DE102004036918A1 - Protective agent and remuneration for wood - Google Patents

Abstract

Wood preservative with an amino-modified silicone of the general formula R5 - A¶n¶ - B¶m¶ - R6 with the structural units DOLLAR F1, which are arranged arbitrarily, the substituents R1 to R4 being selected 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; DOLLAR A n is 0 to 50, preferably 1 to 10; DOLLAR A m is 0 to 50, preferably 1 to 10; DOLLAR A R5 and R6 are selected from alkyl or alkoxy groups, in particular from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, methoxy, ethoxy, propoxy, isopropoxy, butoxy and / or isobutoxy.

Description

The The present invention relates to wood preservatives, as well as agents which suitable are wood and other substances based on cellulose and / or Lignin to be preserved, especially against the weather and Microorganisms. Furthermore, this invention relates to methods for compensation of lignocellulosic materials and with the wood preservatives according to the invention treated lignocellulosic materials, especially wood.

It is known, the resistance of wood against the weather through a coating of paints and colors increase. dimensional changes of wood, for example due to swelling and shrinkage due to of water uptake or release caused by external humidity fluctuations are, lead however, to the chipping of such paints.

It is also known, the visual appearance and durability of wood against harmful Microorganisms, such as fungal or white rot, brown rot and soft rot by impregnation protected with a mixture of arsenic, ionic copper and chromium VI.

At This wood preservative is disadvantageous that at least chromium and Arsenic health and harmful to the environment are.

Farther are water-soluble Wood preservatives known, consisting of a quaternary ammonium, for example Didecylpolyoxethylammoniumborat (benzalkonium chloride) exist. On these wood preservatives is disadvantageous that they due to their immediate binding to wood only superficially deposited on this can be.

Further biocidal agents are 3-iodo-2-propynyl-butylcarbamate (IPBC) or Triazoles (propiconnazole, tebuconnazole).

The known organic wood preservatives are for use classes 1, 2 and 3 are used according to DIN EN 351 and do not lead to a hydrophobing of the wood, so that the inclination of the wood for water absorption and thus the dimensional stability unchanged remains.

to Reduction in the water absorption of wood were essentially Compounds based on oils, Fats and waxes (paraffins, silicones) used.

Known Wood preservatives used for water repellency and have a content of silicon compounds are also known. Thus, JP 2002348567A describes wood preservatives which are from a Mixture of different alkoxysilanes exist, including amino-containing Alkoxysilanes.

The US 6294608 discloses aqueous emulsions for treating mineral building materials and wood with a mixture of silanes provided with alkyl and alkoxy groups or aminoalkyl groups. Polysiloxane compounds having at least one amine group are not disclosed.

The 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.

The EP 0716128 discloses aminoalkyl-alkoxysilanes which can be used inter alia for the hydrophobization of cellulose products or as additives for paints and coatings. Polysiloxanes are not disclosed here.

The US 2002/0026881 describes a composition for hydrophobing of surfaces, which contains silicone, among other things. Amine-containing silicones are not specified.

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 with the present invention hydrophobing leads to the fact that the inclination of the wood is reduced to absorb water and thus the dimensional stability even when changing the water content of Environment is preserved.

Of Further provide the funds previously used for hydrophobing no effective protection against damage to wood by fungi ready. The combination of these properties can so far only by a two-stage treatment of the wood can be achieved.

When example for the combination of a hydrophobizing substance with a biocidal Fabric is the so-called Royal process to call. In this Two-stage process, the wood is first in a first step with an organic copper salt (Cu-HDO) or an inorganic Impregnated copper salt, subsequently becomes a second step an impregnation performed in oil to to prevent the leaching of biocidal copper.

General Description of the invention

Compared to the known prior art, it is the object of the present Invention, a protective agent for To provide wood and other materials based on lignocellulose, with the consistency against the weather and microbial infestation can be improved.

Generally The present invention relates to preservatives for wood and other lignocellulosic materials to increase their resistance, for example, opposite microbial degradation and / or weathering, such as sunlight (UV radiation), rain and other variations in humidity. The agent according to the invention is intended for use as a protective agent for lignocellulosic materials.

In In another aspect, the present invention relates to a method for improving the properties of wood or lignocellulosic Materials by treatment with a protective agent according to the invention. In a further aspect, the present invention relates on wood or other lignocellulosic materials, the or with protective agents according to the invention were treated.

The Inventive preservatives for wood and wood-based panels, chipboard, medium density fibreboard, Oriented Beach boards (OSB), paper, cardboard, lignocellulose-based insulation boards, Plywood, veneers and packaging material containing biodegradable compounds, summarized below lignocellulosic materials, contains an amino-modified Silicone.

The Inventive preservatives has an amino-modified silicone, also called aminosilicone is designated, and improves after application to the surface of the lignocellulosic material and / or in its volume, for example by impregnation, its weather resistance as well as the resilience against microbial infestation.

Farther has the aminosilicone according to the invention a high resistance against washing out.

When further advantage allows the protective agent of the invention a method of application, e.g. As an impregnation, in a single Process step.

The protective agent 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 the amino-modified silicone at least one amine substituent is present , 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. The following 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 ₃ ) ₂ N (CH ₂ ) -; H ₂ N (CH ₂ ) ₅ -; H (NHCH ₂ CH ₂ ) ₃ -; nC ₄ H ₉ NHCH ₂ CH ₂ NHCH ₂ CH ₂ -.

The Number of siloxane units containing a SiC-bonded radical with a primary, secondary tertiary or quaternary Have 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.

An example of a protective agent according to the invention is given by the following general formula I: R5-A _n -B _m -R6 (I)

The substituents R1 to R4 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 of which is an amine substituent which is a primary, secondary, tertiary or quaternary amine; the substituents R1 to R4 can 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 vinyl, allyl or butadienyl radicals. As a further possibility, 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.
m is 1 to 100, preferably 2 to 10;
n is 1 to 1000, preferably 10 to 500;
R5 and R6 are selected from hydroxyl, alkyl or alkoxy groups, in particular from hydroxymethyl, hydroxyethyl, dihydroxyethyl, hydroxypropyl, dihydroxypropyl, trihydroxypropyl, hydroxyisopropyl, hydroxybutyl, dihydroxybutyl, trihydroxybutyl, hydroxyisobutyl, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, Methoxy, ethoxy, propoxy, isopropoxy, butoxy and / or isobutoxy.

alternative can also one or more of R1 to R4 substituents accordingly R5 and R6 have.

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,
R5- (AB) _n -A _m -B _n -R 6 and
R5-A _n -B _m -A _n -R 6.

Preferably, R 1 to R 3 are alkyl, more preferably methyl and / or ethyl, most preferably methyl, and R 4 is an amine, most preferably a quaternary amine. Preferred quaternary amine substituents are -XN ⁺ (R 1) ₂ (R ₂ ) wherein X is a (CH ₂ ) chain of 0-10 methylene units ^and R 1 ^and R _{2 are} as defined above, preferably methyl, R _{2 is} a long chain alkyl or fatty acid chain with 8 to 20 carbon atoms, preferably lauryl, and n = 2 to 10, m = 1 to 2.

When another embodiment contains the protective agent of the invention a mixture of different amino-modified silicones of the general Formula I.

If the invention as a protective agent Amino silicone to be used directly to silicon bonded condensable groups contains so it may be mixed with an organopolysiloxane or a mixture these are used, wherein the organopolysiloxane at least has three Si-bonded hydrogen atoms per molecule. Optionally, that is Addition of a catalyst for condensation of directly bonded to silicon condensable Groups possible.

Preferably in mixture with the aminosilicone to be used organopolysiloxanes having at least three hydrogen atoms per molecule bonded to Si are those of the formula II (CH ₃ ) ₃ SiO (SiR 7 ₂ O) _p Si (CH ₃ ) ₃ (II), wherein R7 is hydrogen, methyl, ethyl or phenyl, p is 10 to 500 with the proviso that a silicon atom is bonded to at most one hydrogen atom and that the ratio of R7 is ₂ SiO ₂ structural units in which both R 4 are hydrocarbon radicals to the Si-bonded hydrogen structural units is 3: 1 to 1: 4. Preferably, R4 is methyl when it is not hydrogen. Further, it is preferable that Si-bonded hydrogen is present in a proportion of 0.01 to 0.2% by weight based on the aminosilicone.

alternative or additionally for mixing with one or more organopolysiloxanes, such as such according to formula II, the aminosilicone according to the invention in admixture with at least one trialkoxy- or tetraalkoxysilane, which are used individually or in combination with each other, if the aminosilicone directly attached to silicon condensable groups contains. Optionally, an additional Catalyst for the condensation of condensable groups bonded directly to silicon be included in the mixture.

Trialkoxy- or tetraalkoxysilanes preferably to be used in admixture with the aminosilicone are those of the formula IIIa or IIIb: RSi (OR1) ₃ (IIIa), Si (OR1) ₄ (IIIb), or partial hydrolysates of trialkoxy- or tetraalkoxysilanes having up to 10 silicon atoms per partial hydrolyzate,
wherein R and R1 are as defined for formula I. The compounds IIIa and / or IIIb are preferably used in a ratio of 1-20% by weight, based on the aminosilicone according to the invention.

When Catalysts can for example, carboxylic acid salts be used by tin or zinc, wherein hydrocarbon radicals can be bound directly to tin, such as di-n-butyltin dilaurate, Tin octoate, di-2-ethyltin dilaurate, di-n-butyltin di-2-ethylhexoate, di-2-Ethylhexylzinn di-2-ethylhexoate, di-butyl or di-octyltin diacylates. As catalysts can also Alkoxy titanates, for example butyl titanate and triethanolamine titanate, as well as zirconium compounds or mixtures of one or more of the aforementioned catalysts.

Preferably is the catalyst or the catalyst mixture in amounts of 1 to 10% by weight based on aminosilicone used.

The Combination of aminosilicone having condensable groups with the aforementioned organopolysiloxanes and / or with trialkoxy or Tetraalkoxysilanes, optionally with additional catalyst for acceleration the condensation in the protective agent of the invention leads to Networking. The crosslinking gives a protective agent that is stronger in embedded in or associated with the lignocellulosic material is. This is especially the case when the preservative having the aforementioned ingredients in a formulation, so that this only during or after the impregnation process, for example during a tempering step, network with each other and so on high molecular weight protective agent with amino groups, which in the material is included.

The Inventive preservatives can be a solver and / or an emulsifier which contributes to an increase in stability of the aqueous Mix leads, the one solution or emulsion can be. As a solubilizer or emulsifier come in particular compounds from the group in The amino-modified silicones of formula I, quaternary fatty amine alcohols, especially a quaternary Fatty amine ethanolate, polyalcohols, especially propylene glycol, ethylene glycol or butyldiglycol and organic solvents such as ethanol, (iso) propanol, THF, DMSO, dioxane, aliphatic and / or chlorinated hydrocarbons contains.

In a further embodiment becomes the protective agent of the invention in admixture with a boron compound, for example borax, borate and / or boric acid used.

In a further embodiment, the protective agent according to the invention is used in conjunction with a soluble copper compound, for example copper ²⁺ salt (copper (II) 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.

In a further embodiment becomes the protective agent of the invention used in conjunction with organic biocidal compounds, such as triazoles (azaconazole, cyproconazole, propiconazole, Tebuconazole, TCMTB), phenylsulfamides (dichlorofluid, tolylfluanid), Carbamates (IPBC, carbendazim), aromatic fungicides (ortho-phenylphenol, Chlorothalonil) and other fungicides (betoxazine, isothiazolone), synthetic pyrethroids (permethrin, cypermethrin, cyfluthrin, Deltamethrin, silafluofen) and other insecticides (imidacloprid, Flufenoxuron, chlorpyrifos, fenoxycarb).

The Combination of the protective agent according to the invention with copper and / or boron compounds and / or organic biocides Protective agents can be used both in a one-step process as well be used in a two-stage process. One-step process are, for example, brushing, dipping or impregnating with formulations protection agent according to the invention in organic solvents or as watery Emulsion. In two-step process is preferably only the organic, biocidal protective agents applied, for example by Painting, dipping or impregnating, and subsequently the protective agent of the invention.

In preferred embodiment is the protective agent of the invention as an emulsion, for example in aqueous emulsion. For the production and / or stabilization of such an aqueous emulsion may be an emulsifier be added, wherein the emulsifier is an amino-modified Silicone of the general formula I can be.

The Inventive preservatives can by painting, spraying or other application methods are applied to wood, or by Impregnate, for example by vacuum with subsequent overpressure. In this case, the protective agent according to the invention, optional with an additional Boron compound and / or an additional Copper compound and / or at least one additional organic, biocidal protective agent, consisting of one or more compounds of the formula I and preferably in the form of an aqueous Emulsion can be used. As aqueous emulsions so-called Microemulsions and / or macroemulsions are used.

to Fixation of the protective agent according to the invention in wood or other lignocellulosic materials can be a drying step be made, for example one at a temperature between 10 and 200 ° C, preferably between 60 and 120 ° C. The treated material can also by freeze-drying under vacuum and / or by using Microwaves are dried.

A preferred method for applying protective agents 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 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. Then the pressure can be adjusted to ambient pressure. The substrate is removed from the impregnating solution or emulsion, it is drained off and the thus vacuum- and pressure-impregnated substrate can be fed to the drying.

The Drying of the substrate before and / or after impregnation can be achieved by technical drying or by outdoor drying be, preferably up to a wood moisture of about 10 to 20%, preferably about 13 to 17%. A conventional technical drying is by heating to about 50 to 120 ° C over a Duration of about 4 hours to 4 weeks, preferably about 6 h to Reached 3 weeks. The principle of technical drying lies in the coordination of humidity and temperature, to reduce the formation of cracks. As a variant of the technical Drying can be the hot steam drying be used at temperatures above the boiling point, i.e. above 100 ° C at ambient pressure. The hot steam drying can in one Temperature range from above 100 ° C to, for example, 140 ° C, preferably up to 130 ° C, even more preferably up to 121 ° C over a Duration of about 2 hours to 2 weeks, more preferably about 6 to 180 hours carried out become. The suitable drying temperature and drying time is dependent from the dimensions of the substrate to be dried and can be obtained by a person skilled in the art be determined. The initial one Humidity is about 100% and will be in the course of drying reduced.

It is believed that the mechanism by which the preservative of the invention Making wood and other lignocellulosic materials more resistant to weathering and / or variations in moisture content is at least partly due to the fact that the surface, preferably the layers adjacent to the surface, are rendered hydrophobic up to the entire volume of the wood or lignocellulosic material.

For wood is assumed that the protective agent of the invention to a reduced Moisture absorption leads, which in turn contributes to a smaller variation in dimensions changing ambient humidity leads. So leads the protective agent of the invention Therefore, to a better dimensional stability of wood, because it in the Cell wall of the wood penetrates and remains there permanently. Thereby is the wooden one Cell wall even when dry in a form that is a pre-swollen State is similar and therefore absorbs less water than untreated wood. The Penetration of the protective agent of the invention is mainly with so-called microemulsions, for example with Particle sizes of 10 to 100 nm achieved. Such microemulsions can be used in the pores of wooden cell walls penetrate and also between cellulose strands, so that further recording is permanently reduced by water. That's how it works the dimensional change, for example, reduces the shrinkage when drying wood, when the moisture content of the environment decreases.

in the Case of macroemulsions, for example with a particle size greater than 50 to 100 nm, it is assumed that the protective agent of the invention the inner surfaces of wood cells at least partially coated and in pores of the Wood cell wall penetrates.

Of the Content of the protective agent according to the invention on at least one amine substituent, one or more of the same or different substituents from the group of primary, secondary, tertiary or quaternary Amin may be, on the one hand, a better association of the protective agent with the lignocellulosic material, on the other hand a confer some antimicrobial effect. The antimicrobial effect is especially opposite Fungi inhibiting or biocidal, so that with the protective agent of the invention treated lignocellulosic material such as wood, less strong from discoloring, for example infesting fungi or mold, or destructive fungi (white rot, brown rot) and therefore greater durability against microbial degradation.

Detailed description of invention

The The present invention will now be explained in more detail by way of examples, in those the Aminosilikone invention (AS) are numbered consecutively.

Short description of pictures:

1 Figure 4 is a graphical representation of water uptake of pinewood samples treated with aminosilicone compounds and comparative compounds of the present invention during a 4 hour dipping test;

2 FIG. 2 shows the water absorption in percent of pine wood samples treated with aminosilicone compounds according to the invention and pinewood samples treated with two comparison compounds and untreated wood during a dipping test over 24 hours, FIG.

3 shows mass loss in percent of treated and untreated beech wood samples after 12 weeks of incubation with Trametes versicolor

4 shows the mass loss in percent of treated and untreated pine wood samples after 12 weeks of incubation with Coniophora puteana,

5 shows the attack of the surface of treated and untreated pinewood samples by mold fungi at an ambient humidity of about 95% over a period of 7 weeks,

6 shows the cracking, infestation by surface fungi in direct sunlight exposed to solar radiation to the south, and infestation by mold on the sun-facing, north-facing surface of treated and untreated pine wood samples after natural weathering in the period from September 2003 to April 2004;

7 shows the weight gain of pine wood by treatment with protection agents according to the invention in comparison with water and the anti-shrinkage / anti-swelling effect of inventive protection agents at 20 ° C between 0 and 65% and between 0 and 100% wood moisture,

8th shows the weight gain of beech wood and anti-shrinkage / anti-swelling effect like 7 .

9 shows the course of weight loss of milled pine wood samples treated untreated (control) or with an aminosilicone (AS 3) or a conventional flame retardant (Impralit F3 / 66) during a thermogravimetric analysis and

10 Figure 1 shows the reduction in weight loss of aminosilicone treated pine wood samples during a flame test compared to untreated pine wood samples.

11 Figure 10 shows the reduction of the burn-up distance (afterburning) of aminosilicone-treated pine wood samples during a flame test after ignition source removal compared to untreated pine wood samples.

12 shows the weight loss of aminosilicone-treated pine plinth wood samples through soft rot fungi in contact with the soil according to the European prestandard ENv 807 over a period of 8 or 16 weeks.

Example 1: Impregnation with aminosilicones to reduce the water absorption of pinewood

to impregnation were wood samples of dimensions 5 × 10 × 30 mm (radial, tangential, longitudinally) under vacuum and subsequent pressure.

to impregnation were the specimens in a vacuum of less than 100 mbar for vented for about an hour and subsequently in an aqueous Emulsion of protective agents according to the invention and comparative emulsions under a pressure of 6 bar for about 2 Kept for hours. The concentration of the aminosilicone in the impregnation emulsion was about 5 wt .-%. Subsequently followed by drying at ambient temperature for 12 hours.

For the determination of the water-repellent (hydrophobic) surface properties of the wood samples, the water absorption was measured in a dip test. The results of the determination of water absorption over 4 hours are in 1 shown, those over a period of 24 hours in 2 , The water absorption was determined by weighing the individual wood samples before and after the immersion time.

In the 1 and 2 used according to the invention aminosilicone compounds (AS) 1 to 3 are:
AS 1: Amino silicone according to formula I (primary amine) with R 1, R 2 and R ₃ = -CH ₃ , R 4 = - (CH ₂ ) ₃ -NH ₂ ; R5 and R6 = -CH _3. The number of Diorganosiloxanstruktureinheiten is about 300-400, the viscosity of the pure compound at about 3000 mPas. The proportion of amino groups is 0.25%. The formulation used was a macroemulsion with fatty alcohol ethanolates as emulsifiers.
AS 2: aminosilicone according to formula I (quaternary ammonium) with R 1, R 2 and R ₃ = -CH ₃ , R 4 = - (CH ₃ ) ₂ N (CH ₃ ) ₂ X, wherein X is lauryl; R5 and R6 = -CH _3. The molecular mass is about 6500, with each molecule having two quaternary ammonium groups. The formulation used was a macroemulsion with fatty alcohol ethanolates as emulsifiers.
AS 3: aminosilicone (primary amine) with R1-R3 = -CH _3; R 4 = - (CH ₂ ) ₃ -NH- (CH ₂ ) ₂ -NH ₂ ; 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 formulation used was a macroemulsion (particle size of the emulsion about 200 microns).

For comparison, silicone S1 (epoxy-functional polydimethylsiloxane, the epoxy group (CHOCH ₂ ) is bonded to Si as - (CH ₂ ) ₃ -O-CH ₂ -CHOHCH ₂ ), S2 (monomeric silane, Wacker Chemie BS1701) and silicone S3 ( Silane / siloxane mixture, Wacker Chemie BS1702), each carrying no amino group, as well as untreated wood used as control K.

In the 1 and 2 shown results show that the amino silicones AS 1 to AS 3 according to the invention in each case the water absorption compared to the comparative compounds S2 and S3 or unbehan Deltem wood K significantly reduced during a dipping time of 4 h and 24 h, while the silicone S1 gives a similar high hydrophobicity as the compounds of the invention.

Example 2: Impregnation of beech wood to increase the resilience against wood-degrading mushrooms

To the Evidence of the antiperspirant effect of the invention aminosilicones were with Protective agent according to the invention impregnated Beech wood samples exposed to degradation by Trametes versicolor (white rot). The impregnation took place according to example 1.

to Determination of increase the resilience the wood samples opposite the white rot fungus the mass loss was determined after 12 weeks. The concentration the aminosilicon in the impregnating emulsion was about 5 wt .-%.

The Beechwood samples had the dimensions 5 × 10 × 30 mm, radial, tangential, longitudinally, the aminosilicon AS 1, AS 2, AS 3 were those in Example 1 compounds.

AS 4 is an aminosilicone according to formula I (primary amine) with R 1, R 2 and R ₃ = -CH ₃ , R 4 = - (CH ₂ ) ₃ -NH (CH ₂ ) ₂ NH ₂ ; R5 and R6 = -OH. The number of Diorganosiloxanstruktureinheiten 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 fatty alcohol ethanolates as emulsifiers.

The Silicones S1 to S3 are polydimethylsiloxanes without amino or ammonium group as comparative compounds according to Example 1.

W denotes a wax emulsion, K denotes untreated wood.

The results are in 3 and it is clearly visible that the wood samples treated with aminosilicones according to the invention have the lowest mass loss. It should be noted that the small size of the specimens (significantly smaller than EN 113) and the duration of the fungal degradation test of 12 weeks represent very extreme experimental conditions that allow the degradation by Trametes versicolor (white rot). In particular, the duration of 12 weeks is very long compared to conventional tests. Therefore, it can be concluded from the test results that the protective effect of the aminosilicones according to the invention is based not only on their hydrophobizing effect but also on a fungus-inhibiting action.

Example 3: Impregnation of pine wood to increase the resilience against brown rot

Pine wood samples (5 × 10 × 30 mm, radial, tangential, longitudinal), with the aminosilicones according to the invention AS 1 to AS 4, comparative compounds S1 to S3 or with wax emulsion W according to example 1 impregnated were as well as untreated wood (marked as K) were the wood-destroying brown rot Coniophora puteana over Exposed for 12 weeks. The mass loss was determined by weighing the Samples were detected before and after the incubation period.

The measurement results are in 4 in which it is clear that the aminosilicones AS 1 to AS 4 according to the invention lead compared to the comparative compounds S1 to S3, wax emulsion W or untreated wood K to a significantly reduced mass loss of the treated pine wood samples.

Example 4: Impregnation with aminosilicones to reduce the infestation by mold fungi

To the Detection of the inhibiting effect of aminosilicones according to the invention on one Infestation by molds were with protective agents according to the invention impregnated Pinewood samples measuring 15 × 20 × 50 mm (radial, tangential, longitudinally) stored in a closed container above a water surface, around a wood moisture near the fiber saturation point of the wood (about 30%). The impregnation took place according to example 1 in aqueous solutions with 5 wt .-% of the respective silicone compound. In addition was added to the water forest soil, to increase the density of mold spores in the container. The air of the container was Continuously circulated by means of a fan.

At intervals of one week, the infestation by mold on the surface of the samples was optically evaluated on an arbitrary scale from 0 to 3, where 0 no infestation, 1 low infestation, 2 mitt ler infestation and 3 strong infestations. The results of the evaluation are in 5 shown graphically. 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
AS 5: Amino silicone according to formula I (primary amine) with R 1, R 2 and R ₃ = -CH ₃ , R 4 = - (CH ₂ ) ₃ -NH ₂ ; R5 and R6 = -CH _3; the number of Diorganosiloxanstruktureinheiten is about 300-400, the viscosity of the pure compound at about 3000 mPas. The proportion of amino groups is 0.25%; the formulation used was a microemulsion with fatty alcohol ethoxylates as emulsifiers, as well as
AS 6: an aminosilicone according to formula I (quaternary ammonium) with R 1, R 2 and R ₃ = -CH ₃ , R 4 = - (CH ₂ ) ₃ N (CH ₃ ) ₂ X, wherein X is lauryl; R5 and R6 = -CH _3. 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.

When Another reference substance B was the conventional organic used biocidal wood preservative Bethoxazine.

The Results clearly show that the aminosilicones according to the invention Treated wood samples significantly less affected by mold as untreated samples. This showed the comparative compounds S1 and S2, which carry no amino group, no or only a small improvement across from the untreated control K. The aminosilicones according to the invention with primary amine groups (AS 1, AS 3, AS 5) show a significantly lower infestation than the untreated wood sample K or the comparative compounds S1 and S2.

The Wood samples containing amino silicones with quaternary amino group according to the invention were treated (AS 6, AS 2) also after the entire treatment period of 7 weeks no mold. Therefore show protection agents according to the invention a comparable effectiveness as a conventional fungicidal Protective agent (B).

moreover show the results that the effect of silicones against mold not solely on the hydrophobization of the lignocellulosic material back, but that the aminosilicones according to the invention due to their amino groups increased effectiveness against mold to have.

Example 5: Impregnation with aminosilicones to improve the weathering resistance and for protection against wood discoloring Mushrooms (blue)

To the Evidence of an improvement in the weathering resistance lignocellulosic Materials by the aminosilicones according to the invention were with Protective agent according to the invention impregnated Pinewood samples measuring 15 × 75 × 150 mm (radial, tangential, longitudinal) from the end of September 2003 to the beginning of April 2004 (approx 24 weeks) on a weathering stand in Göttingen (Germany) of the external weathering exposed.

The surfaces the wood samples were going south aligned, taking an angle of 120 ° to the earth's surface. In connection to the weathering time was the cracking, the infestation by surface fungi on the south turned side and the infestation by mold on the post North facing side visually to a scale of 0 (no infestation or no cracking), 1 (low infestation), 2 (medium infestation) and 3 (heavy infestation, severe cracking) classified.

The Wood samples were according to example 1 with the aminosilicones according to the invention AS 1 and AS 6 with a proportion of 5 wt .-% in the impregnating solution according to Example 1 impregnated.

The results are in 6 and it can be clearly seen that wood samples treated with the amino silicones according to the invention have a significantly lower crack formation and a lower infestation by surface fungi (blue-blue, mold) than the control samples (comparison silicone S3 or untreated wood K). This discoloration is caused by the blue fungus Aureobasidium pullulans, which feeds mainly on degradation products of the wood, which are released by UV irradiation and subsequent leaching by water.

Therefore, it can be concluded from these results that the degradation caused by the weathering is significantly reduced by the aminosilicones of the present invention. This was further indicated by the fact that the untreated wood samples lost their brown color to a greater extent than those with the inventive preservative impregnated samples.

Example 6: Reduction the water absorption and increase the dimensional stability

wood samples with the dimensions 25 × 25 × 10 mm (radial, tangential, longitudinal) were in accordance with Example 1 under vacuum / pressure with aminosilicone compounds according to the invention AS 5 in a concentration of 5% by weight or AS 6 in concentrations of 30% by weight, 15% by weight and 7.5% by weight, respectively, of the aminosilicone in water, the comparative silicone S3 without amino function or water as a control K treated. Following drying, the pine wood samples Measured in radial, tangential and longitudinal direction and subsequently in a climatic chamber at 20 ° C and 65% ambient humidity conditioned to constant weight. Subsequently, the length dimensions were determined again. Subsequently, the Samples immersed in water and it was a vacuum of about 50 mbar, so that a water-saturated state of the samples could adjust. Subsequently in turn, the dimensions of the wood samples were determined.

In the 7 (Pinewood) and 8th (Beechwood) values for the weight increase (GZ, percent) represent the change in weight of the wood samples due to the incorporation of the protective agent according to the invention. The water used for the control led to a slight reduction in weight. Here it becomes clear that the different amino silicones were absorbed in different masses by the wood.

S_(r,t,l)

= relative Quellung/Schwindung (radial, tangential, longitudinal),

Lk

= Länge der klimatisierten Proben (radial, tangential, longitudinal),

Ld

= Länge der klimatisierten Proben (radial, tangential, longitudinal)

From the determined length measurements before and after immersion, the relative swelling / shrinkage was calculated as: S (R, t, l) = (L k - L d ) / L d [%] in which

S _{(r, t, l)}

= relative swelling / shrinkage (radial, tangential, longitudinal),

lk

= Length of air-conditioned samples (radial, tangential, longitudinal),

Ld

= Length of conditioned samples (radial, tangential, longitudinal)

Sv

= Volumenquellung/-schwindung

Sr

= radiale Quellung/Schwindung,

St

= tangentiale Quellung/Schwindung.

The relative volume swelling or shrinkage of the can be calculated according to: Sv = (Sr + 1) * (St + 1) -1 [%], in which

Sv

= Volume swelling / shrinkage

Sr

= radial swelling / shrinkage,

St

= tangential swelling / shrinkage.

ASQW_(r,t,l)

= anti-Schwind-/anti-Quellwirkung (radial, tangential, longitudinal),

Su

= Quellung/Schwindung der unbehandelten Probe,

Sb

= Quellung/Schwindung der behandelten Probe

From this it is possible to calculate the anti-shrinkage / anti-swelling effect (ASQW), which represents a measure of the increase in dimensional stability as a result of the treatment with the protective agent according to the invention compared to a control or comparative compound: ASQW (R, t, l) = (Su - Sb) / Su [%], in which

ASQW _{(r, t, l)}

= anti-shrinkage / anti-swelling effect (radial, tangential, longitudinal),

Su

= Swelling / shrinkage of the untreated sample,

sb

= Swelling / shrinkage of the treated sample

The anti-shrinkage / anti-swelling action was used for two areas of wood moisture certainly, namely as ASQW 0-20 / 65 between absolutely dry wood (0% wood moisture) and the moisture content of the wood in normal climates (temperature 20 ° C, 65% relative humidity) Humidity) (corresponds to about 12% wood moisture), as well ASQW 0-100 between absolutely dry wood (0% wood moisture) and water-saturated Wood (100% wood moisture).

In the 7 and 8th illustrated results illustrate that the invention with Ami treated wood samples compared to the water-treated control sample have a significantly increased ASQW, ie a significant increase in dimensional stability when changing the wood moisture.

The Effect of the protective agents according to the invention on the increase the dimensional stability of wood can be as well as hardwoods (therefor Beech), as well as for softwoods (therefor Pine shown). The increase in dimensional stability becomes particular achieved by microemulsions of the protective agents according to the invention, while the increase the dimensional stability is lower by macroemulsions of the same protective agent.

Example 7: Durability Inventive protective agent on or in wood.

to Determination of the durability of the application of protection agents according to the invention in wood, the leaching of the preservative was impregnated Wood samples measured. For this test was done according to example 1 impregnated Samples of pine wood measuring 5 × 10 × 30 mm (radial, tangential, longitudinally) following impregnation in a Soxhlet apparatus 8 hours under reflux extracted with water. The wood samples became continuous of returning Water of about 90 ° C lapped. In this way it was ensured that there was no balance between wood sample and extractant could stop, but each unloaded extractant washed around the wood samples and a maximum extraction took place.

A weighing of the extract obtained after removal of the extractant Water revealed that about 2 to 5% of the aminosilicones according to the invention were washed out. This even under extreme conditions (90 ° C, 8 h) only Low leaching of the protective agents according to the invention shows their good fixation on or in the impregnated wood.

Example 8: Flame protection or reduction of flammability by aminosilicones

To the Evidence of the reduction in flammability was obtained from pine wood samples the dimensions 5 × 10 × 30 mm (radial, tangential, longitudinal) with amino-silicone according to the invention AS 3 (5 wt .-% in impregnating solution) and for comparison with a commercial flame retardant for wood (Impralit F 3/66, Rütgers Organics) according to example 1 impregnated. Untreated wood was used as control K. Subsequently were the wood samples ground. The wood flour was on a thermobalance (STA 409 PC, Netzsch) continuously under oxygen with a Heating rate of 20 ° C / minute from 0 ° C at 800 ° C heated, with the weight changes were measured.

The results are in 9 and show that the pine wood sample treated with the aminosilicone according to the invention suffers weight loss only at a significantly higher temperature than the control sample or the sample treated with the conventional flame retardant. This suggests a significant reduction in the burning rate in the case of fire by means of the protective agent according to the invention.

In a further test for reducing the flammability or flame retardancy by the protective agents according to the invention by the method of Example 1 with aminosilicones AS 1, AS 3, AS 4, AS 5 and AS 6 impregnated pine wood samples with dimensions of 5 × 10 × 100 mm (radial, tangential, longitudinal) air-conditioned at 20 ° C and 65% relative humidity. One treated and one untreated wood sample were placed in a V-shape at an angle of about 45 ° to the horizontal and were spaced 5 mm at the lower end. 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 in 10 represented, the burning distance in 11 ,

From the 10 and 11 It is clear that the treatment with preservatives of the invention compared to untreated wood leads to a significant reduction in weight loss or the burning distance in the same time.

Example 9: Fixation of boric acid by aminosilicones

Samples of pine sapwood with the dimensions 5 × 10 × 30 mm (radial, tangential, longitudinal) are until reaching the equilibrium moisture content in a climatic chamber at 20 ° C and 65% relative humidity stored. The samples are treated with a solution of (a) 3% by weight of boric acid, 5% by weight of aminosilicone AS 1, 92% of water, (b) 3% by weight of boric acid, 5% by weight of aminosilicone AS 5, 92 % Water or (c) 3 wt .-% boric acid, 97% water in a vacuum process according to Example 1 impregnated.

To Removal from the drinking liquid the samples are allowed to stand for 4 hours at 60 ° C and for a further 16 hours Dried 120 ° C. and subsequently 24 hours in the climatic chamber at 20 ° C and 65% relative humidity stored. Five each Samples were completely covered with 37.5 mL of demineralized water and saturated with the help of a vacuum of 100 mbar and remain for another 4 days in demineralized water submerged. The fixation the boron compound was determined from the boron emanating from the samples. The analysis of water samples after 4 days showed a concentration at boron of 2.38 g / L for (c) only boron-treated wood and 1,22 g / L in (b) and 1.68 g / L in the case of (a) treated with aminosilicones according to the invention Rehearse.

The selected Experimental conditions for the leaching of boric acid from the wood samples show that the aminosilicone leaching boric acid significantly reduce. Therefore, the aminosilicones of the invention are capable of using the conventionally used as biocidal wood preservatives Boron compounds, such as boric acid and other boron salts to fix in the lignocellulosic material or withhold, and thus to maintain the effect of the boron compound over a longer period of time.

Example 10: Increase of resistance against soft rot by aminosilicones

Kiefernsplintholzproben the dimensions 5 × 10 × 100 mm (radial, tangential, longitudinal) are in accordance with Example 1 with the aminosilicones AS 1, AS 2 or AS 4 treated and according to the European prestandard ENv 807 over 16 weeks in contact with the ground exposed to the infestation by soft rot fungi. In contact with the ground the wood is exposed to a variety of microorganisms that unprotected Break down 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 in 12 shown.

The lower decrease of dyn. Modulus of elasticity in aminosilicone-treated ones Wood samples opposite The untreated is in contact with the soil both after 8 and 16 weeks clear. This shows that the treatment with protective agents according to the invention the degradation by soft rot fungi drastically slows down, the resistance of the treated according to the invention Pine sapwood even significantly above that of untreated, moderately durable Pine heartwood lay.

The Examples make it clear that the protective agents according to the invention Wood and other lignocellulosic materials significantly reduced ability for water absorption. This reduced water absorption allows it shut down, that the protective agents of the invention Wood and other lignocellulosic materials to change in the moisture content of the environment, for example, to weathering, make them more resistant.

It It has also been proved that wood containing the protective agents of the invention has been treated, a significantly lower infestation by superficial Mold and blue mushrooms subject. This is a consequence of the combined effect of hydrophobing and imparting antiperspirant properties by the aminosilicones of the invention.

there offers the invention the further advantage that as a protective agent are less toxic than known fungicides Compounds of wood preservatives. This is partly due to that the protective agents of the invention due to their high molecular mass and their chemically rather inert character hardly of humans or Animal can be absorbed and metabolized.

When Another advantage of the lignocellulosic protective agents according to the invention Materials, such as wood, increased resistance against the infestation with algae and harmful marine organisms, such as for example, shells. As a further advantage, the protective agents of the invention provide wood an increased resistance against the infestation with algae.

Furthermore, the preservatives of the invention, the resistance of wood against wood-destroying insects, such as termites, domestic goats, Common Ragweed, sapwood increase the distance. This is the case in particular if, in addition to the protective agents according to the invention, insecticides are introduced into the lignocellulosic material.

Of Furthermore, the degradation experiments, i. the measured mass loss on beech and pine in contact with the white rot fungus Trametes versicolor or brown rot fungus Coniophora puteana, that the protective agent of the invention wood and others lignocellulosic materials against wood-destroying fungi more resistant do. The protective agents of the invention to lead also that lignocellulosic materials, for example wood, significantly more resistant against the infestation by surface fungi like Mold or blueness become. Here again shows that the protective agents of the invention the treated lignocellulosic material both hydrophobic and also impart as mushzwidrige properties.

tries the swelling and shrinkage behavior of beech and spruce wood samples show that the protective agents of the invention Wood an elevated dimensional stability in the event of moisture fluctuations in the environment. This leads to a markedly reduced malformation, as in weathering experiments could be shown.

The Experiments for outdoor weathering showed that wood samples containing the protective agent of the invention were treated, an increased color stability exhibit. This protection is due in particular to the lignin degradation in the upper cell wall layers of the wood less fast than untreated wood.

Here could the reduced leaching of possibly due to UV irradiation degraded lignins play a role.

The Washing out with boric acid for determining the fixation of hydrophilic substances by the protective agents according to the invention in lignocellulosic materials show that the aminosilicones according to the invention a fixation or restraint hydrophilic substances in wood or lignocellulosic materials to reach. The fixation or retention of lipophilic substances in lignocellulosic materials by the protective agents of the invention go to the general lipophilic properties of these silicone derivatives back. Therefore, the protective agents of the invention are suitable for fixation conventional wood treatment agents, such as flame retardants, fungicides, insecticides or dyes. This concerns above all such conventional ones Compounds that are poor in the matrix of lignocellulosic Materials withheld be easily washed out by water.

The Thermogravimetric analysis shows that the protective agents according to the invention to an increased flame resistance or refractoriness of the lignocellulosic materials treated therewith, demonstrated by the example of wood. This is special then the case, if in addition to the protective agents of the invention conventional Flame retardant in the lignocellulosic material attached are such as those of 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 protection agents according to the invention can also for physical and / or chemical bonding conventional Treatment agent for Serve wood or other materials based on cellulose and so on resistance increase. 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 are or detained there become.

moreover can with protective agents according to the invention treated woods have more resilient surfaces, i.e. for example, harder and / or more abrasion resistant surfaces.

Claims (24)

Protective agent for lignocellulosic materials, characterized in that it has a content of at least one amino-modified silicone. Protective agent according to claim 1, characterized in that the amino-modified silicone has the general formula I: R5-A _n -B _m -R6 (I), with the structural units

wherein the substituents R1 to R4 are each independently selected for each structural unit from the group consisting of saturated and unsaturated, straight-chain, branched and cyclic hydrocarbon radicals having 1 to 20 carbon atoms, at least one radical having an amine substituent which is a primary, secondary, tertiary or quaternary amine; n is 0 to 50, preferably 1 to 10; m is 0 to 50, preferably 1 to 10; R5 and R6 are selected from the group consisting of saturated and unsaturated, straight-chain, branched and cyclic alkyl or alkoxy groups having 1 to 20 carbon atoms. Protective means according to claim 2, characterized R5 and R6 are selected from the group consisting of methyl, ethyl, Propyl, isopropyl, butyl, isobutyl, methoxy, ethoxy, propoxy, isopropoxy, Butoxy and / or isobutoxy. Protective means according to claim 2 or 3, characterized the substituents R1 to R4 are selected from the group from methyl, ethyl, propyl, isopropyl, butyl, iso-butyl and lauryl consists. Protective means according to one of claims 2 to 4, characterized that the structural units A and B are arranged linearly. Protective agent according to one of claims 2 to 5, characterized in that the structural units are arranged as R5-A _n -B _m -A-R 6, where n = 1 to 15, preferably 1 to 10, m = 1 to 5, R 4 is - (CH ₂ ) ₃ -NH ₂ or - (CH ₂ ) ₃ -NH- (CH ₂ ) ₂ -NH ₂ and R 5 and R 6 are methyl. Protective agent according to one of claims 2 to 6, characterized in that the structural units are arranged as R5-A _n -B _m -An -B _m -A _n -R 6, the at least one amine substituent -XN ⁺ (R 1) ₂ ( R2), wherein X is a (CH ₂ ) chain having 1 to 10 methylene units and n = 0 to 15, m = 1 to 2. Protective means according to one of claims 2 to 7, characterized R2 is a long-chain alkyl or fatty acid chain having 8 to 20 carbon atoms, preferably lauryl and n = 2 to 10. Protective means according to one of the preceding claims, characterized characterized in that it is a mixture of different amino-modified Silicones is. Protective means according to one of the preceding claims, characterized characterized in that the amine modified silicone is the product a crosslinking of amino-modified silicones according to formula I. Protective means according to one of the preceding claims, characterized characterized in that the amino-modified silicone directly to silicon bound condensable Has groups and that there is a content of at least one polysiloxane having at least three Si-bonded hydrogen atoms per molecule. Protective means according to one of the preceding claims, characterized characterized in that the amino-modified silicone directly to silicon bound condensable Has groups and that it has a content of at least one trialkoxy and / or tetraalkoxysilane. Protective means according to claim 11 or 12, characterized that it contains a content of catalyst to accelerate the condensation having. Protective means according to one of the preceding claims, characterized in that it has a Ge having at least one boron compound. Protective means according to one of the preceding claims characterized in that it contains at least one copper compound having. Protective means according to one of the preceding claims, characterized in that it contains a content of an insecticide and / or Having fungicide and / or flame retardant. Protective means according to one of the preceding claims, characterized characterized in that the protective agent is in aqueous emulsion or solution. Protective means according to one of the preceding claims, characterized characterized in that it is a solubilizer and / or emulsifier. Protective means according to claim 18, characterized that the solubilizer or emulsifier an amino-modified silicone according to formula I, a quaternary Fatty amine alcoholate, quaternary Fatty amine ethanolate, a polyalcohol, propylene glycol, ethylene glycol or butyl diglycol. Lignocellulosic material, characterized that he has a content of a protective agent according to one of the preceding claims having. Method of preserving lignocellulosic Materials characterized by the treatment with a protective agent according to one of the claims 1 to 19. A method according to claim 21, characterized by the application of the protective agent by brushing, spraying, dipping or pressure impregnation. A method according to claim 21 or 22, characterized by subsequent Annealing at a temperature of 50 to 150 ° C, preferably at 80 to 100 ° C. Lignocellulosic material, characterized that he has been treated by a method according to any one of claims 21 to 23 is.