WO2006117158A1 - Use of aqueous wax dispersions to impregnate lignocellulose materials - Google Patents

Abstract

The present invention relates to the use of aqueous wax dispersions to impregnate lignocellulose materials. The invention also relates to a method of hydrophobicizing lignocellulose materials, which involves impregnating the lignocellulose material with an aqueous wax dispersion, and to the lignocellulose materials obtainable as a result. The aqueous dispersions of the waxes or wax- like polymers are characterized in that the wax constituent has a melting point above 75°C, preferably above 80°C and in particular above 90°C and the dispersed wax particles have an average size below 500 nm.

Description

 Use of aqueous wax dispersions for the impregnation of lignocellulosic materials

description

The present invention relates to the use of aqueous wax dispersions for the impregnation of lignocellulosic materials. The invention also relates to a process for the hydrophobization of lignocellulosic materials, in which the lignocellulose material is impregnated with an aqueous wax dispersion, and the lignocellulosic materials obtainable thereby.

Lignocellulosic materials, especially wood, but also other lignocellulosic materials such as bamboo, natural fibers and the like, are of interest as construction and construction materials for many applications. The disadvantage is that the natural durability of these materials is adversely affected both by the action of moisture, but also by changes in the moisture content in the surrounding atmosphere. The reason for this is the property of lignocellulosic materials to store water on contact with water or in a humid atmosphere and release it again in a dry atmosphere. The associated swelling or shrinkage and the associated lack of dimensional stability of the materials is not only undesirable for many applications, but can also lead to destruction of the material by cracking in extreme cases. In addition, these materials are attacked by wood degrading or wood-discolouring microorganisms in the wet state, which in many cases makes it necessary to equip these materials with fungicides or biocides. Apart from the cost aspect, such equipment is also disadvantageous for environmental reasons.

The hydrophobing of wood and other lignocellulosic materials is a long known technique for reducing the water absorption of these materials. As a result, on the one hand, the dimensional stability of these materials is improved and, on the other hand, the risk of infestation with fungi or bacteria is reduced.

In addition to classic wood preservatives based on tar oils, which are suitable due to their inherent odor, their intense color and their potential carcinogenicity only for a few uses, today increasingly find vegetable oils such as linseed oil, rapeseed oil, peanut oil, soybean oil and tall oil in combination with biocidal and / or fungicidal Wood preservatives Use (see, for example, DE-A-3008263 and A. Treu, H. Militz and S. Breyne "Royal Process - Scientific Background and Practical Application" COST E22 conference in Reinbek, 2001 and literature cited therein) is that when weathered, ie when exposed to moisture, eg by rain, and / or at elevated temperatures, as z. B. occur in strong sunlight, a part of the oil can escape together with the fungicidal / biocidal agents from the wood. As a result, the surface becomes sticky, the oil forms "noses" and the hydrophobizing effect therefore decreases with time in local places.

There have been various reports of the use of waxes for the hydrophobization of wood, the waxes typically being used together with a hydrocarbon solvent (see, for example, US 3,832,463 and US 4,612,255). However, the use of organic hydrocarbon solvents is disadvantageous in terms of working and process safety.

CA 2,179,001, in turn, describes a wood preservative having a hydrophobic effect which contains, in addition to a water-soluble wood preservative such as chromated copper arsenates, an aqueous emulsion of a low-melting wax such as Gatch and a cationic surface-active substance. Disadvantages are the comparatively large amounts of expensive emulsifier required.

WO 00/41861 in turn discloses a process for the hydrophobization of wood substrates, in which the substrate is brought into contact with an aqueous dispersion of a wax at reduced pressure and a temperature above the melting point of the wax. By melting an improved penetration of the liquid wax is to be achieved in the wood pores. However, the required high temperatures can lead to damage to the wood. In addition, the wax emulsions above the melting point of the wax contained therein are unstable, especially under the action of strong shear forces, such as occur in the impregnation of wood under elevated pressure.

The present invention is therefore based on the object to provide agents for the hydrophobization of lignocellulosic materials, in particular of wood, which overcome the disadvantages of the prior art described here. In particular, the water repellents should allow the impregnation even at low temperatures, in particular below 50 ° C, to avoid damage to the wood.

It has surprisingly been found that aqueous dispersions of waxes or waxy polymers having a melting point above 75 ⁰ C, preferably above 80 ⁰ C, in particular above 90 ⁰ C, wherein the dispersed wax particles have an average particle size below 500 nm, for impregnation and thus to Hydrophobing of lignocellulosic materials and in particular of wood are particularly suitable. The invention thus relates to the use of such aqueous dispersions for the impregnation of lignocellulosic materials and in particular of wood. The invention also relates to a process for hydrophobizing lignocellulosic materials, in which the lignocellulosic material is impregnated with such an aqueous dispersion of waxes or waxy polymers. The aqueous dispersions of waxes or waxy polymers used according to the invention are also referred to below as wax dispersions.

The impregnated by the process according to the invention lignocellulosic materials are characterized by a low uptake of water and also show no or to a much lesser extent exudation of the hydrophobing agent, as occurs in oil-impregnated lignocellulosic materials in weathering, especially at elevated temperatures. In addition, the distribution of the wax in the lignocellulosic materials treated according to the invention, in particular in the case of large-sized wood moldings, is more uniform than when using conventional wax emulsions. The lignocellulosic materials obtainable according to the invention, in particular materials made of wood, are therefore likewise the subject matter of the present invention.

Aqueous dispersions of waxes or waxy polymers used in accordance with the invention are basically known from the prior art or can be prepared analogously to known processes from high-melting waxes or wax-like polymers. The waxes or waxy polymers contained in the aqueous dispersion are also referred to below as wax component or wax component. Waxy polymers are understood by the person skilled in the art to be polymers which resemble waxes in their physical and chemical behavior, ie. H. they are insoluble in water, can usually melt undecomposed and have a low viscosity in the molten state.

Typically, the wax component of the dispersion used in the invention is a high melting wax or waxy polymer containing polar functional groups, e.g. As carboxyl groups, hydroxyl groups, aldehyde groups, keto groups, polyether groups or the like, which support the dispersion of the wax component. In particular, the wax has neutralizable carboxyl groups. Advantageously, the wax or waxy polymer has an acid number of at least 5 mg KOH / g and in particular in the range of 15 to 250 mg KOH / g.

Accordingly, the wax components of the wax dispersions used according to the invention are advantageously comprised of montan waxes, including chemically modified montan waxes and montan ester waxes, oxidate waxes, amide waxes and polar polyolefin waxes were selected. Also suitable are oxidation products of Fischer-Tropsch waxes and Sasol waxes, provided they have a melting point above 75 ⁰ C and especially above 80 ⁰ C. Suitable overall are of course also mixtures of the aforementioned waxes and wax-like polymers, as long as the melting point of the mixture above 75 ⁰ C and in particular above 80 ° C.

On the one hand, the polar polyolefin waxes include the oxidation products of nonpolar polyolefin waxes, eg. As oxidation products of polyethylene waxes or polypropylene waxes, which are also referred to as Polyoloxidoxidatwachse, Oxida- te of Fischer-Tropsch waxes and copolymers of olefins, in particular of C ₂ -C _β- olefins such as ethylene or propene with oxygen-bearing monomers, eg , B. monoethylenically unsaturated C ₃ -C _β -monocarboxylic acids such as acrylic acid or methacrylic acid and optionally vinyl esters of aliphatic C ₂ -C ₁₀ carboxylic acids such as vinyl acetate or vinyl propionate, esters of monoethylenically unsaturated C ₃ -C _β -mono- carboxylic acids with Ci-Ciβ-alkanols or C ₅ -C ₁₂ -cycloalkanols, in particular esters of acrylic acid or of methacrylic acid, such as methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, 2-butyl acrylate, tert-butyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, 3-propylheptyl acrylate , Cyclopentyl acrylate, cyclohexyl acrylate and the corresponding esters of methacrylic acid. The polar polyolefin waxes furthermore include the oxidation products of the abovementioned olefin copolymers.

In a preferred embodiment, the wax component of the aqueous dispersion to be used according to the invention comprises at least 50% by weight, in particular at least 80% by weight and in particular at least 90% by weight, based on the total weight of the wax constituents contained in the dispersion a polar polyolefin wax. In particular, the polar polyolefin wax is selected from polar olefin copolymers and their oxidates, the olefin copolymers being essentially composed of:

a) 50 to 99 wt .-%, in particular 55 to 95 wt .-% and especially 60 to 90% by weight, of at least one C ₂ -C _β- olefin, in particular propene, ethene or mixtures thereof, especially ethene ;

b) 1 to 50 wt .-%, in particular 5 to 40 wt .-% and especially 10 to 30 wt .-% of at least one monoethylenically unsaturated C ₃ -C _β -monocarboxylic acid such as acrylic acid or methacrylic acid and / or C ₄ -C _e Dicarboxylic acid, such as maleic acid, fumaric acid, itaconic acid or a mixture thereof, especially acrylic acid, methane acrylic acid and / or maleic acid; and

c) 0 to 49 wt .-%, z. B. 5 to 49 wt .-%, in particular 0 to 40 wt .-%, z. B. 5 to 40 wt .-% of one or more monoethylenically unsaturated monomers containing among the esters monoethylenically unsaturated C ₃ -C _β -monocarboxylic acids with CrCiβ-alkanols or C ₅ -C ₁₂ -cycloalkanols, the diesters monoethylenically unsaturated C ₄ -C ₈ -Dicarbonsäuren with CrC ^ alkanols or C ₅ -C ₁₂ cycloalkanols, especially the esters of acrylic acid or methacrylic acid, with C _r C ₁₈ alkanols or C ₅ -C ₁₂ cycloalkanols, and aliphatic under vinyl esters C ₂ -C ₁₈ carboxylic acids such as vinyl acetate or vinyl propionate are selected.

The monomer proportions given here are each based on the total weight of the monomers constituting the polar polyolefin wax. Essentially, here means that the polymers are at least 95 wt .-%, in particular at least 99 wt .-% and especially exclusively from the aforementioned monomers a), b) and optionally c) are constructed. A person skilled in the art knows, however, that such polymers may contain, in addition to the monomer components, components of the polymerization catalyst (initiator) in copolymerized form.

Typically, the polar polyolefin waxes have a weight average molecular weight in the range of 1000 to 150000 daltons, often in the range of 2000 to 120,000 daltons. In the case of undecomposed melting waxes or waxy polymers with low to medium molecular weight, these are by a melt viscosity at 140 ⁰ C in the range of 100 to 10,000 mm ² / sec (DFG unit method C-IW (68) or non-melting waxy polymers characterized by a minimum melt flow index MFI of at least 1 (at 160 ⁰ C and 325 g load according to DIN 53753).

In a further preferred embodiment, the wax component of the aqueous dispersion to be used according to the invention comprises at least 50% by weight, in particular at least 80% by weight and especially at least 90% by weight, based on the total weight of the wax constituents contained in the dispersion, at least one montan wax, including chemically modified montan waxes and montan ester waxes.

In a further preferred embodiment, the wax component of the aqueous dispersion to be used according to the invention comprises at least 50% by weight, in particular at least 80% by weight and especially at least 90% by weight, in particular to the total weight of the wax components contained in the dispersion, at least one amide wax.

In a further preferred embodiment, the wax component of the aqueous dispersion to be used according to the invention comprises at least 50% by weight, in particular at least 80% by weight and especially at least 90% by weight, based on the total weight of the wax constituents contained in the dispersion, at least one polyolefin oxidate wax.

According to the invention, the wax or waxy polymer present in the dispersion according to the invention has a melting point or softening point of at least 75 ^° C., preferably at least 80 ^° C., especially at least 85 ^° C., more preferably at least 90 ^° C. and especially at least 100 ^° C. Melting points here and below are the values determined according to DIN ISO 3841 by means of DSC or from the cooling curve.

The aforementioned wax components are well known from the prior art, for. From Ullmann's Encyclopaedia of Industrial Chemistry, 5th Ed. On CD-ROM, Wiley VCH ₁ Weinheim 1997, Capital Waxes, in particular Subchapter 3 "Montan Waxes" and subchapter 6 "Polyolefin Waxes" and from DE-A 3420168,

DE-A 3512564 (waxy copolymers) and from Kunststoffhandbuch volume 4, p. 161 ff., Karl-Hanser-Verlag, 1969 and cited there literature, DE-A 2126725, DE 2035706, EP-A 28384, DE-OS 1495938, DE-OS 1520008, DE-OS 1570652, DE-OS 3112163, DE-OS 3720952, DE-OS 3720953, DE-OS 3238652 and WO97 / 41158. Such products are also commercially available, for example under the trade names Luwax® OA grades or Luwax® EAS grades from BASF, Licowax PED from Clariant, AC3 ... and AC6 ... grades from Honeywell and the AC5 ... Types from the company Honeywell.

According to the invention, the waxes or waxy polymers are used in the form of an aqueous dispersion. In these dispersions, the wax components are in the form of a disperse phase, i. H. in the form of the finest particles. According to the invention, these particles have an average particle diameter below 500 nm, in particular below 300 nm, especially below 200 nm and very particularly preferably below 150 nm, z. B. in the range of 20 to 150 nm.

The particle sizes given here are weight-average particle sizes, as can be determined by dynamic light scattering. Methods for this purpose are familiar to the person skilled in the art, for example from H. Wiese in D. Distler, Aqueous Polymer Dispersions, Wiley-VC H 1999, Chapter 4.2.1, p. 40ff and literature cited therein and H. Auweter, D. Horn, J. Colloid Interf. Be. 105 (1985) 399, D. Lie, D. Horn, Colloid Polym. Be. 269 (1991) 704 or H. Wiese, D. Horn, J. Chem. Phys. 94 (1991) 6429.

The concentration of the wax components in the aqueous dispersion is typically in the range of 5 to 50 wt .-%, often 8 to 40 wt .-%, in particular 10 to 35 wt .-% and especially in the range of 15 to 30 wt. %, based on the total weight of the wax dispersion.

The preparation of such dispersions is known in principle and are carried out by dispersing the wax or the wax-like polymer in the aqueous phase using high shear forces and / or pressure at elevated temperature, advantageously at temperatures above 70 ° C, in particular above 90 "C ₁ z., in the range of 90 to 200 ⁰ C and more preferably in the range of 100 to 160 ⁰ C. in particular, carried out the dispersion of the wax component at tempera- tures above its melting point. such aqueous wax dispersions are also commercially available, for example under the trade names Poligen® WE grades from BASF and AquaCer grades from Byk-Cera.

If the particles of the wax component contain an effect substance and / or an active ingredient, the active substance or the effect substance is advantageously first dissolved or uniformly suspended in the wax and then the resulting wax preparation is dispersed in the aqueous phase at the abovementioned temperatures.

The pressure applied during dispersion is typically above 1 bar and often ranges from 1.5 to 40 and in particular from 2 to 20 bar.

If the wax component contains carboxylic acid groups, which is preferred according to the invention, the emulsification is advantageously carried out in the presence of a base. Advantageously, the base is used in an amount such that at least 40% and in particular at least 80% of the carboxylic acid groups present in the wax or waxy polymers are in neutralized form.

Suitable bases are, in principle, alkali metal hydroxides, such as sodium hydroxide or potassium hydroxide, alkaline earth metal hydroxides, such as calcium hydroxide, and ammonia and amines. The amines are advantageously mono-, di- or tri-alkylamines having preferably 1 to 6 and in particular 1 to 4 C atoms in the alkyl radical, mono-, di- or trialkanolamines having preferably 2 to 6 C atoms in the hydroxyalkyl radical Monoalkyldialkanolamines and dialkylmonoalkanolamines of 1 to 12 and in particular 1 to 8 C atoms in the alkyl radical and 2 to 6 C atoms in the hydroxyalkyl radical, furthermore ethoxylated mono- and dialkylamines having preferably 1 to 20 C atoms in the alkyl radical and a degree of ethoxylation of preferably 2 to 60 and in particular 3 to 40. Preferred hydroxyalkyl is in this context Hydroxyethyi and 2-hydroxypropyl. Preferred are those amines which have at least one hydroxyalkyl group and / or one polyethylene oxide group. Examples of preferred amines are diethanolamine, triethanolamine, 2-amino-2-methylpropan-1-ol, dimethylethanolamine, diethylethanolamine, dimethylaminodiglycol, diethylaminodiglycol and diethylenetriamine.

To promote the emulsification can also enforce emulsifiers. The emulsifiers may not be ionic, cationic or anionic, preference being given to anionic emulsifiers and nonionic emulsifiers and mixtures of anionic and nonionic emulsifiers. Particular preference is given to nonionic emulsifiers and mixtures of nonionic emulsifiers with minor amounts, generally less than 40% by weight and especially less than 20% by weight, based on the amount of emulsifier, of anionic emulsifiers.

The anionic emulsifiers include, for example, carboxylates, especially alkali, alkaline earth and ammonium salts of fatty acids, eg. B. potassium stearate, which are commonly referred to as soaps; glutamates; Sarcosinates, e.g. For example, sodium lauroyl sarcosinate; taurates; Methylcelluloses; Alkyl phosphates, especially mono- and diphosphoric acid alkyl esters; Sulfates, in particular alkyl sulfates and alkyl ether sulfates; Sulphonates, other alkyl and alkylarylsulphonates, in particular alkali, alkaline earth and ammonium salts of arylsulfonic acids and alkyl-substituted arylsulfonic acids, alkylbenzenesulfonic acids, such as lignin and phenolsulfonic acid, naphthalene and dibutylnaphthalenesulfonic acids, or dodecylbenzenesulfonates, alkylnaphthalenesulfonates, alkylmethylsulfonates, condensation products of sulfonated Naphthalene and derivatives thereof with formaldehyde, condensation products of naphthalenesulfonic acids, phenolic and / or phenolsulfonic acids with formaldehyde or with formaldehyde and urea, mono- or dialkylsuccinic acid sulfonates; as well as protein hydrolysates and lignin sulphite waste liquors. The aforementioned sulfonic acids are advantageously used in the form of their neutral or optionally basic salts.

Examples of nonionic emulsifiers include:

Fatty alcohol alkoxylates and oxo alcohol alkoxylates, in particular ethoxylates and propoxylates having degrees of alkoxylation of usually 2 to 100 and in particular 3 to 50, for. B. alkoxylates of C ₈ -C ₃₀ alkanols or alk (adi) enols, z. B. iso-tridecyl alcohol, lauryl alcohol, oleyl alcohol or stearyl alcohol and their C 1 -C ₄ -alkyl ethers and C 1 -C -alkyl esters, for example their acetates; alkoxylated animal and / or vegetable fats and / or oils, for example cornoiethoxyethers, castor oil ethoxylates, tallow fatty acid ethoxylates having degrees of acetic acidification of usually 2 to 100 and in particular 3 to 50,

Glycerol esters, such as glycerol monostearate, fatty acid esters of polymeric alkoxylates, in particular of polyethylene oxides with Alkoxilierungsgranden from 3 to 100 such. As PEG 300 oleate, stearate or laurate, as mono- or diesters, - copolymers alkoxylates of ethylene oxide and propylene oxide, eg. B. the Pluronic® brands of BASF,

Alkylphenolalkoxylate, such as ethoxylated iso-octyl, octyl or nonyl-phenol, tributylphenol polyoxyethylene ethers having degrees of alkoxylation of usually 2 to 100 and especially 3 to 50, - fatty amine alkoxylates, fatty acid and fatty acid diethanol-amide alkoxylates with degrees of alkoxylation of usually 2 to 100 and in particular 3 to 50, in particular their ethoxylates,

Sugar surfactants, sorbitol esters, such as, for example, sorbitan fatty acid esters (sorbitan monooleate, sorbitan tristearate), polyoxyethylene sorbitan fatty acid esters, alkyl polyglycosides, N-alkylgluconamides,

Alkylmethylsulfoxide, alkyldimethylphosphine oxides, such as, for example, tetradecyldimethylphosphine oxide.

Other emulsifiers which are to be mentioned by way of example here are perfluoro emulsifiers, silicone emulsifiers, phospholipids, for example lecithin or chemically modified lecithins, amino acid emulsifiers, eg. B. N-lauroylglutamate.

Unless indicated, the alkyl chains of the emulsifiers listed above are linear or branched radicals having usually 6 to 30 and in particular 8 to 20 carbon atoms.

Preferred nonionic emulsifiers are in particular alkoxylated and especially ethoxylated alkanols having 8 to 20 carbon atoms, for. Ethoxylated nonanol, isononanol, decanol, 2-propylheptanol, tridecanol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, C16 / 18 fatty alcohol mixtures, wherein the degree of ethoxylation is typically in the range of 5 to 50 and especially in the range of 6 to 30.

The amount of emulsifier depends in a manner known per se according to the type of wax to be emulsified and will generally not exceed 15% by weight, in particular 10% by weight, based on the aqueous dispersion. At low acid numbers, especially acid numbers below 100 mg KOH / g and especially below 50 mg KOH / g, z. B. in the range of 5 to 100 mg KOH / g and especially 10 to 50 mg KOH / g are typically emulsifiers in an amount of 2 to 15 wt .-% and in particular 3 to 10 wt .-%, based on the total weight the aqueous Wachsdis- persion or from 5 to 50 wt .-%, in particular 10 to 40 wt .-%, based on the emulsified wax component, use.

If the wax component has an acid number above 100 mg KOH / g, the waxes are often self-emulsifying and the emulsifier content is then generally not more than 10% by weight and is advantageously below 3% by weight, in particular below 1% by weight .-% and especially below 0.5 wt .-%, based on the emulsified wax component.

According to the invention, the wax particles of the dispersion may also contain active substances or effect substances which, in addition to their natural properties and the hydrophobization achieved by the wax, impart additional properties such as color, improved weathering stability or stability against attack by harmful organisms. The active substances or effect substances are typically organic low molecular weight compounds with molecular weights below 1000 daltons and typically below 500 daltons or inorganic salts or oxides of

Transition metals. The effect substances include colorants such as pigments and dyes, as well as UV absorbers, antioxidants, stabilizers, further active against wood-damaging organisms, eg. As insecticides, fungicides and bactericides.

Suitable pigments include both organic pigments and inorganic pigments.

Examples of colorants are:

- Organic pigments, as mentioned for example in WO 2004/035277, z. B .:

Monoazo pigments such as Cl. Pigment Brown 25, Cl. Pigment Orange 5, 13, 36, 38, 64 and 67; Cl. Pigment Red 1, 2, 3, 4, 5, 8, 9, 12, 17, 22, 23, 31, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 51: 1, 52: 1, 52: 2, 53, 53: 1, 53: 3, 57: 1, 58: 2, 58: 4, 63, 112, 146, 148, 170, 175, 184, 185, 187, 191: 1, 208, 210, 245, 247 and 251; Cl.

Pigment Yellow 1, 3, 62, 65, 73, 74, 97, 120, 151, 154, 168, 181, 183 and 191; Cl. Pigment Violet 32;

Disazo pigments such as Cl. Pigment Orange 16, 34, 44 and 72; Cl. Pigment Red 144, 166, 214, 220, 221 and 242; Cl. Pigment Yellow 12, 13, 14, 16, 17, 81, 83, 106, 113, 126, 127, 155, 174, 176, 180 and 188; Disazo condensation pigments such as Cl. Pigment Yellow 93, 95 and 128; ^' CI

Pigment Red 144, 166, 214, 220, 242 and 262; Cl. Pigment Brown 23 and 41;

Anthanthrone pigments like Cl. Pigment Red 168;

Anthrachinonpigmentβ as Cl. Pigment Yellow 147, 177 and 199; ! C.. Pigment Violet 31;

Anthrapyrimidine pigments such as Cl. Pigment Yellow 108;

Quinacridone pigments such as Cl. Pigment Orange 48 and 49; Cl. Pigment Red 122,

202, 206 and 209; Cl. Pigment Violet 19;

Quinophthalone pigments such as Cl. Pigment Yellow 138; Diketopyrrolopyrrolpimgente as Cl. Pigment Orange 71, 73 and 81; Cl.

Pigment Red 254, 255, 264, 270 and 272;

Dioxazine pigments such as Cl. Pigment Violet 23 and 37; Cl. Pigment Blue 80;

Flavanthrone pigments such as Cl. Pigment Yellow 24; Indanthrone pigments like Cl.

Pigment Blue 60 and 64; Isoindoline pigments such as Cl. Pigment Orange 61 and 69, Cl. Pigment Red 260,

Cl. Pigment Yellow 139 and 185;

Isoindolinone pigments such as Cl. Pigment Yellow 109, 110 and 173;

Isoviolanthrone pigments such as Cl. Pigment Violet 31;

Metal complex pigments such as Cl. Pigment Red 257; Cl. Pigment Yellow 117, 129, 150, 153 and 177; Cl. Pigment Green 8;

Perinone pigments such as Cl. Pigment Orange 43; Cl. Pigment Red 194;

Perylene pigments such as Cl. Pigment Black 31 and 32; Cl. Pigment Red 123, 149,

178, 179, 190 and 224; Cl. Pigment Violet 29;

Phthalocyanine pigments such as Cl. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6 and 16; Cl. Pigment Green 7 and 36;

Pyranthrone pigments such as Cl. Pigment Orange 51; Cl. Pigment Red 216; Pyrazoloquinazolone pigments such as Cl. Pigment Orange 67; Cl. Pigment Red 251; Thioindigo pigments such as Cl. Pigment Red 88 and 181; Cl. Pigment Violet 38; Triaryl carbonium pigments such as Cl. Pigment Blue 1, 61 and 62; Cl. Pigment Green 1; Cl. Pigment Red 81, 81: 1 and 169; and Cl. Pigment Violet 1, 2, 3 and

27; continue Cl. Pigment Black 1, (aniline black), Cl. Pigment Yellow 101 (Aldazingelb), Cl. Pigment Brown 22; and inorganic color pigments as they are mentioned for example in WO 2004/035277, z. B .: white pigments such as titanium dioxide (CI Pigment White 6), zinc white, colored zinc oxide; Zinc sulfide, lithopone; Black pigment like iron oxide black

(CI Pigment Black 11), iron manganese black, spinel black (CI Pigment Black 27); Carbon black (CI Pigment Black 7) and colored pigments such as chromium oxide, chromium oxide hydrate green; Chrome green (CI Pigment Green 48); Cobalt green (CI Pigment Green 50), ultramarine green, cobalt blue (CI Pigment Blue 28 and 36, CI Pigment Blue 72); Ultramarine blue; Manganese Blue, Ultramarine Violet; Cobalt- and manganese violet, iron oxide red (CI Pigment Red 101), cadmium sulfoselenide (CI Pigment Red 108), cerium sulfide (CI Pigment Red 265); Molybdate red (CI Pigment Red 104), ultramarine red, iron oxide brown (CI Pigment Brown 6 and 7), mixed brown, spinel and corundum phases (CI Pigment Brown 29, 31, 33, 34, 35, 37, 39 and 40), Chromium titanium yellow (CI Pigment Brown 24), chrome orange, cerium sulphide

(CI Pigment Orange 75), iron oxide yellow (CI Pigment Yellow 42); Nickel titanium yellow (CI Pigment Yellow 53, CI Pigment Yellow 157, 158, 159, 160, 161, 162, 163, 164 and 189); Chromium titanium yellow; Spinel phases (CI Pigment Yellow 119); Cadmium sulfide and cadmium zinc sulfide (CI Pigment Yellow 37 and 35); Chrome yellow (CI Pigment Yellow 34); Bismuth vanadate (CI Pigment Yellow 184).

Dyes: z. For example, the dyes described in DE-A 10245209 as well as the color Index referred to as disperse dyes and as solvent dyes compounds, which are also referred to as disperse dyes. A compilation of suitable disperse dyes can be found for example in Ullmann's Encyclopedia of Industrial Chemistry, 4th Edition, Vol. 10, pp. 155-165

7, p. 585ff - Anthrachinonfarbstoffe, Vol 8, p 244ff - Azofarbstoffe fe, Vol 9, p 313ff - Quinophthalonfarbstoffe). This reference and the compounds mentioned therein are hereby incorporated by reference. Disperse dyes and solvent dyes which are suitable according to the invention include a wide variety of different classes of dyes having different chromophores, for example anthraquinone dyes, monoazo and disazo dyes, quinophthalones, methine and azamethine dyes, naphthalimide dyes, naphthoquinone dyes and nitro dyes. Examples of disperse dyes which are suitable according to the invention are the disperse dyes of the following Color Index list: C I. Disperse Yellow 1 - 228, C. I. Disperse Orange 1 - 148, C I. Disperse Red 1 -

Disperse Blue 1 - 97, C I. Disperse Blue 1 - 349, C I. Disperse Green 1 - 9, CI Disperse Brown 1 - 21, C I. Disperse Black 1 - 36. Examples of solvents suitable according to the invention Dyes are the compounds of the following Color Index list: CI Solvent Yellow 2 - 191, C I. Solvent Orange 1 - 113, C I. Solvent Red 1 - 248, CI Solvent Violet 2 - 61, C l. Solvent Blue 2 - 143, C.I.

Solvent Green 1 - 35, CI Solvent Brown 1 - 63, CI Solvent Black 3 - 50. Dyes which are also suitable according to the invention are derivatives of naphthalene, anthracene, perylene, terylene, quarterylene and diketopyrrolopyrrole dyes, perinone dyes, coumarin dyes, Isoindoline and isoindoline dyes, porphyrin dyes, phthalocyanine and naphthalocyanine dyes.

As effect substances it is also possible to use UV absorbers, antioxidants and / or stabilizers. Examples of UV absorbers are the compounds of the following listed groups a) to g). Examples of stabilizers are the compounds of groups i) to q) listed below.

a) 4,4-diaryibutadienes, b) cinnamic acid esters, c) benzotriazoles, d) hydroxybenzophenones, e) diphenylcyanoacrylates, f) oxamides (oxalic acid diamides), g) 2-phenyl-1,3,5-triazines; h) antioxidants, i) sterically hindered amines, j) metal deactivators, k) phosphites and phosphonites, I) hydroxylamines, m) nitrenes, n) amine oxides, o) benzofuranones and indolinones, p) thiosynergists, and q) peroxide-destroying compounds.

The group a) of the 4,4-diarylbutadienes include, for example, compounds of the formula A.

The compounds are known from EP-A-916 335. The substituents R ₁₀ and / or Rn are preferably C ₁ -C ₈ -alkyl and C ₅ -C ₈ -cycloalkyl.

The group b) of cinnamic acid esters includes, for example, isoamyl methoxycinnamate, 2-ethylhexyl 4-methoxycinnamate, methyl α-methoxycarbonyl cinnamate, methyl α-cyano-β-methyl-p-methoxycinnamate, butyl α-cyano-β-methyl- p-methoxy-cinnamate and methyl-α-methoxycarbonyl-p-methoxycinnamate.

The group c) of the benzotriazoles includes, for example, 2- (2'-hydroxyphenyl) benzotriazoles, such as 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (3 ^l , 5'-di-tert-butyl) 2'-hydroxyphenyl) benzotriazole, 2- (5'-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5 '- (1, 1, 3,3-tetramethylbutyl) phenyl) benzotriazole , 2- (3 ^L , 5'-di-tert-butyl-2 ^L -hydroxyphenyl) -5-chloro-benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 ^L -methylphenyl) -5 - chloro-benzotriazole, 2- (3'-sec-butyl-5'-tert-butyl-2 ^l -hydroxyphenyl) -benzotriazole, 2- (2'-hydroxy-4'-octyloxyphenyl) -benzotriazole, 2- (3 ' , 5 ^I -di-tert-amyl-2-hydroxyphenyl ^l) - benzotriazole, 2- (3 ^l ₁ 5'-bis- (α, α-dimethylbenzyl) -2 ^l hydroxyphenyl) benzotriazole, 2- (3 ' Tert-butyl-2 ¹ -hydroxy-5 ^l - (2-octyloxycarbonylthyl) phenyl) -5-chloro-benzotriazoi, 2- (3 ^! -tert-butyl-5 '- [2- (2-ethylhexyloxy ) -carbonylethyl] -2'-hydroxyphenyl) -5-chloro-benzotriazole, 2- (3 ¹ -tβ-n-butyl-2'-hydroxy-5 '- (2-methoxycarbonylethyl-phenyl) -5-chloro-benzotriazole, 2- ( 3'-tert-Butyl-2'-hydroxy-5 '- (2-methoxycarbonylethyl) phenyl) benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5' - (2-octyloxycarbonylethyl) phenyl) benzotriazole, 2- (3'-tert-butyl-5 '- [2- (2-ethylhexyloxy) carbonylethyl] -2'-hydroxyphenyl) benzotriazole, 2- (3'-dodecyl-2'-hydroxy-5' -methylphenyl) benzotriazole and 2- (3'-tert-butyl-2'-hydroxy-5 ^l - (2-isooctyloxycarbonylethyl) phenylbenzotriazole, 2,2'-methylene-bis [4- (1, 1, 3,3-tetramethylbutyl) -6-benzotriazole-2 -yl-phenol]; the product of the esterification of 2- [3'-tert-butyl-5 '- (2-methoxycarbonylethyl) -2'-hydroxyphenyl] -2H-benzotriazole with polyethylene glycol 300; [R-CH ₂ CH ₂ -COO (CH ₂ ) ₃ ] ₂ , with R = S'-tert-Buty-W-hydroxy-δ 'H -benzotriazole-1-phenyl and mixtures thereof.

Examples of groups d) of the hydroxybenzophenones include 2-hydroxybenzophenones, such as 2-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2,2,4,4'-tetra-hydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4- (2-ethylhexyloxy) benzophenone, 2-hydroxy-4- (n- octyloxy) benzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2-hydroxy-3-carboxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its sodium salt, 2,2'-dihydroxy-4,4 ^1- dimethoxybenzophenone-5,5'-bisulfonic acid and its sodium salt.

The group e) of the diphenylcyanoacrylates includes, for example, ethyl-2-cyano-3,3-diphenylacrylate, which is obtainable, for example, commercially under the name Uvinul® 3035 from BASF AG, Ludwigshafen, 2-ethylhexyl-2-cyano-3, 3-diphenylacrylate, which is commercially available, for example, as Uvinul.RTM. 3039 from BASF AG, Ludwigshafen, and 1.S-bis-.beta.-cyano-.sym.-diphenylacryloyoxyloxy-bis-pent-cyano-S '. S'-diphenyl-acryloyl) oxy] methyl} propane, which is available, for example, commercially under the name Uvinul® 3030 Fa. BASF AG, Ludwigshafen.

F to the group) of the oxamides includes for example 4,4'-dioctyloxyoxanilide, 2,2'-di- ethoxyoxanilide, 2,2'-dioctyloxy-5,5 ^l-di- (tert-butyl) oxanilide, 2,2'- Didodecyloxy-5,5'-di (tert-butyl) oxanilide, 2-ethoxy-2'-ethyloxanilide, N, N'-bis (3-dimethylaminopropyl) oxamide, 2-ethoxy-5-tert-butyl-2 ' -ethyloxanilide and its mixture with 2-ethoxy-2'-ethyl-5,4'-di- (tert-butyl) oxanilide and mixtures of ortho, para-methoxy-disubstituted oxanilides and mixtures of ortho and para-ethoxy disubstituted oxanilides. The group g) of 2-phenyl-1,3,5-triazines include, for example, 2- (2-hydroxyphenyl) -1,3,5-triazines such as 2,4 _I 6-tris (2-hydroxy-4-octyloxyphenyl) -1 ₎ 3 _{l of} 5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis (2 _{l of} 4-dimethylpheny!) -1,3,5-triazirj, 2- (2,4- Dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1, 3,5-triazine, 2,4-bis (2-hydroxy-4-propyloxyphenyl) -6- (2,4-dimethylphenyl) -1 , 3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis (4-methylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-dodecyloxyphenyl) - 4,6-bis (2,4-dimethylphenyl) -1, 3,5-triazine, 2- (2-hydroxy-4-tridecyloxyphenyl) -4, β-bis (2,4-dimethylphenyl) -1, 3, 5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-butyloxypropoxy) -phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2 - [2-hydroxy-4- (2-hydroxy-3-octyloxypropoxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [4- (dodecyloxy / tridecyloxy-2-hydroxypropoxy) -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy- 3-dodecyloxy-propoxy) phenyl] -4,6-bis (2,4-dimethyl) 1-phenyl) -1,3,5-triazine, 2- (2-hydroxy-4-hexyloxyphenyl) -4,6-diphenyl-1,3,5-triazine, 2- (2-hydroxy-4-methoxyphenyl) -4 , 6-diphenyl-1, 3,5-triazine, 2,4,6-tris [2-hydroxy-4- (3-butoxy-2-hydroxypropoxy) phenyl] -1,3,5-triazine and 2 - (2-Hydroxyphenyl) -4- (4-methoxyphenyl) -6-phenyl-1,3,5-triazine.

The group h) of the antioxidants includes, for example:

Alkylated monophenols such as, for example, 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di- tert -butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2- (α-methylcyclohexyl) -4,6-dimethylphenol, 2, 6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, unbranched or branched in the side chain nonylphenols such as 2,6-di-nonyl-4-methylphenol , 2,4-dimethyl-6- (1-methylundec-1-yl) -phenol _I 2,4-dimethyl-6- (1-methylheptadec-1-yl) -phenol, 2,4-dimethyl-6- ( 1-methyltridec-1-yl) phenol and mixtures thereof.

Alkylthiomethylphenols such as 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-didodecylthiomethyl-4-nonylphenol.

Hydroquinones and alkylated hydroquinones such as 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol , 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4 - hydroxyphenyl stearate, bis- (3,5-di-tert-butyl-4-hydroxyphenyl) adipate.

Tocopherols, such as α-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol and mixtures thereof (vitamin E). Hydroxylated thiodiphenyl ethers such as 2,2'-thio-bis (6-tert-butyl-4-methylphenol), 2,2'-thio-bis (4-octylphenol), 4,4'-thio-bis (6- tert-butyl-3-methylphenol), 4,4'-thio-bis (6-tert-butyl-2-methylphenol). 4.4 ^1-thio-bis- (3,6-di-sec-amy! Pheno!), 4,4'-bis (2,6-dimethyl-4-hydroxyphenyl) disulfide.

Alkylidene bisphenols such as 2,2'-methylenebis (6-tert-butyl-4-methylphenol), 2,2'-methylenebis (6-tert-butyl-4-ethylphenol), 2,2 ' -Methylene-bis [4-methyl-6- (α-methylcyclohexyl) phenol], 2,2'-methylenebis (4-methyl-6-cyclohexylphenol), 2,2'-methylenebis (6-nonyl 4-methylphenol), 2,2'-methylenebis (4,6-di-tert-butylphenol), 2,2'-ethylidenebis (4,6-di-tert-butylphenol), 2,2 ' Ethylidene bis (6-tert-butyl-4-isobutylphenol), 2,2'-methylenebis [6- (a-methylbenzyl) -4-nonylphenol], 2,2'-methylene-bis [6- (benzothiazole) α, α- dimethylbenzyl) -4-nonylphenol], 4,4 ^{1-methylene-bis} (2,6-di-tert-butylphenol), 4,4'-methylene-bis (6-tert-butyl-2-methylphenol ), 1, 1-Bis (5-tert-butyl-4-hydroxy-2-methylphenyl) -butane, 2,6-bis (3-tert-butyl-5-methyl-2-hydroxybenzyl) -4-methylphenol, 1, 1, 3-tris (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 1,1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) -3-n dodecylmercaptobutane, ethylene glycol bis [3,3-bis (3-tert-butyl-4-hydroxyphenyl) butyrate], bis (3-tert-butyl-4-hydroxy-5-methyl-pheny l) dicyclopentadiene, bis [2- (3'-tert-butyl-2-hydroxy-5-methylbenzyl) -6-tert-butyl-4-methylphenyl] terephthalate, 1, 1-bis (3,5-dimethyl) 2-hydroxyphenyl) butane, 2,2-bis (3,5-di-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) 4-n-dodecylmercaptobutane, 1,1,5,5-tetra- (5-tert-butyl-4-hydroxy-2-methylphenyl) -pentane.

Benzyl compounds such as 3,5,3 ', 5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate, tri-decylM-hydroxy-S.δ-di tert -butylbenzylmercaptoacetate, tris (3,5-di-tert-butyl-4-hydroxybenzyl) amine, ISδ-TrKS.S-di-tert-butyl-m-hydroxybenzyO ^^, β-trimethylbenzene, di- (3,5- Di-tert-butyl-4-hydroxybenzyl) sulfide, 3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetic acid isooctyl ester, bis (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) dithiol terephthalate , 1,3,5-Tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris- (4-tert-butyl-3-hydroxy-2 _> 6 -dimethylbenzyl) isocyanurate, 3,5-di-tert-butyl-4-hydroxybenzyl-phosphoric acid octadecyl ester and 3,5-di-tert-butyl-4-hydroxybenzyl-phosphoric acid monoethyl ester, calcium salt.

Hydroxybenzylated malonates such as dioctadecyl-2,2-bis (3,5-di-tert-butyl-2-hydroxybenzyl) malonate, di-octadecyl-2- (3-tert-butyl-4-hydroxy-5-methylbenzyl ) - malonate, di-dodecylmercaptoethyl-2,2-bis (3,5-di-tert-butyl-4-hydroxybenzyl) malonate, bis (II) SS-tetramethylbutylpheny () - bi (-) di-tert -butyM-hydroxybenzyl) malonate. Hydroxybenzyl aromatics such as 1,3,5-tris- (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,4-bis (3,5-di-tert-butyl) tert -butyl-4-hydroxybenzyl) -2,3,5,6-tetramethylbenzene, 2 ₁ 4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) phenol.

Triazine compounds such as 2,4-bis (octylmercapto) -6- (3,5-di-tert-butyl-4-hydroxyanilino) -1, 3,5-triazine, 2-octylmercapto-4,6-bis (3 , 5-di-tert-butyl-4-hydroxyanilino) -1, 3,5-triazine, 2-octylmercapto-4,6-bis (3,5-di-tert-butyl-4-hydroxyphenoxy) -1,3 , 5-triazine, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxyphenoxy) -1, 3,5-triazine, 1, 3,5-tris (3,5-di tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 2,4,6-tris (3,5 -di-tert-butyl-4-hydroxyphenylethyl) -1, 3,5-triazine, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) -hexahydro-1, 3.5 triazine, 1,3,5-tris (3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate.

Benzyl phosphonates such as dimethyl 2,5-di-tert-butyl-4-hydroxybenzyl phosphonate, diethyl 3,5-di-tert-butyl-4-hydroxybenzyl phosphonate ((3,5-bis (1,1-dimethylethyl) - 4-hydroxyphenyl) methyl) lphosphonic acid diethyl ester), dioctadecyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, calcium salt of 3,5-di tert-butyl-4-hydroxybenzylphosphonic acid monoethyl ester.

Acylaminophenols such as 4-hydroxy-lauric acid anilide, 4-hydroxystearic acid anilide, 2,4-bis-octylmercapto-6- (3,5-di-tert-butyl-4-hydroxyanilino) -s-triazine and octyl-N- (3 , 5-di-tert-butyl-4-hydroxyphenyl) -carbamate.

Esters of ß- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid with monohydric or polyhydric alcohols such. With methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxalic acid diamide, 3-thiaundecanol, 3

Thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane.

Esters of ß- (5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid with mono- or polyhydric alcohols, such. With methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1, 9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxalic acid diamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane , Esters of ß- (3,5-dicyclohexyl-4-hydroxyphenyl) propionic acid with monohydric or polyhydric alcohols such. With methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N ₁ N ¹ - bis (hydroxyethyl) oxalic acid diamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane.

Esters of 3,5-di-tert-butyl-4-hydroxyphenylacetic acid with mono- or polyhydric alcohols, such as. With methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxalic acid diamide, 3-thiaundecanol, 3-thiapentadecanol, t-methylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane.

Amides of .beta .- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid, such as. N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexamethylenediamine, N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) -trimethylenediamine, N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) -hydrazine, N, N'-bis [2- (3- [3,5-di-tert-butyl-4-hydroxyphenyl ] - propionyloxy) ethyl] -oxamide (eg Naugard® XL-1 from Uniroyal).

Ascorbic acid (vitamin C)

Amine antioxidants, such as N, N'-di-isopropyl-p-phenylenediamine, N, N'-di-sec-butyl-p-phenylenediamine, N, N'-bis (1,4-dimethylpentyl) -p- phenylenediamine, N, N'-bis (1-ethyl-3-methylpentyl) -p-phenylenediamine, N, N'-bis (1-methylheptyl) -p-phenylenediamine, N, N'-dicyclohexyl-p-phenylenediamine, N , N'-diphenyl-p-phenylenediamine, N, N'-bis (2-naphthyl) -p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N- (1,3-dimethylbutyl) -N '-phenyl-p-phenylenediamine, N- (1-methylheptyl) -N'-phenyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine, 4- (p-toluenesulfamoyl) diphenylamine, N, N '-Dimethyl-N, N'-di-sec-butyl-p-phenylenediamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxydiphenylamine, N-phenyl-1-naphthylamine, N- (4-tert-octylphenyl) -1-naphthylamine , N-phenyl-2-naphthylamine, octylated diphenylamine, for example p.p'-di-tert-octyldiphenylamine, 4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol, 4-octadecanoylaminophenol, bis ( 4-methoxyphenyl) amine , 2,6-di-tert-butyl-4-dimethylaminomethylphenol, 2,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, NNN'.N'-tetramethylm ^ '- diaminodiphenylmethane, 1,2-Bis - [(2-methylphenyl) amino] ethane, 1,2-bis (phenylamino) -propane, (o-tolyl) -biguanide, bis-O'-S'-dimethylbutyl-quinylamine, tert-octylated N -Phenyl-1-naphthylamine, mixture of mono- and dialkylated tert-butyl / tert-Octyldiphenylaminen, mixture of mono- and dialkylated nonyldiphenylamines, mixture of mono- and dialkyüerten dodecyldiphenylamines, mixture of mono- and dialkylated isopropyl / Isohexyl- diphenylamines, mixture from mono- and dialkylated tert-butyldiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, mixture of mono- and dialkylated tert-butyl / tert-octyl-phenothiazines, mixture of mono and dialkylated tert-octyl-phenothiazines, N-allylphenothiazine, N, N, N ', N'-tetraphenyl-1,4-diaminobut-2-ene, NN-bis-β-β, β-tetramethylpiperidine Φ-yl-hexamethylenediamine, bis (2, 2,6,6-tetramethylpiperidin-4-yl) sebacate, 2,2,6,6-tetramethylpiperidin-4-one, 2,2,6,6-tetramethylpiperidine-4 -ol, the dimethylsuccinate polymer with 4-hydroxy-2,2,6,6-tetramet hyl-1-piperidineethanol [CAS number 65447-77-0], (for example Tinuvin® 622 from Ciba Specialty Chemicals, Switzerland), polymer based on 2,2,4,4-tetramethyl-7-oxa-3, 20-diaza-dispiro [5.1.11.2] -heicosan-21-one and epichlorohydrin [CAS No .: 202483-55- 4], for example (Hostavin®30 from Ciba Specialty Chemicals, Switzerland).

The group i) of the sterically hindered amines include, for example, 4-hydroxy-2,2,6,6-tetramethylpiperidine, 1-allyl-4-hydroxy-2,2,6,6-tetramethylpiperidine, 1-benzyl-4-hydroxy 2,2,2,6,6-tetramethylpiperidine, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethyl-4-piperidyl) succinate, bis (1 , 2,2,6,6-pentamethyl-4-piperidyl sebacate, bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1, 2,2,6,6-pentamethyl 4-piperidyl) -n-butyl-3,5-di-tert-butyl-4-hydroxybenzyl malonate (n-butyl-3,5-di-tert-butyl-4-hydroxy-benzyl-malonic acid bis (1 , 2,2,6,6-pentamethylpiperidyl) ester), condensation product of 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, linear or cyclic condensation products of N, N ^l Bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-1,3,5-triazine, tris (2,2,6,6-tetramethyl 4-piperidyl) nitrilotriacetate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butane-tetracarboxylate, 1,1'- (1,2-ethanediyl) bis (3,3,5,5-tetramethylpiperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine,

4-stearyloxy-2 ₁ 2,6,6-tetramethylpiperidine, bis (1,2,2,6,6-pentamethylpiperidyl) -2-n-butyl-2- (2-hydroxy-3,5-di-tert butylbenzyl) malonate, 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro [4.5] decane-2,4-dione, bis (1-octyloxy-2,2,6 , 6-tetramethylpiperidyl) sebacate, bis (1-octyloxy-2,2,6,6-tetramethylpiperidyl) succinate, linear or cyclic condensation products of N, N'-bis- (2,2,6 , 6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5-triazine, condensation product of N, N'-bis- (2,2,6,6-tetramethyl-4 -piperidyl) hexamethylenediamine and formic acid ester (CAS No. 124172-53-8, eg Uvinul® 4050H from BASF AG, Ludwigshafen), condensation product of 2-chloro-4,6-bis (4-n-butylamino -2,2,6,6-tetramethylpiperidyl) -1,3,5-triazine and 1,2-bis (3-aminopropylamino) ethaπ, condensation product of 2-chloro-4,6-di- (4-n-) butylamino-1, 2,2,6,6-pentamethylpiperidyl) -1,3,5-triazine and 1,2-bis (3-aminopropylamino) ethane, 8-acetyl-3-dodecyl-7,7,9, 9-tetramethyl-1,3,8-triazaspiro [4,5] decane-2,4-dione, 3-dodecyl-1- (2,2,6,6-tetramethyl-4-piperidyl) -pyrrolidine-2,5-dione , 3-dodecyl-1- (1 ^^. β.β-pentamethyl-ΦpiperidyOpyrroüdin ^ .S-dione, mixture of 4-hexadecyloxy-and 4-stearyloxy-2,2,6 ₁ 6-tetramethylpiperidine, condensation product of N, N ^t -Bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, condensation product of 1, 2-bis (3-aminopropylamino ) ethane and 2,4,6-trichloro-1, 3,5-triazine and 4-butylamino-2, 2,6,6-tetramethylpiperidine (CAS Reg. No. [136504-96-6]); N- ( 2,2,6,6-tetramethyl-4-piperidyl-n-dodecylsuccinimide, N- (1, 2,2,6,6-pentamethyl-4-piperidyl) -n-dodecylsuccinimide, 2-undecyl-7,7, 9,9-tetramethyl-1-oxa-3,8-diaza-4-oxospiro [4,5] decane, reaction product of 7,7 _{l of} 9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8- diaza-4-oxospiro [4,5] decane and epichlorohydrate in, 1,1-bis (1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl) -2- (4-methoxyphenyl) ethene, N, N ¹ -bis-formyl-N, N'-bis ( 2, 2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine, diester of 4-methoxymethylenemalonic acid with isopropylamine, poly [methylpropyl-3-oxo-4- (β-β-pentamethyl) -hydroxypiperidine 2,2,6,6-tetramethyl-4-piperidyl)] siloxane, reaction product of maleic anhydride-α-olefin copolymer and 2,2,6,6-tetramethyl-4-aminopiperidine or 1, 2,2,6,6 -Pentamethyl-4-aminopiperidine, copolymers of (partially) N-piperidin-4-yl substituted maleimide and a mixture of α-olefins such. Uvinul® 5050H (BASF AG), 1- (2-hydroxy-2-methylpropoxy) -4-octadecanoyloxy-2,2,6,6-tetramethylpiperidine, 1- (2-hydroxy-2-methylpropoxy) -4- hexadecanoyloxy-2,2,6,6-tetramethylpiperidine, the reaction product of 1-oxyl-4-hydroxy-2, 2,6,6-tetramethylpiperidine and a carbon radical of t-amyl alcohol, 1- (2-hydroxy-2-methylpropoxy ) -4-hydroxy-2,2,6,6-tetramethylpiperidine, 1- (2-hydroxy-2-methylpropoxy) -4-oxo-2,2,6,6-tetramethylpiperidine, bis (1- (2-hydroxy 2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yl) sebacate, bis (1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yl) adipate, bis (1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yl) succinate, bis (1- (2-hydroxy-2-methylpropoxy) -2,2, 6,6-tetramethylpiperidin-4-yl) glutarate, 2,4-bis {N [1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yl] -N-butylamino } -6- (2-hydroxyethylamino) -s-triazine, N, N'-bis- formyl-N, N ^I -bis (1, 2,2,6,6-pentamethyl-4-piperidyl) hexamethylenediamine, hexahydro 2,6-bis (2,2,6, β-tetram ethyl-4-piperidyl) -1H, 4H, 5H, 8H-2,3a, 4a, 6,7a, 8a-hexaazacyclopenta [def] fluorene-4,8-dione (e.g. Uvinul® 4049 from BASF AG, Ludwigshafen), poly [[6 - [(1,1,3,3-tetramethylbutyl) amino] -1,3,5-triazine-2,4-diyl] [( 2,2,6,6-tetramethyl-4-piperidinyl) imino] 1β-hexanediyl ^^, β, Δ-tetramethylm-piperidinylimino]]) [CAS No. 71878-19-8], 1,3,5 triazine-2,4,6-triamine, N, N, N ^{I, N>} tetrakis (4,6-di (butyl- (N-methyl-2,2,6,6-tetramethylpiperidin-4-yl) amino) triazin-2-yl) -4,7-diazadecane-1, 10-diamine (CAS No. 106990-43-6) (for example, Chimassorb 119 from Ciba Specialty Chemicals, Inc.). The group j) of the metal deactivators includes, for example, N, N'-diphenyloxalic diamide, N-salicylal-N'-salicyloyl-hydrazine, N, N'-bis (salicyloyl) hydrazine, N, N'-bis (3,5 di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine, 3-salicyloylamino-1, 2,4-triazole, bis (benzylidene) oxalyl dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenyl hydrazide, N, N'-diacetyl adipic dihydrazide, N, N Bis (salicyloyl) oxalic acid dihydrazide, N, N'-bis (salicyloyl) thiopropionyl dihydrazide.

The group k) of the phosphites and phosphonites includes, for example, triphenylphosphite, diphenylalkylphosphites, phenyldialkylphosphites, tris (nonylphenyl) phosphite, trilaurylphosphite, trioctadecylphosphite, distearylpentaerythritol diphosphite, tris (2,4-di-tert-butylphenyl) phosphite, diisodecylpentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, diisodecyl pentaerythritol diphosphite, bis (2,4-di-tert-butyl-6-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tris (tert-butylphenyl) pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis - ^ -di-tert-butylphenylM ^ ¹ -biphenylene diphosphonite, 6-isoctyloxy-2,4,8,10-tetra tert-butyl-dibenzo [d, f] [1, 3,2] dioxaphosphepin, 6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenzo [d, g] [1, 3,2] dioxaphosphocine, bis (2,4-di-tert-butyl-6-methylphenyl) methyl phosphite, bis (2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite, 2,2 ¹ , 2 "-Nitrilo [triethyltris (3.3 ¹ , 5.5 ¹ -tetra- tert-butyl- 1, ^l 1-biphenyl-2,2'-diyl) phosphite], (2-ethylhexyl) - (3,3 ^l _I 5.5 ^I tetra-tert-butyl-1, 1 ^l-biphenyl - 2.2 ^ dJyI) PHOSPhJt.

The group I) of the hydroxylamines include, for example, N, N-dibenzylhydroxylamine, N, N-diethylhydroxylamine, NN-dioctylhydroxylamine, N, N-dilaurylhydroxylamine, N, N-ditetradecylhydroxylamine, N, N-dihexadecylhydroxylamine, N, N-dioctadecylhydroxylamine, N-hexadecyl-N octadecylhydroxylamine, N-heptadecyl-N-octadecylhydroxylamine, N-methyl-N-octadecylhydroxylamine, and NN-oxyalkylhydroxylamine from hydrogenated tallow fatty amines.

The group m) of the nitron include, for example, N-benzyl-α-phenyl nitrone, N-ethyl-α-methyl nitrone, N-octyl-α-heptyl nitrone, N-lauryl-α-undecyl nitrone, N-tetradecyl-α-tridecyl nitrone, N Hexadecyl-α-pentadecylnitrone, N-octadecyl-α-heptadecylnitrone, N-hexadecyl-α-heptadecylnitrone, N-octadecyl-α-pentadecylnitrone, N-heptadecyl-α-heptadecylnitrone, N-octadecyl-α-hexadecylnitrone, N-methyl -α-heptadecyl nitrone and nitron derived from N, N-dialkylhydroxylamines prepared from hydrogenated tallow fatty amines.

The group n) of the amine oxides includes, for example, amine oxide derivatives as described in US Patent Nos. 5,844,029 and 5,880,191, didecylmethylamine oxide, tridecylamine oxide, tridodecylamine oxide and trihexadecylamine oxide. The group o) of the benzofuranones and indolinones includes, for example, those described in U.S. Patents 4,325,863; 4,338,244; 5,175,312; 5,216,052; 5,252,643; in DE-A-4316611; in DE-A-4316622; in DE-A-4316876; or 3- [4- (2-acetoxyethoxy) phenyl] -5,7-di-tert-butylbenzofuran-2 (3H) -one, 5.7, described in EP-A-0589839 or EP-A-0591102 -Di-tert-butyl-3- [4- (2-stearoyloxyethoxy) phenyl] -benzofuran-2 (3H) -one, 3,3'-bis [5,7-di-tert-butyl-3- (4 - [2-hydroxyethoxy] phenyl) benzofuran-2 (3H) -one], 5,7-di-tert-butyl-3- (4-ethoxyphenyl) -benzofuran-2 (3H) -one, 3- (4 - acetoxy-3,5-dimethylphenyl) -5,7-di-tert-butyl-benzofuran-2 (3H) -one, 3- (3,5-dimethyl-4-pivaloyloxyphenyl) -5,7-di-tert -butyl-benzofuran-2 (3H) -one, 3- (3,4-dimethylphenyl) -5,7-di-tert-butylbenzofuran-2 (3H) -one; Irganoxs HP-136 from Ciba Specialty Chemicals , Switzerland, and 3- (2,3-dimethylphenyl) -5,7-di-tert-butylbenzofuran-2 (3H) -one.

The group p) of thiosynergists include, for example, dilauryl thiodipropionate or distearyl thiodipropionate.

The group q) of the peroxide-destroying compounds includes, for example, esters of β-thiodipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl ester, mercaptobenzimidazole or the zinc salt of 2-mercaptobenzimidazole, zinc dibutyl dithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis (β dodecylmercapto) propionate.

The aqueous dispersions to be used according to the invention may contain, in addition to the wax constituents, one or more active substances which are suitable for protecting wood or comparable lignocellulosic materials from infestation or destruction by harmful organisms.

Examples of such harmful organisms are

- Wood discoloring mushrooms, z. Ascomycetes such as Ophiostoma sp. (e.g., Ophiostoma piceae, Ophiostoma piliferum), Ceratocystis sp. (eg Ceratocystis coerules cens), Aureobasidium pullulans, Sclerophoma sp. (eg Sclerophoma pityophila); Deuteromycetes such as Aspergillus sp. (eg Aspergillus niger), Cladosporium sp. (eg, Cladosporium sphaerospermum), Penicillium sp. (eg Penicillium funiculosum), Trichoderma sp. (eg Trichoderma viride), Alternaria sp. (eg Alternaria altemata), Paecilomyces sp. (eg Paecilomyces variotii); Zygomycetes such as Musc sp. (eg Mucor hiemalis);

Wood-destroying mushrooms: Ascomycetes like Chaetomium sp. (e.g., Chaetomium globosum), Humicola sp. (eg Humicola grisea), Petriella sp. (eg Petriella seti- fera), Trichurus sp. (eg Trichurus spiralis); Basidiomycetes such as Coniophora sp. (e.g., Coniophora puteana), Coriolus sp. (eg Coriolus versicolor), Gloeophyllum sp. (eg Gloeophyllum trabeum), Lentinus sp. (eg Lentinus lepideus), Pleurotus sp. (eg, Pleurotus ostreatus), Poria sp. (eg Poria placenta, Poria vaillantii), Sβφula sp. (eg, Serpula lacrymans) and Tyramyces sp. (eg Tyromyces palustris), and

Wood-destroying insects z. Cerambycidae such as Hylotrupes bajulus, Callidium violaceum; Lyctidae such as Lyctus linearis, Lyctus brunneus; Bostrichidae such as Dendereus minutus; Anobiidae such as Anobium punctatum, Xestobium rufovillosum; Lymexylidae such as Lymexylon navale; Platypodidae such as Piatypus cylindrus; Edemidae, such as Nacerda melanura; Formicidae such as Camponotus abdominalis, Lasius flavus, Lasius brunneus, Lasius fuliginosus;

Accordingly suitable are fungicidal active ingredients, insecticidally active ingredients and bactericides, in particular:

Fungicides from the following groups:

Oicarboximides such as iprodione, myclozoline, procymidone, vinclozolin;

Acylalanines such as benalaxyl, metalaxyl, ofurace, oxadixyl; Amine derivatives such as aldimorph, dodine, dodemorph, fenpropimorph, fenpropidin, guazatine, iminoctadine, spiroxamine, tridemorph;

Anilinopyrimidines such as pyrimethanil, mepanipyrim or cyprodinil;

• antibiotics such as cycloheximide, griseofulvin, kasugamycin, natamycin, polyoxin and streptomycin; Azoles (conazoles) such as azaconazole, bitertanol, bromoconazole, cyproconazole,

Dichlobutrazole, Difenoconazole, Diniconazole, Epoxiconazole, Fenbuconazole, Fluquinconazole, Flusilazole, Flutriafol, Ketoconazole, Hexaconazole, Imazalil, Metconazole, Myclobutanil, Penconazole, Propiconazole, Prochloraz, Prothioconazole, Tebuconazole, Tetraconazole, Triadimefon, Triadimenol, Triflumizole, triticonazole; Dithiocarbamates: Ferbam, Nabam, Maneb, Mancozeb, Metam, Metiram, Propineb, Polycarbamate, Thiram, Zirarπ, Zineb;

Heterocyclic compounds such as anilazine, benomyl, boscalid, carbendazim, carboxin, oxycarboxin, cyazofamide, dazomet, dithianone, famoxadone, fenamidone, fenarimol, fuberidazole, flutolanil, furametpyr, isoprothiolane, mepronil, radinol, probenazole, proquinazide, pyrifenox, Pyroquilon, Quinoxyfen, Silthiofam,

Thiabendazole, thifluzamide, thiophanate-methyl, tiadinil, tricyclazole, triforine;

Nitrophenyl derivatives such as binapacryl, dinocap, dinobutone, nitrophthalic-isopropyl;

Phenylpyrroles such as fenpiclonil and fludioxonil;

2-Methoxybenzophenones, as described in EP-A 897,904 by the general formula I, z. Eg metrafenone; Unclassified fungicides such as acibenzolar-S-methyl, benthia-valicarb, caryropamide, chlorothalonil, cymoxanil, diclomethine, diclocymet, diethofencarb, edifenphos, ethaboxam, fenhexamide, fentin-acetate, fenoxanil, ferimzone, fluazinam, fosetyl, fosetyl-aluminum, iprovaficarb, hexachlorobenzcl , Metrafenone, Pencycuron, Propamocarb, Phthalide, Toloclofos-Methyl,

Quintozene, zoxamide;

Strobilurins, as described in WO 03/075663 by the general formula I, z. For example: azoxystrobin, dimoxystrobin, fluoxastrobin, kresoximomethyl, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin and trifloxystrobin;

Sulfenic acid derivatives such as captafol, captan, dichlofluanid, folpet, tolylfluenotide;

Cinnamic acid amides and analogues such as dimethomorph, flumetover, flumorph;

6-Aryl- [1,2,4] triazolo [1,5-a] pyrimidines as described, for example, in US Pat. In WO 98/46608,

WO 99/41255 or WO 03/004465 are each described by the general formula I;

Amide fungicides such as cyflufenamide and (Z) -N- [α- (cyclopropylmethoxyimino) -2,3-difluoro-6- (difluoromethoxy) benzyl] -2-phenylacetamide;

Iodine compounds such as diiodomethyl-p-tolylsulfone, 3-iodo-2-propynyl alcohol, 4-chlorophenyl-3-iodopropargylformal, 3-bromo-2,3-diiodo-3-propenylethylcarbonate, 2,3,3-triiodoallylalcohol, 3-bromo -2,3-diiodo-2-propenyl,

3-iodo-2-propynyl-n-butylcarbamate, 3-iodo-2-propynyl-n-hexylcarbamate, 3-iodo-2-propynylphenylcarbamate, O-1- (6-iodo-3-oxohex-5-ynyl) -butylcarbamate , O-1- (6-iodo-3-oxohex-5-ynyl) phenylcarbamate, nopcocides;

Phenol derivatives such as tribromophenol, tetrachlorophenol, 3-methyl-4-chlorophenol, dichlorophene, O-phenylphenol, m-phenylphenol, 2-benzyl-4-chlorophenol;

Isothiazolinones such as N-methylisothiazolin-3-one, 5-chloro-N-methylisothiazolin-3-one, 4,5-dichloro-N-octylisothiazolin-3-one, N-octylisothiazolin-3-one;

• (Benz) isothiazolinones such as 1,2-benzisothiazol-3 (2H) one, 4,5-dimethylisothiazol-3-one, 2-octyl-2H-isothiazol-3-one;

Pyridines such as 1-hydroxy-2-pyridinethione (and its Na, Fe, Mn, Zn salts), tetrachloro-4-methylsulfonylpyridine;

Metal soaps such as tin, copper, zinc naphthenate, octoate, 2-ethylhexanoate, oleate, phosphate, benzoate; • organotin compounds, e.g. B. tributyl (TBT) tin compounds such as tributyltin and tributyl (mononapthenoyloxy) tin derivative;

Dialkyldithiocarbamate and the Na and Zn salts of dialkyldithiocarbamates, tetramethylthiouram disulfide;

Nitriles, such as 2,4,5,6-tetrachloroisophthalodinitrile; Benzothiazoles such as 2-mercaptobenzothiazole; Quinolines such as 8-hydroxyquinoline and their Cu salts;

Tris-N- (cyclohexyldiazeniumdioxy) -aluminum, N- (cyclohexyldiazeniumdioxy) -tributyltin, bis-N- (cyclohexyldiazeniumdioxy) -kupfeπ

• 3-Benzo (b) thien-2-y! = 5,6-dihydro-1,2,2-oxathazin-4-oxide (Bethoxazine).

Insecticides from the following groups:

Organophosphates such as azinphos-methyl, azinphos-ethyl, chlorpyrifos, chloropyrifos-methyl, chlorfenvinphos, diazinon, dimethylvinphos, dioxabenzofos, disulfotone, ethion, EPN, fenitrothion, fenthion, heptenophos, isoxathione, malathion,

Methidathion, Methyl Parathion, Paraoxone, Parathion, Phenthoate, Phosalone, Phosmet, Phorate, Phoxim, Pirimiphos-methyl, Profenofos, Prothiofos, Primiphos-ethyl, Pyraclofos, Pyridaphenthion, Sulprofos, Triazophos, Trichlorfon; Tetrachlorovinyl, vamidothion; Carbamates such as alanycarb, benfuracarb, bendiocarb, carbaryl, carbofuran, bosulfan, fenoxycarb, furathiocarb, indoxacarb, methiocarb, pirimicarb, propoxyl, thiodicarb, triazamate;

Pyrethroids such as bifenthrin, cyfluthrin, cycloprothrin, cypermethrin, deltamethrin, esfenvalerate, ethofenprox, fenpropathrin, fenvalerate, cyhalothrin, lambda-cyhalothrin, permethrin, silafluofen, tau-fluvalinate, tefluthrin, tralomethrin, alpha-cypermethrin;

• Arthropod growth regulators: a) chitin synthesis inhibitors z. B. benzoylureas such as chlorofluorazuron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, teflubenzuron, triflumuron; Buprofezin, diophenolane, hexythiazox, etoxazole, clofentazine; b) ecdysone antagonists like

Halofenozide, methoxyfenozide, tebufenozide; c) juvenoids such as pyriproxyfen, methoprene; d) lipid biosynthesis inhibitors such as spirodiclofen;

Neonicotinoids such as flonicamid, clothianidin, dinotefuran, imidacloprid, thiomethoxam, nithiazine, acetamiprid, thiacloprid; • Other unclassified insecticides, such as abamectin, acequinocyl, amitraz, azadirachtin, bifenazate, cartap, chlorfenapyr, chlordimeform, cyromazine, dihidthiuron, diofenolan, emamectin, endosulfan, fenazaquin, formetanate, formetanate hydrochloride, hydramethylnone, indoxacarb, piperonyl butoxide , Pyridabene, Pymetrozine, Spinosad, Thiamethoxam, Thiocyclam, Pyridalyl, Fluacryprim, Milbemectin, Spirosmesifen, Flupyrazofos, NCS 12, Flubendiamide, Bistrifluron,

Benclothiaz, Pyrafluprole, Pyriprole, Amidoflumet, Flufenerin, Cyflumetofen, Leperimectin, Profluthrin, Dimefluthrin and Metafiumizone; and

Bactericides: z. B. isothiazolones such as 1,2-benzisothiazol-3 (2H) -one (BIT), mixtures of 5-chloro-2-methyl-4-isothiazolin-3-one with 2-methyl-4-isothiazolin-3-one and 2-n-octyl-4- isothiazolin-3-one (OIT), further carbendazim, chlorotoluron, 2,2-dibromo-3-nitrilopropionamide (DBNPA), fluometuron, 3-iodo-2-propynyl-butylcarbamate (IPBC), isoproturon, prometry, propiconazole.

The wax dispersions used according to the invention may contain the active ingredient (s) or effect substances, if present, in dissolved or dispersed form or, preferably, in the particles of the wax component.

The concentration of active substance or effect substance in the dispersion depends in a manner known per se on the desired application and is typically in the range from 0.01 to 50% by weight, in particular in the range from 0.1 to 15% by weight .-%, based on the wax component or in the range of 0.03 to 5 wt .-%, based on the total weight of the dispersion. In the case of colorants, the concentration is typically in the range from 0.1 to 10% by weight, based on the weight of the dispersion, with active ingredients typically in the range from 0.01 to 5% by weight, with UV stabilizers typically in the range from 0.1 to 10% by weight Range of from 0.1 to 5% by weight, and in the case of antioxidants typically in the range of from 0.1 to 5% by weight, based on the weight of the dispersion.

In a further preferred embodiment of the invention, in addition to the wax component and optionally the active ingredients and / or effect substances, the aqueous dispersion additionally comprises at least one crosslinkable compound which is selected from low molecular weight compounds V which contain at least two N-bonded groups of the formula CH ₂ OR, in which R is hydrogen or C 1 -C ₄ -alkyl, and / or a 1, 2-bishydroxyethane-1, 2-diyl group bridging two nitrogen atoms, precondensates of the compound V and reaction products or mixtures of the compound V with at least one alcohol, the under

C ₂ -C ₆ - polyols and Oligoalkylenglykolen is selected.

Such dispersions are novel and also the subject of the present invention. The crosslinkable constituents contained in such dispersions can be cured in the lignocellulosic material impregnated therewith in spite of the wax component likewise present, thereby obtaining a lignocellulosic material which, in addition to the hydrophobization achieved by the wax, also has improved mechanical stability, improved surface hardness and lower shrinkage - have training behavior.

The crosslinkable compounds contained in the aqueous compositions are low molecular weight compounds or oligomers with a low molecular weight, which are generally completely dissolved in water. The Molecular weight of the crosslinkable compound is usually below 400 DaIton. These compounds are believed to allow the compounds to penetrate into the cell walls of the wood and, upon hardening, improve the mechanical stability of the cell walls and reduce their swelling caused by water.

Examples of crosslinkable compounds V include, but are not limited to:

1,3-bis (hydroxymethyl) -4,5-dihydroxyimidazolidin-2-one (DMDHEU), 1,3-bis (hydroxymethyl) -4,5-dihydroxyimidazolidinone, which is reacted with a C ₁ -C ₆ -alkyl-N- _1- C ₂ -Ce-polyoxy and / or an oligo-C ₂ -C ₄ -alkylene glycol is modified (modified DMDHEU or mDMDHEU), 1, 3-bis (hydroxymethyl) urea, 1, 3-bis (methoxymethyl) urea; 1-hydroxymethyl-3-methylurea, - 1,3-bis (hydroxymethyl) imidazolidin-2-one (dimethylolethyleneurea),

1, 3-bis (hydroxymethyl) -1,3-hexahydropyrimidin-2-one (dimethylolpropyleneurea),

1,3-bis (methoxymethyl) -4,5-dihydroxyimidazolidin-2-one (DMeDHEU),

Tetra (hydroxymethyl) acetylene diurea, - low molecular weight melamine-formaldehyde resins (MF resins) such as

Poly (hydroxymethyl) melamine with 2, 3, 4, 5 or 6 hydroxymethyl groups and low molecular weight melamine-formaldehyde resins (MF resins) such as poly (hydroxymethyl) melamine with 2, 3, 4, 5 or 6 hydroxymethyl groups which are Cβ-alkanol a C ₂ -C ₆ -Polyi and / or a OHgO-C ₂ -C ₄ - alkylene glycol modified (modified MF resin).

The crosslinkable compounds are typically incorporated into the wax dispersion in the form of an aqueous composition. Aqueous compositions of compounds V, their precondensates and their reaction products are known per se, for example from WO 2004/033171, WO 2004/033170, K. Fisher et al. "Textile Auxiliaries - Finishing Agents" Chap. 7.2.2 in Ullmann's Encyclopedia of Industrial Chemistry, 5th Ed. on CD-ROM, Wiley-VCH, Weinheim 1997 and literature cited therein, US 2,731,364, US 2,930,715, H. Diem et al. "Amino-Resins" Chap. 7.2.1 and 7.2.2 in Ullmann's Encyclopaedia of Industrial Chemistry, 5th Ed. on CD-ROM, Wiley-VCH, Weinheim 1997 and literature cited therein, Houben-Weyl E20 / 3, pp. 1811-1890, and are commonly used as crosslinkers for textile finishing. Reaction products of N-methylolated urea compounds V with alcohols, eg. B. modified 1,3-bis (hydroxymethyl) -4,5-dihydroxyimidazolidin-2-one (mDMDHEU) are known for example from US 4,396,391 and WO 98/29393. Incidentally, are Compounds V and their reaction products and precondensates commercially available.

In a preferred embodiment of the invention, the crosslinkable compound is urea compounds having at each nitrogen atom of the urea unit a group CH ₂ OR as defined above, and the reaction products of these urea compounds with Ci-C _β- alkanols, C ₂ -C ₈ polyols and or oligoalkylene glycols selected. In particular, the crosslinkable compound is 1,3-bis (hydroxymethyl) -4,5-dihydroxyimidazolidin-2-one and one with a CrCβ-alkanol a C ₂ -C ₆ -PoIyOl ₁ and / or a modified polyalkylene glycol

1, 3-bis (hydroxymethyl) -4,5-dihydroxyimidazolidin-2-one selected. Examples of polyalkylene glycols are, in particular, the below-mentioned oligo- and poly-C ₂ -C ₄ -alkylene glycols.

MDMDHEU are reaction products of 1,3-bis (hydroxymethyl) - 4,5-dihydroxyimidazolidin-2-one with a C _r Cβ-alkanol, a C ₂ -C ₆ -POIyl, an oligoethylene glycol or mixtures of these alcohols. Suitable C _1-β- alkanols are, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol and n-pentanol, preference is given to methanol. Suitable polyols are ethylene glycol, diethylene glycol, 1, 2 and 1, 3-propylene glycol, 1,2-, 1,3-, and 1, 4-butylene glycol, glycerol. Examples of suitable polyalkylene glycols are, in particular, the oligo- and poly-C ₂ -C ₄ -alkylene glycols mentioned below. For the production of mDMDHEU DMDHEU is mixed with the alkanol, the polyol or the polyalkylene glycol. Here, the monohydric alcohol, the polyol, or the oligo- or polyalkylene glycol are usually used in a ratio of 0.1 to 2.0, in particular 0.2 to 2 molar equivalents, based on DMDHEU. The mixture of DMDHEU, the polyol or the polyalkylene glycol is usually reacted in water at temperatures of preferably 20 to 70 ⁰ C and a pH of preferably 1 to 2.5, wherein the pH after the reaction in the rule to a Range is set from 4 to 8.

In another preferred embodiment of the invention, the crosslinkable compound is at least 2-fold, e.g. 2-, 3-, 4-, 5- or 6-fold, especially a 3-methylolated melamine (poly (hydroxymethyl) melamine) and one with a C ₁ -C ₆ alkanol, a C ₂ -C ₆ -Polayl, and / or a polyalkylene glycol-modified poly (hydroxymethyl) melamine selected. Examples of polyalkylene glycols are, in particular, the oligo- and poly-C ₂ -C ₄ -alkylene glycols mentioned below.

The aqueous compositions used according to the invention may also contain one or more of the abovementioned alcohols, eg. B. C _r C _β- alkanols, C ₂ -C ₆ -PoIyOIe, oligo- and polyalkylene glycols or mixtures of these alcohols. Suitable C 1-4 alkanols are, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol and n-pentanol, preference being given to methanol. Suitable polyols are ethylene glycol, diethylene glycol, 1,2- and 1,3-propylene glycol, 1,2-, 1, 3, and 1, 4-butylene glycol, glycerol. Suitable oligo- and polyalkylene glycols are, in particular, oligo- and poly-C 1 -C -alkylene glycols, especially homo- and cooligomers of the ethylene oxide and / or of the propylene oxide, which are optionally in the presence of low molecular weight starters, eg. B. aliphatic or cycloaliphatic polyols having at least 2 OH groups such as 1,3-propanediol, 1, 3- and 1, 4-butanediol, 1,5-pentanediol, 1, 6-hexanediol and glycerol, trimethylolethane, trimethylolpropane, erythritol, and pentaerythritol, and also pentites and hexites, such as ribitol, arabitol, xyNt, dulcitol, mannitol and sorbitol, and inositol or aliphatic or cycloaliphatic polyamines having at least 2 -NH ₂ groups, such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, propylenediamine-1,3, dipropylenetriamine , 1,4,8-triazooctane, 1,5,8,12-tetraazadodecane, hexamethylenediamine, dihexamethylenetriamine, 1,6-bis (3-aminopropylamino) hexane, N-methyldipropylenetriamine or polyethyleneimine, among which diethylene glycol, triethylene glycol, di , Tri- and tetrapropylene glycol, low molecular weight Pluronic® brands from BASF (eg Pluronic® PE 3100, PE 4300, PE 4400, RPE 1720, RPE 1740) are preferred.

If present, the concentration of the crosslinkable compounds in the aqueous dispersion is usually in the range from 5 to 30% by weight, frequently in the range from 5 to 20% by weight and in particular in the range from 10 to 20% by weight. , based on the total weight of the dispersion. If the dispersion contains one of the abovementioned alcohols, its concentration is preferably in the range from 1 to 10% by weight, in particular in the range from 3 to 8% by weight.

If the aqueous dispersion comprises one of the aforementioned crosslinkable compounds, it generally contains a catalyst K which brings about the crosslinking of the compound V ₁ or of its reaction product or precondensate. In general, as catalysts K metal salts from the group of metal halides, metal sulfates, metal nitrates, metal phosphates, Metalltetrafluoroborate; boron trifluoride; Ammonium salts from the group of ammonium halides, ammonium sulfate, ammonium oxalate and diammonium phosphate; and organic carboxylic acids, organic sulfonic acids, boric acid, sulfuric acid and hydrochloric acid.

Examples of metal salts suitable as catalysts K are, in particular, magnesium chloride, magnesium sulfate, zinc chloride, lithium chloride, lithium bromide, aluminum chloride, aluminum sulfate, zinc nitrate and sodium tetrafluoroborate. Examples of suitable as catalysts K ammonium salts are in particular ammonium chloride, ammonium sulfate, ammonium oxalate and diammonium phosphate.

Particularly suitable catalysts K are water-soluble organic carboxylic acids such as maleic acid, formic acid, citric acid, tartaric acid and oxalic acid, furthermore benzenesulfonic acids such as p-toluenesulfonic acid, but also inorganic acids such as hydrochloric acid, sulfuric acid, boric acid and mixtures thereof.

Preferably, the catalyst K is selected from magnesium chloride, zinc chloride, magnesium sulfate, aluminum sulfate and mixtures thereof, with magnesium chloride being particularly preferred.

The catalyst K is usually added to the aqueous dispersion only shortly before the impregnation of the lignocellulose material. It is usually used in an amount of 1 to 20 wt .-%, in particular 2 to 10 wt .-%, based on the total weight of the curable components contained in the aqueous composition. The concentration of the catalyst, based on the total weight of the aqueous dispersion, is usually in the range of 0.1 to 10 wt .-% and in particular in the range of 0.5 to 5 wt .-%.

The invention further relates to a process for hydrophobizing lignocellulosic materials, in which the lignocellulosic material is impregnated with one of the above-described aqueous compositions comprising at least one aqueous dispersion of waxes or waxy polymers having a melting point above 75 ^° C., in particular 80 ^° C., wherein the dispersed wax particles have an average particle size below 500 nm.

The inventive method is basically suitable for hydrophobizing any lignocellulosic materials of any dimensions. In particular, the method according to the invention is suitable for impregnating wood. The inventive method allows both the hydrophobization of finely divided materials such as fibers, chips, strands, chips, chips and the like, thin sheet materials with thicknesses ≤ 5 mm, in particular ≤ 1 mm as veneers and in particular the impregnation of large-sized parts with minimum dimensions above 1 mm, in particular> 5 mm, especially ≥ 10 mm. With the method according to the invention, uniform impregnation with the wax component of the wax dispersion is also achieved with these materials, even with large dimensions, whereby penetration depths of the wax component of at least 10 mm, but often also above, are achieved. The wax dispersions used according to the invention are particularly suitable for impregnating wood or wood-based materials, especially for impregnating solid or solid wood. In principle, all types of wood are suitable, in particular those which can take up at least 30%, in particular at least 50%, of their dry weight of water and particularly preferably those which are assigned to the impregnability classes (or impregnability classes) 1 or 2 according to DIN EN 350-2 , These include, for example, woods of coniferous trees such as pine, spruce, Douglas fir, larch, pine, fir, coastal fir, cedar, stone pine, as well as woods of deciduous trees, eg. Maple, hardmaple, acacia, ayons, birch, pear, beech, oak, alder, aspen, ash, berry, hazel, hornbeam, cherry, chestnut, linden, American walnut, poplar, olive, robinia, elm, walnut, rubber tree , Zebrano, willow, Turkey oak and the like. Also suitable are woods which have already been impregnated with a curable compound and cured. The advantages according to the invention are particularly evident in the following woods: beech, spruce, pine, poplar, ash and maple.

The wax dispersions used according to the invention are also suitable for impregnating other, wood-different lignocellulosic materials, for. B. of natural fiber materials such as bamboo, bagasse, cotton stalks, jute, sisal, straw, flax, coconut fibers, banana fibers, reeds, z. As miscanthus, ramie, hemp, Manila hemp, Esparto (Alfagras), rice husks and cork.

The impregnation can be done in a conventional manner, for. By immersion, by use of vacuum optionally in combination with pressure or by conventional application methods such as brushing, spraying and the like. The particular impregnation method used naturally depends on the dimensions of the material to be impregnated. Lignocellulosematerialien small dimensions such as shavings or strands and thin veneers, ie materials with a large surface area to volume ratio, can be with little effort, eg. B. impregnate by dipping or spraying, whereas lignocellulosic materials with larger dimensions, in particular materials whose smallest extension is more than 5 mm, z. As solid wood or molded parts made of solid wood, using pressure, in particular by combined application of pressure and vacuum impregnated. In contrast to the prior art, the use of elevated temperature is generally not required. Advantageously, the impregnation at a temperature below 50 ⁰ C, z. B. in the range of 15 to 50 ⁰ C performed.

For dipping, the lignocellulosic material, optionally after predrying, is immersed in a container containing the aqueous wax dispersion. The dipping is preferably carried out over a period of a few seconds to 24 h, in particular 1 min to 6 h. The temperatures are usually in the range from 15 ^° C. to 50 ^° C. The lignocellulosic material absorbs the aqueous wax dispersion, the concentration of the non-aqueous constituents (ie wax, optionally active substances and / or effect substances and, if appropriate, curable constituents) in the aqueous dispersion, by the temperature and the duration of treatment, the amount of these constituents taken up by the lignocellulosic material can be controlled. The quantity of constituents actually absorbed can be determined and controlled by the skilled person in a simple manner by means of the weight increase of the veneer and the concentration of the constituents in the aqueous dispersion. Veneers, for example, can be pre-pressed by means of press rolls, so-called calenders, which are in the aqueous impregnating composition. The vacuum occurring in the wood when relaxing then leads to an accelerated absorption of aqueous impregnating composition.

The impregnation is advantageously carried out by combined use of reduced and elevated pressure. For this purpose, the lignocellulosic material, which generally has a humidity in the range of 1% to 100%, first under reduced pressure, which is often in the range of 10 to 500 mbar and in particular in the range of 40 to 100 mbar, with the aqueous dispersion brought into contact, z. By dewaxing in the aqueous composition. The time period is usually in the range of 1 minute to 1 hour. This is followed by a phase at elevated pressure, z. B. in the range of 2 to 20 bar, in particular in 4 to 15 bar and especially 5 to 12 bar, to. The duration of this phase is usually in the range of 1 min to 12 h. The temperatures are usually in the range of 15 to 50 ⁰ C. In this case takes the lignocellulose sematerial the aqueous wax dispersion, wherein by the concentration of the non-water ingredients (ie, wax, optionally active substance and / or effect substances, and optionally curable components) in the aqueous composition, by the pressure, the temperature and the treatment time, the amount of these components taken up by the lignocellulosic material can be controlled. The amount actually absorbed can also be calculated here by the weight increase of the lignocellulosic material.

Furthermore, the impregnation can be carried out by conventional methods for applying liquids to surfaces, for. By spraying or rolling or brushing. For this purpose, advantageously a veneer with a humidity of not more than 50%, in particular not more than 30%, z. In the range of 12% to 30%. The application is usually carried out at temperatures in the range of 15 to 50 ⁰ C. The spraying can be carried out in a conventional manner in all suitable for spraying of flat or finely divided bodies devices, for. B. by means of nozzle arrangements and the like. When painting or rolling is the desired Amount of aqueous dispersion with rollers or brushes applied to the sheet material.

If the aqueous wax dispersion used according to the invention contains a crosslinkable compound as described above, the impregnation may be followed by a drying and optionally a curing step at elevated temperature. In principle, however, a further processing of the impregnated material can also take place directly on the impregnation. This is particularly useful when the impregnated lignocellulosic material is a finely divided material that can be used with glue to form parts such as OSB (oriented structural board) boards, chipboards, wafer boards, OSL boards and OSL molded parts ( Oriented Strand Lumber), PSL and PSL (Parallel Strand Lumber) moldings, insulation boards, medium density (MDF) or high density (HDF) fiberboard, wood plastic composites, or the like, or veneer in that it is further processed into a veneer material.

If a curing step is carried out, it is carried out by heating the impregnated material to temperatures of at least 80 ⁰ C, in particular above 90 ⁰ C, z. B. in the range of 90 to 220 ⁰ C and in particular in the range of 100 to 200 ⁰ C. Optionally, a separate drying step may be carried out beforehand. In this case, the volatile constituents of the aqueous composition, in particular the water and excess organic solvents, which do not react in the curing / crosslinking of the urea compounds, partially or completely removed. Predrying in this context means that the lignocellulosic material is dried below the fiber saturation point which, depending on the nature of the material, is about 30% by weight. This predrying counteracts the risk of cracking in large-sized bodies, especially solid wood. For small-sized materials or veneers, the predrying is usually omitted. For materials with larger dimensions, however, the predrying is beneficial. If a separate predrying is carried out, this is advantageously carried out at temperatures in the range of 20 to 80 ^° C. Depending on the chosen drying temperature, partial or complete curing / crosslinking of the curable constituents contained in the composition can take place. The combined predrying / curing of the impregnated materials is usually carried out by applying a temperature profile, which may range from 50 ⁰ C to 220 ° C, in particular from 80 to 200 ⁰ C.

Often, however, one will perform drying and curing in one step. The curing / drying can be carried out in a conventional fresh air exhaust system. Pre-drying preferably takes place in such a way that the moisture content the impregnated lignocellulosic material after predrying is not more than 30%, in particular not more than 20%, based on the dry matter. It may be advantageous to carry out the drying / curing up to a moisture content <10% and in particular <5%, based on the dry mass. The moisture content can be easily controlled by the temperature, the duration and the pressure selected during pre-drying.

The lignocellulosic materials obtained by the process according to the invention are novel and likewise the subject of the present invention.

The inventively treated lignocellulosic materials can, if it is not already ready-made end products are further processed in a conventional manner, in the case of finely divided materials z. For example, shaped articles such as OSB (oriented structural board) boards, chipboard, wafer boards, OSL boards and OSL (Oriented Strand Lumber), PSL and PSL (Parallel Strand Lumber) moldings, insulation boards , medium density (MDF) or high density (HDF) fiberboard, wood-plastic composites (WPC) and the like, in the case of veneers to veneer materials such as veneered fiberboard, veneered blockboard, veneered particleboard including veneered OSL and PSL panels (oriented parallel beach lumber), plywood, laminated wood, plywood, laminated plywood (eg Kerto plywood), multiplex boards, laminated veneer lumber (LVL), decorative veneered materials such as cladding, ceiling and prefinished parquet but also non-paving , 3-dimensionally shaped components such as plywood moldings, plywood moldings and any other, with at least one veneer layer coated moldings. If the impregnated lignocellulosic material is solid wood, this can be processed in the usual way, for. B. by sawing, planing, grinding, etc. According impregnated solid wood is particularly suitable for the production of objects that are exposed to moisture and especially weathering, z. As for timber, beams, components made of wood, for wooden balconies, roof shingles, fences, wooden poles, railway sleepers, in shipbuilding for interior work and deck superstructures.

The following examples serve to illustrate the invention and are not intended to be limiting.

Example 1: Impregnation with undyed wax dispersion

In a pressure-resistant vessel, a pine cube which had been sealed at the end faces with a 2-K varnish was weighted and immersed in a commercial wax emulsion having a wax content of about 20 to 25% by weight. Subsequently, within 10 min. the pressure is lowered to 203 mbar absolute and then the vacuum maintained for 1 h. Then relax to normal pressure and leave the wooden cube for a further 4 hours in the wax emulsion. The wet pieces of wood were placed in a roasting tube. This was sealed and provided with a kiei- NEN hole and then for 36 h at 120 ⁰ C stored in a drying cabinet.

The following wax dispersions were investigated:

- Wax dispersion 1: about 25 wt .-% aqueous dispersion of an oxidate wax having a melting point of 130 ⁰ C, an acid number of 18, which was stabilized with nonionic emulsifier.

Wax dispersion 2: about 25 wt .-% aqueous dispersion of a mixture of two oxidate waxes having a melting point of 94-105 ⁰ C and 102-110 ⁰ C and acid numbers of 19-25 and 15-19, with nonionic Emulsifier was stabilized.

Wax dispersion 3: about 25 wt .-% aqueous dispersion of a Montanester- wax having a melting point of 75-85 ⁰ C, which was stabilized with nonionic emulsifier. Wax dispersion 4: about 25% strength by weight aqueous, emulsifier-free, dimethyl ethanolamine-neutralized dispersion of a copolymer of 80% by weight of ethylene and 20% by weight of methacrylic acid, which has an MFI value of 10 (measured at 160 ⁰ C and 325 g load according to DIN 53753).

In all wax dispersions, the mean particle size of the wax particles was below 300 nm.

Example 2: impregnation with colored wax dispersion

Parts by there was prepared a wax dispersion of 29 wt. A colored with Sudan Blue 670 oxidate wax (melting point of 94-104 ⁰ C, 1 wt .-% of dye, based on wax) in an aqueous mixture of 10 parts by weight of nonionic emulsifiers tors (ethoxylated isotridecanol with 10 ethylene oxide units), 0.6 parts by weight of potassium hydroxide, 0.05 parts by weight of sodium metabisulfite and 55.95 parts by weight of water by dispersing at 95 ⁰ C forth.

The wooden cubes to be examined were sealed with a 2-component lacquer before being impregnated on the end faces, stored in a drying oven for 16 hours at 103 ° C. and then cooled in a desiccator using desiccant. Before the examination, the weight and the dimensions of the wooden cubes were determined. In a pressure-resistant vessel, a wooden cube prepared in this way was weighted with a weight and immersed in the wax emulsion described above. It was then within 10 min. the pressure is lowered to 60 mbar absolute and then the vacuum maintained for 1 h. Then relaxed to atmospheric pressure, transferred the wood to be tested and the wax emulsion in an autoclave stored for 1 h at an absolute pressure of 6 bar. Then you relaxed and left the cubes for another 4 hours in the wax emulsion. The wet pieces of wood were placed in a roasting tube. This was sealed and provided with a small hole and then stored for 36 h at 120 ⁰ C and 36 h at 80 ⁰ C in a drying oven. The wooden cubes were then allowed to cool in a desiccator over desiccant and again determined the weight and the dimension. The results are shown in Table 1.

Table 1:

Example 3: Impregnation with colored wax dispersion without crosslinker

There was prepared a wax dispersion by emulsifying 21.7 wt. Parts by a colored with Sudan Blue 670 montan wax / emulsifier mixture (melting point of the wax around 78-83 ⁰ C, 1 wt .-% of dye, based on wax, Alkylethoxilat as emulsifier) in 78.3 parts by weight of water at 95 ⁰ C ago.

Before being impregnated, the pinewood cubes to be examined were sealed with a 2-component varnish on the end sides, stored in a drying oven at 103 ° C. for 16 hours and then cooled in a desiccator using desiccant. Before the examination, the weight and the dimensions of the wooden cubes were determined.

In a pressure-resistant vessel, a wooden cube prepared in this way was weighted with a weight and immersed in the wax emulsion described above. It was then within 10 min. the pressure is lowered to 60 mbar and then lowered maintain the vacuum for 1 h. Then relax to normal pressure and leave the cubes for another 4 hours in the wax emulsion. The wet pieces of wood were placed in a roasting tube. This was sealed and provided with a small hole and then stored for 36 h at 120 ⁰ C in a drying oven. Finally, the wooden cubes were allowed to cool in a desiccator over desiccant and determined again the weight and the dimension. The weight change was 4.7%. The size change with respect to the width was 0%, with respect to the height at 0.1%. When sawing the cube, a clear penetration of the blue color into the cube interior was evident.

Example 4: Impregnation with Colored Wax Dispersion with Crosslinker

There was prepared a wax dispersion by emulsifying 21, 7 wt. Parts by a colored with Sudan Blue 670 montan wax / emulsifier mixture (melting point of the wax around 78-83 ⁰ C, 1 wt .-% of dye, based on wax, Alkylethoxilat when

Emulsifier) in 78.3 parts by weight of water at 95 ⁰ C ago. 50 parts by weight of the resulting wax dispersion were mixed with 30 parts by weight of a concentrated aqueous composition of N, N-bis (hydroxymethyl) -4,5-bishydroxyimidazolin-2-one (Fixapret CP BASF), 1.5 wt Parts of MgCl ₂ x 6H ₂ O and 17.5 parts by weight of water.

The pinewood cubes to be examined were sealed with a 2-component varnish before impregnation at the ends, stored in a drying oven for 16 hours at 103 ^° C. and then cooled in a desiccator using desiccant. Before the examination, the weight and the dimensions of the wooden cubes were determined.

In a pressure-resistant vessel, a wooden cube prepared in this way was weighted with a weight and immersed in the wax emulsion described above. It was then within 10 min. the pressure is lowered to 60 mbar absolute and then the vacuum maintained for 1 h. Then relax to normal pressure and leave the cubes for another 4 hours in the wax emulsion. The wet pieces of wood were placed in a roasting tube. This was sealed and provided with a small hole and then stored for 36 h at 120 ⁰ C in a drying oven. The wooden cubes were then allowed to cool in a desiccator over desiccant and again determined the weight and the dimension. The weight change was 15.6%. The size change with respect to the width was 0.8%, with respect to the height at 0.1%. When sawing the cube, a clear penetration of the blue color into the cube interior was evident.

Example 5 Impregnation with Colored Wax Dispersion with Crosslinker The wax dispersion described in Example 4 was investigated. The preparation of the wooden blocks was carried out as described in Example 4.

In a pressure-resistant vessel became a prepared pine wood throws! weighted and dipped in wax emulsion described above. It was then within 10 min. the pressure is lowered to 60 mbar absolute and then the vacuum maintained for 1 h. Then relaxed to atmospheric pressure, transferred the wood to be tested and the wax emulsion in an autoclave stored for 1 h at an absolute pressure of 6 bar. Then one relaxed and left the wooden cubes in the wax emulsion for a further 4 hours. The wet pieces of wood were placed in a roasting tube. This was sealed and provided with a small hole and then stored for 36 h at 120 ° C in a drying oven. The wooden cubes were then allowed to cool in a desiccator over desiccant and again determined the weight and the dimension. The weight change was 17%. The size change with respect to the width was 1.2%, with respect to the height at 0%. When sawing the cube showed a strong penetration of the blue color in the cube inside.

Claims

claims

1. Use of aqueous dispersions of waxes or waxy polymers having a melting point above 75 ⁰ G, wherein the dispersed wax particles have an average particle size below 500 nm, for the impregnation of lignocellulosic materials.

2. Use according to claim 1, wherein the wax or the waxy polymer has an acid number in the range of 5 to 250 mg KOH / g.

3. Use according to claim 1 or 2, wherein the wax or waxy polymer is selected from montan waxes and polar polyolefin waxes.

4. Use according to claim 3, wherein the wax or the waxy polymer is selected from polar polyolefin waxes which are essentially composed of:

a) 50 to 99 wt .-% of at least one C ₂ -C _β- olefin; b) 1 to 50% by weight of at least one monoethylenically unsaturated C ₃ -C ₆ -mono- or C ₄ -C ₈ -dicarboxylic acid; c) 0 to 49% by weight of one or more monoethylenically unsaturated monomers which are selected from vinyl esters of aliphatic C ₂ -C ₁₀ -carboxylic acids, the esters monoethylenically unsaturated C ₃ -C ₈ -monocarboxylic acids with C ₁ -C ₁₈ -alkanols or C ₅ - C ₁₂ -cycloalkanols and the diesters monoethylenically unsaturated C ₄ -C ₈ -dicarboxylic acids with C 1 -C ₁₈ -alkanols or C ₅ -C ₂ -cycloalkanols,

wherein the stated amounts of monomer are each based on the total weight of the monomers constituting the polar polyolefin wax.

5. Use according to claim 2 or 3, wherein at least 40% of the acidic groups present in the wax or in the waxy polymer are in neutralized form.

6. Use according to one of the preceding claims, wherein the aqueous dispersion contains the wax or waxy polymer in an amount of 5 to 50 wt .-%, based on the total amount of the dispersion.

7. Use according to one of the preceding claims, wherein the aqueous Disperston contains not more than 10 wt .-%, based on the wax or waxy polymer contained therein of emulsifiers.

8. Use according to one of the preceding claims, wherein the wax particles contain at least one substance which is selected from insecticides, fungicides, biocides, colorants, antioxidants, stabilizers and UV stabilizers.

9. Use according to one of the preceding claims, wherein the aqueous dispersion additionally contains at least one crosslinkable compound which is selected from low molecular weight compounds V containing at least two N-bonded groups of the formula CH ₂ OR, wherein R is hydrogen or C ₁ -C ₄ -AIkYl, and / or a two nitrogen atoms bridging

1, 2-bishydroxyethane-1, 2-diyl group, precondensates of the compound V and reaction products or mixtures of the compound V with at least one alcohol which is C _r C _β -alkanols, C ₂ -C _β -polyols and oligoal kylenglykolen.

10. A method for hydrophobing lignocellulosic materials, characterized in that the lignocellulosic material is impregnated with an aqueous composition comprising at least one aqueous dispersion of waxes or waxy polymers having a melting point above 80 ⁰ C, wherein the dispersed wax particles have an average particle size below 500 nm exhibit.

11. The method of claim 10, wherein the impregnation is carried out by successive application of reduced and elevated pressure.

12. The method according to claim 10 or 11, wherein the impregnation takes place at a temperature below 50 ⁰ C.

13. The method according to any one of claims 10 to 12, wherein the lignocellulosic material is wood or a wood material.

14. An impregnated lignocellulosic material obtainable by a process according to any one of claims 10 to 13.

With a melting point above 80 "C ₁ wherein the dispersed wax particles comprise 15 Aqueous dispersion of waxes or wax-like polymers, a mean particle size below 500 nm, which additionally contains at least one crosslinkable urea compound selected from low molecular weight compounds V _1, the at least two N- bonded groups of the formula CH ₂ OR, in which R is hydrogen or C ₁ -C ₄ -alkyl, and / or a two-membered Substituatome bridging 1, 2-bishydroxyethane-1, 2-diyl group have, precondensates of the compound V and reaction products or mixtures of the compound V with at least one alcohol, which

C ₂ -C ₆ - polyols and Oligoalkylenglykolen is selected.

16. Aqueous dispersion of waxes or waxy polymers having a melting point above 80 ⁰ C, wherein the dispersed wax particles have an average particle size below 500 nm, wherein the wax particles contain at least one substance selected from insecticides, fungicides and biocides.