catalyst to condense the condensable groups bonded directly to silicon.
  • organopolysiloxanes having at least three hydrogen atoms per molecule bonded to Si are those of the formula ⁇
  • R7 is hydrogen, a methyl, ethyl or phenyl radical
  • p is from 10 to 500, with the proviso that at most one hydrogen atom is bonded to one silicon atom and that the ratio of R7 is 2 SiO-structural units in which both R4 are hydrocarbon radicals, to the structural units with Si-bonded hydrogen is 3: 1 to 1: 4.
  • R4 is methyl when it is not hydrogen.
  • Si-bonded hydrogen is present in a proportion of 0.01 to 0.2% by weight based on the aminosilicone.
  • the aminosilicone according to the invention in admixture with at least one trialkoxy- or tetraalkoxysilane used singly or in combination when the aminosilicone contains condensable groups bonded directly to silicon.
  • an additional catalyst may be included for condensing the condensable groups bonded directly to silicon in the mixture.
  • Trialkoxy- or tetraalkoxysilanes preferably to be used in admixture with the aminosilicone are those of the formula ⁇ ia or DIb:
  • Partial hydrolyzate wherein R and Rl are as defined for formula I.
  • the compounds IIIa and / or IIIb are preferably used in a ratio of 1 to 20 wt .-%, based on the inventive
  • Carboxylic acid salts of tin or zinc can be used as catalysts, for example, where hydrocarbon radicals can be bonded directly to tin, such as di-n-butyltin dilaurate, tin octoate, di-2-ethyltin dilaurate, di-n-butyltin di-2-ethylhexoate, di-2- Ethylhexyltin di-2-ethylhexoate, di-butyl or di-octyltin diacylates.
  • hydrocarbon radicals can be bonded directly to tin, such as di-n-butyltin dilaurate, tin octoate, di-2-ethyltin dilaurate, di-n-butyltin di-2-ethylhexoate, di-2- Ethylhexyltin di-2-ethylhexoate, di-butyl or
  • the catalyst or the catalyst mixture is preferably used in amounts of from 1 to 10% by weight, based on aminosilicone.
  • the crosslinking results in a protective agent that is more strongly embedded in or bonded to the lignocellulosic material. This is particularly the case when the protective means are the aforementioned Having components in a formulation, so that they cross-link with each other during or after the impregnation process, for example, during a tempering step, thus leading to a high molecular weight protective agent with amino groups, which is contained in the material.
  • the protective agent to be used according to the invention may contain a solubilizer and / or an emulsifier, which leads to an increase in stability of the aqueous mixture, which may be a solution or emulsion.
  • Suitable solubilizers or emulsifiers are, in particular, compounds from the group which include amino-modified silicones according to formula I, quaternary fatty alcohol derivatives, in particular a quaternary fatty amine ethanolate, polyalcohols, in particular propylene glycol, ethylene glycol or butyl diglycol and organic solvents such as ethanol, (iso) propanol, THF, DMSO, dioxane, aliphatic and / or chlorinated hydrocarbons.
  • the protective agent to be used according to the invention is used in a mixture with a boron compound, for example borax, borate and / or boric acid.
  • a boron compound for example borax, borate and / or boric acid.
  • the protective agent to be used according to the invention is used in conjunction with a soluble copper compound, for example copper salt (copper (H) oxide, copper sulfate, copper hydroxide carbonate, bis (N-cyclohexyldiazeniumdioxy) copper). It is also possible to use the protective agent of the invention in admixture with an aforementioned boron compound and an aforementioned copper compound.
  • a soluble copper compound for example copper salt (copper (H) oxide, copper sulfate, copper hydroxide carbonate, bis (N-cyclohexyldiazeniumdioxy) copper.
  • the protective agent to be used in accordance with the invention is used in conjunction with organic biocidal compounds, for example triazoles (azaconazole, cyproconazole, propiconazole, tebuconazole, TCMTB), phenylsulfamides (dichlorofluidide, tolylfluanid), carbamates (IPBC, carbendazim), aromatic fungicides ( ortho-phenylphenol, chlorothalonil) and other fungicides (bethoxazine, isothiazolone), synthetic pyrethroids (permethrin, cypermethrin, cyfluthrin, deltamethrin, silafluofen) and other insecticides (imidacloprid, flufenoxuron, chlorpyrifos, fenoxycarb).
  • organic biocidal compounds for example triazoles (azaconazole, cyproconazole, propiconazole, tebuconazole
  • the combination of the protective agent to be used according to the invention with copper and / or boron compounds and / or organic biocidal protective agents can be used both in a one-stage process and in a two-stage process.
  • Single-stage processes are, for example, brushing, dipping or impregnating formulations with protective agents according to the invention in organic solvents or as an aqueous emulsion.
  • the organic, biocidal protective agent is first applied, for example by brushing, dipping or impregnating, and then the protective agent according to the invention.
  • the inventive use of the protective agent is carried out in emulsion, for example in aqueous emulsion.
  • emulsifier may be added, wherein the emulsifier may also be an amino-modified silicone of the general formula I.
  • the use of the protective agent can be carried out by brushing, spraying or other application methods on wood, or by impregnation, for example by vacuum followed by overpressure.
  • the protective agent to be used according to the invention optionally with an additional boron compound and / or an additional copper compound and / or at least one additional organic, biocidal protective agent, consist of one or more compounds of the formula I and are preferably used in the form of an aqueous emulsion.
  • aqueous emulsions so-called microemulsions and / or macroemulsions can be used.
  • a drying step may be carried out, for example one at a temperature of between 10 and 200 ° C., preferably between 60 and 120 ° C.
  • the treated material may also be subjected to freeze-drying under vacuum and / or or dried by use of microwaves.
  • a preferred method for applying protective agents to be used according to the invention is impregnation, which comprises the following process steps:
  • the substrate to be impregnated is in a pressure-resistant impregnating reactor for about 5 minutes to 2 hours, preferably about 15 minutes to 1 hour, in particular about half an hour, initially a pressure of 10 to 500 mbar abs, preferably about 50 to 200 mbar abs., In particular about 100 mbar abs., Exposed.
  • This pressure is maintained and the substrate immersed in the protective agent to be used or its aqueous solution or emulsion or covered.
  • the pressure is then for about 0.5 to 4 hours to about 1, 5 to 20 bar abs., Preferably about 5 to 15 bar abs., In particular about 10 to 12 bar abs., Increased.
  • the pressure can be adjusted to ambient pressure.
  • the substrate is removed from the impregnating solution or emulsion, it is drained off and the vacuum and drackimpregnated substrate can be fed to the drying.
  • the drying of the substrate before and / or after the impregnation can be achieved by technical drying or by free-air drying, preferably up to a wood moisture content of about 10 to 20%, preferably about 13 to 17%.
  • a conventional industrial drying is achieved by heating to about 50 to 120 0 C over a period of about 4 hours to 4 weeks, preferably about 6 hours to 3 weeks.
  • the principle of technical drying is the coordination of humidity and temperature on each other to reduce the formation of cracks.
  • the hot steam drying can be used, are used at the temperatures above the boiling point, ie above 100 0 C at ambient pressure.
  • the hot steam drying can be carried out in a temperature range from above 100 ° C.
  • the suitable drying temperature and drying time depends on the dimensions of the substrate to be dried and can be determined by a person skilled in the art.
  • the initial humidity is about 100% and is reduced in the course of drying.
  • the mechanism by which the preservative to be used in the present invention makes wood and other lignocellulosic materials more resistant to weathering and / or variations in moisture content is at least partially due to the surface, preferably the layers adjacent to the surface be rendered hydrophobic to the total volume of the wood or lignocellulosic material.
  • the preservative to be used in the present invention results in reduced moisture absorption, which in turn results in less dimensional variation with changing ambient humidity.
  • the protective agent of the invention therefore leads to a better dimensional stability of wood, because it penetrates into the cell wall of the wood and remains there permanently.
  • the wooden cell wall resembles a preswollen state and therefore absorbs less water than untreated wood.
  • the penetration of the protective agent to be used according to the invention is achieved above all with so-called microemulsions, for example with particle sizes of 10 to 100 nm.
  • microemulsions can penetrate into the pores of wood cell walls and also between cellulosic strands, so that the further uptake of water is permanently reduced. In this way, the dimensional change, for example, the shrinkage in the drying of wood is reduced as the moisture content of the environment decreases.
  • the protective agent to be used according to the invention at least partially coats the inner surfaces of wood cells and penetrates into pores of the wood cell wall.
  • the content of the protective agent to be used according to the invention on at least one amine substituent, which may be one or more identical or different substituents from the group of primary, secondary, tertiary or quaternary amine, on the one hand can provide a better association of the protective agent with the lignocellulosic material, on the other hand confer a certain antimicrobial effect.
  • the antimicrobial action is inhibitory or biocidal, in particular with respect to fungi, so that lignocellulosic material treated with the protective agent according to the invention, for example wood, is less affected by discoloring, for example, fungi or mold, or destructive fungi (white rot, brown rot) and therefore has a greater resistance to having microbial degradation.
  • Figure 1 shows a graphic representation of the water absorption in percent of treated with the invention Aminosilikon compounds and comparative compounds
  • FIG. 2 shows the water absorption in percent of aminosilicone according to the invention
  • FIG. 3 shows the weight loss in percent of treated and untreated beech wood samples after 12 weeks of incubation with Trametes versicolor
  • FIG. 4 shows the weight loss in percent of treated and untreated pine wood samples after 12 weeks of incubation with Coniophoraputeana
  • FIG. 5 shows the infestation of the surface of treated and untreated pine wood specimens by mold fungi at an ambient moisture content of about 95% over a period of 7 weeks
  • FIG. 6 shows cracking, surface fungus infestation with wood exposed directly to solar radiation to the south, and infestation by mold on the sun-facing, north-facing surface of treated and untreated pine wood specimens after natural weathering in the period from September 2003 to April 2004
  • FIG. 7 shows the weight gain of pine wood by treatment with the inventive protection products compared to water and the anti-shrinkage / anti- swelling effect according to the invention retardants at 20 0 C between 0 and 65% and between 0 and 100% wood moisture
  • FIG. 8 shows the weight increase of beech wood and anti-SchwmdVanti swelling effect as in FIG. 7,
  • FIG. 9 shows the course of the weight losses of ground pine wood samples which were treated untreated (control) or with an aminosilicone (AS 3) or a conventional flame retardant (impralit F3 / 66) during a thermogravimetric analysis
  • Figure 10 shows the reduction in weight loss of aminosilicone-treated pine wood samples during a flame test compared to untreated pine wood samples.
  • FIG. 11 shows the reduction of the burn-up distance (afterburning) of aminosilicone-treated pine wood samples during a flame test after removal of the ignition source in comparison to untreated pine wood samples and
  • FIG. 12 shows the weight loss of aminosilicone-treated pine sapwood samples by means of rotten rot fungi in contact with the soil according to the European prestandard ENv 807 over a period of 8 or 16 weeks.
  • wood samples of the dimensions 5 ⁇ 10 ⁇ 30 mm were impregnated under vacuum and subsequent pressure.
  • test pieces were deaerated in a vacuum of less than 100 mbar for about one hour and then kept in an aqueous emulsion of inventive preservative and comparative emulsions under a pressure of 6 bar for about 2 hours.
  • concentration of the aminosilicones in the impregnating emulsion was about 5% by weight. This was followed by drying at ambient temperature for 12 hours.
  • the Wasseraufhahrne was measured in a dip test. The results of the determination of Wasseraufhahrne over 4 hours are shown in Figure 1, those over a period of 24 hours in Figure 2.
  • the water absorption was determined by weighing the individual wood samples before and after the dive time.
  • aminosilicone compounds (AS) 1 to 3 according to the invention used in FIGS. 1 and 2 are:
  • R5, R6 -OH.
  • the molecular weight is about 150,000, the viscosity of the pure chemical at about 3000 mPa s.
  • the proportion of amino groups is 0.12%.
  • the wording used was one
  • Macroemulsion (particle size of the emulsion approx. 200 microns).
  • silicone Sl epoxy-functional polydimethylsiloxane, the epoxy group (CHOCH 2 ) is bonded to Si as - (CH 2 ) 3 -O-CH 2 -CHOHCH 2
  • S2 monomeric silane
  • silicone S3 Silane / siloxane mixture, Wacker Chemie BS 1702
  • FIGS. 1 and 2 show that the aminosilicones AS 1 to AS 3 according to the invention each have the water uptake compared to the Comparative compounds S2 and S3 or untreated wood K during a dipping time of 4 h and 24 h significantly reduced, while the silicone Sl gives a similar high hydrophobicity as the compounds of the invention.
  • Example 2 Impregnation of beech wood to increase the resistance against holzbaubende mushrooms
  • the samples of beech wood had the dimensions 5 ⁇ 10 ⁇ 30 mm, radial, tangential, longitudinal, the aminosilicones AS 1, AS 2, AS 3 were the compounds given in Example 1.
  • the number of Diorganosüoxan fürtechniken was about 200 - 300, the viscosity of the pure compound at about 2000 mPas.
  • the proportion of amino groups lab at 0.20%.
  • the formulation used was a macroemulsion with ready alcohol ethanolates as emulsifiers.
  • the silicones S1 to S3 are polydimethylsiloxanes without an amino or ammonium group as comparative compounds according to Example 1.
  • W denotes a wax emulsion
  • K denotes untreated wood
  • Pine wood samples (5 ⁇ 10 ⁇ 30 mm, radial, tangential, longitudinal), which had been impregnated with aminosilicones AS 1 to AS 4 according to the invention, comparative compounds S1 to S3 or wax emulsion W according to Example 1, and untreated wood (marked K) were used wood-destroying brown rot fungus Coniophora souna exposed for 12 weeks. Mass loss was determined by weighing the samples before and after the incubation period.
  • impregnated pine wood samples having the dimensions 15 ⁇ 20 ⁇ 50 mm (radial, tangential, longitudinal) were stored in a closed container above a water surface with wood preservatives according to the invention in order to determine a wood moisture near the fiber saturation point of the Wood (about 30%).
  • the impregnation was carried out according to Example 1 in aqueous solutions with 5 wt .-% of the respective silicone compound.
  • forest soil was added to the water to increase the density of mold spores in the container.
  • the air of the container was continuously circulated by means of a fan.
  • the infestation by mold on the surface of the samples was optically evaluated on an arbitrary scale from 0 to 3, where 0 indicates no infestation, 1 low infestation, 2 middle infestation and 3 severe infestation.
  • the results of the evaluation are shown graphically in FIG.
  • the compounds used are the untreated control sample K, S2 and S3 as compounds without Amino group, the aminosilicones AS 1, AS 2, AS 3 according to the invention, as defined above and
  • the molecular weight is about 3000, the viscosity of the pure compound is 550-950 mPas. Each molecule has two quaternary ammonium groups.
  • the formulation used was in the form of a 50% solution of AS 6 in propylene glycol, which was then used in aqueous dilution with a final concentration of 5 wt .-% AS 5 for impregnation.
  • the cracking, the infestation by surface fungi on the south-facing side and the infestation by mold on the north-facing side were visually on a scale of 0 (no infestation or no cracking), 1 (low infestation) , 2 (moderate infestation) and 3 (severe infestation, severe cracking) classified.
  • the wood samples were impregnated according to Example 1 with the aminosilicones AS 1 and AS 6 according to the invention with a proportion of 5 wt .-% in the impregnating solution according to Example 1.
  • Example 6 Reduction of Water Absorption and Increasing Dimensional Stability Wood samples having the dimensions 25 ⁇ 25 ⁇ 10 mm (radial, tangential, longitudinal) were vacuum-bonded according to Example 1 with amino silicone compounds AS 5 according to the invention in a concentration of 5% by weight.
  • Lk length of air-conditioned samples (radial, tangential, longitudinal),
  • Ld length of conditioned samples (radial, tangential, longitudinal)
  • the relative volume swelling or shrinkage of the can be calculated according to:
  • ASQW anti-shrinkage / anti-swelling effect
  • the anti-shrinkage / anti-swelling effect was determined for two ranges of wood moisture content, namely ASQW 0-20 / 65 between absolutely dry wood (0% wood moisture) and the moisture content of wood in normal climate (temperature 20 0 C, 65% relative humidity) (corresponds to about 12% wood moisture), and ASQW 0-100 between absolutely dry wood (0% wood moisture) and water-saturated wood (100% wood moisture).
  • the effect of the protective agents according to the invention on increasing the dimensional stability of wood can be demonstrated both for hardwoods (shown here for beech) and for softwoods (shown here for pine).
  • the increase in dimensional stability is achieved in particular by microemulsions of the protective agents according to the invention, while the increase in the dimensional stability by macroemulsions of the same protective agents is lower.
  • Example 7 Durability of Inventive Protection Agents on or in Wood.
  • the leaching of the preservatives from impregnated wood samples was measured.
  • Example 1 impregnated samples of pine wood with the Dimensions 5 x 10 x 30 mm (radial, tangential, longitudinal) following impregnation in a Soxhlet apparatus for 8 hours under reflux with water.
  • the wood samples were continuously washed by returning water of about 90 0 C. In this way it was ensured that no equilibrium between wood sample and extractant could be established, but in each case unladen extractant washed around the wood samples and a maximum extraction was carried out.
  • EXAMPLE 8 Flame Retardation or Reduction of Flammability by Aminosilicones
  • STA 409 PC thermobalance
  • pinewood samples impregnated with aminosilicones AS 1, AS 3, AS 4, AS 5 and AS 6 and having dimensions of 5 ⁇ 10 ⁇ 100 mm are impregnated according to the method of Example 1 (radial, tangential, longitudinal) at 20 0 C and 65% relative humidity air-conditioned.
  • One treated and one untreated wood sample were arranged in a V-shape at an angle of about 45 ° to the horizontal and were at the bottom End 5 mm. Both wood samples were simultaneously ignited with a Bunsen burner for 25 seconds. By the time the untreated sample was about 2/3 burnt, the flames were extinguished.
  • the burn-up distance and the weight loss of the treated wood samples were compared with the values of the untreated wood samples. The weight loss is shown in FIG. 10, the burn-up path in FIG. 11.
  • Samples of Kiefemsplintholz with the dimensions 5 x 10 x 30 mm (radial, tangential, longitudinal) are stored until reaching the equilibrium moisture in a climatic chamber at 20 0 C and 65% relative humidity.
  • the samples are treated with a solution of (a) 3% by weight boric acid, 5% by weight aminosilicone AS 1, 92% water, (b) 3% by weight boric acid, 5% by weight aminosilicone AS 5, 92 % Water or (c) 3 wt .-% boric acid, 97% water in a vacuum process according to Example 1 impregnated.
  • the samples After removal from the impregnating liquid, the samples are dried for 4 hours at 60 0 C and a further 16 hours at 120 0 C and then stored for 24 hours in the climatic chamber at 20 0 C and 65% relative humidity.
  • Each of five samples was completely covered with 37.5 mL of demineralized water and soaked with the aid of a negative pressure of 100 mbar and remained submerged in demineralized water for a further 4 days.
  • the fixation of the boron compound was determined on the basis of the boron emerging from the samples.
  • the aminosilones of the present invention are capable of fixing the boron compounds conventionally used as the biocidal wood preservatives, such as boric acid and other boron salts, in the lignocellulosic material, thus maintaining the effect of the boron compound for a long period of time.
  • Example 10 Increasing resistance to soft rot by aminosilicones
  • Pine sapwood samples of the dimensions 5 ⁇ 10 ⁇ 100 mm (radial, tangential, longitudinal) are treated according to Example 1 with the aminosilicones AS 1, AS 2 or AS 4 and according to the European prestandard ENv 807 over 16 weeks in contact with the ground exposed to the infestation by soft rot fungi.
  • the wood In contact with the ground, the wood is exposed to a variety of microorganisms that break down unprotected wood very quickly and lead to a loss of strength.
  • the controls are untreated non-durable pine sapwood samples and moderately durable pine heartwood samples.
  • the degree of degradation of the wood samples was determined by the loss of the dynamic modulus of elasticity (dyn. E modulus). Results are shown in FIG.
  • the protective agents to be used according to the invention provide lignocellulosic materials, for example wood, increased resistance to attack by algae and harmful marine organisms, such as, for example, shells.
  • the use of wood according to the invention offers increased resistance to attack by algae.
  • the preservatives to be used according to the invention can increase the resistance of wood to wood-destroying insects, for example termites, domestic goat beetles, common ruffians, sapwood beetles. This is the case in particular if, in addition to the protective agents according to the invention, insecticides are introduced into the lignocellulosic material.
  • the degradation experiments i. the measured mass loss of beech and pine in contact with the white rot fungus Trametes versicolor or the brown rot fungus Coniophora souna, that the inventive use of amino silicones as a protective agent wood and other lignocellulosic materials against wood-destroying fungi resistant.
  • amino-modified silicones also leads to lignocellulosic materials, for example wood, being markedly more resistant to attack by surface fungi, such as mold or blueness.
  • the protective agents to be used according to the invention can impart both hydrophobic and also antiperspirant properties to the treated lignocellulosic material.
  • the leaching tests with boric acid for determining the fixation of hydrophilic substances by the protective agents according to the invention in lignocellulosic materials show that the use according to the invention of the aminosilicones achieves fixation or retention of hydrophilic substances in wood or lignocellulosic materials.
  • the fixation or retention of lipophilic substances in lignocellulosic materials by the use according to the invention as protective agents go back to the general lipophilic properties of these silicone derivatives. Therefore, the protective agents to be used according to the invention are suitable for fixing conventional wood treatment agents, such as, for example, flame retardants, fungicides, insecticides or dyes. This applies above all to those conventional compounds which are poorly retained in the matrix of the lignocellulosic material and easily washed out by water.
  • thermogravimetric analysis shows that the use according to the invention as protective agents leads to an increased flame resistance or fire resistance of the lignocellulosic materials treated therewith, as demonstrated by the example of wood.
  • conventional flame retardants are applied to the lignocellulosic material, for example those from phosphorus compounds (phosphates, polyphosphates), magnesium compounds (magnesium hydroxide), aluminum compounds (aluminum hydroxide), bromine / chlorine compounds (hydrogen halides) and flame retardant systems with inflating substances.
  • the protective agents to be used according to the invention can also serve for the physical and / or chemical bonding of conventional treatment agents for wood or other materials based on cellulose and thus increase their stability.
  • This relates in particular to the combination of protective agents according to the invention with flame retardants, insecticides or dyes, especially those compounds which are preferably stable in a hydrophobic environment or are retained there.
  • woods treated with protectors used in accordance with the present invention may have more resilient surfaces, i. For example, harder and / or more abrasion resistant surfaces.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Chemical And Physical Treatments For Wood And The Like (AREA)

Abstract

L'invention concerne un produit de protection du bois comprenant du silicium modifié par des amines de formule R5 - A<sub
PCT/EP2005/053399 2004-07-29 2005-07-14 Produit de protection et de traitement du bois WO2006013146A1 (fr)

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DE102004036918.6 2004-07-29
DE102004036918A DE102004036918A1 (de) 2004-07-29 2004-07-29 Schutzmittel und Vergütung für Holz

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EP2444447A3 (fr) * 2010-10-25 2012-07-18 Evonik Goldschmidt GmbH Polysiloxane doté de groupes contenant de l'azote
WO2012143371A1 (fr) * 2011-04-18 2012-10-26 Momentive Performance Materials Gmbh Polyorganosiloxanes ou silanes fonctionnalisés pour traiter des matériaux lignocellulosiques
EP3146842A1 (fr) * 2015-09-25 2017-03-29 Leader Optronics Technology Co., Ltd. Procédé de transmission d'une activité antimicrobienne à un article ou à un produit d'hygiène et article et produit d'hygiène auxquels l'activité antimicrobienne a été transmise
CN114206112A (zh) * 2019-08-09 2022-03-18 特洛伊公司 包含聚合甜菜碱和氨基甲酸酯的协同木材防腐组合物

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WO2011131668A1 (fr) 2010-04-19 2011-10-27 Georg-August-Universität Göttingen Stiftung Öffentlichen Rechts Composés de polyorganosiloxane pour protéger le bois contre les termites
DE102012103372A1 (de) 2011-04-18 2012-10-18 Momentive Performance Materials Gmbh Verwendung von aminofunktionellen Polyorganosiloxanen als Holzschutzmittel
CA3242204A1 (fr) 2021-12-07 2023-06-15 Archroma Ip Gmbh Traitement du bois avec des polyorganosiloxanes
EP4194163A1 (fr) 2021-12-07 2023-06-14 Archroma IP GmbH Traitement du bois avec des polyorganosiloxanes

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EP0631999A2 (fr) * 1993-06-30 1995-01-04 Osi Specialties, Inc. Emulsion cationique des alkylalkoxysilanes
EP0882555A2 (fr) * 1997-06-04 1998-12-09 Shin-Etsu Chemical Co., Ltd. Méthode pour la préparation des composites antibactériens et antifongiques de bois avec de la matière inorganique et produits ainsi fabriqués
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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2444447A3 (fr) * 2010-10-25 2012-07-18 Evonik Goldschmidt GmbH Polysiloxane doté de groupes contenant de l'azote
WO2012143371A1 (fr) * 2011-04-18 2012-10-26 Momentive Performance Materials Gmbh Polyorganosiloxanes ou silanes fonctionnalisés pour traiter des matériaux lignocellulosiques
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EP3146842A1 (fr) * 2015-09-25 2017-03-29 Leader Optronics Technology Co., Ltd. Procédé de transmission d'une activité antimicrobienne à un article ou à un produit d'hygiène et article et produit d'hygiène auxquels l'activité antimicrobienne a été transmise
CN114206112A (zh) * 2019-08-09 2022-03-18 特洛伊公司 包含聚合甜菜碱和氨基甲酸酯的协同木材防腐组合物
CN114206112B (zh) * 2019-08-09 2024-04-12 特洛伊公司 包含聚合甜菜碱和氨基甲酸酯的协同木材防腐组合物

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