JP2009500189A - Light wood material board - Google Patents

Abstract

  Light woody board made from wood fibers that have been bleached and colored with a liquid colorant formulation containing at least one pigment and a dye that absorbs in the visible region of the electromagnetic spectrum.

Description

  The present invention relates to light colors produced from wood fibers that have been bleached and colored with a liquid colorant formulation containing at least one pigment and at least one dye that absorbs in the visible region of the electromagnetic spectrum. Relates to wooden material boards.

  The invention further relates to the use of these wood-based boards for producing furniture (Einrichtungsgegenstaende), as well as to furniture containing these wood-made boards.

  In the area of wood materials, the market for so-called medium density fiberboard (medium density fiberboard, MDF board) and high density fiberboard (high density fiberboard, HDF board) has greatly increased. It's getting on. The production volume has more than tripled over the past decade.

  MDF and HDF plates can be processed in the same way as conventional particle boards. Due to their regular structure, they are, however, also suitable for the production of grooved parts and are therefore used more often in furniture construction. Thus, furnishings, for example for spaces and for decorative purposes (eg in trade fair construction), but also already relatively expensive furniture, are made up of these boards, and the wooden structure continues to be visible. In order to obtain, simply a colorless lacquer is applied or coated with an overlay.

  Naturally these boards have a more or less characteristic brown shade depending on the type of wood used, which has little aesthetic value for application in the furniture area.

  By coloring the material with a colorant formulation containing pigments and dyes known from WO-A-04 / 35276, the inherent shade of the wood fibers can be corrected in the dark shade range and with a high color density. In this way, colored, completely firmly colored, non-fading and thereby aesthetically valuable MDF boards are obtained, which are suitable for the production of long-lasting products, for example furniture in the residential area.

Has a bright bright tone (L ^* ≧ 75) even at high color densities, for example colored yellow or orange, or colored at a low color density, ie lightened pastel shades, eg neutral Wood material boards with gray color, in particular MDF boards, have not been known so far. For the manufacture of furniture and upholstery, for example in the kitchen and bathroom, these boards are particularly interesting.

  JP-A-55-164142 describes a particleboard made from wood chips that are first oxidatively bleached with sodium chlorite and then colored with a direct dye. In this case, bleaching is performed to improve the full coloration of the wood chips and a dark color is produced.

  Finally, unpublished DE-A-102004050278, unpublished on the priority date of the present description, describes a light to white wood material board made from bleached wood fibers and / or colored with white pigments. Is described.

  It was therefore the basis of the present invention to provide a light-colored wood board.

  Accordingly, a light-colored wood board made from wood fibers that have been bleached and colored with a liquid colorant formulation containing pigments and dyes has been found.

The wood material board according to the invention is characterized by its clear and bright color. It has a “soft” pastel shade mixed with white, or a lightness value L ^* ≧ 75, which can be obtained by coloring at a standard color density (standardfarbtiefe) of ≦ 1/9, in particular ≦ 1/25. The color may be dark.

  The wood material board according to the present invention is, for example, an MDF board, an HDF board or a particle board. Particularly advantageous is the MDF plate.

  Usually, MDF and HDF plates are manufactured in a continuous process. In that case, the washed, water-moist, small crushed pieces of wood (pulverized pieces) are first preheated to about 80 ° C. and then in a boiler at a pressure of 2-5 bar and a temperature of 100-150 ° C. It is softened by. The shredded pieces are then loosened into fibers in the connected sculpture machine. The refiner consists of two metal slabs equipped with radial reliefs, which rotate closely in opposite directions. The fiber exits the refiner via a so-called blow line. In this case, an adhesive (Leim) is usually applied. As binder, urea-formaldehyde-resin reinforced partly with melamine or urea-melamine-formaldehyde-resin for moisture-resistant plates is usually used. Isocyanates are also used as binders. Usually the binder is applied onto the fibers together with the desired additives (eg hardeners, paraffin dispersions, colorants). The fibers to which the adhesive has been applied subsequently pass through a dryer in which they are dried to a humidity of 8-15% by weight. The dried fibers are applied individually and also only afterwards in a special mixer operating continuously.

  In the production of particleboard, the pre-dried wood chip adhesive is applied in a continuous mixer.

  Subsequently, the fibers or wood chips to which the adhesive has been applied are poured into a mat, optionally pressed in a cold pre-compressed and heated press at a temperature of 170-240 ° C. to obtain a plate.

  As the base material, all fibrous materials which can be obtained in principle from plants for the wood board according to the invention may be used. Thus, for example, fibers that can be obtained from palm besides the commonly used wood fibers are suitable. An advantageous base material is a light wood species, in particular spruce or pine, however, relatively dark wood species such as beech can also be used.

  In the following, the concept "wood fiber" and "wood waste" will not be distinguished, but rather the concept "wood fiber" should also include "wood waste".

  The wood fibers used in the wood material board according to the invention are bleached.

  During the chemical bleaching of wood fibers, the wood-associated entraining substances are destroyed or lost their effectiveness by oxidizing chemicals and / or reducing chemicals. For oxidative bleaching, for example hydrogen peroxide, ozone, oxygen, halogen oxyacid salts such as chlorites, and organic and inorganic peracid salts such as peracetates, percarbonates and perborate Salts, in particular their alkali metal salts, in particular the sodium salt, are suitable, in which percarbonates and hydrogen peroxide are preferred. For reductive bleaching, for example, reduced sulfur compounds, dithionites, disulfites, sulfites or sulfur dioxide, sulfinic acids and their salts, especially alkali metal salts and especially sodium salts, and hydroxycarboxylic acids such as citric acid. Acid and malic acid are suitable. Preferred reducing agents are disulfites and sulfites, in particular sodium hydrogen sulfite, and malic acid and citric acid.

  For the wood board according to the invention, wood fibers that are first oxidatively bleached and then reductively bleached are particularly advantageous.

  Very advantageously, the oxidative bleaching is carried out with percarbonate or hydrogen peroxide and the reductive bleaching is carried out with sulfite or malic acid or citric acid.

  In terms of processing technology, during bleaching, preferably an aqueous 5 to 40% by weight wood fiber dispersion is continuously applied in a countercurrent tower at a temperature of 90 to 150 ° C. and a pressure of up to 3 bar. Alternatively, the treatment is performed with a dispersion. Usually, work is performed in the presence of a complexing agent such as EDTA to avoid degradation of the bleach by transition metal ions.

  In particular in the production of MDF / HDF boards according to the invention, the bleaching of the fibers can preferably be carried out during the board production. The bleaching agent may then be added to the crushed pieces in a pre-warmer or in a boiler. A complexing agent is also preferably added.

  The wood fibers used in the wood board according to the invention are, after bleaching, colored with a liquid colorant formulation containing at least one pigment and at least one dye that absorbs in the visible region of the electromagnetic spectrum.

  In general, these colorant formulations contain 0.01 to 10% by weight, preferably 0.5 to 10% by weight, of dye, based on the pigment.

Particularly preferably, these colorant formulations are (A) from 10 to 70% by weight of at least one pigment,
(B) 0.05-7% by weight of at least one dye that absorbs in the visible region of the electromagnetic spectrum,
(C) 1-50% by weight of at least one dispersant,
(D) water or a mixture of water and at least one water-retaining agent (Wasserrueckhaltemittel) 10 to 88.95% by weight and (E) 0 to 5% by weight of usual further ingredients for colorant formulations
Containing.

  As the component (A), an organic pigment or an inorganic pigment may be contained in the colorant formulation. Of course, the colorant formulation may also contain various organic pigments or mixtures of various inorganic pigments or mixtures of organic and inorganic pigments.

  The pigment is preferably present in fine form and accordingly has an average particle size of usually 0.1 to 5 μm, in particular 0.1 to 3 μm and in particular 0.1 to 1 μm.

  Usually, organic pigments are organic colored pigments and organic black pigments. Inorganic pigments can likewise be colored pigments (colored pigments, black pigments and white pigments) and glossy pigments.

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

For example, suitable inorganic color pigments are:
-White pigment: 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; chromium 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 violet and manganese violet;
Iron oxide red (CI Pigment Red 101); cadmium sulfoselenide (CI Pigment Red 108); cerium sulfide (CI Pigment Red 265); molybdate red (CI Pigment Red 104) ); Ultramarine Red;
Iron oxide brown (CI Pigment Brown 6 and 7), mixed brown, spinel phase and corundum phase (CI Pigment Brown 29, 31, 33, 34, 35, 37, 39 and 40), chrome titanium yellow (C.I. Pigment Brown 24), chrome orange;
Cerium sulfide (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); Chrome titanium yellow; spinel phase (CI Pigment Yellow 119); cadmium sulfide and zinc cadmium sulfide (CI Pigment Yellow 37 and 35); chrome yellow (CI Pigment Yellow 34); bismuth vanadate ( CI Pigment Yellow 184).

  A luster pigment is a plaettchenfoermige Pigmente composed of a single phase or multiple phases, and its color change is created by the interaction of interference, reflection and absorption phenomena. Examples include aluminum sheets, and in particular, aluminum sheets coated once or repeatedly with metal oxides, iron oxide sheets and mica sheets.

  In general, the colorant formulation contains 10 to 70% by weight, preferably 10 to 60% by weight, of pigment (A).

  As component (B), the colorant formulation contains at least one dye that absorbs in the visible region of the electromagnetic spectrum from the group of cationic dyes, anionic dyes and disperse dyes. Particularly suitable here are dyes which are soluble in water or in water-miscible or water-soluble organic solvents. Advantageously, the dye (B) used has in each case a hue comparable to that of the pigment (A). This is because, in this way, particularly intensive coloration of the wooden board can be achieved even in the case of light tones. However, dyes (B) with different colors can also be used, which makes it possible to add nuance to the colors.

  Particularly suitable are cationic dyes, anionic dyes and disperse dyes. Very suitable are direct dyes and disperse dyes.

  Suitable cationic dyes (B) are diarylmethane- and triarylmethane-, xanthene-, azo-, cyanine-, azacyanin-, methine-, acridine-, safranine-, oxazine-, indulin-, nigrosine- and phenazine systems. Preference is given to dyes from the azo, triarylmethane and xanthene systems.

  The following are individually mentioned as examples: C.I. I. Basic Yellow 1, 2 and 37; I. Basic Orange 2; C.I. I. Basic Red 1 and 108; C.I. I. Basic Blue 1, 7, and 26; I. Basic Violet 1,3,4,10,11 and 49; I. Basic Green 1 and 4; I. Basic Brown 1 and 4.

  The cationic dye (B) may be a dye containing an external basic group. A suitable example is in this case C.I. I. Basic Blue 15 and 161.

  The corresponding color base as cationic dye (B) can also be used in the presence of acidic agents that render it soluble. Examples include the following: C.I. I. Solvent Yellow 34; C.I. I. Solvent Orange 3; C.I. I. Solvent Red 49; C.I. I. Solvent Violet 8 and 9; C.I. I. Solvent Blue 2 and 4; I. Solvent Black 7.

  Particularly suitable anionic dyes are sulfonic acid group-containing compounds from the azo-, anthraquinone-, metal complex-, triarylmethane-, xanthene- and stilbene systems, in which triarylmethane-, azo- and Preference is given to dyes from the metal complex-particularly copper-, chromium- and cobalt complexes-systems.

  Individually, for example, the following are described: C.I. I. Acid Yellow 3, 19, 36, 59, 119 and 204; C.I. I. Acid Orange 7, 8, 44, 74, 92 and 142; C.I. I. Acid Red 52, 88, 159, 351 and 357; I. Acid Violet 17, 46, 56, 58, 65 and 90; C.I. I. Acid Blue 9, 193 and 199; C.I. I. Acid Brown 355; I. Acid Black 52 and 194; C.I. I. Direct Yellow 4 and 11; C.I. I. Direct Red 80, 81 and 254; C.I. I. Direct Violet 35 and 51; C.I. I. Direct Blue 47, 67, 199, 267 and 279.

  In particular, these dyes are water-soluble when they are present as alkali metal salts, in particular as lithium, sodium or potassium salts, or as unsubstituted or substituted ammonium salts, in particular as alkanol ammonium salts.

  The disperse dyes are preferably used in the form of commercially available aqueous dispersions and exhibit their coloring action at high temperatures by diffusion in the production process of the wood board.

  Particularly suitable are disperse dyes, for example from the quinophthalone and anthraquinone system.

  The colorant formulation generally contains the dye (B) in an amount of 0.5 to 10% by weight, preferably 1 to 8% by weight, in each case based on the pigment (A). This generally corresponds to an amount of 0.05 to 7% by weight, in particular 0.1 to 5.6% by weight, based on the total weight of the formulation.

  Advantageous pigment / dye combinations for light shades are for example: C.I. I. Pigment Orange 34 and C.I. I. Direct Yellow 11; C.I. I. Pigment Yellow 74 and C.I. I. Direct Yellow 4.

  Light pastel shade systems are especially white pigments, especially C.I. I. Pigment White 6 and colored pigments with nuances such as C.I. I. Pigment Black 7 and C.I. I. It can be obtained by mixing with Basic Violet 3. The light gray shade is preferably a white pigment with a corresponding dye such as C.I. I. Blue dyes such as Direct Blue 47, 67, 267 and 279, and / or C.I. I. Purple dyes such as Direct Violet 35 and 51, and optionally C.I. I. It can also be achieved by adding nuance with a yellow dye such as Direct Yellow 4. At that time, the ratio of the white pigment is usually 80 to 99% by mass with respect to the total amount of the colorant.

  As component (C), at least one dispersant is contained in the colorant formulation.

  Particularly suitable dispersants (C) are nonionic and anionic water-soluble surface active additives.

  Particularly suitable nonionic additives (C) are based on polyethers (additive (C1)).

In addition to the unmixed polyalkylene oxide, preferably C ₂ -C ₄ -alkylene oxide and phenyl-substituted C ₂ -C ₄ -alkylene oxide, in particular polyethylene oxide, polypropylene oxide and poly (phenylethylene oxide), in this case Particularly suitable are block copolymers, in particular polymers having polypropylene oxide and polyethylene oxide blocks or poly (phenylethylene oxide) and polyethylene oxide blocks, and random copolymers of these alkylene oxides.

These polyalkylene oxides are, for example, saturated or unsaturated aliphatic and aromatic alcohols, phenols or naphthols (which in each case are alkyl, in particular C ₁ -C ₁₂ -alkyl, preferably C ₄ -C 12 _- or C ₁ -C 4 _- to be) optionally substituted by alkyl, and aromatic amines aliphatic, saturated or unsaturated, carboxylic acids and carboxylic acid aliphatic, saturated or unsaturated It can be prepared by polyaddition of alkylene oxides to amides. Usually 1 to 300 mol, preferably 3 to 150 mol, of alkylene oxide are used per mol of starter molecule.

Suitable aliphatic alcohols here generally contain 6 to 26 C atoms, preferably 8 to 18 C atoms, and may be unbranched, branched or cyclic. Examples include 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-octadecanol and also of these alcohols mixtures, for example _{C 8 / C 10 -, C} 13 / C 15 - and _C 16 _{/ C 18} - alcohol, and cyclopentanol and cyclohexanol. Of particular importance are saturated and unsaturated fatty alcohols obtained by lipolysis and reduction from natural sources and synthetic fatty alcohols from oxo synthesis. Adducts of alkylene oxide to these alcohols have an average molecular weight _{M n} of normal 200 to 5,000.

  As examples for the above aromatic alcohols, in addition to unsubstituted phenol and α- and β-naphthol, hexylphenol, heptylphenol, octylphenol, nonylphenol, isononylphenol, undecylphenol, dodecylphenol, di- and Tributylphenol and dinonylphenol are mentioned.

  Suitable aliphatic amines correspond to the aliphatic alcohols described above. Again, saturated and unsaturated fatty amines having preferably 14 to 20 C atoms have a special meaning. Examples of the aromatic amine include aniline and derivatives thereof.

  In particular, as aliphatic carboxylic acids, preferably saturated and unsaturated fatty acids containing from 14 to 20 C atoms, and hydrogenated, partially hydrogenated and non-hydrogenated resin acids and many Divalent carboxylic acids such as dicarboxylic acids such as maleic acid are suitable.

  Suitable carboxylic amides are derived from these carboxylic acids.

  In addition to the addition of alkylene oxides to monovalent amines and alcohols, the addition of alkylene oxides to at least bifunctional amines and alcohols is extremely important.

As at least bifunctional amines, in particular 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; 2-5 functional amines corresponding to n: 1 to 5) are preferred. The following are individually mentioned as examples: ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, propylenediamine-1,3, dipropylenetriamine, 3-amino-1-ethyleneaminopropane, hexamethylenediamine, Dihexamethylenetriamine, 1,6-bis- (3-aminopropylamino) hexane and N-methyldipropylenetriamine, hexamethylenediamine and diethylenetriamine being particularly advantageous, and ethylenediamine being very advantageous.

  Advantageously, these amines are first reacted with propylene oxide and subsequently with ethylene oxide. Usually, the content of block copolymer of ethylene oxide is about 10 to 90% by mass.

  In general, block copolymers based on polyvalent amines have an average molecular weight of 1000 to 40000, preferably 1500 to 30000.

Preference is given to divalent to pentavalent alcohols as at least difunctional alcohols. For example, C ₂ -C ₆ -alkylene glycols and corresponding di- and polyalkylene glycols such as ethylene glycol, propylene glycol-1,2 and -1,3, butylene glycol-1,2 and -1,4, hexylene Examples include glycol-1,6, dipropylene glycol and polyethylene glycol, glycerol and pentaerythritol, with ethylene glycol and polyethylene glycol being particularly advantageous and propylene glycol and dipropylene glycol being very advantageous.

  Particularly advantageous alkylene oxide adducts to at least difunctional alcohols have a central polypropylene oxide block, ie starting from propylene glycol or polypropylene glycol, which is first of all further propylene oxide and then ethylene oxide. Allowed to react. Usually, the content of the block copolymer of ethylene oxide is 10 to 90% by mass.

  In general, block copolymers based on polyhydric alcohols have an average molecular weight of 1000 to 20000, preferably 1000 to 15000.

Such alkylene oxide block copolymers are known and are commercially available, for example under the names Tetronic ^(R) and Pluronic ^(R) (BASF).

  Examples for water-soluble anionic surfactants particularly suitable as component (C) include additives based on polymers of ethylenically unsaturated carboxylic acids (C2), additives based on polyurethane (C3) and Additives based on the acidic phosphate esters, phosphonate esters, sulfate esters and / or sulfonate esters of the polyethers (C4) mentioned above.

  Naturally, mixtures of a plurality of additives (C), i.e. mixtures of various nonionic additives as well as mixtures of various anionic additives as well as mixtures of nonionic and anionic additives, Can be used.

  As anionic water-soluble surface-active additives based on polymers of unsaturated carboxylic acids (C2), in particular homopolymers and copolymers of ethylenically unsaturated monocarboxylic acids and / or ethylenically unsaturated dicarboxylic acids (they are Vinyl monomers not containing acid functional groups may be additionally polymerized), the alkoxylation products of these homopolymers and copolymers and the salts of these homopolymers and copolymers and the groups of their alkoxylation products Additives from are suitable.

Examples for carboxyl group-containing monomers and vinyl monomers include the following:
Acrylic acid, methacrylic acid and crotonic acid;
Maleic acid, maleic anhydride, maleic acid monoester, maleic acid monoamide, reaction product of maleic acid with a diamine which may be oxidized to an amine oxide group-containing derivative, and fumaric acid, maleic acid, anhydrous Maleic acid and maleic acid monoamide are preferred;
Vinyl aromatic compounds such as styrene, methylstyrene and vinyl toluene; ethylene, propylene, isobutene, diisobutene and butadiene; vinyl ethers such as polyethylene glycol monovinyl ether; vinyl esters of linear or branched monocarboxylic acids such as vinyl acetate and vinyl Propionates; alkyl and aryl esters of ethylenically unsaturated monocarboxylic acids, in particular acrylic and methacrylic esters, such as methyl-, ethyl-, propyl-, isopropyl-, butyl-, pentyl-, hexyl-, 2-ethylhexyl-, nonyl-, lauryl- and hydroxyethyl- (meth) acrylates and phenyl-, naphthyl- and benzyl (meth) acrylates; Dialkyl esters of renically unsaturated dicarboxylic acids such as dimethyl-, diethyl-, dipropyl-, diisopropyl-, dibutyl-, dipentyl-, dihexyl-, di-2-ethylhexyl-, dinonyl-, dilauryl- and di-2-hydroxy Preference is given to ethyl maleate and -fumarate; vinyl pyrrolidone; acrylonitrile and methacrylonitrile, styrene, isobutene, diisobutene, acrylates and polyethylene glycol monovinyl ether.

  In particular, polyacrylic acid should be mentioned as an example for an advantageous homopolymer of these monomers.

  The described copolymer of monomers may be composed of two or more, in particular three different monomers. There may be random copolymers, alternating copolymers, block copolymers and graft copolymers. Preferred copolymers include 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 ( In each case, they may contain acrylate esters and / or maleates as additional monomer components).

  Advantageously, the carboxyl groups of the non-alkoxylated homopolymers and copolymers are present at least partly in the form of salts in order to ensure water solubility. Suitable are, for example, alkali metal salts, such as sodium and potassium salts, and ammonium salts.

Usually, it alkoxylated not polymeric additives (C2) has an average molecular weight _{M w} of the 900 to 250,000. The particularly suitable molecular weight range for an individual polymer will of course depend on its composition. In the following, for various polymers, molecular weight data are described by way of example: polyacrylic acid: 900-250,000 _Mw ; styrene / acrylic acid-copolymer: 1000-50000 _Mw ; acrylic acid / methacrylic acid-copolymer: 1000 _{M w} of ～250000; acrylic acid / maleic acid - copolymer: from 2000 to 70000 of _M w.

  In addition to these homopolymers and copolymers themselves, their alkoxylation products are of particular importance as additives (C2).

  This is to be understood according to the invention, in particular as a polymer which is partly (to the extent possible) completely esterified with polyether alcohols. Generally, the degree of esterification of these polymers is 30 to 80 mol%.

Suitable for esterification are in particular the polyether alcohols themselves, preferably polyethylene glycols and polypropylene glycols, and their end-capped derivatives, in particular the corresponding monoethers such as monoaryl ethers such as monophenyl. Conversion of the terminal OH groups of ethers and in particular mono-C ₁ -C ₂₆ -alkyl ethers, such as ethylene- and propylene glycol etherified with fatty alcohols, and corresponding polyether alcohols, or preferably first It is a polyetheramine that can be produced by polyaddition of alkylene oxides to secondary aliphatic amines. Preference is given here to polyethylene glycol, polyethylene glycol monoethers and polyetheramines. Usually, the average molecular weight _Mn of the polyether alcohol and its derivative used is 200-10000.

  By controlling the ratio of polar groups to nonpolar groups, the surface activity characteristics of the additive (C2) can be set according to the purpose.

Such anionic surface active additives (C2) are also known and are, for example, Sokalan ^(R) (BASF), Joncryl ^(R) (Johnson Polymer), Alcosperse ^(R) (Alco), Geronpon ^(R) (Rhodia), Good-Rite ^(R) (Goodrich), Neoresin ^(R) (Avecia), Orotan ^(R) and Morez ^(R) (Rohm & Haas), Disperbyk ^(R) (Byk) and Tegospers ^(R) Goldschmidt) is obtained commercially.

  As an anionic surface active additive, the pigment formulation according to the invention may further contain a polyurethane-based (C3) additive.

  In that case, the concept of polyurethane according to the present invention is not only a pure reaction product of a polyvalent isocyanate (C3a) and an organic compound (C3b) containing an isocyanate-reactive hydroxy group, but also other isocyanate reactivity. It should also be understood that the reaction product is additionally functionalized by the addition of a compound, for example a carboxylic acid having a primary or secondary amino group.

  These additives are characterized by their low ionic conductivity and their neutral pH value compared to other surface active additives.

  Diisocyanates are particularly suitable as polyisocyanates (C3a) for the preparation of additives (C3), but compounds having 3 or 4 isocyanate groups can also be used. Aliphatic isocyanates can be used as well as aromatic isocyanates.

  The following are described as examples for advantageous di- and triisocyanates: 2,4-toluylene diisocyanate (2,4-TDI), 4,4′-diphenylmethane diisocyanate (4,4′-MDI) , P-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, trimethylhexa 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).

  Of course, mixtures of isocyanates (C3a) can also be used. For example, mention may be made here of: mixtures of structural isomers of 2,4-toluylene diisocyanate and triisocyanatotoluene, for example 80 mol% of 2,4-toluylene diisocyanate and 20 mol of 2.6-toluylene diisocyanate A mixture from cis-cyclohexane-1,4-diisocyanate and trans-cyclohexane-1,4-diisocyanate; 2,4-toluylene diisocyanate or 2,6-toluylene diisocyanate and aliphatic diisocyanates such as hexa Mixtures with methylene diisocyanate and isophorone diisocyanate.

  A compound having at least two isocyanate-reactive hydroxy groups per molecule is preferably used as the isocyanate-reactive organic compound (C3b). However, compounds having only one isocyanate-reactive hydroxy group per molecule are also suitable as compound (C3b). These monofunctionalized compounds may partially or even fully replace compounds containing at least two isocyanate-reactive hydroxy groups per molecule upon reaction with polyisocyanate (C3a).

  In the following, examples for particularly advantageous isocyanate-reactive compounds (C3b) having at least two isocyanate-reactive hydroxy groups per molecule are described.

  It is a polyether diol, polyester diol, lactone based polyester diol, diols and triols with 12 C atoms, dihydroxy carboxylic acid, dihydroxy sulfonic acid, dihydroxy phosphonic acid, polycarbonate diol, polyhydroxy olefin and on average at least per molecule It is a polysiloxane having two hydroxy groups.

For example, a suitable polyether diols (C3b) are, C 2 _-C 4 _- alkylene oxide such as ethylene oxide, propylene oxide and butylene oxide, tetrahydrofuran, a homopolymer and copolymers of styrene oxide and / or epichlorohydrin, they Obtained in the presence of a suitable catalyst, such as boron trifluoride. Further suitable polyether diols are those compounds which start compounds having at least two acidic hydrogen atoms, such as water, ethylene glycol, thioglycol, mercaptoethanol, 1,3-propanediol, 1,4-butanediol, 1 , 6-hexanediol, 1,12-dodecanediol, ethylenediamine, aniline or (co) polymerization in the presence of 1,2-di- (4-hydroxyphenyl) propane.

  Examples for particularly suitable polyether diols (C3b) are polyethylene glycol, polypropylene glycol, polybutylene glycol and polytetrahydrofuran and copolymers thereof.

The molecular weight M _n of the polyether diol is preferably from 250 to 5000, particularly preferably from 500 to 2500.

  Polyester diols (hydroxypolyesters) suitable as isocyanate-reactive compounds (C3b) are generally known.

  Preferred polyester diols (C3b) are the reaction products of diols with dicarboxylic acids or their reactive derivatives such as anhydrides or dimethyl esters.

  Suitable dicarboxylic acids are saturated and unsaturated aliphatic and aromatic dicarboxylic acids, which may have additional substituents such as halogens. Preferred aliphatic dicarboxylic acids are saturated unbranched α, ω-dicarboxylic acids containing 3 to 22, in particular 4 to 12 C atoms.

  Examples for particularly suitable dicarboxylic acids are: succinic acid, glutaric acid, adipic acid, corkic acid, azelaic acid, sebacic acid, 1,12-dodecanedicarboxylic acid, maleic acid, maleic anhydride, fumaric acid Acid, itaconic acid, phthalic acid, isophthalic acid, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, tetrachlorophthalic anhydride, endomethylenetetrahydrophthalic anhydride, terephthalic acid, terephthalic acid dimethyl ester and isophthalic acid dimethyl ester .

  Saturated and unsaturated aliphatic and alicyclic diols are particularly suitable as diols. Particularly preferred aliphatic α, ω-diols are unbranched and have 2 to 12, especially 2 to 8, in particular 2 to 4 C atoms. Preferred alicyclic diols are derived from cyclohexane.

  Examples for 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-ene-1,4- Diols, 2-butyne-1,4-diol and cis- and trans-1,4-di (hydroxymethyl) cyclohexane.

The molecular weight M _n of the polyester diol is preferably from 300 to 5000.

Lactone-based polyester diols suitable as isocyanate-reactive compounds (C3b) are in particular based on aliphatic saturated unbranched ω-hydroxycarboxylic acids having 4 to 22, preferably 4 to 8 C atoms. . Also suitable are branched ω-hydroxy carboxylic acids in which one or more —CH ₂ — groups in the alkylene chain are replaced by —CH (C ₁ -C ₄ -alkyl)-.

  Examples for advantageous ω-hydroxycarboxylic acids are γ-hydroxybutyric acid and δ-hydroxyvaleric acid.

  Of course, the above diols are also suitable as isocyanate-reactive compounds (C3b), with the same advantages as above.

  Also suitable as isocyanate-reactive compounds (C3b) are in particular triols having 3 to 12, especially 3 to 8 C atoms. An example for a particularly suitable triol is trimethylolpropane.

［式中、Ａ^１およびＡ^２は同じまたは異なるＣ_１〜Ｃ_４−アルキレン基を意味しかつ、Ｒは水素またはＣ_１〜Ｃ_４−アルキルである］のジヒドロキシカルボン酸である。 As dihydroxycarboxylic acids suitable as isocyanate-reactive compounds (C3b), especially aliphatic saturated dihydroxycarboxylic acids, preferably containing 4 to 14 C atoms, are particularly suitable. Very suitable is the formula

Wherein A ¹ and A ² are the same or different C ₁ -C ₄ -alkylene groups and R is hydrogen or C ₁ -C ₄ -alkyl].

  A particularly advantageous example for these dihydroxy carboxylic acids is dimethylolpropionic acid (DMPA).

  Furthermore, suitable dihydroxysulfonic acids and dihydroxyphosphonic acids, for example 2,3-dihydroxypropanephosphonic acid, are suitable as isocyanate-reactive compounds (C3b).

In so doing, the concept of dihydroxycarboxylic acid also encompasses compounds containing one or more carboxyl functional groups (or anhydride functional groups or ester functional groups). Such compounds are produced in a molar ratio of 2: 1 to 1.05: 1 by reaction of a dihydroxy compound with a tetracarboxylic dianhydride such as pyromellitic dianhydride or cyclopentanetetracarboxylic dianhydride. It is obtained in an addition reaction and preferably has an average molecular weight M _n of 500 to 10,000.

  Examples for suitable polycarbonate diols (C3b) are phosgene and excess diols, in particular unbranched saturated aliphatic α having 2 to 12, especially 2 to 8, in particular 2 to 4 C atoms. The reaction product with ω-diol should be mentioned.

  Polyhydroxyolefins suitable as isocyanate-reactive compounds (C3b) are in particular α, ω-dihydroxyolefins, with α, ω-dihydroxybutadiene being preferred.

Furthermore, polysiloxanes suitable as isocyanate-reactive compounds (C3b) contain on average at least two hydroxy groups per molecule. Particularly suitable polysiloxanes have on average 5 to 200 Si atoms (number average) and are especially substituted by C ₁ -C ₁₂ -alkyl groups, in particular methyl groups.

  Examples for isocyanate-reactive compounds (C3b) having only one isocyanate-reactive hydroxy group are in particular aliphatic, cycloaliphatic, araliphatic or aromatic monohydroxycarboxylic acids and sulfonic acids Is mentioned.

  Polyurethane base (C3) adducts are prepared by reaction of compounds (C3a) and (C3b), wherein the molar ratio of (C3a) to (C3b) is generally from 2: 1 to 1: 1, preferably 1.2 to 1: 1.2.

  In this case, in addition to the aforementioned isocyanate-reactive compound (C3b), further compounds having an isocyanate-reactive group such as dithiols, thioalcohols such as thioethanol, aminoalcohols such as ethanolamine and the like are possible. Adding N-methylethanolamine, or diamine, for example ethylenediamine, and thereby producing polyurethanes having in addition to urethane groups isocyanurate groups, allophanate groups, urea groups, biuret groups, uretdione groups or carbodiimide groups It is. Still other examples for such isocyanate-reactive compounds are aliphatic, cycloaliphatic, araliphatic or aromatic having at least two primary amino groups and / or secondary amino groups Carboxylic acids and sulfonic acids.

  Of course, corresponding compounds having only one isocyanate-reactive group, such as monoalcohols, primary and secondary monoamines, monoaminocarboxylic acids and monoaminosulfonic acids and mercaptans may also be added. The usual amount used is up to 10 mol% with respect to (C3a).

  Advantageously, the carboxyl group of the reaction product (C3) is present at least partially in the form of a salt to ensure water solubility. Suitable are alkali metal salts such as, for example, sodium and potassium salts, and ammonium salts.

Usually, the adduct (C3) has an average molecular weight _{M w} of the 500 to 250,000.

  By controlling the ratio of polar groups to nonpolar groups, the surface active properties of the adduct (C3) can be set to suit the purpose.

Such anionic surface active adduct (C3) are known and can be obtained under the name commercially for example ^{Borchi (R) GEN SN 95 (} Borchers).

  Water-soluble anionic surface-active adducts based on acidic phosphate esters, phosphonate esters, sulfate esters and / or sulfonate esters of polyethers (C4) are in particular the polyethers (C1) and phosphorus Based on the reaction products of acids, phosphorus pentoxide and phosphonic acid or sulfuric acid and sulfonic acid. In this case, the polyether is converted into the corresponding phosphoric acid monoester or phosphoric acid diester and phosphonic acid ester or sulfuric acid monoester and sulfonic acid ester. These acidic esters are preferably present in the form of water-soluble salts, in particular as alkali metal salts, in particular sodium salts and aluminum salts, however they can also be used in the free acid form.

  Preferred phosphates and phosphonates are derived in particular from alkoxylated, in particular ethoxylated, fatty and oxo alcohols, alkylphenols, fatty amines, fatty acids and resin acids, and preferred sulfates and sulfonates are in particular Based on alkoxylated, in particular ethoxylated, fatty alcohols, alkylphenols and amines, and also polyvalent amines such as hexamethylenediamine.

Such anionic surface-active adducts are known and include, for example, Nekal ^(R) (BASF), Tamol ^(R) (BASF), Crodafos ^(R) (Croda), Rhodafac ^(R) (Rhodia), Maphos ⁽ Mathos) ^R) (BASF), Texapon ^(R) (Cognis), Empicol ^(R) (Albright & Wilson), Matexil ^(R) (ICI), Soprophor ^(R) (Rhodia) and Lutensit ^(R) (BASF) Obtained commercially.

  Usually the colorant formulation has a content of dispersant (C) of 1 to 50% by weight, in particular 1 to 40% by weight.

  Water forms a liquid carrier material for the colorant formulation.

  Advantageously, the colorant formulation contains a mixture of water and a water retention agent as a liquid phase. In particular, organic solvents are used as water-retaining agents which are not easily vaporized (ie generally have a boiling point> 100 ° C.) and are therefore water-retaining and soluble in water or miscible with water.

Examples for suitable water-retaining agents are polyhydric alcohols, preferably unbranched and branched polyhydric alcohols having 2 to 8 C atoms, in particular 3 to 6, such as ethylene glycol, 1,2 -And 1,3-propylene glycol, glycerol, erythritol, pentaerythritol, pentitols such as arabitol, adonitol and xylitol, and hexitols such as sorbitol, mannitol and dulcitol. Furthermore, for example, di -, tri - and tetra alkylene glycols and their mono - (particularly _C 1 -C ₆ -, especially _C 1 -C ₄ -) are also suitable alkyl ether. For example, di-, tri- and tetraethylene glycol, diethylene glycol monomethyl-, -ethyl-, -propyl- and -butyl ether, triethylene glycol monomethyl-, -ethyl-, -propyl- and -butyl ether, di-, tri- and tetra -1,2- and -1,3-propylene glycol and di-, tri- and tetra-1,2- and -1,3-propylene glycol monomethyl-, -ethyl-, -propyl- and butyl ether.

  In general, the colorant formulation contains 10 to 88.95% by weight, preferably 10 to 80% by weight of the liquid phase (D). When water is present in a mixture with an organic solvent that retains water, this solvent will generally represent 1 to 80% by weight, preferably 1 to 60% by weight of phase (D).

  Furthermore, the colorant formulation contains further customary additives, such as insecticides, antifoaming agents, suspending agents and rheology modifiers, whose proportions can generally be up to 5% by weight as component (E). It's okay.

  Colorant formulations can be obtained in various ways. Preference is given first to the pigment dispersion which is then added to the dye as a solid or in particular in dissolved or liquid, in particular in aqueous, dispersed form.

  The colorant formulation can be added in various ways and at various points in the manufacturing process as a base for the mixture from wood fibers or sawdust and binder used for the wood material board according to the invention. In the case of advantageous MDF / HDF plates, they are preferably introduced directly into the sheet manufacturing process separately from or together with the adhesive via a blow line.

EXAMPLE Production of an MDF board according to the invention Example 1
In 5l container having a heating device to be adjusted with a) bleaching horseshoe stirrer and thermostat, wood fiber (spruce) 70 g and ethylenediaminetetraacetic acid ^{(Trilon (R) B, BASF} ) and 1g with stirring 70 ° C. in a water 3l Heated. Stir at 70-75 ° C. for 1 hour after the addition of 7 g of sodium percarbonate, then add 7 g of sodium dithionite and then stir at 70-75 ° C. for another 30 minutes.

  The pulp slurry (Holzstoffmaisch) was separated from the liquid components after cooling through a sieve having a mesh width of 1 mm at room temperature, washed in a short time while flowing water, and completely rolled. The spread filter material was then dried at 60 ° C. in a circulating air dryer (Umlufttrockenschrank) for 3 days.

b Coloring Bleached wood fibers are thoroughly mixed in a blade mixer and sprayed with the adhesive batch (Leimansatz) listed in the table below, where the batch also contains a gray pigment formulation of the composition indicated Contained.

  Subsequently, the fiber to which the adhesive had been applied was cast to form a mat, pre-compressed at a low temperature and pressed at 190 ° C. to form a plate.

  For comparison, an MDF board was produced from unbleached wood fibers by a processing method that could not be changed otherwise.

In both cases, a light gray MDF plate was obtained. However, the MDF board produced for comparison has a yellowish-brownish gray shade, while the MDF board according to the invention from bleached wood fibers is a light gray with no mixing. (Lightness difference ΔL ^* : 2 for comparison).

Example 2
The MDF pilot plant was loaded with wood chips from spruce wood (Fichtenholz) and the MDF production process was started at a flow rate of 21 kg / h. Immediately before being subjected to the refiner, a 20% by weight aqueous sodium dithionite solution corresponding to 5% sodium dithionite / atro fiber was pumped into the process.

  The resulting bleached wood fibers were sprayed continuously by means of a blow line with the adhesive batch described in Table 2 which contained a pigment formulation of the composition similarly indicated there.

  The glued wood fiber is dried to about 9% residual moisture in a connected continuous dryer, then poured discontinuously to form a mat and pre-compressed at low temperature. And it pressed with the press time coefficient of 15 s / mm at 190 degreeC, and formed the board of thickness 16mm.

In the case of MDF plates made with processing methods that were not bleached but not otherwise changed, a lightness difference ΔL ^{* of} 3 units was revealed.

Claims (9)

  Light woody board made from wood fibers that have been bleached and colored with a liquid colorant formulation containing at least one pigment and a dye that absorbs in the visible region of the electromagnetic spectrum.   The wood material board according to claim 1, wherein the wood fibers are first subjected to oxidative bleaching and then to reduction bleaching.   The wood material board according to claim 1 or 2, wherein the wood fiber is colored with a colorant blend containing 0.01 to 10% by mass of a dye with respect to the pigment. Wood fiber
(A) 10 to 70% by mass of at least one pigment,
(B) 0.05-7% by weight of at least one dye that absorbs in the visible region of the electromagnetic spectrum,
(C) 1-50% by weight of at least one dispersant,
(D) 10 to 88.95% by weight of water or a mixture of water and at least one water-retaining agent and (E) 0 to 5% by weight of other ingredients usual for colorant formulations.
The wood material board according to any one of claims 1 to 3, which is colored with a colorant blend containing   5. A wood material board according to any one of claims 1 to 4, wherein the wood fibers are colored with a colorant formulation at a standard color concentration of ≦ 1/9. The woody material board according to any one of claims 1 to 4, wherein the wood fibers are colored with a colorant formulation having a CIELAB brightness value L ^* ≥75.   The wood material board according to any one of claims 1 to 6, wherein the wood material board is an MDF board, an HDF board, or a particle board.   Use of the woody material according to any one of claims 1 to 7 for producing furniture.   A furniture containing the wood material board according to any one of claims 1 to 7.