DE102006019816A1 - Method to impregnate lignocellulosic material with effect agent, comprises impregnating lignocellulosic material with fluid formation and hardneable aqueous composition and treating the material at elevated temperature - Google Patents

Abstract

Method for impregnating lignocellulosic material with effect agents, comprises impregnating the lignocellulosic material with a fluid formation, which contains at least one effect agent in a dissolved or dispersed form; impregnating the material with a hardenable aqueous composition, which contains at least one cross-linkable compound; and treating the material obtained at an elevated temperature. Method for impregnating lignocellulosic material with effect agents, comprises impregnating the lignocellulosic material with a fluid formation, which contains at least one effect agent in a dissolved or dispersed form; impregnating the material with a hardenable aqueous composition, which contains at least one cross-linkable compound such as low-molecular weight compounds (V), having at least two N-bonded groups of formula (CH 2OR) and/or one 1,2-bishydroxyethane-1,2-diyl group, bridging two nitrogen atoms, precondensates the compound (V), and reaction products or mixtures of the compound (V) with at least one alcohol such as 1-6C alkanols, 2-6C polyols and oligoalkylene glycols; and treating the material obtained at an elevated temperature. R : H or 1-4C alkyl. Independent claims are also included for: (1) a lignocellulosematerial, is obtained by the process; and (2) an aqueous composition comprising dissolved or dispersed form of effect agent and hardenable compound.

Description

The The present invention relates to a method of impregnation of lignocellulosic materials, in particular wood, wood-based materials or of materials for the production of wood-based materials with effect materials. The invention also relates to novel compositions, the effect substances contain.

The Impregnate Of wood with effect substances such as colorants, but also with active ingredients against wood discoloring or wood destroying Microorganisms have been known for a long time (see, for example, E.-H. Pommer 'Wood - Wood Preservation "especially chapter 2 in Ullmann's Encyclopedia of Industrial Chemistry, 5th Ed. On CD-ROM, Wiley-VCH - Weinheim 1997).

The DE 3621856 describes a process for coloring wood in which aqueous colorant preparations are introduced into the wood by application of pressure over the faces of a wood body. The transport of the colorant is carried out selectively on the lumens of Leitbündelzellen of the wood, whereby an artificial grain is produced in the wood. A complete impregnation is not achieved by this.

The DE 4316234 describes the staining of wood, in which wood is first moistened with water, then impregnated with an aqueous dye solution using pressure in the heat, and then several rinses are carried out with decreasing temperature.

Water-soluble dyes however, have the disadvantage of being damaged by the action of moisture, e.g. be washed out under the influence of weather. Basically should the use of pigments remedy this, since they are insoluble and thus be washed out worse.

own Investigations by the Applicant have now shown that also to water-insoluble effect substances like pigments, presumably because of the impregnating agents contained surface-active substances, which remain due to the manufacturing process in the wood, under the action be washed out by water. This not only leads to a loss of the effect substance and thus to a decrease in the desired property, or, in the case of colorants, to a less attractive appearance, but also to an environmental impact.

It was now surprisingly found that the leaching of effect substances diminished or can even be avoided if one impregnated with an effect substance Lignocellulosematerial or the lignocellulose material during the impregnation with the effect substance with a curable, defined below aqueous Impregnated composition, and subsequently treating the lignocellulosic material at elevated temperature, a cure to reach.

• a) Imprägnieren des Lignocellulosematerials mit einer flüssigen Zubereitung, die wenigstens einen Effektstoff in gelöster oder dispergierter Form enthält, und
• b) während oder im Anschluss an Schritt a) das Imprägnieren mit einer härtbaren wässrigen Zusammensetzung, die wenigstens eine vernetzbare Verbindung enthält, die ausgewählt ist unter α) niedermolekularen Verbindungen V, welche wenigstens zwei N-gebundene Gruppen der Formel CH₂OR, worin R für Wasserstoff oder C₁-C₄-Alkyl steht, und/oder eine zwei Stickstoffatome verbrückende 1,2-Bishydroxyethan-1,2-diyl-Gruppe aufweisen, β) Präkondensaten der Verbindung V und γ) Umsetzungsprodukten oder Mischungen der Verbindung V mit wenigstens einem Alkohol, der unter C₁-C₈-Alkanolen, C₂-C₆-Polyolen und Oligoalkylenglykolen ausgewählt ist, und
• c) Behandeln des in Schritt b) erhaltenen Materials bei erhöhter Temperatur.

Accordingly, the present invention relates to a process for impregnating lignocellulosic materials with effect substances, comprising the following steps:

• a) impregnating the lignocellulosic material with a liquid preparation containing at least one effect substance in dissolved or dispersed form, and
• b) during or after step a) impregnating with a curable aqueous composition containing at least one crosslinkable compound selected from α) low molecular weight compounds V which contain at least two N-linked groups of the formula CH ₂ OR, where R is hydrogen or C ₁ -C ₄ -alkyl, and / or have a 1,2-bishydroxyethane-1,2-diyl group bridging two nitrogen atoms, β) precondensates of compound V and γ) reaction products or mixtures of compound V with at least one alcohol selected from C ₁ -C ₈ -alkanols, C ₂ -C ₆ -polyols and oligoalkylene glycols, and
• c) treating the material obtained in step b) at elevated temperature.

The inventive method is associated with a number of advantages. It allows a uniform impregnation of lignocellulosic materials with effect materials and also for large-sized materials a uniform distribution of the effect substance in the lignocellulosic material. Other than that known from the prior art, treated with effect substances Lignocellulosematerialien occurs bleeding of the effect substance Influence of organic solvents and / or moisture to a much lesser extent or even not up. The invention therefore also the by the inventive method available Lignocellulosic materials.

The inventive method unlike many prior art methods, it is suitable for impregnation any lignocellulosic materials with effect substances, wherein the Lignocellulosematerialien may have any dimensions. Especially the method according to the invention is suitable for impregnation of wood. The inventive method allows both impregnation finely divided materials such as fibers, chips, strands, chips, chips and the like, areal thinner Materials with thicknesses ≤ 5 mm in particular ≤ 1 mm as veneers and in particular also the impregnation of large-sized parts with minimum dimensions above 1 mm, in particular> 5 mm, especially ≥ 10 mm. By the method according to the invention can be achieved even with these materials even with large dimensions a uniform impregnation with the effect substance over the entire cross section of the material.

The inventive method is particularly suitable for impregnating wood or wood-based materials, especially for impregnation solid or solid wood. Suitable are basically all types of wood, in particular those which account for at least 30%, in particular at least 50% of their Dry weight can absorb water and particularly preferred those included in the saturability classes 1 and 2 classified according to DIN-EN 350-2 become. Which includes for example, woods of coniferous trees like pine (pinus spp.), spruce, Douglas fir, larch, pine, fir, coastal fir, Cedar, stone pine, as well as woods of deciduous trees, z. Maple, hardmaple, acacia, ayons, birch, pear, beech, oak, Alder, aspen, ash, dew, hazel, hornbeam, cherry, chestnut, Linden, American walnut, Poplar, Olive, Robinia, Elm, Walnut, Rubber tree, zebrano, willow, Turkey oak and the like. Are suitable also woods, which already with a curable compound waterproof are and cured were. The advantages of the invention come especially with the following woods to bear: beech, spruce, Pine, poplar, ash and maple. Therefore, a preferred embodiment the invention impregnation of wood or wood-based materials with effect materials, wherein the wood component is selected from the aforementioned types of wood.

The inventive method are also suitable for impregnation other wood-derived lignocellulosic materials, e.g. B. of natural fiber materials such as bamboo, bagasse, cotton stalks, jute, Sisal, straw, flax, coconut fiber, banana fiber, reed, e.g. Miscanthus, Ramie, hemp, manila hemp, esparto (alfagras), rice husks and cork.

Of the The term "effect substance" includes here and hereinafter both organic and inorganic materials, which give the lignocellulosic material a property which it does not or only partially in untreated form, e.g. Color, improved oxidation stability or UV stability, but also resistant to wood-damaging Microorganisms or insects. Accordingly, it is in the Effect substances, in particular colorants, including dyes and pigments to UV stabilizers, antioxidants, fungicides and / or insecticides.

According to the invention Effect substance in the form of a liquid Preparation used, which dissolved the effect substance in or dispersed or suspended form contains. The liquid preparation of the effect substance can be solvent-based or water-based, with water-based preparations being preferred are. Solvent based is called in this context, that the liquid components of the composition in the Essentially, i. at least 60% by weight, based on the liquid constituents, of organic solvents include. Water based means in this connection, that the liquid components of the composition essentially, i. at least 60% by weight, in particular at least 80 wt .-% based on the liquid Ingredients, include water. According to the invention, water-based preparations are preferred.

Around a uniform penetration of the effect substance into the lignocellulosic material is it is advantageous if the effect substance in the composition, in particular in the aqueous Composition, in dissolved or dispersed form with particle diameters of not more is present as 2000 nm and in particular not more than 1000 nm.

According to one preferred embodiment the invention is in the used in step a) Composition around a water-based composition that at least one in the aqueous phase dispersed pigment and / or a dispersed effect substance with an average particle diameter in the range of 50 to 2000 nm and in particular 50 to 1000 nm.

It has proved to be advantageous if this composition contains at least one anionic, polymeric dispersant. The use of such compositions for impregnation ren of lignocellulosic materials is new and also the subject of the invention. These compositions achieve a particularly uniform coloring not only in finely divided or thin materials such as veneers but also in solid wood or solid wood, which has minimum dimensions above 5 mm, in particular above 10 mm. In particular, penetration depths of> 10 mm or> 20 mm are achieved, and thus a uniform impregnation even of very large wooden parts with minimum dimensions of 40 mm or more.

When anionic, polymeric dispersants come both anionically modified Polyurethanes and anionic homo- and copolymers monoethylenically unsaturated Monomers into consideration. The anionic groups may be Phosphate, phosphonate, carboxylate, or sulfonate groups, these groups may also be present in the acid form. Provided the acid groups present in neutralized form, these polymers have corresponding Counterions on. Typical counterions are the cations of alkali metals such as sodium, potassium or lithium as well as ammonium or protonated primary, secondary or tertiary Amines.

The molecular weight of the polymeric anionic dispersants is typically in the range of 800 to 100,000 daltons, in particular in the range of 1,000 to 20,000 daltons (number average M _n ) or in the range of 1,000 to 250,000 and in particular in the range of 1,800 to 100,000 (weight average M _w ). ,

According to one first preferred embodiment If the anionic dispersant is a homo- or copolymer of monoethylenically unsaturated carboxylic acids, in particular a homo- or copolymer monoethylenically unsaturated Monocarboxylic acids and / or ethylenically unsaturated dicarboxylic acids, the additional contain copolymerized as comonomers neutral vinyl monomers can, or their alkoxylation products including the salts.

• – Monocarbonsäuren wie Acrylsäure, Methacrylsäure und Crotonsäure;
• – Dicarbonsäuren wie Maleinsäure, Maleinsäurenanhydrid, Maleinsäuremonoester, Maleinsäuremonoamide, Umsetzungsprodukte von Maleinsäure mit Diaminen, die zu aminoxidgruppenhaltigen Derivaten oxidiert sein können, und Fumarsäure, wobei Maleinsäure, Maleinsäureanhydrid und Maleinsäuremonoamide bevorzugt sind;

Examples of the carboxyl-containing monoethylenically unsaturated monomers are

• Monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid;
• Dicarboxylic acids such as maleic acid, maleic anhydride, maleic acid monoesters, maleic acid monoamides, reaction products of maleic acid with diamines which may be oxidized to aminoxide group-containing derivatives, and fumaric acid, of which maleic acid, maleic anhydride and maleic acid monoamides are preferred;

• – Vinylaromaten, wie Styrol, Methylstyrol und Vinyltoluol;
• – Olefine und Diene, wie Ethylen, Propylen, Isobuten, Diisobuten und Butadien;
• – Vinylether, wie Polyethylenglykolmonovinylether und Octadecylvinylether;
• – Vinylester linearer oder verzweigter aliphatischer Monocarbonsäuren, wie Vinylacetat, Vinylpropionat, Vinyllaurat, Vinylstearat und Vinylversatate;
• – Alkylester, Cycloalkylester und Arylester monoethylenisch ungesättigter Monocarbonsäuren, insbesondere Acrylsäure- und Methacrylsäureester, wie Methyl-, Ethyl-, Propyl-, Isopropyl-, Butyl-, Pentyl-, Hexyl-, 2-Ethylhexyl-, Nonyl-, Lauryl- und Hydroxyethyl-(meth)acrylat sowie Phenyl-, Naphthyl- und Benzyl(meth)acrylat;
• – Dialkylester von monoethylenisch ungesättigten Dicarbonsäuren, wie Dimethyl-, Diethyl-, Dipropyl-, Di-isopropyl-, Dibutyl-, Dipentyl-, Dihexyl-, Di-2-ethylhexyl-, Dinonyl-, Dilauryl- und Di-2-hydroxyethylmaleinat und -fumarat; Vinylpyrrolidon;
• – Acrylnitril und Methacrylnitril, wobei Styrol, Isobuten, Diisobuten, Acrylsäureester und Polyethylenglykolmonovinylether bevorzugte Comonomere sind.

Suitable neutral comonomers are especially monoethylenically unsaturated neutral monomers, e.g. B .:

• Vinyl aromatics, such as styrene, methylstyrene and vinyltoluene;
• Olefins and dienes, such as ethylene, propylene, isobutene, diisobutene and butadiene;
• Vinyl ethers, such as polyethylene glycol monovinyl ether and octadecyl vinyl ether;
• Vinyl esters of linear or branched aliphatic monocarboxylic acids, such as vinyl acetate, vinyl propionate, vinyl laurate, vinyl stearate and vinyl versatates;
• - Alkyl esters, cycloalkyl esters and aryl esters of monoethylenically unsaturated monocarboxylic acids, especially acrylic and methacrylic esters, such as methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, 2-ethylhexyl, nonyl, lauryl and hydroxyethyl - (meth) acrylate and phenyl, naphthyl and benzyl (meth) acrylate;
• Dialkyl esters of monoethylenically unsaturated dicarboxylic acids, such as dimethyl, diethyl, dipropyl, diisopropyl, dibutyl, dipentyl, dihexyl, di-2-ethylhexyl, dinonyl, dilauryl and di-2-hydroxyethyl maleate and fumarate; vinylpyrrolidone;
• - Acrylonitrile and methacrylonitrile, styrene, isobutene, diisobutene, acrylic acid esters and Polyethylenglykolmonovinylether are preferred comonomers.

When examples for preferred homopolymers are, in particular, polyacrylic acids call.

The Copolymers of said monomers may consist of two or more, in particular be constructed three different monomers. It can be statistical Copolymers, alternating copolymers, block copolymers and graft copolymers are present. As preferred copolymers be styrene / acrylic acid, Acrylic acid / maleic acid, acrylic acid / methacrylic acid, butadiene / acrylic acid, isobutene / maleic acid, diisobutene / maleic acid and Styrene / maleic acid copolymers, each as additional Monomer Components Acrylic acid ester and / or maleic acid esters can contain called.

Preferably, the carboxyl groups of the non-alkoxylated homo- and copolymers are at least partially in salt form to ensure water solubility. Suitable examples are the Alka limestone salts, such as sodium and potassium salts, and the ammonium salts.

Usually, the non-alkoxylated dispersants have average molecular weights M _w of 1000 to 250000 (weight average). The molecular weight ranges which are particularly suitable for the individual polymers naturally depend on their composition. In the following, molecular weight data are given by way of example for various polymers: polyacrylic acids: M _w from 900 to 250,000; Styrene / acrylic acid copolymers: M _w from 1000 to 50,000; Acrylic acid / methacrylic acid copolymers: M _w from 1000 to 250,000; Acrylic acid / maleic acid copolymers: M _w from 2000 to 70,000.

In addition to these homopolymers and copolymers themselves, their alkoxylation products are suitable and preferred as anionic polymeric dispersants. This is understood to mean, in particular, the polymers partially esterified with poly-C ₂ -C ₃ -alkylene ether alcohols. In general, the degree of esterification of these polymers is 30 to 80 mol%.

Particularly suitable for the esterification are the poly-C ₂ -C ₃ -alkylene ether alcohols themselves, preferably polyethylene glycols and polyethylene / propylene glycols, and their unilaterally end-capped derivatives, especially the corresponding monoethers, such as monoaryl ethers, eg monophenyl ethers, and in particular mono-C ₁ - C ₂₆ -alkyl ethers, for example ethylene glycols and propylene glycols etherified with fatty alcohols, and the polyetheramines which can be prepared, for example, by conversion of a terminal OH group of the corresponding polyether alcohols or by polyaddition of alkylene oxides to preferably primary aliphatic amines. Polyethylene glycols, polyethylene glycol monoethers and polyether amines are preferred. The average molecular weights M _{n of} the polyether alcohols and their derivatives used are usually 200 to 10,000.

Such anionic surface active additives are also known and commercially available for example under the name Sokalan ^® (BASF), Joncryl ^® (Johnson Polymer), Alcosperse ^® (Alco), Geropon ^® (Rhodia), Good-Rite ^® (Goodrich), Neoresin ^® ( Avecia), Orotan ^® and Morez ^® (Rohm & Haas), Disperbyk ^® (Byk) and Tegospers ^® (Goldschmidt) available.

In a further preferred embodiment contains the water-based composition of a dispersed effect substance at least one dispersant based on water-soluble or water-dispersible polyurethanes, in particular based on a polyether urethane which is nonionic or anionic modified is. This is understood to mean water-soluble or water-dispersible Reaction products of polyfunctional isocyanates (I), e.g. Di- or Triisocyanates, with polyfunctional, in particular difunctional, Isocyanate-reactive compounds RI, which may be anionic Groups, in particular carboxyl groups. The molecular weight the water-soluble / water-dispersible Polyurethanes typically range from 1000 to 250,000 (Weight average).

When polyfunctional isocyanates I are particularly suitable diisocyanates, also in combination with compounds with three or four isocyanate groups can be used.

When examples for preferred compounds I are: 2,4-tolylene diisocyanate (2,4-TDI), 4,4'-diphenylmethane diisocyanate (4,4'-MDI), para-xylylene diisocyanate, 1,4-diisocyanatobenzene, tetramethylxylylene diisocyanate (TMXDI), 2,4'-diphenylmethane diisocyanate (2,4'-MDI) and triisocyanatotoluene and isophorone diisocyanate (IPDI), 2-butyl-2-ethylpentamethylene diisocyanate, Tetramethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, 2,2-bis (4-isocyanatocyclohexyl) propane, trimethylhexane diisocyanate, 2-isocyanatopropylcyclohexyl isocyanate, 2,4,4- and 2,2,4-trimethylhexamethylene diisocyanate, 2,4'-methylenebis (cyclohexyl) diisocyanate, cis-cyclohexane-1,4-diisocyanate, trans-cyclohexane-1,4-diisocyanate and 4-methylcyclohexane-1,3-diisocyanate (H-TDI) and their mixtures.

When In principle, all isocyanate-reactive organic compounds (RI) are suitable Compounds having at least two functional groups with Isocyanate groups react to form bonds, e.g. hydroxyl groups, primary Amino groups and SH groups. Preferred compounds RI have two hydroxyl groups per molecule.

The Compounds RI can also be used in combination with compounds RI ', which is only an isocyanate-reactive Group, e.g. have one hydroxyl group per molecule.

Examples of compounds RI are polyether diols, polyester diols, polylactone diols (lactone-based polyester diols), polycarbonate diols, diols and triols having up to 12 C atoms, dihydroxycarboxylic acids, dihydro xysulfonic acids, dihydroxyphosphonic acids and polycarbonate diols

Suitable polyether diols are, for example, homopolymers and copolymers of C ₂ -C ₄ -alkylene oxides, such as ethylene oxide, propylene oxide and butylene oxide, tetrahydrofuran, styrene oxide and / or epichlorohydrin. Preferred polyether diols are polyethylene glycol, polypropylene glycol, poly (ethylene zide-co-propylene oxide) polybutylene glycol and polytetrahydrofuran. The molecular weight M _{n of} the polyether diols is preferably 250 to 5000, particularly preferably 500 to 2500.

Particularly suitable polyester diols are OH-terminated reaction products of diols with dicarboxylic acids. Examples of suitable dicarboxylic acids are aliphatic dicarboxylic acids having preferably 3 to 12 C atoms, such as succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, 1,12-dodecanedicarboxylic acid, maleic acid, fumaric acid, itaconic acid, and aromatic and cycloaliphatic dicarboxylic acids, such as phthalic acid, isophthalic acid, terephthalic acid. Instead of the dicarboxylic acids, it is also possible to use their esters, in particular their methyl esters, or their anhydrides, such as maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, tetrachlorophthalic anhydride or endo-methylene tetrahydrophthalic anhydride. Particularly suitable diols are saturated and unsaturated aliphatic and cycloaliphatic diols. The particularly preferred aliphatic α, ω-diols are unbranched and have 2 to 12, in particular 2 to 8, especially 2 to 4 C-atoms. Preferred cycloaliphatic diols are derived from cyclohexane. Examples of particularly suitable diols are: ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 2-methylpropane-1,3-diol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1.8 Octanediol, 1,10-decanediol, 1,12-dodecanediol, cis- and trans-but-2-en-1,4-diol, 2-butyne-1,4-diol and cis- and trans-1,4 -di (hydroxymethyl) cyclohexane. The molecular weight M _{n of} the polyester diols is preferably from 300 to 5,000.

When isocyanate-reactive compound RI suitable lactone-based polyester diols are aliphatic, saturated unbranched ω-hydroxycarboxylic acids with 4 to 22, preferably 4 to 8 C atoms, preferably, e.g. the reaction products of γ-hydroxybutyric acid and δ-hydroxyvaleric acid.

When Isocyanate-reactive compounds are furthermore suitable for the above-mentioned Diols, especially saturated ones and unsaturated aliphatic and cycloaliphatic diols, with the same preferences as above.

Also suitable as isocyanate-reactive compounds RI are polyols with more than 2 OH groups, e.g. Triols, in particular 3 to 12, before all have 3 to 8 C atoms. Example of a particularly suitable Triol is trimethylolpropane.

anionic Modified polyurethanes naturally have anionic groups as mentioned above, in particular Carboxyl groups. Such groups are included in a suitable manner the preparation by means of isocyanate-reactive compounds RI ', which additionally at least have an anionic group incorporated into the polyurethane. Suitable compounds of this type are dihydroxycarboxylic acids, for example aliphatic saturated dihydroxy, which preferably have 4 to 14 carbon atoms. A particularly preferred example for these dihydroxycarboxylic acids is dimethylolpropionic acid (DMPA). Also suitable are corresponding dihydroxysulfonic acids and dihydroxyphosphonic, such as 2,3-dihydroxypropanephosphonic acid.

The introduction anionic groups in the polyurethane can also be used by isocyanate-reactive compounds which are only one isocyanate-reactive Group and at least one anionic group, carried out. Examples which may be mentioned are in particular aliphatic, cycloaliphatic, araliphatic or aromatic monohydroxycarboxylic acids and sulfonic acids called.

The Polyurethane-based dispersants are prepared by reacting the Compounds I, RI and optionally RI 'prepared, wherein the molar ratio of Isocyanate groups to hydroxyl groups usually 2: 1 to 1: 2, preferably 1.2: 1 to 1: 1.2. In particular, this indicates anionic polyurethane no free isocyanate groups on.

Such surface-active polyurethanes are known and commercially available, for example under the name Borchi ^® GEN SN95 (Borchers).

preferred aqueous Preparation of the dispersed effect substance include at least one anionic dispersant and / or a polyurethane.

It may be advantageous if the aqueous preparation of the dispersed effect substance additionally contains at least one further surface-active substance. This is preferably a nonionic, water-soluble surface-active substance having a polyether structure, in particular those having one or more polyethylene oxide groups. Suitable examples thereof are homopolymers and copolymers of C ₂ -C ₄ -alkylene oxides, in particular polyethylene oxides, polypropylene oxides, poly (ethylene oxide-co-propylene oxide), copolymers of C ₂ -C ₄ -alkylene oxides with styrene oxide, in particular block copolymers with polypropylene oxide and polyethylene oxide blocks or block copolymers with poly (phenylethylene oxide) and polyethylene oxide blocks and also random copolymers of these alkylene oxides.

Also suitable are poly-C ₂ -C ₄ -alkylene oxides, in particular polyethylene oxides, polypropylene oxide and poly (ethylene oxide-co-propylene oxides), by reacting corresponding C ₂ -C ₄ alkylene oxides to mono- or polyfunctional starter molecules, such as saturated or unsaturated aliphatic and aromatic alcohols, such as phenol or naphthol, which in turn may each be substituted by alkyl, in particular C ₁ -C ₁₂ -alkyl, preferably C ₄ -C ₁₂ - or C ₁ -C ₄ -alkyl, saturated or unsaturated aliphatic and aromatic amines, saturated or unsaturated aliphatic carboxylic acids and carboxylic acid amides. Usually, 1 to 300 mol, preferably 3 to 150 mol, of alkylene oxide are used per mole of starter molecule.

Suitable aliphatic alcohols generally contain 6 to 26 C atoms, preferably 8 to 18 C atoms, and may be unbranched, branched or cyclic. Examples which may be mentioned are octanol, nonanol, decanol, isodecanol, undecanol, dodecanol, 2-butyloctanol, tridecanol, isotridecanol, tetradecanol, pentadecanol, hexadecanol (cetyl alcohol), 2-hexyldecanol, heptadecanol, octadecanol (stearyl alcohol), 2-heptylundecanol, 2-octyldecanol , 2-nonyltridecanol, 2-decyltetradecanol, oleyl alcohol and 9-octadecenol, as well as mixtures of these alcohols, such as C ₈ / C ₁₀ , C ₁₃ / C ₁₅ and C ₁₆ / C ₁₈ alcohols, and cyclopentanol and cyclohexanol. Of particular interest are the saturated and unsaturated fatty alcohols obtained by lipid cleavage and reduction from natural raw materials, and the synthetic fatty alcohols from the oxo process. The alkylene oxide adducts to these alcohols usually have average molecular weights M _{n of} from 200 to 5,000.

When examples for the above-mentioned aromatic alcohols are besides unsubstituted Phenol and α- and β-naphthol, Hexylphenol, heptylphenol, octylphenol, nonylphenol, isononylphenol, Undecylphenol, dodecylphenol, di- and tributylphenol and dinonylphenol called.

suitable Aliphatic amines correspond to the aliphatic alcohols listed above. Of particular importance here are the saturated and unsaturated ones Fatty amines which preferably have 14 to 20 carbon atoms. As aromatic Amines may be mentioned, for example, aniline and its derivatives.

When aliphatic carboxylic acids are particularly saturated and unsaturated fatty acids, which preferably contain 14 to 20 carbon atoms, and hydrogenated, partially hydrogenated and unhydrogenated resin acids as well as polyvalent carboxylic acids, e.g. dicarboxylic acids, like maleic acid.

suitable carboxamides are derived from these carboxylic acids from.

Next the alkylene oxide adducts to the monohydric amines and alcohols the alkylene oxide adducts to at least difunctional amines and alcohols of very special interest.

As at least difunctional amines, preference is given to bifunctional amines which are in particular of the formula H ₂ N- (R ¹ -NR ² ) _n H (R ¹ : C ₂ -C ₆ -alkylene; R ² : hydrogen or C ₁ -C _6- alkyl; n: 1 to 5, where n may be the same or different). Specific examples which may be mentioned are: ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, propylenediamine-1,3, dipropylenetriamine, 1,4,8-triazaoctane, 1,5,8,12-tetraazadodecane, hexamethylenediamine, dihexamethylenetriamine, 1,6-bis-triamine (3-aminopropylamino) hexane, and N-methyl dipropylenetriamine and polyethyleneimine (Lupasol ^® brands from BASF), said hexamethylene diamine and diethylene triamine are more preferred and ethylene diamine is most preferred.

Preferably These amines are first with propylene oxide and then reacted with ethylene oxide. The content of the block copolymers Ethylene oxide is usually at about 10 to 90 wt .-%.

The block copolymers based on polyvalent amines generally have average molecular weights M _{n of} from 1,000 to 40,000, preferably from 1,500 to 30,000.

As at least bifunctional alcohols dihydric to pentahydric alcohols are preferred. For example C ₂ -C ₆ -alkylene glycols and the corresponding di- and polyalkylene glycols, such as ethylene glycol, 1,2-propylene glycol and 1,3, 1,2-butylene glycol and -1,4, hexylene glycol-1,6, dipropylene glycol and polyethylene glycol Glycerol and pentaerythritol, with ethylene glycol and polyethylene glycol being particularly preferred, and propylene glycol and dipropylene glycol being most preferred.

Especially preferred alkylene oxide adducts to at least difunctional alcohols have a central polypropylene oxide block, so go from a propylene glycol or polypropylene glycol, the first with further propylene oxide and then reacted with ethylene oxide. Of the Content of the block copolymers of ethylene oxide is usually at 10 to 90 wt .-%.

The block copolymers based on polyhydric alcohols generally have average molecular weights M _{n of} from 1,000 to 20,000, preferably from 1,000 to 15,000.

Such alkylene oxide are known and commercially available eg under the name Tetronic ^® and Pluronic ^® (BASF).

To the nonionic surfactant Counting substances also low molecular weight substances which typically have molecular weight (Number average) below 1500 daltons and often below 800 daltons have and hereinafter also referred to as nonionic emulsifiers become. Nonionic emulsifiers are known in the art, e.g. from Ullmann's Encyclopedia of Industrial Chemistry, 5th ed. on CD-ROM, Wiley-VCH, Weinheim 1997, Emulsifiers, chapter 7.

Examples of nonionic emulsifiers are, in particular, ethoxylated C ₈ -C ₂₀ -alkanols having ethoxylation degrees in the range from 3 to 50 and especially 5 to 30, and also ethoxylated C ₄ -C ₂₀ -alkylphenols having ethoxylation degrees in the range from 3 to 50 and especially 5 to 30.

In addition, the surface-active substances in a minor amount may also comprise low molecular weight anionic emulsifiers. These include in particular emulsifiers based on acidic phosphoric acid, phosphonic acid, sulfuric acid and / or sulfonic acid esters of C ₆ -C ₂₀ -alkanols, C ₄ -C ₂₀ -alkylphenols, ethoxylated C ₆ -C ₂₀ -alkanols and ethoxylated C ₄ C ₂₀ -Alkylphenolen, further based on the aforementioned reaction products of the polyethers listed above with phosphoric acid, phosphorus pentoxide and phosphonic acid or sulfuric acid and sulfonic acid. In this case, the polyethers are converted into the corresponding phosphoric acid mono- or diesters and phosphonic acid esters or the sulfuric acid monoesters and sulfonic acid esters. These acid esters are preferably in the form of water-soluble salts, especially as alkali metal salts, especially sodium salts, and ammonium salts, but they can also be used in the form of the free acids.

preferred Phosphates and phosphonates are mainly derived from alkoxylated, in particular ethoxylated, fatty and oxo alcohols, alkylphenols, Fatty amines, fatty acids and resin acids preferred sulfates and sulfonates are based in particular on alkoxylated, especially ethoxylated, fatty alcohols, alkylphenols and amines, also polyvalent amines, such as hexamethylenediamine.

Such anionic surface active additives are known and commercially available for example under the name Nekal ^® (BASF), Tamol ^® (BASF), Crodafos ^® (Croda), Rhodafac ^® (Rhodia), Maphos ^® (BASF), Texapon ^® (Cognis), Empicol ^® (Albright & Wilson), Matexil ^® (ICI), Soprophor ^® (Rhodia) and Lutensit ^® (BASF).

Of the Proportion of the aforementioned polymeric dispersants makes in the Rule 5 to 100 wt .-%, based on the dispersed solid and in particular 10 to 80 wt .-%, based on the dispersed Solid off.

In a first preferred embodiment of the invention the composition used in step a) comprises at least one colorant, in particular a pigment, optionally in combination with a or several other effect substances, in particular a soluble one Dye.

• – Monoazopigmente: C.I. Pigment Brown 25; C.I. Pigment Orange 5, 13, 36, 38, 64 und 67; C.I. 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 und 251; C.I. Pigment Yellow 1, 3, 62, 65, 73, 74, 97, 120, 151, 154, 168, 181, 183 und 191; C.I. Pigment Violet 32;
• – Disazopigmente: C.I. Pigment Orange 16, 34, 44 und 72; C.I. Pigment Red 144, 166, 214, 220, 221 und 242; C.I. Pigment Yellow 12, 13, 14, 16, 17, 81, 83, 106, 113, 126, 127, 155, 174, 176, 180 und 188;
• – Disazokondensationspigmente: C.I. Pigment Yellow 93, 95 und 128; C.I. Pigment Red 144, 166, 214, 220, 242 und 262; C.I. Pigment Brown 23 und 41;
• – Anthanthronpigmente: C.I. Pigment Red 168;
• – Anthrachinonpigmente: C.I. Pigment Yellow 147, 177 und 199; C.I. Pigment Violet 31;
• – Anthrapyrimidinpigmente: C.I. Pigment Yellow 108;
• – Chinacridonpigmente: C.I. Pigment Orange 48 und 49; C.I. Pigment Red 122, 202, 206 und 209; C.I. Pigment Violet 19;
• – Chinophthalonpigmente: C.I. Pigment Yellow 138;
• – Diketopyrrolopyrrolpigmente: C.I. Pigment Orange 71, 73 und 81; C.I. Pigment Red 254, 255, 264, 270 und 272;
• – Dioxazinpigmente: C.I. Pigment Violet 23 und 37; C.I. Pigment Blue 80;
• – Flavanthronpigmente: C.I. Pigment Yellow 24;
• – Indanthronpigmente: C.I. Pigment Blue 60 und 64;
• – Isoindolinpigmente: C.I. Pigmente Orange 61 und 69; C.I. Pigment Red 260; C.I. Pigment Yellow 139 und 185;
• – Isoindolinonpigmente: C.I. Pigment Yellow 109, 110 und 173;
• – Isoviolanthronpigmente: C.I. Pigment Violet 31;
• – Metallkomplexpigmente: C.I. Pigment Red 257; C.I. Pigment Yellow 117, 129, 150, 153 und 177; C.I. Pigment Green 8;
• – Perinonpigmente: C.I. Pigment Orange 43; C.I. Pigment Red 194;
• – Perylenpigmente: C.I. Pigment Black 31 und 32; C.I. Pigment Red 123, 149, 178, 179, 190 und 224; C.I. Pigment Violet 29;
• – Phthalocyaninpigmente: C.I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6 und 16; C.I. Pigment Green 7 und 36;
• – Pyranthronpigmente: C.I. Pigment Orange 51; C.I. Pigment Red 216;
• – Pyrazolochinazolonpigmente: C.I. Pigment Orange 67; C.I. Pigment Red 251;
• – Thioindigopigmente: C.I. Pigment Red 88 und 181; C.I. Pigment Violet 38;
• – Triarylcarboniumpigmente: C.I. Pigment Blue 1, 61 und 62; C.I. Pigment Green 1; C.I. Pigment Red 81, 81:1 und 169; C.I. Pigment Violet 1, 2, 3 und 27;
• – C.I. Pigment Black 1 (Anilinschwarz);
• – C.I. Pigment Yellow 101 (Aldazingelb);
• – C.I. Pigment Brown 22.

Examples of suitable organic color pigments are:

• Monoazo pigments: CI Pigment Brown 25; CI Pigment Orange 5, 13, 36, 38, 64 and 67; CI 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; CI Pigment Yellow 1, 3, 62, 65, 73, 74, 97, 120, 151, 154, 168, 181, 183 and 191; CI Pigment Violet 32;
• - Disazo pigments: CI Pigment Orange 16, 34, 44 and 72; CI Pigment Red 144, 166, 214, 220, 221 and 242; CI Pigment Yellow 12, 13, 14, 16, 17, 81, 83, 106, 113, 126, 127, 155, 174, 176, 180 and 188;
• Disazo condensation pigments: CI Pigment Yellow 93, 95 and 128; CI Pigment Red 144, 166, 214, 220, 242 and 262; CI Pigment Brown 23 and 41;
• - anthanthrone pigments: CI Pigment Red 168;
• Anthraquinone pigments: CI Pigment Yellow 147, 177 and 199; CI Pigment Violet 31;
• Anthrapyrimidine pigments: CI Pigment Yellow 108;
• - Quinacridone pigments: CI Pigment Orange 48 and 49; CI Pigment Red 122, 202, 206 and 209; CI Pigment Violet 19;
• Quinophthalone pigments: CI Pigment Yellow 138;
• Diketopyrrolopyrrole pigments: CI Pigment Orange 71, 73 and 81; CI Pigment Red 254, 255, 264, 270 and 272;
• Dioxazine pigments: CI Pigment Violet 23 and 37; CI Pigment Blue 80;
• Flavanthrone pigments: CI Pigment Yellow 24;
• Indanthrone pigments: CI Pigment Blue 60 and 64;
• - isoindoline pigments: CI pigments orange 61 and 69; CI Pigment Red 260; CI Pigment Yellow 139 and 185;
• Isoindolinone pigments: CI Pigment Yellow 109, 110 and 173;
• - isoviolanthrone pigments: CI Pigment Violet 31;
• - metal complex pigments: CI Pigment Red 257; CI Pigment Yellow 117, 129, 150, 153 and 177; CI Pigment Green 8;
• - perinone pigments: CI Pigment Orange 43; CI Pigment Red 194;
• Perylene pigments: CI Pigment Black 31 and 32; CI Pigment Red 123, 149, 178, 179, 190 and 224; CI Pigment Violet 29;
• Phthalocyanine pigments: CI Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6 and 16; CI Pigment Green 7 and 36;
• - Pyranthrone pigments: CI Pigment Orange 51; CI Pigment Red 216;
• - Pyrazoloquinazolone pigments: CI Pigment Orange 67; CI Pigment Red 251;
• Thioindigo pigments: CI Pigment Red 88 and 181; CI Pigment Violet 38;
• Triaryl carbonium pigments: CI Pigment Blue 1, 61 and 62; CI Pigment Green 1; CI Pigment Red 81, 81: 1 and 169; CI Pigment Violet 1, 2, 3 and 27;
• CI Pigment Black 1 (aniline black);
• CI Pigment Yellow 101 (aldazine yellow);
• CI Pigment Brown 22.

• – Weißpigmente: Titandioxid (C.I. Pigment White 6), Zinkweiß, Farbenzinkoxid; Zinksulfid, Lithopone;
• – Schwarzpigmente: Eisenoxidschwarz (C.I. Pigment Black 11), Eisen-Mangan-Schwarz, Spinellschwarz (C.I. Pigment Black 27); Ruß (C.I. Pigment Black 7);
• – Buntpigmente: Chromoxid, Chromoxidhydratgrün; Chromgrün (C.I. Pigment Green 48); Cobaltgrün (C.I. Pigment Green 50); Ultramaringrün; Kobaltblau (C.I. Pigment Blue 28 und 36; C.I. Pigment Blue 72); Ultramarinblau; Manganblau; Ultramarinviolett; Kobalt- und Manganviolett; Eisenoxidrot (C.I. Pigment Red 101); Cadmiumsulfoselenid (C.I. Pigment Red 108); Cersulfid (C.I. Pigment Red 265); Molybdatrot (C.I. Pigment Red 104); Ultramarinrot; Eisenoxidbraun (C.I. Pigment Brown 6 und 7), Mischbraun, Spinell- und Korundphasen (C.I. Pigment Brown 29, 31, 33, 34, 35, 37, 39 und 40), Chromtitangelb (C.I. Pigment Brown 24), Chromorange; Cersulfid (C.I. Pigment Orange 75); Eisenoxidgelb (C.I. Pigment Yellow 42); Nickeltitangelb (C.I. Pigment Yellow 53; C.I. Pigment Yellow 157, 158, 159, 160, 161, 162, 163, 164 und 189); Chromtitangelb; Spinellphasen (C.I. Pigment Yellow 119); Cadmiumsulfid und Cadmiumzinksulfid (C.I. Pigment Yellow 37 und 35); Chromgelb (C.I. Pigment Yellow 34); Bismutvanadat (C.I. Pigment Yellow 184).

Suitable inorganic color pigments are, for example:

• White pigments: titanium dioxide (CI Pigment White 6), zinc white, colored zinc oxide; Zinc sulfide, lithopone;
• Black pigments: iron oxide black (CI Pigment Black 11), iron manganese black, spinel black (CI Pigment Black 27); Carbon black (CI Pigment Black 7);
• - colored pigments: 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 sulphoselenide (CI Pigment Red 108); Cerium sulphide (CI Pigment Red 265); Molybdate red (CI Pigment Red 104); ultramarine; 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), chrome 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).

preferred Dyes are those that are water or water miscible or water-soluble organic solvents soluble are. If pigment and dye are used together, have she prefers a respective comparable hue on there Way a particularly intense coloring the lignocellulosic materials is achievable. It can, however also in the color different colorants are used, whereby Nuances of coloring possible are. Particularly suitable are cationic and anionic dyes.

Suitable cationic dyes are derived in particular from di- and triarylmethane, xanthene, Azo, cyanine, azacyanine, methine, acridine, safranine, oxazine, induline, nigrosine and phenazine series, with dyes from the azo, triarylmethane and xanthene series being preferred. Specific examples are: CI Basic Yellow 1, 2 and 37; CI Basic Orange 2; CI Basic Red 1 and 108; CI Basic Blue 1, 7 and 26; CI Basic Violet 1, 3, 4, 10, 11 and 49; CI Basic Green 1 and 4; CI Basic Brown 1 and 4. Cationic dyes (B) may also be colorants containing external basic groups. Suitable examples here are CI Basic Blue 15 and 161. As cationic dyes (B) it is also possible to use the corresponding color bases in the presence of solubilizing acidic agents. Examples include: CI Solvent Yellow 34; CI Solvent Orange 3; CI Solvent Red 49; CI Solvent Violet 8 and 9; CI Solvent Blue 2 and 4; CI Solvent Black 7.

suitable anionic dyes are in particular sulfonic acid group-containing compounds from the series of azo, anthraquinone, metallocene, triarylmethane, Xanthene and stilbene series, where dyes from the triarylmethane, Azo and metal complex (especially copper, chromium and cobalt complex) Row are preferred. The following may be mentioned in detail: C.I. Acid Yellow 3, 19, 36 and 204; C.I. Acid Orange 7, 8 and 142; C.I. Acid Red 52, 88, 351 and 357; C.I. Acid Violet 17 and 90; C.I. Acid Blue 9, 193 and 199; C.I. Acid Black 194; anionic chromium complex dyes like C.I. Acid Violet 46, 56, 58 and 65; C.I. Acid Yellow 59; C.I. Acid Orange 44, 74 and 92; C.I. Acid Red 195; C.I. Acid Brown 355 and C.I. Acid Black 52; anionic cobalt complex dyes such as C.I. Acid Yellow 119 and 204; C.I. Direct Red 80 and 81. Preferred water-soluble Dyes.

• a) 4,4-Diarylbutadiene,
• b) Zimtsäureester,
• c) Benzotriazole,
• d) Hydroxybenzophenone,
• e) Diphenylcyanacrylate,
• f) Oxamide,
• g) 2-Phenyl-1,3,5-triazine;
• h) Antioxidantien,
• i) sterisch gehinderte Amine,
• j) Metalldesaktivatoren,
• k) Phosphite und Phosphonite,
• l) Hydroxylamine,
• m) Nitrone,
• n) Aminoxide,
• o) Benzofuranone und Indolinone,
• p) Thiosynergisten, und
• q) Peroxid-zerstörende Verbindungen.

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

• a) 4,4-diarylbutadienes,
• b) cinnamic acid ester,
• c) benzotriazoles,
• d) hydroxybenzophenones,
• e) diphenyl cyanoacrylates,
• f) Oxamide,
• g) 2-phenyl-1,3,5-triazines;
• h) antioxidants,
• i) sterically hindered amines,
• j) metal deactivators,
• k) phosphites and phosphonites,
• l) hydroxylamines,
• m) lemon,
• n) amine oxides,
• o) benzofuranones and indolinones,
• p) thiosynergists, and
• q) peroxide-destroying compounds.

to Group a) of the 4,4-diarylbutadienes include, for example, compounds the formula A.

The compounds are known from EP-A-916 335. The substituents R ₁₀ and / or R _{11 are} preferably C ₁ -C ₈ -alkyl and C ₅ -C ₈ -cycloalkyl.

to Group b) the cinnamic acid ester counting for example, 4-methoxycinnamic acid 2-isoamyl ester, 4-methoxycinnamic acid 2-ethylhexyl ester, 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 ', 5'-di-tert-butyl) 2'-hydroxyphenyl) benzotriazole, 2- (5'-tert-Bu tyl-2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5 '- (1,1,3,3-tetramethylbutyl) phenyl) benzotriazole, 2- (3', 5'-di-tert-butyl -2'-hydroxyphenyl) -5-chloro-benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'-methylphenyl) -5-chloro-benzotriazole, 2- (3'-sec-butyl) 5'-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-4'-octyloxyphenyl) benzotriazole, 2- (3 ', 5'-di-tert-amyl-2'-hydroxyphenyl ) benzotriazole, 2- (3 ', 5'-bis (α, α-dimethylbenzyl) -2'-hydroxyphenyl) benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5' - ( 2-octyloxycarbonylethyl) phenyl) -5-chloro-benzotriazole, 2- (3'-tert-butyl-5 '- [2- (2-ethylhexyloxy) -carbonylethyl] -2'-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3'-tert-Butyl-2'-hydroxy-5 '- (2-methoxycarbonylethyl) phenyl) -5-chlorobenzotriazole, 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'-methylp henyl) benzotriazole and 2- (3'-tert-butyl-2'-hydroxy-5 '- (2-isooctyloxycarbonylethyl) -phenylbenzotriazole, 2,2'-methylene-bis [4- (1,1,3,3 tetramethylbutyl) -6-benzotriazol-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 = 3'-tert-butyl-4'-hydroxy-5'-2H-benzotriazol-2-ylphenyl and mixtures thereof.

to Group d) of the hydroxybenzophenones include, for example, 2-hydroxybenzophenones such as 2-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 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 their sodium salt, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone-5,5'-bisulfonic acid and their sodium salt.

Group e) of the diphenylcyanoacrylates include, for example ethyl 2-cyano-3,3-diphenyl, available commercially for example under the name Uvinul ^® 3035 from. BASF AG, Ludwigshafen, 2-ethylhexyl 2-cyano-3, 3-diphenylacrylate, obtainable commercially for example as Uvinul ^® 3039 from BASF AG, Ludwigshafen, and 1,3-bis -. [(2'-cyano-3 ', 3'-diphenylacryloyl) oxy] -2,2 -bis {(2'-cyano-3 ', 3'-diphenylacryloyl) oxy] methyl} propane, commercially for example under the name Uvinul ^® 3030 from. BASF AG, Ludwigshafen is available.

to Group f) of oxamides count for example, 4,4'-dioctyloxyoxanilide, 2,2'-diethoxyoxanilide, 2,2'-dioctyloxy-5,5'-di-tert-butyloxanilide, 2,2'-dodecyloxy-5,5-di-tert-tertbutyloxanilide, 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-butyloxanilide and mixtures of ortho-, para-methoxy-disubstituted oxanilides and mixtures of ortho- and para-ethoxy-disubstituted oxanilides.

to Group g) of the 2-phenyl-1,3,5-triazines include, for example, 2- (2-hydroxyphenyl) -1,3,5-triazines such as 2,4,6-tris (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) - 1,3,5-triazine, 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) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-butyloxy-propoxy) -phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2- hydroxy-4- (2-hydroxy-3-octyloxy-propoxy) 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-dimethylphenyl) -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 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-butylphenol 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-methyl phenol, 2,4-dimethyl-6- (1-methylundec-1-yl) -phenol, 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'-thiobis (6-tert-butyl-3-methylphenyl), 4,4'-thiobis (6-tert-butyl-2-methylphenol), 4,4'-thiobis (3,6-di-sec-amylphenol), 4,4'-bis (2,6-dimethyl-4-hydroxyphenyl) disulfide.

Alkylidene bisphenols such as 2,2'-methylenebis (6-tert-butyl-4-methylphenol), 2,2'-methylene-bis (6-tert-butyl-4-ethylphenol), 2,2'-methylene-bis [4-methyl-6- (α-methylcyclohexyl) -phenol], 2,2'-methylene-bis (4-methyl-6-cyclohexylphenol), 2,2'-methylene-bis (6-nonyl-4-methylphenol), 2,2'-methylene-bis (4,6-di-tert-butylphenol), 2,2'-ethylidene-bis (4,6-di-tert-butylphenol), 2,2'-ethylidene-bis (6-tert-butyl-4-isobutylphenol), 2,2'-methylene-bis [6- (α-methylbeezyl) -4-nonylphenol], 2,2'-methylene-bis [6- (α, α-dimethylbenzyl) -4-nonylphenol], 4,4'-methylene-bis (2,6-di-tert-butylphenol), 4,4'-methylenebis (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-methyl-phenyl) -3-n-dodecylmercaptobutan, Ethylene glycol bis [3,3-bis (3-tert-butyl-4-hydroxyphenyl) butyrate], bis (3-tert-butyl-4-hydroxy-5-methylphenyl) 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-dodecylmercaptobutan, 1,1,5,5-tetra (5-tert-butyl-4-hydroxy-2-methylphenyl) pentane.

benzyl such as 3,5,3 ', 5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether, Octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate, tridecyl-4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetate, tris (3,5-di-tert-butyl-4-hydroxybenzyl) amine, 1,3,5-tri (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, di- (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide . Isooctyl 3,5-di-tert-butyl-4-hydroxybenzyl-mercaptoacetic acid, 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-hydroxybenzylphosphoric acid dioctadecyl ester and 3,5-di-tert-butyl-4-hydroxybenzylphosphoric 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 [4- (1,1,3,3-tetramethylbutyl) phenyl] -2,2-bis (3,5-di-tert-butyl-4-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-4-hydroxybenzyl) -2,3,5,6-tetramethylbenzene, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) phenol.

triazine 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.

Benzylphosphonates such as dimethyl 2,5-di-tert-butyl-4-hydroxybenzylphosphonate, Diethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate ((3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl) methyl) -phosphonic 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-hydroxy phenyl) carbamate.

ester the β- (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.

ester the β- (5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid with monohydric or polyhydric alcohols, such as. 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.

ester the β- (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, N'-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane.

ester of 3,5-di-tert-butyl-4-hydroxyphenylacetic acid with mono- or polyvalent ones 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, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane.

Amides of β- (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 (z. B. Naugard ^® XL-1 of 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, N, N, N ', N'-tetramethyl-4,4'-diaminodiphenylmethane, 1,2-bis - [( 2-methylphenyl) amino] ethane, 1,2-bis (phenylamino) -propane, (o-tolyl) biguanide, bis [4- (1 ', 3'-dimethylbutyl) phenyl] amine, 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 dialkylated dodecyldiphenylamines, mixture of mono- and dialkylated isopropyl / Isohexyldiphenylaminen, mixture of 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 Octylphenothiazines, N-allylphenothiazine, N, N, N ', N'-tetraphenyl-1,4-diaminobut-2-ene, N, N-bis (2,2,6,6-tetramethylpiperidine) 4-yl hexamethylenediamine, bis (2,2,6,6-tetramethylpiperidin-4-yl) sebacate, 2,2,6,6-tetramethylpiperidin-4-one, 2,2,6,6 tetramethylpiperidin-4-ol, the dimethyl succinate polymer with 4-hydroxy-2,2,6,6-tetramethyl-1 -piperidinethanol [CAS number 65447-77-0], (for example, Tinuvin ^® 622 of Messrs. Ciba Specialty Chemicals, Switzerland), polymer of 2,2,4,4-tetramethyl-7-oxa-3,20-diaza-dispiro [5.1.11.2] -heeicosan-21-one and epichlorohydrin [CAS-No .: 202483-55-4], for example (Hostavin ^® 30 from. Ciba Specialty Chemicals, Switzerland).

The group i) of the 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 2,2,6,6-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-hydroxybenzylmalonate, (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'-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-2,2,6,6-tetramethylpiperidine, bis (1,2,2,6,6-pentamethylpiperidyl) -2- n-butyl-2- (2-hydroxy-3,5-di-tert-butylbenzyl) m alonate, 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 tetramethylpiperidy) 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 of Fa. 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) ethane, 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- (1,2,2,6,6-pentamethyl-4-) piperidyl) pyrrolidine-2,5-dione, mixture of 4-hexadecyloxy- and 4-stearyloxy-2,2,6,6-tetramethylpiperidine, condensation product of N, N'-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 7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa 3,8-diaza-4-oxospiro [4,5] decane and epichlorohydrin, 1,1-bis (1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl) -2- (4-methoxyphenyl) ethene, N, N'-bis-formyl-N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine, diester of 4-methoxymethylene-malonic acid with 1,2,2,6, 6-pentamethyl-4-hydroxypiperidine, poly [methylpropyl-3-oxo-4- (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-piperidi-4-yl substituted maleimide and a mixture of α-olefins such as. B. Uvinul ^® 5050H (BASF AG, Ludwigshafen, Germany), 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) -4oxo-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'-bis (1,2,2,6,6-pentamethyl-4-piperidyl) hexamethylenediamine, hexahydro -2,6-bis (2,2,6,6-tetramethyl- 1-4-piperidyl) -1H, 4H, 5H, 8H-2,3a, 4a, 6,7a, 8a-hexaacacyclopenta [def] fluorene-4,8-dione (e.g. B. Uvinul ^® 4049 from BASF AG, Ludwigshafen), poly [[6 -. ((1,1,3,3-tetramethylbutyl) amino) -1,3,5-triazine-2,4-diylj [(2 , 2,6,6-tetramethyl-4-piperidinyl) imino] 1,6-hexanediyl [(2,2,6,6-tetramethyl-4-piperidinyl) imino]]) [CAS No. 71878-19-8] , N, N ', N', N'-tetrakis (4,6-bis (butyl- (N-methyl-2,2,6,6-tetramethylpiperidin-4-yl) -amino) triazin-2-yl) - 4,7-diaza-decane-1,10-diamine (e.g., Chimassorb ^® 119 from Ciba Specialty Chemicals, Switzerland..) (CAS No. 106990-43-6.).

to Group j) of the metal deactivators include, 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) -oxalyldihydrazide, Oxanilide, isophthaloyldihydrazide, sebacoylbisphenylhydrazide, N, N'-diacetyladipic 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, triphenyl phosphite, diphenylalkyl phosphites, phenyl dialkyl phosphites, tris (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris (2,4-di-tert-butylphenyl) phosphite, bisisodecyl pentaerythritol diphosphite, bis (2,4 -di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) -pentaerythritol diphos phit, diisodecyloxypentaerythritol diphosphite, bis (2,4-di-tert-butyl-6-methylphenyl) -pentaerythritol diphosphite, bis (2,4,6-tris (tert-butylphenyl) pentaerythritol diphosphite, tristearylsorbitol triphosphite, tetrakis (2,4-di-tert-butylphenyl) tert-butylphenyl) -4,4'-biphenylene diphosphonite, 6-isooctyloxy-2,4,8,10-tetra-tert-butyl-dibenzo [d, fj [1,3,2] dioxaphosphepin, 6-fluoro-2, 4,8,10-tetra-tert-butyl-12-methyldibenzo [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 ', 2 "-nitrilo [triethyltris (3,3', 5,5'-tetra-tert-butyl-1, 1'-biphenyl-2,2'-diyl) phosphite], 2-ethylhexyl- (3,3 ', 5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl) phosphite.

to Group I) of the hydroxylamines for example N, N-dibenzylhydroxylamine, N, N-diethylhydroxylamine, N, N-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 N, N-dialkylhydroxylamine from hydrogenated tallow fatty amines.

to Group m) belong to the Nitrone for example N-benzyl-α-phenylnitrone, N-ethyl-α-methylnitrone, N-octyl-α-heptylnitrone, N-lauryl-α-undecyl nitrone, N-tetadecyl-α-tridecylnitrone, N-hexadecyl-α-pentadecylnitrone, N-octadecyl-α-heptadecylnitrone, N-hexadecyl-α-heptadecylnitrone, N-octadecyl-α-pentadecylnitrone, N-heptadecyl-α-heptadecyl nitrone, N-octadecyl-α-hexadecyl N-methyl-α-heptadecylnitrone and nitrones derived from N, N-dialkylhydroxylamines from hydrogenated talc fatty amines.

to Group n) of the amine oxides belong For example, amine oxide derivatives as disclosed in U.S. Pat. Patent No. 5,844,029 and 5,880,191, didecylmethylamine oxide, tridecylamine oxide, Tridodecylamine oxide and trihexadecylamine oxide.

to Group o) of the benzofuranones and indolinones are, for example, those 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; in EP-A-0589839 or EP-A-0591102 or 3- [4- (2-acetoxyethoxy) phenyl] -5,7-di-tert-butylbenzofuran-2-one, 5,7-di-tert-butyl-3- [4- (2-stearoyloxyethoxy) phenyl] benzofuran-2-one, 3,3'-bis [5,7-di-tert-butyl-3- (4- [2-hydroxyethoxy] phenyl) benzofuran-2-one], 5,7-di-tert-butyl-3- (4-ethoxyphenyl) benzofuran-2-one, 3- (4-acetoxy-3,5-dimethylphenyl) -5,7-di-tert-butyl-benzofuran-2-one, 3- (3,5-dimethyl-4-pivaloyloxyphenyl) -5,7-di tert-butyl-benzofuran-2-one, 3- (3,4-dimethylphenyl) -5,7-di-tert-butylbenzofuran-2-one, Irganoxs HP-136 from Ciba Specialty Chemicals, Switzerland, and 3- (2,3-dimethylphenyl) -5,7-di-tert-butyl-benzofuran-2-one.

to Group p) of thiosynergists include, for example, dilauryl thiodipropionate or distearyl thiodipropionate.

to Group q) the peroxide-destroying Belong to connections for example, esters of β-thiodipropionic acid, for Example of lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole or the zinc salt of 2-mercaptobenzimidazole, zinc dibutyldithiocarbamate, Dioctadecyl disulfide, pentaerythritol tetrakis (β-dodecylmercapto) propionate.

The in compositions used in step a) can also as effect substances contain one or more active substances that are suitable wood or comparable lignocellulosic materials prior to infestation with or a destruction protected by harmful organisms.

• – Holzverfärbende Pilze, z.B. Ascomyceten wie Ophiostoma sp. (z. B. Ophiostoma piceae, Ophiostoma piliferum), Ceratocystis sp. (z. B. Ceratocystis coerulescens), Aureobasidium pullulans, Sclerophoma sp. (z. B. Sclerophoma pityophila); Deuteromyceten wie Aspergillus sp. (z. B. Aspergillus niger), Cladosporium sp. (z. B. Cladosporium sphaerospermum), Penicillium sp. (z. B. Penicillium funiculosum), Trichoderma sp. (z. B. Trichoderma viride), Alternaria sp. (z. B. Alternaria alternata), Paecilomyces sp. (z. B. Paecilomyces variotii); Zygomyceten wie Mucor sp. (z. B. Mucor hiemalis);
• – Holzzerstörende Pilze: Ascomyceten wie Chaetomium sp. (z. B. Chaetomium globosum), Humicola sp. (z. B. Humicola grisea), Petriella sp. (z. B. Petriella setifera), Trichurus sp. (z. B. Trichurus spiralis); Basidiomyceten wie Coniophora sp. (z. B. Coniophora puteana), Coriolus sp. (z. B. Coriolus versicolor), Gloeophyllum sp. (z. B. Gloeophyllum trabeum), Lentinus sp. (z. B. Lentinus lepideus), Pleurotus sp. (z. B. Pleurotus ostreatus), Poria sp. (z. B. Poria placenta, Poria vaillantü), Serpula sp. (z. B. Serpula lacrymans) und Tyromyces sp. (z. B. Tyromyces palustris), und
• – Holzzerstörende Insekten z.B. Cerambycidae wie Hylotrupes bajulus, Callidium violaceum; Lyctidae wie Lyctus linearis, Lyctus brunneus; Bostrichidae wie Dinoderus minutus; Anobiidae wie Anobium punctatum, Xestobium rufovillosum; Lymexylidae wie Lymexylon navale; Platypodidae wie Platypus cylindrus; Oedemeridae wie Nacerda melanura; Formicidae wie Camponotus abdominalis, Lasius flavus, Lasius brunneus, Lasius fuliginosus;

Examples of such harmful organisms are

• Wood discolouring fungi, eg ascomycetes such as Ophiostoma sp. (e.g., Ophiostoma piceae, Ophiostoma piliferum), Ceratocystis sp. (eg, Ceratocystis coerulescens), Aureobasidium pullulans, Sclerophoma sp. (eg Sclerophoma pityophila); Deuteromycetes such as Aspergillus sp. (eg Aspergillus niger), Cladosporium sp. (eg, Cladosporium sphaerospermum), Penicillium sp. (e.g., Penicillium funiculosum), Trichoderma sp. (eg Trichoderma viride), Alternaria sp. (eg Alternaria alternata), Paecilomyces sp. (eg Paecilomyces variotii); Zygomycetes such as Mucor sp. (eg Mucor hiemalis);
• - Wood-destroying mushrooms: Ascomycetes such as Chaetomium sp. (e.g., Chaetomium globosum), Humicola sp. (eg Humicola grisea), Petriella sp. (eg Petriella setifera), 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 vaillantu), Serpula sp. (eg Serpula lacrymans) and Tyromyces sp. (eg Tyromyces palustris), and
• - Wood-destroying insects eg Cerambycidae such as Hylotrupes bajulus, Callidium violaceum; Lyctidae like Lyctus linearis, Lyctus brunneus; Bostrichidae such as Dinoderus minutus; Anobiidae such as Anobium punctatum, Xestobium rufovillosum; Lymexylidae such as Lymexylon navale; Platypodidae such as Platypus cylindrus; Oedemeridae such as Nacerda melanura; Formicidae such as Camponotus abdominalis, Lasius flavus, Lasius brunneus, Lasius fuliginosus;

Suitable are accordingly fungicidal active ingredients, insecticidal agents and bactericides, in particular:

Fungicides from the following Groups:

• • dicarboximides such as iprodione, mycelzolin, procymidone, vinclozolin;
• • acylalanine 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, Ziram, Zineb;
• • heterocyclic Compounds such as anilazine, benomyl, boscalid, carbendazim, carboxin, Oxycarboxine, cyazofamide, dazomet, dithianone, famoxadone, fenamidone, Fenarimol, fuberidazole, flutolanil, furametpyr, isoprothiolane, mepronil, Nuarimol, probenazole, proquinazid, 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. be, e.g. metrafenone;
• • Not Classified fungicides such as Acibenzolar-S-methyl, Benthiavalicarb, Carpropamide, chlorothalonil, cymoxanil, diclomezine, diclocymet, Diethofencarb, edifenphos, ethaboxam, fenhexamide, fentin acetate, fenoxanil, Ferimzone, fluazinam, fosetyl, fosetyl-aluminum, iprovalicarb, hexachlorobenzene, Metrafenone, Pencycuron, Propamocarb, Phthalide, Toloclofos-Methyl, Quintozene, zoxamide;
• • strobilurins, as described in WO 03/075663 by the general formula I. be, for. For example: azoxystrobin, dimoxystrobin, fluoxastrobin, kresoximethyl, Metominostrobin, Orysastrobin, Picoxystrobin, Pyraclostrobin and trifloxystrobin;
• Sulfosenic acid derivatives such as captafol, captan, dichlofluanid, folpet, tolylfluanid;
• • cinnamic acid amides and analogs such as dimethomorph, flumetover, flumorph;
• • 6-Aryl- (1,2,4] triazolo [1,5-a] pyrimidines as they are e.g. in WO 98/46608, WO 99/41255 or WO 03/004465, respectively are described by the general formula I;
• • amide fungicides such as Cyflufenamid 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-chloroorphenyl-3-iodopropargylformal, 3-bromo-2,3-diiodo-3-propenylethyl carbonate, 2,3,3-triiodoallyl alcohol, 3-bromo-2,3-diiodo-2-propenyl alcohol, 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, napcocide;
• • phenol derivatives such as tribromophenol, tetrachlorophenol, 3-methyl-4-chlorophenol, dichlorophen, O-phenylphenol, m-phenylphenol, 2-benzyl-4-chlorophenol;
• Isothiazolinone such as N-methylisothiazolin-3-one, 5-chloro-N-methylisothiazolin-3-one, 4,5-dichloro-N-octylisothiazolin-3-one, N-octylisothiazolin-3-one;
• • (Benz) isothiazolinone such as 1,2-benzisothiazol-3 (2H) on, 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, z. B. tributyl (TBT) tin compounds such as tributyltin and tributyl (mononapthenoyloxy) tin derivatives;
• • dialkyl dithiocarbamate and the Na and Zn salts of dialkyldithiocarbamates, tetramethylthiouram disulfide;
• • nitriles such as 2,4,5,6-Tertrachlorisophthalodinitril;
• Benzothiazoles such as 2-mercaptobenzothiazole;
• • Chinoline such as 8-hydroxyquinoline and its Cu salts;
• Tris-N- (cyclohexyldiazeniumdioxy) aluminum, N- (cyclohexyldiazeniumdioxy) -tributylzinn, Bis-N- (cyclohexyldiazeniumdioxy) copper;
• • 3-Benzo (b) thien-2-yl-5,6-dihydro-1,4,2-oxathiazine-4-oxide (Bethoxazin).

Insecticides from the following Groups:

• • organophosphates such as azinphos-methyl, azinphos-ethyl, chlorpyrifos, chlorpyrifos-methyl, Chlorfenvinphos, Diazinon, Dimethylvinphos, Dioxabenzofos, Disulfoton, 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, trichlorophone; Tetrachlorovinyl, vamidothion;
• Carbamate such as alanycarb, benfuracarb, bendiocarb, carbaryl, carbofuran, carbosulfan, Fenoxycarb, furathiocarb, indoxacarb, methiocarb, pirimicarb, propoxur, Thiodicarb, triazamates;
• • 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 e.g. benzoylureas such as chlorofluorurane, diflubenzuron, flucycloxuron, flufenoxuron, Hexaflumuron, lufenuron, novaluron, teflubenzuron, triflumuron; Buprofezin, diofenolan, hexythiazox, etoxazole, clofentazine; b) Ecdysone antagonists such as halofenozide, methoxyfenozide, tebufenozide; c) juvenoids such as pyriproxyfen, methoprene; d) lipid biosynthesis inhibitors like spirodiclofen;
• • Neonicotinoids such as flonicamid, clothianidin, dinotefuran, imidacloprid, thiamethoxam, Nithiazine, acetamiprid, thiacloprid;
• • Further unclassified insecticides such as abamectin, acequinocyl, amitraz, Azadirachtin, Bifenazate, Cartap, Chlorfenapyr, Chlordimeform, Cyromazine, Diafenthiuron, Diofenolan, Emamectin, Endosulfan, Fenazaquin, Formetanate, Formetanate hydrochloride, hydramethylnone, indoxacarb, piperonyl butoxide, Pyridaben, Pymetrozine, Spinosad, Thiamethoxam, Thiocyclam, Pyridalyl, Fluacyprim, Milbemectin, Spirosmesifen, Flupyrazofos, NCS 12, Flubendiamide, Bistrifluron, Benclothiaz, Pyrafluprole, Pyriprole, Amidoflumet, Flufenerin, Cyflumetofen, lepimectin, profluthrin, dimefluthrin and metaflumizone; and

bactericides: e.g. 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), furthermore carbendazim, chlorotoluron, 2,2-dibromo-3-nitrilopropionamide (DBNPA), fluometuron, 3-iodo-2-propynyl-butylcarbamate (IPBC), isoproturon, Prometry, Propiconazole.

The Concentration of effect or effect substance in the composition directed in a conventional manner according to the desired application and is typically in the range of 0.01 to 60 wt .-%, in particular in the range of 0.05 to 20 wt .-%, based on the total weight the composition. For colorants, the concentration is typically in the range of 0.1 to 20% by weight, based on the weight of the dispersion, for active ingredients typically in the range of 0.05 to 5 wt .-%, in the case of UV stabilizers typically in the range from 0.05 to 5% by weight and for antioxidants, typically in the range of 0.05 to 5 Wt .-%, based on the weight of the composition.

In a further preferred embodiment of the invention the watery Dispersion in addition to the effect substance already at least one of those crosslinkable compounds used in the in step b) Composition are included. Such compositions are new and also the subject of the present invention. Regarding the preferred ingredients, the concentrations etc. of these compositions The following explanations apply for the in step b) composition used analogously.

The impregnation of the lignocellulosic material with the effect composition in step a) can be carried out in a conventional manner, for example by dipping, by applying 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 impregnated with little effort, for example by dipping or spraying, whereas lignocellulosic materials with larger dimensions, in particular materials whose smallest extent is more than 5 mm, for example solid wood, molded parts made of solid wood or wood-based materials, under application of pressure or vacuum, in particular by combined application of pressure and vacuum impregnated. Advantageously, the impregnation is carried out at a temperature below 50 ° C, for example in the range of 15 to 50 ° C.

The Conditions of impregnation are usually chosen like this be that the absorbed amount of aqueous composition at least 20, often at least 30 wt .-%, based on the dry weight of the untreated Materials, amounts. The absorbed amount of aqueous Composition can be up to 100 wt .-%, based on the dry matter Of the untreated materials amount and is often in Range of 20 to 100 wt .-%, preferably in the range of 30 to 100 wt .-%, and in particular in the range of 40 to 100 wt .-%, based on the dry matter of the untreated material used. The Moisture to impregnate used, untreated materials is not critical and can, for example to 100%. Here and below, the term "moisture" is synonymous with the Term Residual moisture content according to DIN 52183. Preferably, the Residual moisture content below the fiber saturation point of the wood. Often it is in the range of 1 to 80% and especially 5 to 50%.

To the Dipping is the lignocellulosic material, optionally after one Pre-drying, in a container, which the watery Contains composition dipped. The dipping is preferably done over a period of a few Seconds to 24 h, especially 1 min to 6 h. The temperatures are usually in the range of 15 ° C up to 50 ° C. Here, the lignocellulosic material absorbs the aqueous composition, wherein by the concentration of effect substances in the aqueous Composition, by the temperature and the duration of treatment the amount of effect substances absorbed by the lignocellulosic material can be controlled. Actually absorbed amount of effect substances, the expert in a simple Way over the weight gain of the impregnated Materials and the concentration of effect substances in the aqueous Identify and control composition. Veneers, for example using press rolls, called calenders, which are in the aqueous impregnating be pre-pressed. The occurring when relaxing in the wood Vacuum leads then to accelerated uptake of aqueous impregnating composition.

The Impregnate takes place advantageously by combined use of reduced and elevated Print. For this purpose, the lignocellulosic material, which is usually has a humidity in the range of 1% to 100%, initially below reduced pressure, often in the range of 10 to 500 mbar and especially in the range of 40 to 100 mbar, with the aqueous Composition brought into contact, for. B. by diving in the aqueous Composition. The time period is usually in the range of 1 min to 1 h. This concludes a phase at elevated Pressure, z. B. in the range of 2 to 20 bar, in particular in 4 bis 15 bar and especially 5 to 12 bar, on. 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 ° C. Here, the lignocellulosic material absorbs the aqueous composition, whereby by the concentration of the effect substances in the aqueous Composition, pressure, temperature and duration of treatment the amount of composition taken up by the lignocellulosic material and thus can be controlled at effect materials. The actually recorded Amount of effect substances can also be discussed here about the weight gain of the Lignocellulosematerials be calculated.

Farther can the impregnation by conventional methods of applying liquids surfaces take place, e.g. by spraying or rolling or brushing. For this one sets advantageously a material having a humidity of not more than 50%, in particular not more than 30%, e.g. in the range of 12% to 30%. The Application is usually done at temperatures in the range of 15 to 50 ° C. The spraying can be done in the usual way Way in all for the spraying of flat or finely divided bodies suitable Devices are made, for. B. by means of nozzle arrangements and the same. When painting or rolling, the desired amount at watery Composition with rollers or brushes on the sheet materials applied.

Possibly you can before impregnation in step b) the lignocellulosic material obtained in step a) dry, e.g. on one for the impregnation in step b) suitable residual moisture. But you can also go to one Drying step omitted or step a) and step b) together carry out, by giving a watery Composition of a net, which in addition to the effect fabric also the cross-linkable Contains connection.

The crosslinkable compounds of the aqueous compositions used in step b) or the crosslinkable compounds in the compositions of the effect substance are lower molecular compounds or low molecular weight oligomers which are usually completely dissolved in water. The molecular weight of the crosslinkable compound is usually below 400 daltons. 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.

• – 1,3-Bis(hydroxymethyl)-4,5-dihydroxyimidazolidin-2-on (DMDHEU),
• – 1,3-Bis(hydroxymethyl)-4,5-dihydroxyimidazolidinon, das mit einem C₁-C₈-Alkanol einem C₂-C₆-Polyol oder einem Oligoalkylenglykol modifiziert ist (modifiziertes DMDHEU bzw. mDMDHEU),
• – 1,3-Bis(hydroxymethyl)harnstoff,
• – 1,3-Bis(methoxymethyl)harnstoff;
• – 1-Hydroxymethyl-3-methylharnstoff,
• – 1,3-Bis(hydroxymethyl)imidazolidin-2-on (Dimethylolethylenharnstoff),
• – 1,3-Bis(hydroxymethyl)-1,3-hexahydropyrimidin-2-on (Dimethylolpropylenharnstoff)
• – 1,3-Bis(methoxymethyl)-4,5-dihydroxyimidazolidin-2-on (DMeDHEU),
• – Tetra(hydroxymethyl)acetylendiharnstoff
• – niedermolekulare Melamin-Formaldehyd Harze (MF-Harze) wie 2-, 3-, 4-, 5-, oder 6-fach methyloliertes Melamin, z.B. Tri(hydroxymethyl)melamin (= 2,4,6-Tris-(N-(hydroxymethyl)amino)-1,3,5-triazin und
• – niedermolekulare Melamin-Formaldehyd Harze (MF-Harze) wie 2-, 3-, 4-, 5-, oder 6-fach methyloliertes Melamin, z.B. Tri(hydroxymethyl)melamin, die mit einem C₁-C₆-Alkanol einem C₂-C₈-Polyol oder einem Oligoalkylenglykol modifiziert sind (modifiziertes MF-Harz).

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

• 1,3-bis (hydroxymethyl) -4,5-dihydroxyimidazolidin-2-one (DMDHEU),
• 1,3-bis (hydroxymethyl) -4,5-dihydroxyimidazolidinone modified with a C ₁ -C ₈ -alkanol, a C ₂ -C ₆ -polyol or an oligoalkyleneglycol (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) acetylenediurea
• Low molecular weight melamine-formaldehyde resins (MF resins) such as 2-, 3-, 4-, 5- or 6-times methylolated melamine, eg tri (hydroxymethyl) melamine (= 2,4,6-tris- (N-) (hydroxymethyl) amino) -1,3,5-triazine and
• - Low molecular weight melamine-formaldehyde resins (MF resins) such as 2-, 3-, 4-, 5-, or 6-fold methylolated melamine, for example tri (hydroxymethyl) melamine, with a C ₁ -C ₆ alkanol a C ₂ -C ₈ polyol or an oligoalkylene glycol are modified (modified MF resin).

The Crosslinkable compounds are typically in the form of an aqueous Composition used.

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 there, 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-dihydroxyimidazolidinon-2 (mDMDHEU) are for example from US 4,396,391 and WO 98/29393. Incidentally, compounds V and their reaction products and precondensates are commercially available.

In a preferred embodiment of the invention, the crosslinkable compound is selected from urea compounds V, which carry on the nitrogen atoms of the urea unit (NC (O) -N) in each case a group CH ₂ OR, as defined above, and the reaction products of such urea compounds V with C ₁ -C ₆ alkanols, C ₂ -C ₆ polyols and Oligoalkylenglykolen. In particular, the crosslinkable compound is selected from 1,3-bis (hydroxymethyl) -4,5-dihydroxyimidazolidin-2-one and one having a C ₁ -C ₆ -alkanol a C ₂ -C ₆ -polyol, and / or a polyalkylene glycol modified 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-dihydroxyimidazolidinone-2 with a C ₁ -C ₆ alkanol, a C ₂ -C ₆ polyol, an oligoethylene glycol or mixtures of these alcohols. Examples of suitable C _1-6 -alkanols are 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 and glycerine. Examples of suitable polyalkylene glycols are, in particular, the oligo- and poly-C ₂ -C ₄ -alkylene glycols mentioned below. To produce mDMDHEU, DMDHEU are 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 ° C and a pH of preferably 1 to 2.5, wherein the pH after the reaction usually to a Range is set from 4 to 8.

In a further preferred embodiment of the invention, the crosslinkable compound is under at least 2-fold, eg 2-, 3-, 4-, 5- or 6-fold, especially a 3-times methylolated melamine (poly (hydroxymethyl) melamine) and one with a C ₁ -C ₆ -alkanol, a C ₂ -C ₆ polyol 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, for example C ₁ -C ₆ -alkanols, C ₂ -C ₆ -polyols, oligo- and polyalkylene glycols or mixtures of these alcohols. Examples of suitable C _1-6 -alkanols are 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 and glycerine. Suitable oligo- and polyalkylene glycols are, in particular, oligo- and poly-C ₂ -C ₄ -alkylene glycols, especially homo- and cooligomers of ethylene oxide and / or of propylene oxide, optionally in the presence of low molecular weight starters, for example 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, glycerol, trimethylolethane, trimethylolpropane, erythritol, and pentaerythritol, as well as pentites and hexites such as ribitol, Arabitol, xylitol, 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-triazaoctane, 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 tetrap ropylenglykol and low molecular weight Pluronic from BASF ^® brands (for example Pluronic ^® PE 3100, PE 4300, PE 4400, RPE 1720, RPE 1740) are preferred.

The Concentration of the crosslinkable compounds in the aqueous Composition is usually in the range 1 to 60 wt .-%, often in the range of 10 to 60% by weight and in particular in the range of 15 to 50 wt .-%, based on the Total weight of the composition. If the curable, aqueous composition has a containing the aforementioned alcohols, its concentration is preferably in the range of 1 to 50 Wt .-%, in particular in the range of 5 to 40 wt .-%. The total amount of crosslinkable compound and alcohol usually makes 10 to 60% by weight and in particular 20 to 50 wt .-% of the total weight of the aqueous Composition off.

In the rule contains the aqueous used in step b) Composition at least one catalyst K, which is the crosslinking the compound V, or its reaction product or precondensate causes. In general, as catalysts K metal salts from the Group of metal halides, metal sulphates, metal nitrates, metal phosphates, Metalltetrafluoroborate; boron trifluoride; Ammonium salts from the group the ammonium halides, ammonium sulfate, ammonium oxalate and diammonium phosphate; and organic carboxylic acids, organic sulfonic acids, boric acid, Phosphoric acid, sulfuric acid and hydrochloric acid suitable.

Examples for as Catalysts K suitable metal salts are in particular magnesium chloride, Magnesium sulfate, zinc chloride, lithium chloride, lithium bromide, aluminum chloride, Aluminum sulfate, zinc nitrate and sodium tetrafluoroborate.

Examples for as Catalysts K suitable ammonium salts are in particular ammonium chloride, ammonium sulfate, Ammonium oxalate and diammonium phosphate.

When Catalysts K are especially water-soluble organic carboxylic acids such maleic acid, formic acid, Citric acid, tartaric acid and oxic acid, benzenesulfonic acids, such as p-toluenesulfonic acid, but also inorganic acids, like hydrochloric acid, Phosphoric acid, Sulfuric acid, boric acid and their mixtures are suitable.

Preferably the catalyst K is magnesium chloride, zinc chloride, magnesium sulfate, Aluminum sulfate and mixtures thereof, with magnesium chloride is particularly preferred.

The Catalyst K is usually used the aqueous Add dispersion only shortly before impregnation in step b). He usually becomes in an amount of 1 to 20% by weight, in particular 2 to 10% by weight, based on the total weight of those contained in the aqueous composition curable Components used. The concentration of the catalyst, based on the total weight of the aqueous Composition is usually in the range of 0.1 to 10 wt .-% and in particular in the range of 0.5 to 5 wt .-%.

The impregnation in step b) can be carried out in a conventional manner, for example by dipping, by An 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. Small-sized lignocellulosic materials such as chips or strands and thin veneers, ie materials with a high surface-to-volume ratio, can be impregnated with little effort, for example by dipping or spraying, whereas lignocellulosic materials of larger dimensions, especially materials, have their least expansion 5 mm, eg solid wood, molded parts made of solid wood or wood-based materials, using pressure or vacuum, in particular by combined application of pressure and vacuum impregnated. Advantageously, the impregnation is carried out at a temperature below 50 ° C, for example in the range of 15 to 50 ° C.

The Conditions of impregnation in step b) will usually be chosen so that the recorded Amount of curable Constituents of the aqueous Composition at least 1 wt .-%, based on the dry matter of the material obtained in step a). The recorded amount of curable Ingredients may be up to 100 wt .-%, based on the dry matter the materials obtained in step a) are and often are in the Range of from 1 to 60% by weight, preferably in the range of from 5 to 50% by weight, and in particular in the range of 10 to 30 wt .-%, based on the Dry matter of the material obtained in step a). The Moisture for watering used in step b) is not critical and may, for example to 100%. Here and below, the term "moisture" is synonymous with the Term Residual moisture content according to DIN 52183. Preferably, the Residual moisture content below the fiber saturation point of the wood. Often it is in the range of 1 to 80% and especially 5 to 50%.

To the Dipping is the lignocellulosic material, optionally after one Pre-drying, in a container, which the watery Contains composition dipped. The dipping is preferably done over a period of a few Seconds to 24 h, especially 1 min to 6 h. The temperatures are usually in the range of 15 ° C up to 50 ° C. Here, the lignocellulosic material absorbs the aqueous composition, wherein the concentration of the non-aqueous constituents (i.e. curable Constituents) in the aqueous Composition, temperature and duration of treatment amount of these components taken up by the lignocellulosic material can be controlled. Actually absorbed amount of components, the expert in a simple Way over the weight gain of the impregnated Materials and the concentration of the components in the aqueous Identify and control composition. Veneers, for example by means of pressing rollers, so-called calenders, which are in the aqueous impregnating be pre-pressed. The vacuum that occurs when relaxing in the wood then leads for accelerated uptake of aqueous impregnating composition.

The Impregnate takes place advantageously by combined use of reduced and elevated Print. For this purpose, the lignocellulosic material, which is usually has a humidity in the range of 1% to 100%, initially below reduced pressure, often in the range of 10 to 500 mbar and especially in the range of 40 to 100 mbar, with the aqueous Composition brought into contact, for. B. by diving in the aqueous Composition. The time period is usually in the range of 1 min to 1 h. This concludes a phase at elevated Pressure, z. B. in the range of 2 to 20 bar, in particular in 4 bis 15 bar and especially 5 to 12 bar, on. 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 ° C. Here, the lignocellulosic material absorbs the aqueous composition, wherein the concentration of the non-aqueous constituents (i.e. curable Constituents) in the aqueous Composition, pressure, temperature and duration of treatment the amount of these absorbed by the lignocellulosic material Components can be controlled. The actually recorded amount can over here too the weight gain of the lignocellulosic material is calculated.

Farther can the impregnation by conventional methods of applying liquids surfaces take place, e.g. by spraying or rolling or brushing. For this one sets advantageously a material having a humidity of not more than 50%, in particular not more than 30%, e.g. in the range of 12% to 30%. The Application is usually done at temperatures in the range of 15 to 50 ° C. The spraying can be done in the usual way Way in all for the spraying of flat or finely divided bodies suitable Devices are made, for. B. by means of nozzle arrangements and the same. When painting or rolling, the desired amount at watery Composition with rollers or brushes on the sheet materials applied.

Subsequently, in step c), the curing of the crosslinkable constituents of the aqueous composition used in step b) takes place. Curing can be analogous to those described in the prior art Procedures are performed. for example, according to the methods described in WO 2004/033170 and WO 2004/033171.

The hardening typically occurs by treating the product obtained in step b) Materials at temperatures above 80 ° C, especially above 90 ° C, e.g. in the Range from 90 to 220 ° C and especially in the range of 100 to 200 ° C. The time required for curing is typically in the range of 10 minutes to 72 hours. For veneers and finely divided lignocellulosic materials may tend to have higher temperatures and shorter times be applied. When curing not only the pores in the lignocellulosic material with the hardened impregnating agent become stuffed, but it creates a cross-linking between impregnating agent and the lignocellulosic material itself.

possibly you can before hardening a drying step, in the following also predrying step carry out. Here are the volatile Ingredients of the aqueous Composition, in particular the water and excess organic solvents, those in the curing / networking the urea compounds do not react, partially or completely removed. Predrying means that the lignocellulosic material among the Fiber-saturation point is dried, which is depending on the type of material at about 30 wt .-%. This pre-drying is effective for large-sized bodies, in particular in solid wood, the risk of cracking. For small format Materials or veneers, the pre-drying can be omitted. at Materials with larger dimensions However, the predrying is beneficial. If a separate pre-drying is performed, this is done advantageously at temperatures in the range of 20 to 80 ° C. Dependent on from the chosen one Drying temperature may be a partial or complete cure / crosslinking the curable components contained in the composition take place. The combined predrying / hardening of the impregnated Materials are usually made by applying a temperature profile ranging from 50 ° C to 220 ° C, in particular from 80 to 200 ° C can reach.

The Curing / drying can in a conventional fresh air exhaust system, eg. B. one Drum dryer performed become. Pre-drying preferably takes place in such a way that the moisture content of the finely divided lignocellulosic materials the pre-drying not more than 30%, in particular not more than 20%, based on the dry matter. It can be an advantage the drying / hardening up to a moisture content <10 % and in particular <5 %, based on the dry matter. The moisture content can by the temperature, duration and pressure selected during pre-drying be controlled in a simple manner.

Possibly will be before drying / curing adhering liquid remove by mechanical means.

at large format Materials, it has proven these during drying / hardening to fix, e.g. in heating presses.

The in step b) impregnated or hardened in step c) Lignocellulosic materials can, if it is not already made-up end products, be further processed in a conventional manner, in the case of finely divided Materials e.g. to moldings such as oriented structural board (OSB), chipboard, wafer boards, OSL panels and OSL moldings (Oriented Strand Lumber), PSL panels and PSL moldings (Parallel beach lumber), insulation panels and Medium Density (MDF) and 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 chipboard including veneered OSL and PSL panels (oriented or parallel strand lumber), Plywood, laminated wood, laminated wood, laminated veneer lumber (eg Kerto plywood), Multiplex panels, laminated veneer materials (Laminated Veneer Lumber LVL), decorative veneer materials such as cladding, ceiling and prefabricated parquet panels but also non-planar, 3-dimensionally shaped Components such as plywood moldings, plywood moldings and any other, with at least one veneer layer coated moldings. The further processing may immediately after impregnation in step b), during or following the hardening in step c). In the case of impregnated veneers one becomes advantageously, the further processing before the curing step or together with the curing step carry out. For moldings made of finely divided materials the shaping step and curing step performed simultaneously become.

If the impregnated lignocellulosic material is solid wood or a ready-made wood material, it can be processed in a conventional manner before treatment in step c), eg by sawing, planing, grinding etc. Solid wood impregnated and hardened in accordance with the invention is particularly suitable for the production of Objects, moisture and especially the weather are set, eg for timber, beams, wooden components, for wooden balconies, roof shingles, fences, lignocellulosic towers, railway sleepers, in shipbuilding for interior work and deck superstructures.

The The following examples serve to illustrate the invention.

General rule for impregnation with pigments:

A commercially available solid or aqueous pigment preparation or a liquid dye preparation (see Table 1) is diluted with water to the concentration indicated in Table 2. By adding sulfuric acid, a pH of 6-8 is set. To 100 parts by weight of the aqueous formulation are added at room temperature with stirring 30 parts by weight of a commercial concentrated aqueous formulation of N, N-bis (hydroxymethyl) -4,5-bishydroxyimidazolin-2-one (Fixapret CP ^® BASF -Actiengesellschaft) and 1.5 parts by weight of MgCl ₂ × 6H ₂ O.

To For comparison purposes, corresponding compositions were tested, which is not N, N-bis (hydroxymethyl) -4,5-bishydroxyimidazolin-2-one was added.

In the preparation thus obtained was a pine wood cube with the dimensions 3 cm × 3 cm × 3 cm, which was sealed on the front sides with a 2-component paint, completely submerged, weighted with a weight and stored for 1 h with slight negative pressure. Then you left the impregnating composition 4 hours at atmospheric pressure. Then the so impregnated pieces of wood dried in a convection oven for 36 h at 120 ° C.

Application testing:

The were obtained test specimens with a saw Halved and visually checked for staining. Both the inventively produced wooden body as well as not produced according to the invention wooden body were complete colored.

1

kein Ausbluten

2

leichtes Ausbluten

3

Ausbluten

4

starkes Ausbluten

To assess migration resistance, the halved pieces of wood were each stored in water for one week at ambient temperature and the bleeding of the colorant was assessed visually. Bleeding was assessed according to the following grading scale

1

no bleeding

2

easy bleeding

3

bleed out

4

heavy bleeding

The Results are given in Table 2.

Table 1: Colorants used

• 1) Farbmittelgehalt, bezogen auf Handelsprodukt.

• 1) colorant content, based on commercial product.

• * nicht erfindungsgemäß
• +) Menge an eingesetztem Handelsprodukt gemäß allgemeiner Vorschrift.
• ++) N,N-Bis(hydroxymethyl)-4,5-bishydroxyimidazolin-2-on

All pigment preparations tested contained polymeric anionic dispersants. Table 2:

• * not according to the invention
• +) Amount of commercial product used according to general instructions.
• ++) N, N-bis (hydroxymethyl) -4,5-bishydroxyimidazolin-2-one

Claims (24)

Process for impregnating lignocellulosic materials with effect substances, comprising the following steps: a) impregnating the lignocellulosic material with a liquid preparation containing at least one effect substance in dissolved or dispersed form, and b) during or after step a) impregnating with a curable one aqueous composition containing at least one crosslinkable compound selected from α) low molecular weight compounds V, which are at least two N-bonded groups of the formula CH ₂ OR, wherein R is hydrogen or C ₁ -C ₄ alkyl, and / or a 1,2-bishydroxyethane-1,2-diyl group bridging two nitrogen atoms, β) precondensates of the compound V and γ) reaction products or mixtures of the compound V with at least one alcohol selected from C ₁ -C ₆ -alkanols, C C ₂ -C ₆ polyols and Oligoalkylenglykolen is selected, and c) treating the material obtained in step b) at elevated temperature. The method of claim 1, wherein the effect material selected is colored, UV stabilizers, antioxidants, Fungicides and insecticides. The method of claim 1 or 2, wherein the effect material in the form of an aqueous Composition in which the effect substance in dissolved or dispersed form with particle diameters of not more than 2000 nm is present. The method of claim 3, wherein in step a) used composition at least one dispersed in the aqueous phase Pigment and / or a dispersed of pigments different Effect substance with an average particle diameter in the range of 50 to 2000 nm. The method of claim 4, wherein in step a) composition used at least one polymeric dispersant contains that under anionic and neutral polymeric dispersants is selected. Method according to one of the preceding claims, wherein the composition used in step a) the effect substance in a concentration of 0.01 to 60 wt .-%. A process according to any one of the preceding claims, wherein the crosslinkable compound of the curable composition is selected from - 1,3-bis (hydroxymethyl) -4,5-dihydroxyimidazolidin-2-one, - 1,3-bis (hydroxymethyl) -4,5 dihydroxyimidazolidinone modified with a C ₁ -C ₆ -alkanol, a C ₂ -C ₆ -polyol or an oligoalkyleneglycol, - 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) acetylenediurea - low molecular weight melamine-formaldehyde resins and - low molecular weight melamine-formaldehyde resins containing a C ₁ -C ₆ Alkanol a C ₂ -C ₆ polyol or a Oligoalkylenglykol are modified (modified MF resin). Method according to one of the preceding claims, wherein Concentration of crosslinkable compound in the aqueous curable Composition in the range of 1 to 60 wt .-%, based on the Total weight of the composition is. Method according to one of the preceding claims, wherein the watery Composition in addition contains a catalyst K, which is a cure the crosslinkable compound causes. The method of claim 9, wherein the catalyst K selected is among metal salts from the group of metal halides, metal sulfates, Metal nitrates, metal phosphates, metal tetrafluoroborates; boron trifluoride; Ammonium salts from the group of ammonium halides, ammonium sulfate, Ammonium oxalate and diammonium phosphate; organic carboxylic acids, organic sulfonic acids, boric acid, Phosphoric acid, sulfuric acid and hydrochloric acid. Method according to one of the preceding claims, wherein one carries out step b) following step a). Method according to one of claims 1 to 10, wherein the steps a) and b) are carried out simultaneously. Process according to claim 12, wherein an aqueous composition is used which contains i) at least one dissolved or dispersed effect substance and ii) b) at least one crosslinkable compound selected from α) low molecular weight compounds V which contain at least two N-bonded groups Formula CH ₂ OR, in which R is hydrogen or C ₁ -C ₄ -alkyl, and / or has a 1,2-bishydroxyethane-1,2-diyl group bridging two nitrogen atoms, β) precondensates of compound V and γ) Reaction products or mixtures of the compound V with at least one alcohol selected from C ₁ -C ₆ -alkanols, C ₂ -C ₆ -polyols and Oligoalkylenglykolen. Method according to one of the preceding claims, wherein the impregnation at a temperature below 50 ° C he follows. Method according to one of the preceding claims, wherein the lignocellulosic material is wood or a wood material. Lignocellulosic material, obtainable by a process according to one of the preceding claims. Aqueous composition containing i) at least one dissolved or dispersed effect substance and ii) at least one crosslinkable compound selected from α) low molecular weight compounds V which contain at least two N-bonded groups of the formula CH ₂ OR, where R is hydrogen or C ₁ -C ₄ alkyl, and / or a 1,2-bishydroxyethane-1,2-diyl bridging two nitrogen atoms, β) precondensates of the compound V and γ) reaction products or mixtures of the compound V with at least one alcohol, the is selected from C ₁ -C ₆ -alkanols, C ₂ -C ₆ -polyols and oligo-C ₂ -C ₄ -alkylene glycols. A composition according to claim 17, wherein the effect substance selected is among dyes, pigments, UV stabilizers and antioxidants, Fungicides, insecticides. A composition according to claim 18, containing at least one in watery Phase dispersed pigment and / or a dispersed effect substance with an average particle diameter in the range of 50 to 2000 nm. A composition according to claim 19, additionally containing at least an anionic polymeric dispersant. A composition according to any one of claims 17 to 20, containing the effect substance in a concentration of 0.1 to 20% by weight. Use of aqueous Effect compositions containing at least one in aqueous Phase dispersed pigment and / or a dispersed effect substance with an average particle diameter in the range of 50 to 2000 nm and at least one among anionic and neutral polymers Dispersants selected Dispersant, for impregnation of lignocellulosic materials. Use according to claim 22, wherein the lignocellulosic material Wood covers. Use according to claim 23, wherein the lignocellulosic material a solid wood body is.