EP1899427A1 - Light-colored engineered wood boards - Google Patents

Light-colored engineered wood boards

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Publication number
EP1899427A1
EP1899427A1 EP06777443A EP06777443A EP1899427A1 EP 1899427 A1 EP1899427 A1 EP 1899427A1 EP 06777443 A EP06777443 A EP 06777443A EP 06777443 A EP06777443 A EP 06777443A EP 1899427 A1 EP1899427 A1 EP 1899427A1
Authority
EP
European Patent Office
Prior art keywords
wood
pigment
acid
pigments
acids
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP06777443A
Other languages
German (de)
French (fr)
Inventor
Andres Carlos Garcia Espino
Juliane Krüsemann
Norbert Jäger
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from DE200510030788 external-priority patent/DE102005030788A1/en
Priority claimed from DE200610009479 external-priority patent/DE102006009479A1/en
Application filed by BASF SE filed Critical BASF SE
Publication of EP1899427A1 publication Critical patent/EP1899427A1/en
Withdrawn legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27N—MANUFACTURE BY DRY PROCESSES OF ARTICLES, WITH OR WITHOUT ORGANIC BINDING AGENTS, MADE FROM PARTICLES OR FIBRES CONSISTING OF WOOD OR OTHER LIGNOCELLULOSIC OR LIKE ORGANIC MATERIAL
    • B27N1/00—Pretreatment of moulding material
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D15/00—Woodstains

Definitions

  • the present invention relates to light colored engineered wood panels made from wood fibers bleached and dyed with liquid colorant formulations containing at least one pigment and at least one dye which absorbs in the visible region of the electromagnetic spectrum.
  • the invention relates to the use of these wood-based panels for the production of furnishings and furnishings that contain these wood-based panels.
  • MDF panels medium-density fibreboards
  • HDF panels high-density fibreboards
  • MDF and HDF boards can be processed like conventional chipboard. Due to their uniform structure, they are also suitable for the production of profiled parts and are therefore becoming increasingly popular in furniture construction. Thus, for example, furnishings for rooms and for decorative purposes (for example, in trade fair construction), but also higher-quality furniture made from these plates and then, in order to preserve the wood-like structure visible, only colorless or coated with overlay.
  • Wood-based panels in particular MDF panels, which have bright bright shades (L * ⁇ 75) even at high depths of color, for example yellow or orange, or are dyed to a shallow depth of shade, ie pastel shades, eg a neutral gray, are not yet known.
  • L * ⁇ 75 bright bright shades
  • JP-A-55-164142 particleboard are described, which are made of Hofzschnitzeln, which were first oxidatively bleached with sodium chlorite and then dyed with a direct dye. The bleaching is done here to improve the fürstobles- the wood chips, and it should be produced strong colors.
  • unpublished DE-A-10 2004 050 278 describes light to white wood-based panels made of bleached wood fibers and / or mass colored with a white pigment.
  • the invention therefore an object of the invention to provide light-colored wood-based panels available
  • wood-based panels which are made of wood fibers, which are bleached and dyed with liquid, pigment and dye-containing colorant preparations.
  • the wood-based panels according to the invention are distinguished by their pure, bright shades. These can be "white” mixed pastel shades, which can be obtained by dyeing in a standard color depth of ⁇ 1/9, in particular of ⁇ 1/25, or strong shades with brightness values L * > 75.
  • the wood-based panels according to the invention are e.g. MDF or HDF boards or chipboards, MDF boards are particularly preferred.
  • MDF and HDF boards are usually produced in a continuous process. This washed, water-moist, small chopped pieces of wood (wood chips) are first preheated to about 8O 0 C and then in a digester under a pressure of 2 to 5 bar and a temperature of 100 to 150 0 C geweicht. In the adjoining refiner the wood chips are then shredded.
  • the refiner consists of two metal discs with radial relief, which rotate close to each other in the opposite direction. The fibers write the refiner on the so-called blowline.
  • the glue is usually applied.
  • Urea-formaldehyde resins sometimes reinforced with melamine, or urea-melamine-formaldehyde resins for moisture-resistant boards, are usually used as binders.
  • Isocyanates are also used as binders.
  • the binders are usually applied to the fibers together with the desired additives (eg hardener, paraffin dispersion, colorant).
  • the glued fibers then pass through a dryer in which they are dried to humidities of 8 to 15 wt .-%. Occasionally, the dried fibers are also subsequently glued in special, continuously operating mixers. For chipboard production, the pre-dried chips are glued in continuous mixers.
  • the glued fibers or chips are then poured into mats, where appropriate ka t precompressed and pressed in a heated press at temperatures of 170-240 0 C to form plates.
  • Preferred base materials are light wood species, especially spruce or pine, but darker woods such as beech can also be used.
  • wood fibers used in the wood-based panels according to the invention are bleached
  • the coloring impurities of the wood are destroyed or rendered ineffective by oxidizing and / or reducing chemicals.
  • oxidative bleaching e.g. Hydrogen peroxide, ozone, oxygen, salts of halo-oxygen acids, such as chlorites, and salts of organic and inorganic peracids, such as peracetates, percarbonates and perborates, especially their alkali metal salts, in particular sodium salts, wherein the percarbonates and hydrogen peroxide are preferred.
  • reductive bleaching e.g.
  • reducing sulfur compounds such as dithionites, disulphites, sulfites or sulfur dioxide, sulfinic acids and their salts, in particular the alkali metal salts and, in particular, the sodium salts, and hydroxycarboxylic acids, such as citric acid and malic acid.
  • Preferred reducing agents are the disulfides and sulfites, in particular sodium hydrogen sulfite, as well as malic and citric acid.
  • wood fibers which have been firstly oxidatively and then reductively bleached are particularly preferred.
  • the oxidative bleaching is carried out with percarbonates or hydrogen peroxide and the reductive bleaching with sulfites or malic or citric acid.
  • bleaching is expediently carried out in such a way that aqueous, 5 to 40% by weight wood fiber dispersions are continuously poured into countercurrent at temperatures of 90 to 15O 0 C and pressures up to 3 bar treated with aqueous solutions or dispersions of bleach.
  • it is carried out in the presence of complexing agents, such as EDTA, to avoid the degradation of the bleaching agents by transition metal ions.
  • the bleaching of the fibers can be advantageously carried out during the board production.
  • the bleaching agents can be added to the wood chips in the preheater or in the cooker. Preferably also Kompiexsentner be added.
  • the wood fibers used in the wood-based panels according to the invention are dyed after bleaching with liquid colorant preparations containing at least one pigment and at least one in the visible range of the electromagnetic spectrum absorbing dye.
  • These colorant preparations generally contain 0.01 to 10 wt .-%, preferably 0.5 to 10 wt .-% of dye, based on the pigment.
  • colorant preparations particularly preferably contain
  • organic or inorganic pigments may be present in the colorant preparations.
  • the colorant preparations can also contain mixtures of various organic or various inorganic pigments or mixtures of organic and inorganic pigments.
  • the pigments are preferably present in finely divided form and accordingly usually have average particle sizes of 0.1 to 5 .mu.m, in particular 0.1 to 3 .mu.m and especially 0.1 to 1 .mu.m.
  • the organic pigments are usually organic colored and black pigments.
  • Inorganic pigments may also be color pigments (color, black and white pigments) and luster pigments.
  • Dtsazocondensation pigments Cl. Pigment Yetlow 93, 95 and 128;
  • Anthraquinone pigments Cl. Pigment Yellow 147, 177 and 199; Cl. Pigment Violet 31;
  • Anthrapyrimidine pigments Cl. Pigment Yellow 108;
  • Diketopyrrolopyrrole Pimgente Cl. Pigment Orange 71, 73 and 81;
  • Flavanthrone pigments Cl. Pigment Yeliow 24;
  • Indanthrope pigments CJ. Pigment Blue 60 and 64;
  • Phthalocyanine pigments Cl. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6 and 16;
  • Suitable inorganic color pigments are, for example:
  • White pigments titanium dioxide (CJ Pigment White 6), zinc white, colored zinc oxide;
  • Black pigments iron oxide black (CI Pigment Black 11), iron manganese black, spin black (CI Pigment Black 27); Carbon black (Cl.
  • Cobalt blue (CI Pigment Blue 28 and 36; CI Pigment Blue 72); Ultramarine blue; Manganese blue;
  • CJ Pigment Red 101 Iron oxide red
  • Cadmium sulphoselenide CI Pigment Red 108
  • Cerium sulphide CJ Pigment Red 265
  • Molybdate red CI Pigment Red 104
  • Iron oxide brown (CJ Pigment Brown 6 and 7), mixed brown
  • Cerium sulphide (CJ Pigment Orange 75);
  • Iron oxide yellow (CJ Pigment Yellow 42); Cotenite yellow (CJ Pigment Yeow 53, CI Pigment Yellow 157, 158, 159, 160, 161, 162, 163, 164 and 189); Chromium titanium yellow; Spinel phases (CI Pigment Yellow 119); Cadmium suicide and cadmium zinc sulfide (CJ Pigment Yellow 37 and 35); Chrome yellow (CJ Pigment Yellow 34); Bismuth vanadate (CJ Pigment Yellow 184).
  • the luster pigments are single-phase or multi-phase pixiliferous pigments whose color palette is characterized by the interplay of interference, reflection and absorption phenomena. Examples include aluminum flakes and one or more times, in particular aluminum oxide, iron oxide and mica flakes coated with metal oxides.
  • the colorant preparations contain from 10 to 70% by weight, preferably from 10 to 60% by weight, of pigment (A).
  • the colorant formulations contain at least one visible spectrum of the electromagnetic spectrum absorbing dye from the group of cationic dyes, anionic dyes and disperse dyes.
  • Particularly suitable dyes are those which are soluble in water or in a water-miscible or water-soluble organic solvent.
  • the dyes used (B) to the pigments (A) in each case comparable hue, since in this way a particularly intense coloration of the wood-based panels can be achieved even in light shades.
  • colorants (B) which deviate in color, as a result of which nuances of the coloration are possible.
  • cationic dyes particularly suitable are cationic dyes, anionic dyes and Disperstonsfarbstoffe.
  • direct dyes and disperse dyes are particularly suitable.
  • Suitable cationic dyes (B) are derived in particular from the di- and triary methane, xanthene, azo, cyanine, azacyanine, methine, acridine, safranine, oxazine, induline, nigrosine and phenazine series , wherein dyes from the azo, triarylmethane and xanthene series are preferred.
  • Cationic dyes (B) may also be colorants containing external basic groups. Suitable examples are here Ci. Basic Blue 15 and 161.
  • cationic dyes (B) it is also possible to use the corresponding color bases in the presence of solubilizing acidic agents. Examples given are: Cl. Solvent Yellow 34; Cl. Solvent orange 3; Cl. Solvent Red 49; Cl. Solvent Violet 8 and 9; Cl. Solvent Blue 2 and 4; Cl. Solvent Black 7.
  • Suitable anionic dyes are, in particular, sulfonic acid-containing compounds from the series of the azo, anthraquinone, metalic complex, triarylmethane, xanthene and stilbene series, dyes of the triarylmethane, azo and metal complex (especially copper, chromium and cobalt complex -) are preferred.
  • These dyes are especially water-soluble if they are present as alkali metal salt, especially lithium, sodium or potassium salt, or as unsubstituted or substituted ammonium salt, especially alkanolammonium salt.
  • Dispersäonsfarbstoffe are preferably used in the form of commercially available, aqueous dispersions and unfold their coloring effect in the manufacturing process of wood-based panels by diffusion at high temperatures.
  • Disperse dyes from the series of quinophthalones and anthraquinones are particularly suitable.
  • the colorant preparations contain the dye (B) generally in amounts of from 0.5 to 10% by weight, preferably from 1 to 8% by weight, in each case based on the pigment (A). Based on the total weight of the preparation, this corresponds to amounts of generally 0.05 to 7 wt .-%, especially 0.1 to 5.6 wt .-%.
  • Preferred pigment / dye combinations for light shades are, for example: Cl. Pigment Orange 34 and Cl. Direct Yellow 11; C I. Pigment Yeilow 74 and Cl. Direct Yellow 4.
  • Pure bright pastel shades are particularly by mixing white pigments, especially Cl. Pigment White 6, with nuanced color pigments, e.g. Cl. Pigment Black 7 and Cl. Basic Violet 3, to get. Heal shades of gray can advantageously also be obtained by shading the wetting pigment with appropriate dyes, e.g. blue dyes, such as Cl. Direct Blue 47, 67, 267 and 279, and / or violet dyes such as CJ. Direct Violet 35 and 51, and optionally yellow dyes, such as Ci. Direct Yeiiow 4, to be achieved.
  • the proportion of the white pigment is usually in each case 80 to 99 wt .-%, based on the total colorant amount.
  • At least one dispersing agent is contained in the colorant preparations.
  • Particularly suitable dispersants (C) are nonionic and anionic water-soluble surface-active additives.
  • nonionic additives (C) are based on polyethers (additives (C1)).
  • Enoxiden especially polyethylene oxides, polypropylene oxides, and poly (phenylethylenoxiden), here in particular block copolymers, in particular Poiypropylenoxid- and polyethylene oxide blocks or polymers comprising poly (phenylethylene oxide) and polyethylene oxide blocks, and also random copolymers of these alkylene oxides.
  • polyalkylene oxides can be substituted by polyaddition of the alkylene oxides onto starter molecules, such as saturated or unsaturated aliphatic and aromatic alcohols, phenol or naphthol, each substituted by alkyl, in particular C 1 -C 2 -cycloalkyl, preferably C 4 -C 2 2 or C 1 -C 4 -alkyl may be prepared, 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 per mo! Starter molecule used.
  • starter molecules such as saturated or unsaturated aliphatic and aromatic alcohols, phenol or naphthol, each substituted by alkyl, in particular C 1 -C 2 -cycloalkyl, preferably C 4 -C 2 2 or C 1 -C 4 -alkyl may be prepared, saturated or unsaturated aliphatic and
  • 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, isodecanoi, undecanol, dodecanol, 2-butyloctanol, tridecanol, isotridecanol, tetradecanol, pentadecanol, hexadecanol (cetyl alcohol), 2-hexy!
  • the saturated and unsaturated fatty alcohols which are obtained through the addition of fat 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.
  • aromatic alcohols examples include, in addition to unsubstituted phenol and .alpha.- and .beta.-naphthol, hexylphenol, heptyiphe ⁇ ol, octylphenof, nonynphenol, isononiphenol, undecylphenol, dodecylphenol, di- and tributhenol and dinonylphenol! called.
  • Suitable aliphatic amines correspond to the aliphatic alcohols listed above. Of particular importance are the saturated and unsaturated fatty acids. amines, which preferably have 14 to 20 carbon atoms. Examples of aromatic amines are aniline and its derivatives.
  • aliphatic carboxylic acids are particularly suitable saturated and unsaturated fatty acids, preferably containing 14 to 20 carbon atoms, and hydrogenated, partially hydrogenated and unhydrogenated resin acids, as well as polybasic carboxylic acids, e.g. Dicarboxylic acids, such as maleic acid.
  • Suitable carboxylic acid amides are derived from these carboxylic acids.
  • the alkylene oxide adducts to the monohydric amines and alcohols are of very particular interest,
  • bifunctional amines which are in particular of the formula H 2 N- (R 1 -NR 2 ) n -H (R 1 : C 2 -C 6 -alkyl, R 2 : hydrogen or d-ce) Alkyl; n: 1 to 5).
  • ethylenediamine diethylenetriamine, triethylenetetramine, tetraethylenepentamine, propylenediamine-1,3-dipropylenetriamine, 3-amino-1-ethyleneaminopropane, hexamethylenediamine, dihexamethylenediamine, 1,6-bis (3-aminopropyl) amino ) hexane and N-Methyidtpropylent ⁇ amin, with hexamethylenediamine and diethylenetriamine are particularly preferred and ethylenediamine is very particularly preferred.
  • these amines are first reacted with propylene oxide and then with ethylene oxide.
  • the content of the B ⁇ ockcopolymerisate of ethylene oxide is usually about 10 to 90 wt .-%.
  • the polybasic amine-based block copolymers generally have average molecular weights M n of from 1,000 to 40,000, preferably from 1,500 to 30,000.
  • di- to pentahydric alcohols are preferred.
  • examples are C 2 -C 6 -alkylene glycols and the corresponding di- and polyalkylene glycols, such as ethylene glycol, propylene glycol-1, 2 and 1,3, butylene glycol-1,2 and -1,4, hexylene glycol-1,6 Dipropylene glycol and polyethylene glycol, glycerol and pentaerythritol, ethylene glycol and polyethylene glycol being particularly preferred, and propylene glycol! and dipropylene glycol are most preferred.
  • Particularly preferred Alkylenoxidaddukte to at least bifunctional alcohols have a central Polypropyienoxidblock, so go from a Propylengiykol or poly propylene glycol, which is reacted first with more propylene oxide and then with ethylene oxide.
  • the content of the block copolymers of ethylene oxide is usually from 10 to 90% by weight.
  • the polyhydric alcohol block copolymers generally have average molecular weights M n of from 1,000 to 20,000, preferably from 1,000 to 15,000.
  • AI kyienoxid block copolymers are known and commercially available, for example under the name Tetronic ® and Pluronic ® (BASF).
  • water-soluble anionic surface active agents which are particularly suitable as component (C) are additives based on polymers of ethylenically unsaturated carboxylic acids (C2), additives based on polyurethanes (C3) and additives based on acidic phosphoric acid, phosphonic acid, Sulfuric acid and / or Sulfonklam the above polyether (C4) mentioned.
  • mixtures of several additives that is to say both mixtures of different nonionic additives and mixtures of various anionic additives and also mixtures of nonionic and anionic additives.
  • Suitable anionic, water-soluble surface-active additives based on polymers of unsaturated carboxylic acids (C2) are, in particular, additives from the group of the homopolymers and copolymers of ethylenically unsaturated monocarboxylic acids and / or ethylenically unsaturated dicarboxylic acids which additionally contain polymerized vinyl monomers which contain no acid function can, the alkoxylation of these homo- and copolymers and the salts of these homo- and copolymers and their Aikoxyljêts occur.
  • Vinyl aromatics such as styrene, methylstyrene and vinyltoluene; 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 propionate; Alkyl esters and aryl esters of ethylenically unsaturated monocarboxylic acids, in particular acrylic and methacrylic acid esters, such as methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, 2-ethylhexyl, nonyl, lauryl and hydroxycarboxylic acids; xyethyl (meth) acrylate and phenyl, naphthyl and benzyl (meth) acrylate; Dialkyl esters of ethylen
  • Examples of preferred homopolymers of these monomers are, in particular, polyacrylic acids.
  • the copolymers of the monomers mentioned may be composed of two or more, in particular three, different monomers. They may be random copolymers, alternating copolymers, block copolymers and graft copolymers.
  • Preferred copolymers are styrene / acrylic acid, acrylic acid / maleic acid, acrylic acid / methacrylic acid, butadiene / acrylic acid, isobutene / maleic acid, diisobutene / maleic acid and styrene / malonic acid copolymers, which are each acrylic acid ester as additional monomer constituents and / or or maleic acid esters may be mentioned.
  • the carboxyl groups of the non-alkoxylated homopolymers and copolymers are at least partially in salt form in order to ensure water-solubility.
  • Suitable examples are the Aikalimetallsalze, such as sodium and potassium salts, and the ammonium salts.
  • the non-aoxylated polymeric additives (C2) have average molecular weights M w of from 900 to 250,000.
  • 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 1 000 to 50 000; Acrylic acid / methacrylic acid copolymers: M w from 1,000 to 250,000; Acrylic acid / maleic acid copolymers: M w from 2,000 to 70,000.
  • these include in particular the partially to (as far as is possible) completely polymerized with polyether alcohols polymers.
  • the degree of esterification of these polymers is 30 to 80 mol%.
  • polyether alcohols themselves, preferably polyethylene glycols and polypropylene glycols, and their one-sided end group-capped derivatives, in particular the corresponding monoethers, such as monoarylethers, eg monophenyiethers, and in particular mono-C 1 -C -alkyl ethers, for example ethylenediols and propyleneglycols etherified with fatty alcohols, and the polyetheramines which are obtained, for example, by conversion of a terminal OH- Group of the corresponding Pofyetherai- alcohols or by Poiyadd ⁇ tion of alkylene oxides to preferably primary aliphatic see amines can be produced.
  • Polyethylene glycols, polyethylene glycol ethers 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.
  • the surface-active properties of the additives (C2) can be adjusted in a targeted manner.
  • anionic surface-active additives are also known and commercially available for example under the name Sokalan ® (BASF), Joncryl ® ⁇ Johnson Polymer), Aicosperse ® (Alco), Geropon ® (Rhodia), Good-Rite ® (Goodrich) Neoresin ® (Avecia), Orotan ® and Morez ® (Rohm & Haas), Disperbyk ® (Byk) and Tegospers ® (Goldschmidt) available.
  • the pigment preparations according to the invention may furthermore contain polyurethane-based additives (C3).
  • polyurethane is to be understood as meaning not only the pure reaction products of polyfunctional isocyanates (C3a) with isocyanate-reactive organic compounds (C3b) containing isocyanate-reactive groups, but also those reaction products obtained by the addition of further isocyanate-reactive compounds, e.g. of primary or secondary amino-bearing carboxylic acids are additionally functionalized.
  • additives are distinguished from other surface-active additives by their low ionic conductivity and their neutral pH.
  • Suitable polyfunctional isocyanates (C3a) for the preparation of the additives (C3) are in particular diisocyanates, but it is also possible to use compounds having three or four isocyanate groups. Both aromatic and aliphatic isocyanates can be used.
  • di- and triisocyanates examples include: 2,4-tolylene diisocyanate (2,4-TDI), 4,4'-diphenylmethane diisocyanate (4,4'-MDI), para-xylylene diisocyanate, 1,4-diisocyanatobenzene , Tetramethylxiyl diisocyanate (TMXDI), 2,4'-diphenylmethane diisocyanate (2,4'-MDI) and triisocyanatotoluene and isophorone diisocyanate (IPDI),
  • mixtures of isocyanates can also be used.
  • mixtures of structural isomers of 2,4-toluene diisocyanate and triisocyanato toluene e.g. Mixtures of 80% by mole of 2,4-tolylene diisocyanate and 20% by mole of 2,6-toluethylene diisocyanate; Mixtures of cis- and trans-cyclohexane-1,4-diisocyanate; Mixtures of 2,4- or 2,6-tofuylene diisocyanate with aliphatic diisocyanates such as hexamethylene diisocyanate and isophorone diisocyanate.
  • Suitable isocyanate-reactive organic compounds (C3b) are preferably compounds having at least two isocyanate-reactive hydroxyl groups per molecule. However, suitable compounds (C3b) are also compounds which have only one isocyanate-reactive hydroxy group per molecule. These m ⁇ ofunktionaüsäerten compounds, the at least two isoeyanatreepte hydroxy groups per molecule containing compounds in the reaction with the polyisocyanate (C3a) partially or completely replace.
  • C3b particularly preferred isocyanate-reactive compounds having at least two isocyanate-reactive hydroxy groups per molecule.
  • polyethers polyesterdiols, lactone-based polyesterdiols, diols and triols having up to 12 carbon atoms, dihydroxycarboxylic acids, dihydroxysulphonic acids, dihydroxyphosphonic acids, polycarbonatediols, polyhydroxyolefans and polysialoxanes having on average at least two hydroxyl groups per molecule.
  • Suitable polyethers (C3b) 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, which are reacted in the presence of a suitable catalyst, e.g. Boron trifluoride, are available. Further suitable polyethers are by (co) polymerization of these compounds in the presence of a starter having at least two normal hydrogen atoms, e.g.
  • polyethers (C3b) are polyethylene glycol, polypropylene glycol, polybutylene glycol and polytetrahydrofuran, and also copolymers thereof.
  • the molecular weight M n of the polyether diols is preferably 250 to 5,000, more preferably 500 to 2,500.
  • Polyester diols (hydroxypolyesters) suitable as isocyanate-reactive compound (C3b) are well known.
  • Preferred polyester dioxides (C3b) are the reaction products of diols with dicarboxylic acids or their reactive derivatives, e.g. Anhydrides or dimethyesters.
  • Suitable dicarboxylic acids are saturated and unsaturated aliphatic and aromatic dicarboxylic acids which may carry additional substituents, such as halogen.
  • Preferred aliphatic dicarboxylic acids are saturated unbranched ⁇ , ⁇ -dicarboxylic acids containing 3 to 22, especially 4 to 12, carbon atoms.
  • dicarboxylic acids examples include: succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, 1,12-dodecanedicarboxylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, phthalic acid, isophthalic acid, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, tetrachlorophthalic anhydride, endomethylenetetrahydrophthalic anhydride - drid, terephthalic acid, terephthalic acid dimethyl ester and isophthalic acid dimethylester.
  • Particularly suitable diols are saturated and unsaturated aliphatic and cycloaliphatic diols.
  • the particularly preferred aliphatic ⁇ . ⁇ -Dioie are unbranched and have 2 to 12, in particular 2 to 8, especially 2 to 4 C-atoms.
  • Preferred cycloaliphatic dioxides are derived from cyclohexane.
  • diols examples include: 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-diol, 2-butyne-1, 4-dioi and cis- and trans-1 , 4-di (hydroxymethyl) cyclohexane.
  • the molecular weight M n of the polyester film is preferably 300 to 5,000.
  • Lactone-based polyester diols suitable as isocyanate-reactive compound (C3b) are based in particular on aliphatic saturated unbranched ⁇ -hydroxycarboxylic acids having 4 to 22, preferably 4 to 8, carbon atoms. Also suitable are branched ⁇ - hydroxy carboxylic acids in which one or more -CH 2 groups in the alkylene chain by -CH (Ci-C 4 alkyl) - are replaced.
  • ⁇ -hydroxycarboxylic acids examples include ⁇ -hydroxybutyric acid and ⁇ -hydroxyvaleric acid.
  • Dioie a isocyanate-reactive compounds (C3b), where the same preferences apply as above,
  • isocyanate-reactive compounds C3b
  • triols which, in particular, have 3 to 12, above all 3 to 8 C atoms. Step Example! a particularly suitable triol is trimethylolpropane.
  • Dihydroxycarboxylic acids which are suitable as isocyanate-reactive compounds (C3b) are, in particular, particularly suitable aiiphatic saturated dihydroxycarboxylic acids which preferably contain 4 to 14 C atoms. Especially suitable are dihydroxycarboxylic acids of the formula
  • a 1 and A 2 are the same or different C 1 -C 4 -alkylene radicals and R is hydrogen or C 1 -C 4 -alkyl.
  • DMPA dimethylolpropionic acid
  • isocyanate-reactive compounds C3b
  • dihydroxysulfonic acids and dihydroxyphosphonic acids such as 2,3-dihydroxypropane-phosphonic acid.
  • dihydroxycarboxylic acid is intended to include compounds which contain more than one carboxyl function (or anhydride or ester function). Such compounds are obtainable by reacting dihydroxy compounds with tetracarboxylic dianhydrides, such as pyromelitic dianhydride or cyclopentanetetracarboxylic dianhydride, in a molar ratio of 2: 1 to 1:05 in a polyaddition reaction and preferably have an average molecular weight M n of from 500 to 10,000.
  • tetracarboxylic dianhydrides such as pyromelitic dianhydride or cyclopentanetetracarboxylic dianhydride
  • Suitable polycarbonate diols (C3b) are the reaction products of phosgene with an excess of diols, in particular unbranched saturated aliphatic ⁇ , ⁇ -diols having 2 to 12, especially 2 to 8, especially 2 to 4 carbon atoms.
  • Suitable as isocyanate-reactive compound (C3b) are polyhydroxyolefins ⁇ before aiiern, ⁇ -dihydroxy olefins, said ⁇ - ⁇ f dihydroxybutadienes are preferred.
  • the further suitable as isocyanate-reactive compound (C3b) polysiloxanes contained in the middle! at least two hydroxy groups per moieküi.
  • Particularly suitable polysiloxanes comprise on average 5 to 200 silicon atoms (number average) and are mainly with Ci-Ci 2 alkyl groups, especially methyl groups.
  • isocyanate-reactive compounds (C3b) which have only one isocyanate-reactive hydroxy group include, in particular, aliphatic, cycloaliphatic, araliphatic or aromatic monohydroxycarboxylic acids and -sulfonic acids.
  • the polyurethane-based additives (C3) are prepared by reacting the compounds (C3a) and (C3b), wherein the molar ratio of (C3a) to (C3b) is usually 2: 1 to 1: 1, preferably 1, 2: 1 to 1: 1.2.
  • isocyanate-reactive compounds C3b
  • further compounds with isocyanate-reactive groups for example dithiols, thioalcohols, such as thioethanol, amino alcohols, such as ethanolamine and N-methylethanolamine, or diamines, such as ethylenediamine, and thereby produce polyurethanes which, in addition to the urethane groups, also carry isocyanurate groups, allophanate groups, urea groups, biuret groups, uretdione groups or carbodiimide groups.
  • isocyanate-reactive compounds are aliphatic, cycloaliphatic, araliphatic or aromatic carboxylic acids and sulfonic acids which carry at least two primary and / or secondary amino groups.
  • the carboxy groups of the reaction products (C3) are at least partially in salt form to ensure water solubility.
  • Suitable examples are alkali metal salts, such as sodium and potassium salts, and ammonium salts.
  • the additives (C3) have average molecular weights M w of 500 to 250,000.
  • the surface-active properties of the additives (C3) can be adjusted in a targeted manner.
  • anionic surface-active additives are known and commercially available, for example under the name Borchi ® GEN SN95 (Borchers).
  • Water-soluble anionic surface-active additives based on acidic phosphoric acid, phosphonic acid, sulfuric acid and / or sulfonic acid esters of polyesters (C4) are based in particular on the reaction products of the abovementioned polyethers (C1) 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 suifonic acid esters.
  • These acidic 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 derived primarily from alkoxylated, in particular ethoxylated, fatty and oxo alcohols, Aikylphenolen, fatty amines, fatty acids and resin acids, preferred sulfates and sulfonates are based in particular on alko- xyl faced, especially ethoxylated, fatty alcohols, Aikylphenolen and amines, also polyhydric amines, such as hexamethylenediamine.
  • 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), Matextl ® (ICI), Soprophor ® (Rhodia) and Lutensit ® (BASF).
  • Nekal ® BASF
  • Tamol ® BASF
  • Crodafos ® Crodafos ® (Croda)
  • Rhodafac ® Rhodia
  • Maphos ® BASF
  • Texapon ® Cognis
  • Empicol ® Albright & Wilson
  • Matextl ® ICI
  • Soprophor ® Rosit ®
  • Lutensit ® BASF
  • the colorant preparations usually have a content of dispersant (C) of from 1 to 50% by weight, in particular from 1 to 40% by weight.
  • Water forms the liquid carrier material of the colorant preparations.
  • the colorant formulations contain a mixture of water and a water retention agent as the liquid phase.
  • water-retaining agents in particular organic solvents have high boiling points are used (ie usually a boiling point> 100 0 C have), therefore water back reserved, and are miscible in water soluble or water.
  • suitable water retention agents are polyhydric alcohols, preferably unbranched and branched polyhydric alcohols having 2 to 8, in particular 3 to 6, carbon atoms, such as ethylene glycol, 1,2- and 1,3-propylene glycol, glycerol, erythritol, pentaerythritol, Pentites such as arabitol, adonite and xylitol, and hexites such as sorbitol, mannitol and dulctt.
  • Examples of these are di-, tri- and tetraethylene glycol, diethylene glycol monomethyl ethyl, propyl and butyl ethers, triethylene glycol monomethyl, ethyl, propyl and butyl ethers, di-, tri- and tetra-1, 2- and -1, 3-propylene glycol and di-, tri- and tetra-1, 2- and -1, 3-propylene glycol monomethyl, called -ethyi-, -propyl- and -butyiether.
  • the colorant preparations generally contain from 10 to 88.95% by weight, preferably from 10 to 80% by weight, of liquid phase (D). If water is present in a mixture with a water-retaining organic solvent, this solvent generally constitutes from 1 to 80% by weight, preferably from 1 to 60% by weight, of phase (D).
  • colorant preparations as component (E) may contain conventional additives, such as biocides, defoamers, anti-settling agents and rheology modifiers, the proportion of which may generally be up to 5% by weight.
  • the colorant preparations can be obtained in various ways.
  • a pigment dispersion is first prepared, to which the dye is then added as a solid or in particular in dissolved or in liquid, in particular aqueous, phase-dispersed form.
  • the colorant preparations can be added to the mixture of wood fibers or chips and binder used as a basis for the wood-based panels according to the invention in various ways and at different points in the fabrication process.
  • they are advantageously introduced directly into the plate making process via the blowline, separate from or together with the glue.
  • the bleached wood fibers were mixed in a paddle mixer and sprayed with the glue formulation listed in the following table, which contained a gray pigment preparation of the composition likewise indicated there.
  • the glued fibers were then poured into a mat, precompressed cold and pressed at 19O 0 C to a plate.
  • an MDF board was made of unbleached wood fibers with an otherwise unchanged procedure.
  • An MDF plant was fed with wood chips from spruce and the MDF production process was started at a rate of 21 kg / h. Immediately before the refiner a 20 wt .-% aqueous sodium dithionite, corresponding to 5% Nat ⁇ umdithionit atro fibers, was pumped into the process.
  • the resulting bleached wood fibers were continuously sprayed by the blowline with the flax formulation listed in Table 2, which contained a gray pigment preparation of the composition also indicated there.
  • the ismeimten wood fibers were dried in the subsequent continuous dryer to a residual moisture content of about 9 wt .-% and then poured discontinuously into a mat kaft precompressed and at 19O 0 C with a pressing time factor of 15 s / mm to a 16 mm thick plate pressed.

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Abstract

The invention relates to light-colored engineered wood boards produced from wood fibers that are bleached and dyed with liquid dye preparations. Said preparations comprise at least one pigment and at least one dye that absorbs light in the visible range of the electromagnetic spectrum.

Description

Hellfarbige Holzwerkstoffplatten Light colored wood-based panels
Beschreibungdescription
Die vorliegende Erfindung betrifft hellfarbige Holzwerkstoffplatten, die aus Holzfasern hergestellt sind, die gebleicht und mit flüssigen Farbmittelzubereitungen, enthaltend mindestens ein Pigment und mindestens einen im sichtbaren Bereich des elektromagnetischen Spektrums absorbierenden Farbstoff, gefärbt sind.The present invention relates to light colored engineered wood panels made from wood fibers bleached and dyed with liquid colorant formulations containing at least one pigment and at least one dye which absorbs in the visible region of the electromagnetic spectrum.
Außerdem betrifft die Erfindung die Verwendung dieser Holzwerkstoff platten zur Herstellung von Einrichtungsgegenständen sowie Einrichtungsgegenstände, die diese Holzwerkstoffplatten enthalten.In addition, the invention relates to the use of these wood-based panels for the production of furnishings and furnishings that contain these wood-based panels.
Im Bereich der Holzwerkstoffe ist der Markt an sog. mitteldtchten Faserplatten (medium density fibreboard, MDF-Platten) und hochverdichteten Faserplatten (high density fibreboard, HDF-Platten) stark im Anstieg begriffen. Die Produktionsmengen haben sich in den letzten zehn Jahren mehr als verdreifacht.In the field of wood-based panels, the market for so-called medium-density fibreboards (MDF panels) and high-density fibreboards (HDF panels) is growing rapidly. The production volumes have more than tripled in the last ten years.
MDF- und HDF-Piatten können wie herkömmliche Spanplatten verarbeitet werden. Durch ihren gleichmäßigen Aufbau sind sie aber auch zur Herstellung von profilierten Teilen geeignet und setzen sich deshalb verstärkt im Möbelbau durch. So werden beispielsweise Einrichtungsgegenstände für Räume und für dekorative Zwecke (z.B. im Messebau), aber auch schon höherwertige Möbel aus diesen Platten gefertigt und anschließend, um die holzartige Struktur sichtbar zu erhalten, nur noch farblos lackiert oder mit Overlay beschichtet.MDF and HDF boards can be processed like conventional chipboard. Due to their uniform structure, they are also suitable for the production of profiled parts and are therefore becoming increasingly popular in furniture construction. Thus, for example, furnishings for rooms and for decorative purposes (for example, in trade fair construction), but also higher-quality furniture made from these plates and then, in order to preserve the wood-like structure visible, only colorless or coated with overlay.
Naturgemäß besitzen diese Platten, je nach verwendeter Holzart, eine mehr oder weniger ausgeprägte braune Färbung, die für eine Anwendung im Möbelbereich nur von geringem ästhetischen Wert ist.Naturally, these boards, depending on the type of wood used, a more or less pronounced brown color, which is of little aesthetic value for an application in the furniture sector.
Durch Massefärbung mit den aus der WO-A-04/35276 bekannten Pigment und Farbstoff enthaltenden Farbmtttelzubereiiungen kann die Eigenfärbung der Holzfasern im Bereich dunkler Farbtöne und bei hohen Farbtiefen kompensiert werden. Auf diese Weise sind bunte, vollständig durchgefärbte, lichtechte und damit ästhetisch hochwer- tige MDF-Platten zu erhalten, die zur Herstellung langlebiger Artikel, z.B. von Möbeln für den Wohnbereich, geeignet sind.By mass coloration with the known from WO-A-04/35276 colorant and Farbmtttelzubereiiungen the intrinsic color of the wood fibers in the range of dark hues and high color depths can be compensated. In this way, it is possible to obtain colorful, completely colored, light-fast and therefore aesthetically high-quality MDF boards which are suitable for producing durable articles, e.g. of furniture for the living area, are suitable.
Holzwerkstoffplatten, insbesondere MDF-Platten, die auch bei hohen Farbtiefen brillante helle Farbtöne (L* ≥ 75) aufweisen, z.B. gelb oder orange gefärbt sind, oder in ge- ringer Farbtiefe gefärbt sind, d.h. aufgehellte Pastellfarbtöne, z.B. ein neutrales Grau, aufweisen, sind bislang jedoch nicht bekannt. Für die Herstellung von Möbeln und Innendekorationsobjekten z.B. für Küche oder Bad wären diese Platten aber von besonderem Interesse. In der JP-A-55- 164142 sind Spanplatten beschrieben, die aus Hofzschnitzeln hergestellt sind, die zunächst mit Natriumchlorit oxidativ gebleicht und dann mit einem Direktfarbstoff gefärbt worden sind. Die Bleichung wird hier zur Verbesserung der Durchfärb- barkeit der Holzschnitzel vorgenommen, und es sollen kräftige Farben erzeugt werden.Wood-based panels, in particular MDF panels, which have bright bright shades (L * ≥ 75) even at high depths of color, for example yellow or orange, or are dyed to a shallow depth of shade, ie pastel shades, eg a neutral gray, are not yet known. For the production of furniture and interior decoration objects such as kitchen or bathroom but these plates would be of particular interest. In JP-A-55-164142 particleboard are described, which are made of Hofzschnitzeln, which were first oxidatively bleached with sodium chlorite and then dyed with a direct dye. The bleaching is done here to improve the Durchstobbarkeit- the wood chips, and it should be produced strong colors.
Schließlich werden in der nichtvorveröffentlichten DE-A-10 2004 050 278 helle bis weiße Holzwerkstoffplatten beschrieben, die aus gebleichten Holzfasern hergestellt und/oder mit einem Weißpigment massegefärbt sind.Finally, unpublished DE-A-10 2004 050 278 describes light to white wood-based panels made of bleached wood fibers and / or mass colored with a white pigment.
Der Erfindung lag daher die Aufgabe zugrunde, hellfarbige Holzwerkstoff platten zur Verfügung zu stellenThe invention therefore an object of the invention to provide light-colored wood-based panels available
Demgemäß wurden hellfarbige Holzwerkstoffplatten gefunden, die aus Holzfasern her- gestellt sind, die gebleicht und mit flüssigen, pigment- und farbstoffhaltigen Farbmittelzubereitungen gefärbt sind.Accordingly, light-colored wood-based panels were found, which are made of wood fibers, which are bleached and dyed with liquid, pigment and dye-containing colorant preparations.
Die erfindungsgemäßen Holzwerkstoffplatten zeichnen sich durch ihre reinen hellen Farbtöne aus. Dabei kann es sich um mit Weiß abgemischte "zarte" Pastellfarbtöne, die durch Färben in einer Standardfarbtiefe von < 1/9, insbesondere von < 1/25, erzielt werden können, oder um kräftige Farbtöne mit Helligkeitswerten L* > 75 handeln.The wood-based panels according to the invention are distinguished by their pure, bright shades. These can be "white" mixed pastel shades, which can be obtained by dyeing in a standard color depth of <1/9, in particular of <1/25, or strong shades with brightness values L * > 75.
Die erfindungsgemäßen Holzwerkstoffplatten sind z.B. MDF- oder HDF-Platten oder Spanplatten, Besonders bevorzugt sind MDF-Piatten.The wood-based panels according to the invention are e.g. MDF or HDF boards or chipboards, MDF boards are particularly preferred.
MDF- und HDF-Platten werden üblicherweise in einem kontinuierlichen Prozeß hergestellt. Dabei werden gewaschene, wasserfeuchte, klein zerhackte Holzstücke (Hackschnitzel) zunächst auf ca. 8O0C vorgewärmt und dann in einem Kocher unter einem Druck von 2 bis 5 bar und einer Temperatur von 100 bis 1500C geweicht. In dem sich anschließenden Refiner werden die Hackschnitzet dann zerfasert. Der Refiner besteht aus zwei mit radialem Relief versehenen Metallscheiben, die sich dicht aneinander im entgegengesetztem Sinn drehen. Die Fasern verfassen den Refiner über die sog. Blowline. Hier wird meist der Leim aufgebracht. Als Bindemittel werden üblicherweise Harnstoff-Formaldehyd-Harze, zum Teil mit Melamin verstärkt, oder für feuchtebestän- dige Platten Harnstoff-Melamin-Formaldehyd-Harze eingesetzt. Auch Isocyanate sind als Bindemittel im Gebrauch. Die Bindemittel werden meist zusammen mit den gewünschten Zusatzstoffen (z.B. Härter, Paraffin-Dispersion, Farbmittel) auf die Fasern aufgebracht. Die beleimten Fasern laufen anschließend durch einen Trockner, in dem sie auf Feuchten von 8 bis 15 Gew.-% getrocknet werden. Vereinzelt werden die ge- trockneten Fasern auch erst nachträglich in speziellen kontinuierlich arbeitenden Mischern beleimt. Bei der Spanplattenhersteüung erfolgt die Beleimung der vorher getrockneten Späne in kontinuierlichen Mischern.MDF and HDF boards are usually produced in a continuous process. This washed, water-moist, small chopped pieces of wood (wood chips) are first preheated to about 8O 0 C and then in a digester under a pressure of 2 to 5 bar and a temperature of 100 to 150 0 C geweicht. In the adjoining refiner the wood chips are then shredded. The refiner consists of two metal discs with radial relief, which rotate close to each other in the opposite direction. The fibers write the refiner on the so-called blowline. Here, the glue is usually applied. Urea-formaldehyde resins, sometimes reinforced with melamine, or urea-melamine-formaldehyde resins for moisture-resistant boards, are usually used as binders. Isocyanates are also used as binders. The binders are usually applied to the fibers together with the desired additives (eg hardener, paraffin dispersion, colorant). The glued fibers then pass through a dryer in which they are dried to humidities of 8 to 15 wt .-%. Occasionally, the dried fibers are also subsequently glued in special, continuously operating mixers. For chipboard production, the pre-dried chips are glued in continuous mixers.
Die beleimten Fasern bzw. Späne werden anschließend zu Matten geschüttet, gege- benenfalls ka!t vorverdichtet und in beheizten Pressen bei Temperaturen von 170 bis 2400C zu Platten gepreßt.The glued fibers or chips are then poured into mats, where appropriate ka t precompressed and pressed in a heated press at temperatures of 170-240 0 C to form plates.
Ais Basismateria! können für die erfindungsgemäßen Holzwerkstoffplatten im Prinzip alle aus Pflanzen zu gewinnenden faserigen Materialien dienen. So sind z.B. neben den üblicherweise eingesetzten Holzfasern Fasern, die aus Palmen zu gewinnen sind, geeignet. Bevorzugte Basismaterialien stellen helle Holzarten, insbesondere Fichte oder Kiefer, dar, jedoch können auch dunklere Holzarten, wie Buche, verwendet werden.Ais basic materials! In principle, all fibrous materials to be obtained from plants can serve for the wood-based panels according to the invention. Thus, e.g. in addition to the wood fibers commonly used fibers that are to win from palm trees, suitable. Preferred base materials are light wood species, especially spruce or pine, but darker woods such as beech can also be used.
Im folgenden wird nicht zwischen den Begriffen "Holzfasern" und "Spänen" differenziert, vielmehr soll der Begriff "Holzfasern" auch "Späne" umfassen.In the following, no distinction is made between the terms "wood fibers" and "chips", but rather the term "wood fibers" should also include "chips".
Die in den erfindungsgemäßen Holzwerkstoff platten eingesetzten Holzfasern sind gebleicht,The wood fibers used in the wood-based panels according to the invention are bleached,
Bei der chemischen Bleiche von Holzfasern werden die färbenden Begleitstoffe des Holzes durch oxidierende oder/und reduzierende Chemikalien zerstört oder unwirksam gemacht. Für die oxidative Bleiche eignen sich z.B. Wasserstoffperoxid, Ozon, Sauerstoff, Salze von Halogensauerstoffsäuren, wie Chlorite, und Salze organischer und anorganischer Persäuren, wie Peracetate, Percarbonate und Perborate, vor allem deren Alkaltmetallsalze, insbesondere Natriumsalze, wobei die Percarbonate und Wasserstoffperoxid bevorzugt sind. Für die reduktive Bleiche sind z.B. reduzierende Schwefelverbindungen, wie Dithionite, Disulflte, Sulfite bzw. Schwefeldioxid, Sulfinsau- ren und deren Salze, insbesondere die Alkalimetalisalze und vor allem die Natriumsal- ze, und Hydroxycarbonsäuren, wie Citronensäure und Äpfelsäure, geeignet. Bevorzugte Reduktionsmittel sind die Disulflte und Sulfite, insbesondere Natriumhydrogensulfit, sowie Äpfel- und Citronensäure.In the chemical bleaching of wood fibers, the coloring impurities of the wood are destroyed or rendered ineffective by oxidizing and / or reducing chemicals. For oxidative bleaching, e.g. Hydrogen peroxide, ozone, oxygen, salts of halo-oxygen acids, such as chlorites, and salts of organic and inorganic peracids, such as peracetates, percarbonates and perborates, especially their alkali metal salts, in particular sodium salts, wherein the percarbonates and hydrogen peroxide are preferred. For the reductive bleaching, e.g. reducing sulfur compounds, such as dithionites, disulphites, sulfites or sulfur dioxide, sulfinic acids and their salts, in particular the alkali metal salts and, in particular, the sodium salts, and hydroxycarboxylic acids, such as citric acid and malic acid. Preferred reducing agents are the disulfides and sulfites, in particular sodium hydrogen sulfite, as well as malic and citric acid.
Für die erfindungsgemäßen Holzwerkstoffplatten sind Holzfasern, die zunächst oxidativ und dann reduktiv gebleicht worden sind, besonders bevorzugt.For the wood-based panels according to the invention, wood fibers which have been firstly oxidatively and then reductively bleached are particularly preferred.
Ganz besonders bevorzugt wird die oxidative Bleiche dabei mit Percarbonaten oder Wasserstoffperoxid und die reduktive Bleiche mit Sulfiten oder Äpfel- oder Citronensäure durchgeführt.Most preferably, the oxidative bleaching is carried out with percarbonates or hydrogen peroxide and the reductive bleaching with sulfites or malic or citric acid.
Verfahrenstechnisch geht man beim Bleichen zweckmäßigerweise so vor, daß man wäßrige, 5 bis 40 gew.~%ige Holzfaserdispersionen kontinuierlich in Gegenstromtür- men bei Temperaturen von 90 bis 15O0C und Drücken bis zu 3 bar mit wäßrigen Lösungen oder Dispersionen der Bleichmittel behandelt. Üblichweise wird in Gegenwart von Komplexbildnern, wie EDTA, gearbeitet, um den Abbau der Bleichmittel durch Übergangsmetallionen zu vermeiden.In terms of process technology, bleaching is expediently carried out in such a way that aqueous, 5 to 40% by weight wood fiber dispersions are continuously poured into countercurrent at temperatures of 90 to 15O 0 C and pressures up to 3 bar treated with aqueous solutions or dispersions of bleach. Usually, it is carried out in the presence of complexing agents, such as EDTA, to avoid the degradation of the bleaching agents by transition metal ions.
Insbesondere bei der Herstellung von erfindungsgemäßen MDF-/HDF~Platten kann die Bleichung der Fasern vorteilhaft während der Plattenherstetlung vorgenommen werden. Die Bleichmittel können den Hackschnitzeln dabei im Vorerwärmer oder im Kocher zugegeben werden. Vorzugsweise werden auch Kompiexbildner zugesetzt.In particular, in the production of MDF / HDF boards according to the invention, the bleaching of the fibers can be advantageously carried out during the board production. The bleaching agents can be added to the wood chips in the preheater or in the cooker. Preferably also Kompiexbildner be added.
Die in den erfindungsgemäßen Holzwerkstoffpfatten eingesetzten Holzfasern werden nach der Bleichung mit flüssigen Farbmittelzubereitungen gefärbt, die mindestens ein Pigment und mindestens einen im sichtbaren Bereich des elektromagnetischen Spektrums absorbierenden Farbstoff enthalten.The wood fibers used in the wood-based panels according to the invention are dyed after bleaching with liquid colorant preparations containing at least one pigment and at least one in the visible range of the electromagnetic spectrum absorbing dye.
Diese Farbmittelzubereitungen enthalten in der Regel 0,01 bis 10 Gew.-%, bevorzugt 0,5 bis 10 Gew.-% Farbstoff, bezogen auf das Pigment.These colorant preparations generally contain 0.01 to 10 wt .-%, preferably 0.5 to 10 wt .-% of dye, based on the pigment.
Besonders bevorzugt enthalten diese FarbmittelzubereitungenThese colorant preparations particularly preferably contain
(A) 10 bis 70 Gew.-% mindestens eines Pigments,(A) 10 to 70% by weight of at least one pigment,
(B) 0,05 bis 7 Gew.-% mindestens eines im sichtbaren Bereich des elektromagnetischen Spektrums absorbierenden Farbstoffs,(B) 0.05 to 7% by weight of at least one dye which absorbs in the visible region of the electromagnetic spectrum,
(C) 1 bis 50 Gew.-% mindestens eines Dispergiermittels,(C) 1 to 50% by weight of at least one dispersing agent,
(D) 10 bis 88,95 Gew.-% Wasser oder eines Gemischs von Wasser und mindestens einem Wasserrückhaltemittel und(D) 10 to 88.95% by weight of water or a mixture of water and at least one water retention agent and
(E) 0 bis 5 Gew.-% weitere für Farbmittelzubereitungen übliche Bestandteile.(E) 0 to 5 wt .-% further common for colorant preparations ingredients.
Als Komponente (A) können in den Farbmittelzubereitungen organische oder anorganische Pigmente enthalten sein. Selbstverständlich können die Farbmittelzubereitun- gen auch Mischungen verschiedener organischer oder verschiedener anorganischer Pigmente oder Mischungen von organischen und anorganischen Pigmenten enthalten.As component (A), organic or inorganic pigments may be present in the colorant preparations. Of course, the colorant preparations can also contain mixtures of various organic or various inorganic pigments or mixtures of organic and inorganic pigments.
Die Pigmente liegen bevorzugt in feinteiliger Form vor und haben dementsprechend üblicherweise mittlere Teilchengrößen von 0,1 bis 5 μm, insbesondere 0,1 bis 3 μm und vor allem 0,1 bis 1 μm. Bei den organischen Pigmenten handelt es sich üblicherweise um organische Bunt- und Schwarzpigmente. Anorganische Pigmente können ebenfalls Farbpigmente (Bunt-, Schwarz- und Weißpigmente) sowie Glanzpigmente sein.The pigments are preferably present in finely divided form and accordingly usually have average particle sizes of 0.1 to 5 .mu.m, in particular 0.1 to 3 .mu.m and especially 0.1 to 1 .mu.m. The organic pigments are usually organic colored and black pigments. Inorganic pigments may also be color pigments (color, black and white pigments) and luster pigments.
Im folgenden seien als Beispiele für geeignete organische Farbpigmente genannt:The following may be mentioned as examples of suitable organic color pigments:
- Monoazopigrnente: Cl. Pigment Brown 25;- Monoazopigrnente: Cl. Pigment Brown 25;
Cl. Pigment Orange 5, 13, 36, 38, 64 und 67;Cl. Pigment Orange 5, 13, 36, 38, 64 and 67;
Cl. Pigment Red 1 , 2, 3, 4, 5, 8, 9, 12, 17, 22, 23, 31 , 48:1 , 48:2, 48:3, 48:4, 49, 49:1 , 51 :1, 52:1 , 52:2,Cl. Pigment Red 1, 2, 3, 4, 5, 8, 9, 12, 17, 22, 23, 31, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 51: 1, 52: 1, 52: 2,
53, 53:1, 53:3, 57:1 , 58:2, 58:4, 63, 112, 146, 148,53, 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 ;170, 175, 184, 185, 187, 191: 1, 208, 210, 245, 247 and 251;
Cl. Pigment Yellow 1 , 3, 62, 65, 73, 74, 97, 120, 151, 154, 168, 181 , 183 und 191;Cl. Pigment Yellow 1, 3, 62, 65, 73, 74, 97, 120, 151, 154, 168, 181, 183 and 191;
Cl. Pigment Violet 32;Cl. Pigment Violet 32;
- Disazopigmente: Cl. Pigment Orange 16, 34, 44 und 72;- Disazo pigments: Cl. Pigment Orange 16, 34, 44 and 72;
Cl. Pigment Yellow 12, 13, 14, 16, 17, 81, 83, 106, 113, 126, 127, 155, 174, 176, 180 und 188;Cl. Pigment Yellow 12, 13, 14, 16, 17, 81, 83, 106, 113, 126, 127, 155, 174, 176, 180 and 188;
- Dtsazokondensationspigmente: Cl. Pigment Yetlow 93, 95 und 128;Dtsazocondensation pigments: Cl. Pigment Yetlow 93, 95 and 128;
Cl. Pigment Red 144, 166, 214, 220, 221, 242 und 262; Cl. Pigment Brown 23 und 41 ;Cl. Pigment Red 144, 166, 214, 220, 221, 242 and 262; Cl. Pigment Brown 23 and 41;
- Anthanthronpigmente: Cl. Pigment Red 168;- Anthanthrone pigments: Cl. Pigment Red 168;
- Anthrachinonpigmente: Cl. Pigment Yellow 147, 177 und 199; Cl. Pigment Violet 31;Anthraquinone pigments: Cl. Pigment Yellow 147, 177 and 199; Cl. Pigment Violet 31;
- Anthrapyrimidinpigmente: Cl. Pigment Yellow 108;Anthrapyrimidine pigments: Cl. Pigment Yellow 108;
- Chinacridonpigmente: Cl. Pigment Orange 48 und 49; Cl. Pigment Red 122, 202, 206 und 209;- Quinacridone pigments: Cl. Pigment Orange 48 and 49; Cl. Pigment Red 122, 202, 206 and 209;
Cl. Pigment Violet 19;Cl. Pigment Violet 19;
- Chinophthalonpigmente: Ci. Pigment Yellow 138;- Quinophthalone pigments: Ci. Pigment Yellow 138;
- Diketopyrrolopyrrolpimgente: Cl. Pigment Orange 71 , 73 und 81;Diketopyrrolopyrrole Pimgente: Cl. Pigment Orange 71, 73 and 81;
Ci. Pigment Red 254, 255, 264, 270 und 272; - Dioxazinpigmente: Cl. Pigment Vioiet 23 und 37; Cl. Pigment Blue 80;Ci. Pigment Red 254, 255, 264, 270 and 272; Dioxazine pigments: Cl. Pigment Vioiet 23 and 37; Cl. Pigment Blue 80;
- Flavanthronpigmente: Cl. Pigment Yeliow 24;Flavanthrone pigments: Cl. Pigment Yeliow 24;
- Indanthroπpigmente: CJ. Pigment Blue 60 und 64;Indanthrope pigments: CJ. Pigment Blue 60 and 64;
- Isoindolrnpigmente: Cl. Pigmente Orange 61 und 69;- isoindole pigments: Cl. Pigments orange 61 and 69;
Cl. Pigment Red 260;Cl. Pigment Red 260;
Cl. Pigment Yeliow 139 und 185;Cl. Pigment Yeliow 139 and 185;
- Isoindolinonpigmente: Cl. Pigment Yeliow 109, 110 und 173;- isoindolinone pigments: Cl. Pigment Yeliow 109, 110 and 173;
- isoviolanthronpigmente: Cl. Pigment Vioiet 31 ;- isoviolanthrone pigments: Cl. Pigment Vioiet 31;
- Metallkornplexpigmente: Cl. Pigment Red 257;- Metallkornplexpigmente: Cl. Pigment Red 257;
Cl. Pigment Yeliow 117, 129, 150, 153 und 177;Cl. Pigment Yeliow 117, 129, 150, 153 and 177;
Cl. Pigment Green 8;Cl. Pigment Green 8;
- Perinonpigmente: Cl. Pigment Orange 43; Cl. Pigment Red 194;- Perinone pigments: Cl. Pigment Orange 43; Cl. Pigment Red 194;
- Perylenpigmente: Cl. Pigment Black 31 und 32;- Perylene pigments: Cl. Pigment Black 31 and 32;
Cl. Pigment Red 123, 149, 178, 179, 190 und 224;Cl. Pigment Red 123, 149, 178, 179, 190 and 224;
Cl. Pigment Vioiet 29;Cl. Pigment Vioiet 29;
- Phthaiocyaninpigmente: Cl. Pigment Blue 15, 15:1 , 15:2,15:3, 15:4, 15:6 und 16;Phthalocyanine pigments: Cl. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6 and 16;
CA. Pigment Green 7 und 36;CA. Pigment Green 7 and 36;
- Pyranthron pigmente: Cl. Pigment Orange 51 ; Cl. Pigment Red 216;- Pyranthrone pigments: Cl. Pigment Orange 51; Cl. Pigment Red 216;
- Pyrazolochinazolonpigmente: Ci. Pigment Orange 67; Cl. Pigment Red 251;- Pyrazoloquinazolone pigments: Ci. Pigment Orange 67; Cl. Pigment Red 251;
- Thioindigopigmente: Cl. Pigment Red 88 und 181; Cl. Pigment Vioiet 38;- thioindigo pigments: Cl. Pigment Red 88 and 181; Cl. Pigment Vioiet 38;
- Triarylcarboniumpigmente; C.\. Pigment Blue 1, 61 und 62;- triaryl carbonium pigments; C. \. Pigment Blue 1, 61 and 62;
Cl. Pigment Green 1 ;Cl. Pigment Green 1;
Cl. Pigment Red 81 , 81:1 und 169; CJ. Pigment Vioiet 1 , 2, 3 und 27;Cl. Pigment Red 81, 81: 1 and 169; CJ. Pigment Vioiet 1, 2, 3 and 27;
- CJ. Pigment Black 1 (Anilinschwarz);- CJ. Pigment Black 1 (aniline black);
- CJ. Pigment Yellow 101 (Aldazingelb);- CJ. Pigment Yellow 101 (Aldazingelb);
- CJ. Pigment Brown 22.- CJ. Pigment Brown 22.
Geeignete anorganische Farbpigmente sind z.B.:Suitable inorganic color pigments are, for example:
- Weißpigmente: Titandioxid (CJ. Pigment White 6), Zinkweiß, Farbenzinkoxid;White pigments: titanium dioxide (CJ Pigment White 6), zinc white, colored zinc oxide;
Zinksulfid, Lithopone;Zinc sulfide, lithopone;
- Schwarzpigmente: Eisenoxidschwarz (Cl. Pigment Black 11), Eisen-Mangan- Schwarz, Spineil schwarz (Cl. Pigment Black 27); Ruß (Cl.Black pigments: iron oxide black (CI Pigment Black 11), iron manganese black, spin black (CI Pigment Black 27); Carbon black (Cl.
Pigment Black 7);Pigment Black 7);
- Buntpigmente: Chromoxäd, Chromoxidhydratgrün; Chromgrün (Cl. Pigment- Colored pigments: Chromoxad, Chromoxidhydratgrün; Chrome green (Cl. Pigment
Green 48); Cobaltgrün (CJ. Pigment Green 50); Ultramaringrün;Green 48); Cobalt green (CJ Pigment Green 50); Ultramarine green;
Kobaltblau (Cl. Pigment Blue 28 und 36; Cl. Pigment Blue 72); Ultramarinblau; Manganblau;Cobalt blue (CI Pigment Blue 28 and 36; CI Pigment Blue 72); Ultramarine blue; Manganese blue;
Ultramarinviolett; Kobalt- und Manganviolett;Ultramarine violet; Cobalt and manganese violet;
Eisenoxidrot (CJ. Pigment Red 101); Cadmiumsuifoselenid (Cl. Pigment Red 108); Cersulfid (CJ. Pigment Red 265); Molybdatrot (Cl. Pigment Red 104); Ultramarinrot;Iron oxide red (CJ Pigment Red 101); Cadmium sulphoselenide (CI Pigment Red 108); Cerium sulphide (CJ Pigment Red 265); Molybdate red (CI Pigment Red 104); ultramarine;
Eisenoxidbraun (CJ. Pigment Brown 6 und 7), Mischbraun,Iron oxide brown (CJ Pigment Brown 6 and 7), mixed brown,
Spinell- und Korundphasen (Cl. Pigment Brown 29, 31 , 33, 34, 35, 37, 39 und 40), Chromtitangelb (Cl. Pigment Brown 24), Chromorange;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;
Cersulfid (CJ. Pigment Orange 75);Cerium sulphide (CJ Pigment Orange 75);
Eisenoxidgelb (CJ. Pigment Yellow 42); Nickeititangelb (CJ. Pigment Yeüow 53; Ci. Pigment Yellow 157, 158, 159, 160, 161 , 162, 163, 164 und 189); Chromtitangelb; Spinellphasen (Cl. Pigment Yellow 119); Cadmiumsuifid und Cadmiumzink- sulfid (CJ. Pigment Yellow 37 und 35); Chromgelb (CJ. Pigment Yellow 34); Bismutvanadat (CJ. Pigment Yellow 184). Bei den Glanzpigmenten handelt es sich um einphasig oder mehrphasig aufgebaute piättchenförrnige Pigmente, deren Farbenspief durch das Zusammenspiel von Interferenz-, Reflexions- und Absorptionsphänomenen geprägt ist. Ais Beispiele seien Aluminiumplättchen und ein- oder mehrfach, insbesondere mit Metalioxiden beschichtete Aluminium-, Eisenoxid- und Glimmerplättchen genannt.Iron oxide yellow (CJ Pigment Yellow 42); Nicitenite yellow (CJ Pigment Yeow 53, CI Pigment Yellow 157, 158, 159, 160, 161, 162, 163, 164 and 189); Chromium titanium yellow; Spinel phases (CI Pigment Yellow 119); Cadmium suicide and cadmium zinc sulfide (CJ Pigment Yellow 37 and 35); Chrome yellow (CJ Pigment Yellow 34); Bismuth vanadate (CJ Pigment Yellow 184). The luster pigments are single-phase or multi-phase pixiliferous pigments whose color palette is characterized by the interplay of interference, reflection and absorption phenomena. Examples include aluminum flakes and one or more times, in particular aluminum oxide, iron oxide and mica flakes coated with metal oxides.
in der Regel enthalten die Farbmittelzubereitungen 10 bis 70 Gew.-%, vorzugsweise 10 bis 60 Gew.-%, Pigment (A).As a rule, the colorant preparations contain from 10 to 70% by weight, preferably from 10 to 60% by weight, of pigment (A).
Als Komponente (B) enthalten die Farbmittelzubereitungen mindestens einen im sichtbaren Bereich des elektromagnetischen Spektrums absorbierenden Farbstoff aus der Gruppe der kationϊschen Farbstoffe, der anionischen Farbstoffe und der Dispersionsfarbstoffe. Geeignet sind dabei insbesondere Farbstoffe, die in Wasser oder einem mit Wasser mischbaren oder in Wasser löslichen organischen Lösungsmittel löslich sind. Bevorzugt weisen die eingesetzten Farbstoffe (B) einen den Pigmenten (A) jeweils vergleichbaren Farbton auf, da auf diese Weise eine besonders intensive Färbung der Holzwerkstoffplatten auch bei hellen Farbtönen erzielbar ist. Es können jedoch auch im Farbton abweichende Farbstoffe (B) eingesetzt werden, wodurch Nuancierungen der Färbung möglich sind.As component (B), the colorant formulations contain at least one visible spectrum of the electromagnetic spectrum absorbing dye from the group of cationic dyes, anionic dyes and disperse dyes. Particularly suitable dyes are those which are soluble in water or in a water-miscible or water-soluble organic solvent. Preferably, the dyes used (B) to the pigments (A) in each case comparable hue, since in this way a particularly intense coloration of the wood-based panels can be achieved even in light shades. However, it is also possible to use colorants (B) which deviate in color, as a result of which nuances of the coloration are possible.
Geeignet sind insbesondere kationische Farbstoffe, anionische Farbstoffe und Disperstonsfarbstoffe. Ganz besonders geeignet sind Direktfarbstoffe und Dispersionsfarbstoffe.Particularly suitable are cationic dyes, anionic dyes and Disperstonsfarbstoffe. Especially suitable are direct dyes and disperse dyes.
Geeignete kationische Farbstoffe (B) entstammen insbesondere der Di- und Triaryf- methan-, Xanthen-, Azo-, Cyanin-, Azacyanin-, Methin-, Acridin-, Safranin-, Oxazin-, Indulin-, Nigrosin- und Phenazin-Reihe, wobei Farbstoffe aus der Azo-, Triarylmethan- und Xanthenreihe bevorzugt sind.Suitable cationic dyes (B) are derived in particular from the di- and triary methane, xanthene, azo, cyanine, azacyanine, methine, acridine, safranine, oxazine, induline, nigrosine and phenazine series , wherein dyes from the azo, triarylmethane and xanthene series are preferred.
im einzelnen seien beispielhaft aufgeführt: Cl. Basic Yellow 1, 2 und 37; CJ. Basic Orange 2; Cl. Basic Red 1 und 108; Cl. Basic Blue 1, 7 und 26; Cl. Basic Violet 1 , 3, 4, 10, 11 und 49; Cl. Basic Green 1 und 4; Cl, Basic Brown 1 und 4.in detail may be mentioned by way of example: Cl. Basic Yellow 1, 2 and 37; CJ. Basic Orange 2; Cl. Basic Red 1 and 108; Cl. Basic Blue 1, 7 and 26; Cl. Basic Violet 1, 3, 4, 10, 11 and 49; Cl. Basic Green 1 and 4; Cl, Basic Brown 1 and 4.
Kationische Farbstoffe (B) können auch externe basische Gruppen enthaltende Farbmittel sein. Geeignete Beispiele sind hier Ci. Basic Blue 15 und 161.Cationic dyes (B) may also be colorants containing external basic groups. Suitable examples are here Ci. Basic Blue 15 and 161.
Als kationische Farbstoffe (B) können auch die korrespondierenden Farbbasen in Gegenwart von löslich machenden sauren Agentien eingesetzt werden. Als Beispiele sei- en genannt: Cl. Solvent Yellow 34; Cl. Solvent Orange 3; Cl. Solvent Red 49; Cl. Solvent Violet 8 und 9; Cl. Solvent Blue 2 und 4; Cl. Solvent Black 7. Geeignete anionische Farbstoffe sind insbesondere sulfonsäuregruppenhaltige Verbindungen aus der Reihe der Azo-, Anthrachinon-, Metalikomplex-, Triarylmethan-, Xanthen- und Stilbenreihe, wobei Farbstoffe aus der Triarylmethan-, Azo- und Metallkomplex- (vor allem Kupfer-, Chrom- und Kobaltkomplex-) Reihe bevorzugt sind.As cationic dyes (B) it is also possible to use the corresponding color bases in the presence of solubilizing acidic agents. Examples given are: Cl. Solvent Yellow 34; Cl. Solvent orange 3; Cl. Solvent Red 49; Cl. Solvent Violet 8 and 9; Cl. Solvent Blue 2 and 4; Cl. Solvent Black 7. Suitable anionic dyes are, in particular, sulfonic acid-containing compounds from the series of the azo, anthraquinone, metalic complex, triarylmethane, xanthene and stilbene series, dyes of the triarylmethane, azo and metal complex (especially copper, chromium and cobalt complex -) are preferred.
Im einzelnen genannt seien beispielsweise: Cl. Acid Yellow 3, 19, 36, 59, 119 und 204; C.!. Acid Orange 7, 8, 44, 74, 92 und 142; Cl. Acid Red 52, 88, 159, 351 und 357; Cl. Acid Violet 17, 46, 56, 58, 65 und 90; CL Acid Blue 9, 193 und 199; Ci. Acid Brown 355; Cl. Acid Black 52 und 194; Cl. Direct Yellow 4 und 1 1 ; Ci. Direct Red 80, 81 und 254; Cl. Direct Violet 35 und 51 ; Cl. Direct Blue 47, 67, 199, 267 und 279.Specific examples include: Cl. Acid Yellow 3, 19, 36, 59, 119 and 204; ! C.. Acid Orange 7, 8, 44, 74, 92 and 142; Cl. Acid Red 52, 88, 159, 351 and 357; Cl. Acid Violet 17, 46, 56, 58, 65 and 90; CL Acid Blue 9, 193 and 199; Ci. Acid Brown 355; Cl. Acid Black 52 and 194; Cl. Direct Yellow 4 and 1 1; Ci. Direct Red 80, 81 and 254; Cl. Direct Violet 35 and 51; Cl. Direct Blue 47, 67, 199, 267 and 279.
Diese Farbstoffe sind insbesondere dann wasserlöslich, wenn sie als Alkalimetallsalz, vor allem Lithium-, Natrium- oder Kaliumsalz, oder als nichtsubstituiertes oder substituiertes Ammoniumsalz, vor allem Alkanolammoniumsalz, vorliegen.These dyes are especially water-soluble if they are present as alkali metal salt, especially lithium, sodium or potassium salt, or as unsubstituted or substituted ammonium salt, especially alkanolammonium salt.
Dispersäonsfarbstoffe werden vorzugsweise in Form kommerziell erhältlicher, wäßriger Dispersionen eingesetzt und entfalten ihre färbende Wirkung im Herstellungsprozeß der Holzwerkstoff platten durch Diffusion bei hohen Temperaturen.Dispersäonsfarbstoffe are preferably used in the form of commercially available, aqueous dispersions and unfold their coloring effect in the manufacturing process of wood-based panels by diffusion at high temperatures.
Besonders geeignet sind z.B. Dispersionsfarbstoffe aus der Reihe der Chinophthalone und Anthrachinone.Particularly suitable are e.g. Disperse dyes from the series of quinophthalones and anthraquinones.
Die Farbmittelzubereitungen enthalten den Farbstoff (B) im allgemeinen in Mengen von 0,5 bis 10 Gew.-%, vorzugsweise 1 bis 8 G ew.-%, jeweils bezogen auf das Pigment (A). Bezogen auf das Gesamtgewicht der Zubereitung, entspricht dies Mengen von in der Regel 0,05 bis 7 Gew.-%, vor allem 0,1 bis 5,6 Gew.-%.The colorant preparations contain the dye (B) generally in amounts of from 0.5 to 10% by weight, preferably from 1 to 8% by weight, in each case based on the pigment (A). Based on the total weight of the preparation, this corresponds to amounts of generally 0.05 to 7 wt .-%, especially 0.1 to 5.6 wt .-%.
Bevorzugte Pigment/Farbstoff-Kombinationen für helle Farbtöne sind z.B.: Cl. Pigment Orange 34 und Cl. Direct Yellow 11 ; C I. Pigment Yeilow 74 und Cl. Direct Yellow 4.Preferred pigment / dye combinations for light shades are, for example: Cl. Pigment Orange 34 and Cl. Direct Yellow 11; C I. Pigment Yeilow 74 and Cl. Direct Yellow 4.
Reine helle Pastellfarbtöne sind insbesondere durch Mischen von Weißpigmenten, insbesondere Cl. Pigment White 6, mit nuancierten Farbpigmenten, z.B. Cl. Pigment Black 7 und Cl. Basic Violet 3, zu erhalten. Heile Grautöne können vorteilhaft auch durch Nuancierung des Weäßpigments mit entsprechenden Farbstoffen, z.B. blauen Farbstoffen, wie Cl. Direct Blue 47, 67, 267 und 279, und/oder violetten Farbstoffen, wie CJ. Direct Violet 35 und 51, und gegebenenfalls gelben Farbstoffen, wie Ci. Direct Yeiiow 4, erzielt werden. Der Anteil des Weißpigments beträgt dabei jeweils üblicherweise 80 bis 99 Gew.-%, bezogen auf die Gesamtfarbmittelmenge.Pure bright pastel shades are particularly by mixing white pigments, especially Cl. Pigment White 6, with nuanced color pigments, e.g. Cl. Pigment Black 7 and Cl. Basic Violet 3, to get. Heal shades of gray can advantageously also be obtained by shading the wetting pigment with appropriate dyes, e.g. blue dyes, such as Cl. Direct Blue 47, 67, 267 and 279, and / or violet dyes such as CJ. Direct Violet 35 and 51, and optionally yellow dyes, such as Ci. Direct Yeiiow 4, to be achieved. The proportion of the white pigment is usually in each case 80 to 99 wt .-%, based on the total colorant amount.
Als Komponente (C) ist in den Farbmttteizubereitungen mindestens ein Dispergiermittel enthalten. Besonders geeignete Dispergiermittel (C) sind nichtionische und anionische wasserlösliche oberflächenaktive Additive.As component (C), at least one dispersing agent is contained in the colorant preparations. Particularly suitable dispersants (C) are nonionic and anionic water-soluble surface-active additives.
Besonders geeignete nichtionische Additive (C) basieren auf Polyethern (Additive (C1)).Particularly suitable nonionic additives (C) are based on polyethers (additives (C1)).
Neben den ungemischten Potyalkylenoxiden, bevorzugt C2~C4-Alkylenoxiden und phe- nyfsubstituierten C2-C4-Alky!enoxiden, insbesondere Polyethylenoxiden, Polypropylen- oxiden und Poly(phenylethylenoxiden), sind hier vor allem Blockcopolymerisate, insbe- sondere Poiypropylenoxid- und Polyethylenoxidblöcke oder Poly(phenylethylenoxid)- und Polyethylenoxidblöcke aufweisende Polymerisate, und auch statistische Copoly- merisate dieser Alkylenoxide geeignet.In addition to the unmixed Potyalkylenoxiden, C 2 ~ C 4 -alkylene and preferably C 2 -C 4 phe nyfsubstituierten -Alky! Enoxiden, especially polyethylene oxides, polypropylene oxides, and poly (phenylethylenoxiden), here in particular block copolymers, in particular Poiypropylenoxid- and polyethylene oxide blocks or polymers comprising poly (phenylethylene oxide) and polyethylene oxide blocks, and also random copolymers of these alkylene oxides.
Diese Polyalkylenoxide können durch Polyaddition der Alkylenoxide an Startermolekü- Ie, wie an gesättigte oder ungesättigte aliphatische und aromatische Alkohole, Phenol oder Naphthol, das jeweils durch Alkyl, insbesondere CrCi2-Aikyl, vorzugsweise C4- C12- bzw. CrC4-Alkyl, substituiert sein kann, gesättigte oder ungesättigte aliphatische und aromatische Amine, gesättigte oder ungesättigte aliphatische Carbonsäuren und Carbonsäureamide hergestellt werden. Üblicherweise werden 1 bis 300 mol, bevorzugt 3 bis 150 mol, Alkylenoxid je mo! Startermolekül eingesetzt.These polyalkylene oxides can be substituted by polyaddition of the alkylene oxides onto starter molecules, such as saturated or unsaturated aliphatic and aromatic alcohols, phenol or naphthol, each substituted by alkyl, in particular C 1 -C 2 -cycloalkyl, preferably C 4 -C 2 2 or C 1 -C 4 -alkyl may be prepared, 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 per mo! Starter molecule used.
Geeignete aliphatische Alkohole enthalten dabei in der Regel 6 bis 26 C-Atome, bevorzugt 8 bis 18 C-Atome, und können unverzweigt, verzweigt oder cyciisch aufgebaut sein. Als Beispiele seien Octanol, Nonanol, Decanol, isodecanoi, Undecanol, Dodeca- nol, 2-Butyloctanol, Tridecanol, Isotridecanol, Tetradecanol, Pentadecanol, Hexadeca- nol (Cetylalkohol), 2-Hexy!decanol, Heptadecanol, Octadecanol (Stearylalkohol), 2- Heptylundecanol, 2-Octyldecanol, 2-Nonyltridecanol, 2-Decyltetradecanol, Oleylalkohol und 9-Octadeceno! sowie auch Mischungen dieser Alkohole, wie Ce/Cio-. C13/C15- und Cie/Ciβ-Alkohole, und Cyclopentanoi und Cyclohexanol genannt. Von besonderem In- teresse sind die gesättigten und ungesättigten Fettalkohoie, die durch Fettspaitung und Reduktion aus natürlichen Rohstoffen gewonnen werden, und die synthetischen Fettalkohole aus der Oxosynthese. Die Alkylenoxidaddukte an diese Alkohole weisen üblicherweise mittlere Molekulargewichte Mn von 200 bis 5 000 auf.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, isodecanoi, undecanol, dodecanol, 2-butyloctanol, tridecanol, isotridecanol, tetradecanol, pentadecanol, hexadecanol (cetyl alcohol), 2-hexy! Decanol, heptadecanol, octadecanol (stearyl alcohol), 2 Heptylundecanol, 2-octyldecanol, 2-nonyltridecanol, 2-decyltetradecanol, oleyl alcohol and 9-octadeceno! as well as mixtures of these alcohols, such as Ce / Cio-. C13 / C15 and Cie / Ciβ alcohols, and cyclopentanoi and cyclohexanol called. Of particular interest are the saturated and unsaturated fatty alcohols, which are obtained through the addition of fat 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.
Als Beispiele für die obengenannten aromatischen Alkohole seien neben unsubstituier- tem Phenol und α- und ß-Naphthol Hexylphenol, Heptyipheπol, Octylphenof, Nonyi- phenol, Isononyiphenol, Undecylphenol, Dodecylphenol, Di- und Tributyiphenol und Dinonylpheno! genannt.Examples of the abovementioned aromatic alcohols include, in addition to unsubstituted phenol and .alpha.- and .beta.-naphthol, hexylphenol, heptyipheπol, octylphenof, nonynphenol, isononiphenol, undecylphenol, dodecylphenol, di- and tributhenol and dinonylphenol! called.
Geeignete aliphatische Amine entsprechen den oben aufgeführten aliphatischen Alkoholen. Besondere Bedeutung haben auch hier die gesättigten und ungesättigten Fett- amine, die vorzugsweise 14 bis 20 C-Atome aufweisen. Als aromatische Amine seien beispielsweise Anilin und seine Derivate genannt.Suitable aliphatic amines correspond to the aliphatic alcohols listed above. Of particular importance are the saturated and unsaturated fatty acids. amines, which preferably have 14 to 20 carbon atoms. Examples of aromatic amines are aniline and its derivatives.
Ais aliphatische Carbonsäuren eignen sich insbesondere gesättigte und ungesättigte Fettsäuren, die bevorzugt 14 bis 20 C-Atome enthalten, und hydrierte, teilhydrierte und unhydrierte Harzsäuren sowie auch mehrwertige Carbonsäuren, z.B. Dicarbonsäuren, wie Maleinsäure.As aliphatic carboxylic acids are particularly suitable saturated and unsaturated fatty acids, preferably containing 14 to 20 carbon atoms, and hydrogenated, partially hydrogenated and unhydrogenated resin acids, as well as polybasic carboxylic acids, e.g. Dicarboxylic acids, such as maleic acid.
Geeignete Carbonsäureamide leiten sich von diesen Carbonsäuren ab.Suitable carboxylic acid amides are derived from these carboxylic acids.
Neben den Afkylenoxidaddukten an die einwertigen Amine und Alkohole sind die Alky- lenoxidaddukte an mindestens bifunktionelle Amine und Alkohole von ganz besonderem Interesse,In addition to the alkylene oxide adducts to the monohydric amines and alcohols, the alkylene oxide adducts to at least bifunctional amines and alcohols are of very particular interest,
Als mindestens bifunktioneile Amine sind zwei- bis fünfwertige Amine bevorzugt, die insbesondere der Formel H2N-(R1-NR2)n-H (R1: C∑-Ce-Alkyleπ; R2: Wasserstoff oder d- Ce-Alkyl; n: 1 bis 5) entsprechen. Im einzelnen seien beispielhaft genannt: Ethylendia- min, Diethylentriamin, Triethylentetramin, Tetraethylenpentamin, Propylendiamin-1 ,3, Dipropylentriamin, 3-Amino-1-ethylenaminopropan, Hexamethylendiamin, Dihexa- methyientriamin, 1 ,6-Bis-{3-aminopropy!amino)hexan und N-Methyidtpropylentπamin, wobei Hexamethylendiamin und Diethylentriamin besonders bevorzugt sind und Ethy- lendiamin ganz besonders bevorzugt ist.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 -alkyl, R 2 : hydrogen or d-ce) Alkyl; n: 1 to 5). Specific examples which may be mentioned are: ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, propylenediamine-1,3-dipropylenetriamine, 3-amino-1-ethyleneaminopropane, hexamethylenediamine, dihexamethylenediamine, 1,6-bis (3-aminopropyl) amino ) hexane and N-Methyidtpropylentπamin, with hexamethylenediamine and diethylenetriamine are particularly preferred and ethylenediamine is very particularly preferred.
Vorzugsweise werden diese Amine zunächst mit Propylenoxid und anschließend mit Ethylenoxid umgesetzt. Der Gehalt der Bϊockcopolymerisate an Ethylenoxid liegt üblicherweise bei etwa 10 bis 90 Gew.-%.Preferably, these amines are first reacted with propylene oxide and then with ethylene oxide. The content of the Bϊockcopolymerisate of ethylene oxide is usually about 10 to 90 wt .-%.
Die Blockcopolymerisate auf Basis mehrwertiger Amine weisen in der Regel mittlere Molekulargewichte Mn von 1 000 bis 40 000, vorzugsweise 1 500 bis 30 000, auf.The polybasic amine-based block copolymers generally have average molecular weights M n of from 1,000 to 40,000, preferably from 1,500 to 30,000.
Als mindestens bifunktioneile Alkohole sind zwei- bis fünfwertige Alkohole bevorzugt. Beispielsweise seien C2-C6-AJkylenglykole und die entsprechenden Di- und Polyalky- lenglykole, wie Ethyiengiykoi, Propyienglykol-1 ,2 und -1,3, Butylenglykoi-1 ,2 und -1,4, Hexylenglykol-1 ,6, Dipropylenglykol und Polyethylenglykoi, Glycerin und Pentaerythrit genannt, wobei Ethyiengiykoi und Polyethylenglykoi besonders bevorzugt und Propy- lenglyko! und Dipropylenglykol ganz besonders bevorzugt sind.As at least difunctional alcohols, di- to pentahydric alcohols are preferred. Examples are C 2 -C 6 -alkylene glycols and the corresponding di- and polyalkylene glycols, such as ethylene glycol, propylene glycol-1, 2 and 1,3, butylene glycol-1,2 and -1,4, hexylene glycol-1,6 Dipropylene glycol and polyethylene glycol, glycerol and pentaerythritol, ethylene glycol and polyethylene glycol being particularly preferred, and propylene glycol! and dipropylene glycol are most preferred.
Besonders bevorzugte Alkylenoxidaddukte an mindestens bifunktionelle Alkohole weisen einen zentralen Polypropyienoxidblock auf, gehen also von einem Propylengiykol oder PoIy propylengiykol aus, das zunächst mit weiterem Propylenoxid und dann mit Ethylenoxid umgesetzt wird. Der Gehalt der Blockcopolymerisate an Ethylenoxid liegt üblicherweise bei 10 bis 90 Gew.-%. Die Blockcopolymerisate auf Basis mehrwertiger Alkohole weisen im allgemeinen mittlere Molekulargewichte Mn von 1 000 bis 20 000, vorzugsweise 1 000 bis 15 000, auf.Particularly preferred Alkylenoxidaddukte to at least bifunctional alcohols have a central Polypropyienoxidblock, so go from a Propylengiykol or poly propylene glycol, which is reacted first with more propylene oxide and then with ethylene oxide. The content of the block copolymers of ethylene oxide is usually from 10 to 90% by weight. The polyhydric alcohol block copolymers generally have average molecular weights M n of from 1,000 to 20,000, preferably from 1,000 to 15,000.
Derartige AI kyienoxid blockcopolymerisate sind bekannt und im Handel z.B. unter den Namen Tetronic® und Pluronic® (BASF) erhältlich.Such AI kyienoxid block copolymers are known and commercially available, for example under the name Tetronic ® and Pluronic ® (BASF).
Als Beispiele für die als Komponente (C) besonders geeigneten wasserlöslichen anionischen oberflächenaktiven Mittel seien Additive auf Basis von Polymerisaten ethyle- nisch ungesättigter Carbonsäuren (C2), Additive auf Basis von Polyurethanen (C3) und Additive auf Basis von sauren Phosphorsäure-, Phosphonsäure-, Schwefelsäure- und/oder Sulfonsäureestem der oben genannten Polyether (C4) genannt.Examples of the water-soluble anionic surface active agents which are particularly suitable as component (C) are additives based on polymers of ethylenically unsaturated carboxylic acids (C2), additives based on polyurethanes (C3) and additives based on acidic phosphoric acid, phosphonic acid, Sulfuric acid and / or Sulfonsäureestem the above polyether (C4) mentioned.
Selbstverständlich können auch Mischungen mehrerer Additive (C) verwendet werden, also sowohl Mischungen verschiedener nichtionischer Additive als auch Mischungen verschiedener anionischer Additive sowie Mischungen von nichtionischen und anionischen Additiven.Of course, it is also possible to use mixtures of several additives (C), that is to say both mixtures of different nonionic additives and mixtures of various anionic additives and also mixtures of nonionic and anionic additives.
Als anionische wasserlösliche oberflächenaktive Additive auf der Basis von Poiymeri- säten ungesättigter Carbonsäuren (C2) eignen sich insbesondere Additive aus der Gruppe der Homo- und Copolymerisate von ethylenisch ungesättigten Monocarbon- säuren und/oder ethylenisch ungesättigten Dicarbonsäuren, die keine Säurefunktion enthaltende Vinylmonomere zusätzlich einpolymerisiert enthalten können, der Alkoxy- lierungsprodukte dieser Homo- und Copolymerisate und der Salze dieser Homo- und Copolymerisate und ihrer Aikoxyljerungsprodukte.Suitable anionic, water-soluble surface-active additives based on polymers of unsaturated carboxylic acids (C2) are, in particular, additives from the group of the homopolymers and copolymers of ethylenically unsaturated monocarboxylic acids and / or ethylenically unsaturated dicarboxylic acids which additionally contain polymerized vinyl monomers which contain no acid function can, the alkoxylation of these homo- and copolymers and the salts of these homo- and copolymers and their Aikoxyljerungsprodukte.
Als Beispiele für die carboxylgruppenhaltigen Monomere und die Vinylmonomere seien genannt:Examples of the carboxyl-containing monomers and the vinyl monomers are:
- Acrylsäure, Methacrylsäure und Crotonsäure;Acrylic acid, methacrylic acid and crotonic acid;
Maleinsäure, Maleinsäureanhydrid, Maleinsäuremonoester, Maleinsäuremono- amide, Umsetzungsprodukte von Maleinsäure mit Diaminen, die zu aminoxid- gruppenhaitigen Derivaten oxidiert sein können, und Fumarsäure, wobei Malein- säure, Maieinsäureanhydrid und Maleinsäuremonoamide bevorzugt sind;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, with maleic acid, maleic anhydride and maleic acid monoamides being preferred;
Vinylaromaten, wie Styrol, Methylstyrol und Vinyltoluol; Ethyien, Propylen, Isobuten, Diisobuten und Butadien; Vinylether, wie Polyethylenglykolmonovinylether; Vinylester linearer oder verzweigter Monocarbonsäuren, wie Vinylacetat und Vi- nylpropionat; Alkylester und Arylester ethylenisch ungesättigter Monocarbonsäuren, insbesondere Acrylsäure- und Methacrylsäureester, wie Methyl-, Ethyl-, Pro- pyl-, Isopropyi-, Butyl-, Pentyl-, Hexyl-, 2-Ethylhexyl-, Nonyh Lauryl- und Hydro- xyethyl-(meth)acrylat sowie Phenyl-, Naphthy!- und Benzyl(meth)acrylat; Dialkyl- ester von ethylenisch ungesättigten Dicarbonsäuren, wie Dimethyl-, Diethyl-, Dipropyl-, Diisopropyl-, Dibutyl-, Dipentyl-, DihexyS-, Di-2-ethyihexy!-, Dinonyf-, Di- lauryl- und Di-2-hydroxyethylmaieinat und -fumarat; Vinylpyrrolidon; Acrylnitri! und Methacrylnitril, wobei Styrol, Isobuten, Diisobuten, Acrylsäureester und PoIy- ethylengiykolmonovinyiether bevorzugt sind.Vinyl aromatics such as styrene, methylstyrene and vinyltoluene; 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 propionate; Alkyl esters and aryl esters of ethylenically unsaturated monocarboxylic acids, in particular acrylic and methacrylic acid esters, such as methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, 2-ethylhexyl, nonyl, lauryl and hydroxycarboxylic acids; xyethyl (meth) acrylate and phenyl, naphthyl and benzyl (meth) acrylate; Dialkyl esters of ethylenically unsaturated dicarboxylic acids, such as dimethyl, diethyl, dipropyl, diisopropyl, dibutyl, dipentyl, dihexyS, di-2-ethylhexy!, Dinonyf, dilauryl and di-2- hydroxyethyl maizinate and fumarate; vinylpyrrolidone; Acrylnitri! and methacrylonitrile, with styrene, isobutene, diisobutene, acrylic acid esters and polyethyleneglycol monovinyl ethers being preferred.
Ais Beispiele für bevorzugte Homopolymerisate dieser Monomere sind insbesondere Poiyacrylsäuren zu nennen.Examples of preferred homopolymers of these monomers are, in particular, polyacrylic acids.
Die Copolymerisate der genannten Monomere können aus zwei oder mehreren, insbesondere drei verschiedenen Monomeren aufgebaut sein. Es können statistische Copo- iymerisate, alternierende Copolymerisate, Biockcopolymerisate und Pfropfcopolymeri- sate vorüegen. Als bevorzugte Copolymerisate seien Styrol/Acryisäure-, Acryisäu- re/Maleinsäure-, Acrylsäure/Methacryisäure-, Butadien/Acrylsäure-, Isobuten/Maleinsäure-, Düsobuten/Maleinsäure- und Styrol/Maletnsäure-Copoiymerisate, die jeweils als zusätzliche Monomerbestandteile Acrylsäureester und/oder Maleinsäureester enthalten können, genannt.The copolymers of the monomers mentioned may be composed of two or more, in particular three, different monomers. They may be random copolymers, alternating copolymers, block copolymers and graft copolymers. Preferred copolymers are styrene / acrylic acid, acrylic acid / maleic acid, acrylic acid / methacrylic acid, butadiene / acrylic acid, isobutene / maleic acid, diisobutene / maleic acid and styrene / malonic acid copolymers, which are each acrylic acid ester as additional monomer constituents and / or or maleic acid esters may be mentioned.
Vorzugsweise liegen die Carboxylgruppen der nicht aikoxylierten Homo- und Copolymerisate zumindest teilweise in Salzform vor, um Wasserlöslich keit zu gewährleisten. Geeignet sind beispielsweise die Aikalimetallsalze, wie Natrium- und Kaiiumsalze, und die Ammoniumsalze.Preferably, the carboxyl groups of the non-alkoxylated homopolymers and copolymers are at least partially in salt form in order to ensure water-solubility. Suitable examples are the Aikalimetallsalze, such as sodium and potassium salts, and the ammonium salts.
Üblicherweise weisen die nicht aikoxylierten polymeren Additive (C2) mittlere Molekulargewichte Mw von 900 bis 250 000 auf. Die für die einzelnen Polymerisate besonders geeigneten Molekulargewichtsbereiche hängen naturgemäß von deren Zusammensetzung ab. im folgenden werden für verschiedene Polymerisate beispielhaft Molekulargewichtsangaben gemacht: Polyacrylsäuren: Mw von 900 bis 250 000; Styrol/Acryl- säure-Copolymerisate: Mw von 1 000 bis 50 000; Acrylsäure/Methacrylsäure-Copoly- merisate: Mw von 1 000 bis 250 000; Acryisäure/Maleinsäure-Copolymerisate: Mw von 2 000 bis 70 000.Usually, the non-aoxylated polymeric additives (C2) have average molecular weights M w of from 900 to 250,000. 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 1 000 to 50 000; Acrylic acid / methacrylic acid copolymers: M w from 1,000 to 250,000; Acrylic acid / maleic acid copolymers: M w from 2,000 to 70,000.
Neben diesen Homo- und Copolymerisaten selbst sind auch ihre Alkoxylierungspro- dukte als Additive (C2) von besonderem Interesse.In addition to these homopolymers and copolymers themselves, their alkoxylation products are also of particular interest as additives (C2).
Hierunter sind erfindungsgemäß vor allem die teilweise bis (soweit dies möglich ist) vollständig mit Polyetheralkohoien veresterten Polymerisate zu verstehen. In der Regel beträgt der Veresterungsgrad dieser Polymerisate 30 bis 80 mol-%.According to the invention, these include in particular the partially to (as far as is possible) completely polymerized with polyether alcohols polymers. In general, the degree of esterification of these polymers is 30 to 80 mol%.
Für die Veresterung geeignet sind insbesondere die Polyetheralkohole selbst, vorzugsweise Polyethylenglykole und Polypropylenglykole, sowie deren einseitig end- gruppenverschlossene Derivate, vor allem die entsprechenden Monoether, wie Mono- aryiether, z.B. Monophenyiether, und insbesondere Mono-Ci-C26-alky!ether, z.B. mit Fettalkohoien veretherte Ethyien- und Propylenglykoie, und die Polyetheramine, die z.B. durch Umwandlung einer terminalen OH-Gruppe der entsprechenden Pofyetherai- kohole oder durch Poiyaddϊtion von Alkylenoxiden an vorzugsweise primäre aliphati- sehe Amine herstellbar sind. Bevorzugt sind dabei Polyethyienglykole, Polyethyfengly- koimonoether und Polyetheramine. Die mittleren Molekulargewichte Mn der verwendeten Polyetheralkohole und ihrer Derivate liegen üblicherweise bei 200 bis 10 000.Particularly suitable for the esterification are the polyether alcohols themselves, preferably polyethylene glycols and polypropylene glycols, and their one-sided end group-capped derivatives, in particular the corresponding monoethers, such as monoarylethers, eg monophenyiethers, and in particular mono-C 1 -C -alkyl ethers, for example ethylenediols and propyleneglycols etherified with fatty alcohols, and the polyetheramines which are obtained, for example, by conversion of a terminal OH- Group of the corresponding Pofyetherai- alcohols or by Poiyaddϊtion of alkylene oxides to preferably primary aliphatic see amines can be produced. Polyethylene glycols, polyethylene glycol ethers 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.
Durch Steuerung des Verhältnisses von polaren zu unpolaren Gruppen können die oberflächenaktiven Eigenschaften der Additive (C2) gezielt eingestellt werden.By controlling the ratio of polar to non-polar groups, the surface-active properties of the additives (C2) can be adjusted in a targeted manner.
Derartige anionische oberflächenaktive Additive (C2) sind ebenfalls bekannt und im Handel z.B. unter den Namen Sokalan® (BASF), Joncryl® {Johnson Polymer), Aicosperse® (Alco), Geropon® (Rhodia), Good-Rite® (Goodrich), Neoresin® (Avecia), Orotan® und Morez® (Rohm & Haas), Disperbyk® (Byk) sowie Tegospers® (Goldschmidt) erhältlich.Such anionic surface-active additives (C2) are also known and commercially available for example under the name Sokalan ® (BASF), Joncryl ® {Johnson Polymer), Aicosperse ® (Alco), Geropon ® (Rhodia), Good-Rite ® (Goodrich) Neoresin ® (Avecia), Orotan ® and Morez ® (Rohm & Haas), Disperbyk ® (Byk) and Tegospers ® (Goldschmidt) available.
Als anionische oberflächenaktive Additive können die erfindungsgemäßen Pigmentzu- bereitungen weiterhin Additive auf Polyurethanbasis (C3) enthalten.As anionic surface-active additives, the pigment preparations according to the invention may furthermore contain polyurethane-based additives (C3).
Erfindungsgemäß sollen dabei unter dem Begriff Polyurethan nicht nur die reinen Umsetzungsprodukte von mehrwertigen Isocyanaten (C3a) mit isoeyanatreaktive Hydroxy- gruppen enthaltenden organischen Verbindungen (C3b) verstanden werden, sondern auch solche Umsetzungsprodukte, die durch den Zusatz von weiteren isoeyanatreakti- ven Verbindungen, z.B. von primäre oder sekundäre Aminogruppen tragenden Carbonsäuren, zusätzlich funktionalisiert sind.According to the invention, the term polyurethane is to be understood as meaning not only the pure reaction products of polyfunctional isocyanates (C3a) with isocyanate-reactive organic compounds (C3b) containing isocyanate-reactive groups, but also those reaction products obtained by the addition of further isocyanate-reactive compounds, e.g. of primary or secondary amino-bearing carboxylic acids are additionally functionalized.
Diese Additive zeichnen sich gegenüber anderen oberflächenaktiven Additiven durch ihre geringe lonenleitfähigkeit und ihren neutralen pH-Wert aus.These additives are distinguished from other surface-active additives by their low ionic conductivity and their neutral pH.
Als mehrwertige Isocyanate (C3a) für die Herstellung der Additive (C3) eignen sich insbesondere Diisocyanate, es können aber auch Verbindungen mit drei oder vier iso- cyanatgruppen eingesetzt werden. Es können sowohl aromatische als auch aliphati- sehe Isocyanate verwendet werden.Suitable polyfunctional isocyanates (C3a) for the preparation of the additives (C3) are in particular diisocyanates, but it is also possible to use compounds having three or four isocyanate groups. Both aromatic and aliphatic isocyanates can be used.
Als Beispiele für bevorzugte Di- und Triisocyanate seien aufgeführt: 2,4-Toluylendiiso- cyanat (2,4-TDI), 4,4'-Diphenylmethandiisocyanat (4,4'-MDl), para-Xylyiendiisocyanat, 1,4-Diisocyanatobenzol, Tetramethylxyiylenditsocyanat (TMXDI), 2,4'-Diphenylmethan- diisoeyanat (2,4'-MDI) und Triisocyanatotoluol sowie Isophorondiisocyanat (IPDI),Examples of preferred di- and triisocyanates are: 2,4-tolylene diisocyanate (2,4-TDI), 4,4'-diphenylmethane diisocyanate (4,4'-MDI), para-xylylene diisocyanate, 1,4-diisocyanatobenzene , Tetramethylxiyl diisocyanate (TMXDI), 2,4'-diphenylmethane diisocyanate (2,4'-MDI) and triisocyanatotoluene and isophorone diisocyanate (IPDI),
2-Butyl-2-ethy!pentamethylendiisocyanat, Tetramethylendiisocyanat, Hexamethyiendi- isoeyanat, Dodecamethylendüsocyanat, 2,2-Bis(4-isocyanatocyclohexyl)propan, Tri- methylhexandiisocyanat, 2-lsocyanatopropylcycfσhexylisocyanat, 2,4,4- und 2,2,4- Trimethy!hexamethy!endüsocyanat, 2,4'-Methylenbis(cyc!ohexy!)diisocyanat, cis- Cyclohexan-1 ,4-diisocyanat, trans-Cyclohexan-i ^-diisocyanat und 4-Methylcyclo- hexan-1,3-diisocyanat (H-TDi).2-butyl-2-ethylpentamethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, 2,2-bis (4-isocyanatocyclohexyl) propane, triisocyanate methylhexane 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-i-diisocyanate and 4-methylcyclohexane-1,3-diisocyanate (H-TDi).
Selbstverständlich können auch Mischungen von Isocyanaten (C3a) verwendet werden. Beispielhaft seien hier genannt: Mischungen von Strukturisomeren von 2,4-Tolu- ylendiisocyanat und Triisocyanatotoluoi, z.B. Mischungen aus 80 moi-% 2,4-Toluylen- diisocyanat und 20 moi-% 2,6-ToIuyiendiisocyanat; Mischungen aus eis- und trans- Cyclohexan-1 ,4-diisocyanat; Mischungen von 2,4- oder 2,6-Tofuylendiisocyanat mit aliphatischen Diisocyanaten, wie Hexamethylendiisocyanat und isophorondtisoeyanat.Of course, mixtures of isocyanates (C3a) can also be used. By way of example, mixtures of structural isomers of 2,4-toluene diisocyanate and triisocyanato toluene, e.g. Mixtures of 80% by mole of 2,4-tolylene diisocyanate and 20% by mole of 2,6-toluethylene diisocyanate; Mixtures of cis- and trans-cyclohexane-1,4-diisocyanate; Mixtures of 2,4- or 2,6-tofuylene diisocyanate with aliphatic diisocyanates such as hexamethylene diisocyanate and isophorone diisocyanate.
Als isoeyanatreaktive organische Verbindungen (C3b) eignen sich bevorzugt Verbindungen mit mindestens zwei isoeyanatreaktiven Hydroxygruppen pro Molekül. Geeig- net als Verbindung (C3b) sind jedoch auch Verbindungen, die nur eine isoeyanatreaktive Hydroxygruppe pro Molekül aufweisen. Diese mσπofunktionaüsäerten Verbindungen können die mindestens zwei isoeyanatreaktive Hydroxygruppen pro Molekül enthaltenden Verbindungen bei der Umsetzung mit dem Poiyisocyanat (C3a) teilweise oder auch ganz ersetzen.Suitable isocyanate-reactive organic compounds (C3b) are preferably compounds having at least two isocyanate-reactive hydroxyl groups per molecule. However, suitable compounds (C3b) are also compounds which have only one isocyanate-reactive hydroxy group per molecule. These mσπofunktionaüsäerten compounds, the at least two isoeyanatreaktive hydroxy groups per molecule containing compounds in the reaction with the polyisocyanate (C3a) partially or completely replace.
Im folgenden werden Beispiele für besonders bevorzugte isoeyanatreaktive Verbindungen (C3b) mit mindestens zwei isoeyanatreaktiven Hydroxygruppen pro Molekül aufgeführt.The following are examples of particularly preferred isocyanate-reactive compounds (C3b) having at least two isocyanate-reactive hydroxy groups per molecule.
Dabei handelt es sich um Polyetherdioie, Polyesterdiole, Polyesterdiole auf Lactonba- sis, Diole und Triole mit bis zu 12 C-Atomen, Dihydroxycarbonsäuren, Dihydroxysul- fonsäuren, Dihydroxyphosphonsäuren, Polycarbonatdiole, Polyhydroxyolefäne und Po- iysitoxane mit im Mittel mindestens zwei Hydroxygruppen pro Molekül.These are polyethers, polyesterdiols, lactone-based polyesterdiols, diols and triols having up to 12 carbon atoms, dihydroxycarboxylic acids, dihydroxysulphonic acids, dihydroxyphosphonic acids, polycarbonatediols, polyhydroxyolefans and polysialoxanes having on average at least two hydroxyl groups per molecule.
Geeignete Polyetherdioie (C3b) sind beispielsweise Homo- und Copolymerisate von C2-C4-Alkylenoxiden, wie Ethylenoxid, Propytenoxid und Butylenoxid, Tetrahydrofuran, Styroloxid und/oder Epichlorhydrin, die in Gegenwart eines geeigneten Katalysators, z.B. Bortrifluorid, erhältlich sind. Weiterhin geeignete Poiyetherdioie sind durch (Co)Polymerisation dieser Verbindungen in Gegenwart eines Starters mit mindestens zwei aeiden Wasserstoffatomen, z.B. von Wasser, Ethylenglykol, Thioglykol, Mercap- toethanol, 1 ,3-Propandiol, 1 ,4-Butandioi, 1 ,6-Hexandiol, 1 ,12-Dodecandiol, EthySendi- amin, Anilin oder 1 ,2-Di-(4-Hydroxypheny!)propan, zu erhalten.Suitable polyethers (C3b) 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, which are reacted in the presence of a suitable catalyst, e.g. Boron trifluoride, are available. Further suitable polyethers are by (co) polymerization of these compounds in the presence of a starter having at least two normal hydrogen atoms, e.g. of water, ethylene glycol, thioglycol, mercaptoethanol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,12-dodecanediol, ethylenediamine, aniline or 1,2-di- (4- Hydroxypheny!) Propane, to obtain.
Beispiele für besonders geeignete Polyetherdioie (C3b) sind Polyethylengiykol, PoIy- propylenglykol, Polybutylenglykol und Polytetrahydrofuran sowie Copolymerisate davon. Das Molekulargewicht Mn der Polyetherdiole beträgt bevorzugt 250 bis 5 000, besonders bevorzugt 500 bis 2 500.Examples of particularly suitable polyethers (C3b) are polyethylene glycol, polypropylene glycol, polybutylene glycol and polytetrahydrofuran, and also copolymers thereof. The molecular weight M n of the polyether diols is preferably 250 to 5,000, more preferably 500 to 2,500.
Als isocyanatreaktive Verbindung (C3b) geeignete Polyesterdioie (Hydroxypolyester) sind allgemein bekannt.Polyester diols (hydroxypolyesters) suitable as isocyanate-reactive compound (C3b) are well known.
Bevorzugte Polyesterdioie (C3b) sind die Umsetzungsprodukte von Diolen mit Dicar- bonsäuren oder deren reaktiven Derivaten, z.B. Anhydriden oder Dimethyiestern.Preferred polyester dioxides (C3b) are the reaction products of diols with dicarboxylic acids or their reactive derivatives, e.g. Anhydrides or dimethyesters.
Als Dicarbonsäuren eignen sich gesättigte und ungesättigte aliphatische sowie aromatische Dicarbonsäuren, die zusätzliche Substituenten, wie Halogen, tragen können. Bevorzugte aliphatische Dicarbonsäuren sind gesättigte unverzweigte α,ω-Dicarbon- säuren, die 3 bis 22, vor allem 4 bis 12 C-Atome enthalten.Suitable dicarboxylic acids are saturated and unsaturated aliphatic and aromatic dicarboxylic acids which may carry additional substituents, such as halogen. Preferred aliphatic dicarboxylic acids are saturated unbranched α, ω-dicarboxylic acids containing 3 to 22, especially 4 to 12, carbon atoms.
Beispiele für besonders geeignete Dicarbonsäuren sind: Bernsteinsäure, Glutarsäure, Adipinsäure, Korksäure, Azelainsäure, Sebacinsäure, 1,12-Dodecandicarbonsäure, Maleinsäure, Maleinsäureanhydrid, Fumarsäure, Itaconsäure, Phthalsäure, Isophthal- säure, Phthalsäureanhydrtd, Tetrahydrophthalsäureanhydrid, Hexahydrophthalsäure- anhydrid, Tetrachlorphthalsäureanhydrid, Endomethylentetrahydrophthalsäureanhy- drid, Terephthalsäure, Terephthalsäuredimethylester und Isophthalsauredimethylester.Examples of particularly suitable dicarboxylic acids are: succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, 1,12-dodecanedicarboxylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, phthalic acid, isophthalic acid, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, tetrachlorophthalic anhydride, endomethylenetetrahydrophthalic anhydride - drid, terephthalic acid, terephthalic acid dimethyl ester and isophthalic acid dimethylester.
Als Diole eignen sich insbesondere gesättigte und ungesättigte aliphatische und cycio- aliphatische Diole. Die besonders bevorzugten aliphatischen α.ω-Dioie sind unverzweigt und weisen 2 bis 12, insbesondere 2 bis 8, vor allem 2 bis 4 C-Atome auf. Be- vorzugte cycloaliphatische Dioie leiten sich von Cyclohexan ab.Particularly suitable diols are saturated and unsaturated aliphatic and cycloaliphatic diols. The particularly preferred aliphatic α.ω-Dioie are unbranched and have 2 to 12, in particular 2 to 8, especially 2 to 4 C-atoms. Preferred cycloaliphatic dioxides are derived from cyclohexane.
Beispiele für besonders geeignete Diole sind: Ethylenglykol, Propylenglykol, 1,3-Pro- pandiol, 1 ,4-Butandiol, 2-Methylpropan-1,3-diol, 1,5-Pentandiol, Neopentylglykol, 1,6- Hexandiol, 1 ,8-Octandiol, 1,10-Decandiol, 1,12-Dodecandiol, eis- und trans-But-2-en- 1 ,4-diol, 2-Butin-1 ,4-dioi und eis- und trans-1 ,4-Di(hydroxymethyl)cyclohexan.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-ene-1, 4-diol, 2-butyne-1, 4-dioi and cis- and trans-1 , 4-di (hydroxymethyl) cyclohexane.
Das Molekulargewicht Mn der Polyesterdiofe liegt bevorzugt bei 300 bis 5 000.The molecular weight M n of the polyester film is preferably 300 to 5,000.
Als isocyanatreaktive Verbindung (C3b) geeignete Polyesterdioie auf Lactonbasis ba- sieren insbesondere auf aliphatischen gesättigten unverzweigten ω-Hydroxycarbon- säuren mit 4 bis 22, bevorzugt 4 bis 8 C-Atomen. Es eignen sich auch verzweigte ω- Hydroxycarbonsäuren, bei denen ein oder mehrere -CH2-Gruppen in der Alkylenkette durch -CH(Ci-C4-Alkyl)- ersetzt sind.Lactone-based polyester diols suitable as isocyanate-reactive compound (C3b) are based in particular on aliphatic saturated unbranched ω-hydroxycarboxylic acids having 4 to 22, preferably 4 to 8, carbon atoms. Also suitable are branched ω- hydroxy carboxylic acids in which one or more -CH 2 groups in the alkylene chain by -CH (Ci-C 4 alkyl) - are replaced.
Beispiele für bevorzugte ω-Hydroxycarbonsäuren sind γ-Hydroxybuttersäure und δ- Hydroxyvaleriansäure. Selbstverständlich eignen sich auch die oben genannten Dioie ais isocyanatreaktive Verbindungen (C3b), wobei dieselben Bevorzugungen wie oben gelten,Examples of preferred ω-hydroxycarboxylic acids are γ-hydroxybutyric acid and δ-hydroxyvaleric acid. Of course, the above-mentioned Dioie ais isocyanate-reactive compounds (C3b), where the same preferences apply as above,
Ebenfalls als isocyanatreaktive Verbindungen (C3b) geeignet sind Triole, die insbe- sondere 3 bis 12, vor aiiem 3 bis 8 C-Atome aufweisen. Beispie! für ein besonders geeignetes Triol ist Trimethylolpropan.Also suitable as isocyanate-reactive compounds (C3b) are triols which, in particular, have 3 to 12, above all 3 to 8 C atoms. Step Example! a particularly suitable triol is trimethylolpropane.
Als isocyanatreaktive Verbindungen (C3b) geeignete Dihydroxycarbonsäuren sind insbesondere aiiphatische gesättigte Dihydroxycarbonsäuren, die vorzugsweise 4 bis 14 C-Atome enthalten, besonders geeignet. Ganz besonders geeignet sind Dihydroxycarbonsäuren der FormelDihydroxycarboxylic acids which are suitable as isocyanate-reactive compounds (C3b) are, in particular, particularly suitable aiiphatic saturated dihydroxycarboxylic acids which preferably contain 4 to 14 C atoms. Especially suitable are dihydroxycarboxylic acids of the formula
RR
HO-A1 — C— A2— OH COOHHO-A 1 - C - A 2 - OH COOH
in A1 und A2 gleiche oder verschiedene Ci -C4-Al kylenreste bedeuten und R für Wasserstoff oder Ci-C4-Alkyl steht.in A 1 and A 2 are the same or different C 1 -C 4 -alkylene radicals and R is hydrogen or C 1 -C 4 -alkyl.
Besonders bevorzugtes Beispiel für diese Dihydroxycarbonsäuren ist Dimethylolpro- pionsäure (DMPA).A particularly preferred example of these dihydroxycarboxylic acids is dimethylolpropionic acid (DMPA).
Weiterhin eignen sich als isocyanatreaktive Verbindungen (C3b) die entsprechenden Dihydroxysulfonsäuren und Dihydroxyphosphonsäuren, wie 2,3-Dihydroxypropan- phosphonsäure.Also suitable as isocyanate-reactive compounds (C3b) are the corresponding dihydroxysulfonic acids and dihydroxyphosphonic acids, such as 2,3-dihydroxypropane-phosphonic acid.
Der Begriff Dihydroxycarbonsäure soll dabei auch Verbindungen umfassen, die mehr als eine Carboxylfunktion (bzw. Anhydrid- oder Esterfunktion) enthalten. Solche Verbindungen sind durch Umsetzung von Dihydroxyverbindungen mit Tetracarbonsäure- dianhydriden, wie Pyromeilitsäuredianhydräd oder Cyclopentantetracarbonsäuredian- hydrid, im Molverhäitnis 2 : 1 bis 1 ,05 : 1 in einer Polyadditionsreaktion erhältlich und weisen vorzugsweise ein mittleres Molekulargewicht Mn von 500 bis 10 000 auf.The term dihydroxycarboxylic acid is intended to include compounds which contain more than one carboxyl function (or anhydride or ester function). Such compounds are obtainable by reacting dihydroxy compounds with tetracarboxylic dianhydrides, such as pyromelitic dianhydride or cyclopentanetetracarboxylic dianhydride, in a molar ratio of 2: 1 to 1:05 in a polyaddition reaction and preferably have an average molecular weight M n of from 500 to 10,000.
Als Beispiele für geeignete Polycarbonatdiole (C3b) sind die Umsetzungsprodukte von Phosgen mit einem Überschuß an Diolen, insbesondere unverzweigten gesättigten aliphatischen α,ω-Diolen mit 2 bis 12, insbesondere 2 bis 8, vor allem 2 bis 4 C- Atomen zu nennen.Examples of suitable polycarbonate diols (C3b) are the reaction products of phosgene with an excess of diols, in particular unbranched saturated aliphatic α, ω-diols having 2 to 12, especially 2 to 8, especially 2 to 4 carbon atoms.
Als isocyanatreaktive Verbindung (C3b) geeignete Polyhydroxyolefine sind vor aiiern α,ω-Dihydroxyolefine, wobei αfω-Dihydroxybutadiene bevorzugt sind. Die weiterhin als isocyanatreaktive Verbindung (C3b) geeigneten Polysiloxane enthalten im Mitte! mindestens zwei Hydroxygruppen pro Moieküi. Besonders geeignete Polysiloxane weisen im Mittel 5 bis 200 Si-Atome (Zahlenmittel) auf und sind vor allem mit Ci-Ci2-Alkylgruppen, insbesondere Methylgruppen, substituiert.Suitable as isocyanate-reactive compound (C3b) are polyhydroxyolefins α before aiiern, ω-dihydroxy olefins, said α-ω f dihydroxybutadienes are preferred. The further suitable as isocyanate-reactive compound (C3b) polysiloxanes contained in the middle! at least two hydroxy groups per moieküi. Particularly suitable polysiloxanes comprise on average 5 to 200 silicon atoms (number average) and are mainly with Ci-Ci 2 alkyl groups, especially methyl groups.
Als Beispiele für isocyanatreaktive Verbindungen (C3b), die nur eine isocyanatreaktive Hydroxygruppe aufweisen, seien insbesondere aliphatische, cycloaliphatische, arali- phatische oder aromatische Monohydroxycarbonsäuren und -sulfonsäuren genannt.Examples of isocyanate-reactive compounds (C3b) which have only one isocyanate-reactive hydroxy group include, in particular, aliphatic, cycloaliphatic, araliphatic or aromatic monohydroxycarboxylic acids and -sulfonic acids.
Die Additive auf Polyurethanbasis (C3) werden durch Umsetzung der Verbindungen (C3a) und (C3b) hergestellt, wobei das Molverhältnis von (C3a) zu (C3b) in der Regel 2 : 1 bis 1 : 1 , vorzugsweise 1 ,2 : 1 bis 1 : 1,2, beträgt.The polyurethane-based additives (C3) are prepared by reacting the compounds (C3a) and (C3b), wherein the molar ratio of (C3a) to (C3b) is usually 2: 1 to 1: 1, preferably 1, 2: 1 to 1: 1.2.
Dabei ist es möglich, neben den vorstehend genannten isocyanatreaktiven Verbindun- gen (C3b) weitere Verbindungen mit isocyanatreaktiven Gruppen zuzusetzen, beispielsweise Dithiole, Thioalkohole, wie Thioethanol, Aminoalkohole, wie Ethanolamin und N-Methylethaπolamin, oder Diamine, wie Ethylendiamin, und dadurch Polyurethane herzustellen, die neben den Urethangruppen noch Isocyanuratgruppen, Allophanat- gruppen, Harnstoffgruppen, Biuretgruppen, Uretdiongruppen oder Carbodiimidgruppen tragen. Weitere Beispiele für solche isocyanatreaktiven Verbindungen sind aliphatische, cycloaliphatische, araliphatische oder aromatische Carbonsäuren und Sulfonsäuren, die mindestens zwei primäre und/oder sekundäre Aminogruppen tragen.It is possible to add, in addition to the above-mentioned isocyanate-reactive compounds (C3b), further compounds with isocyanate-reactive groups, for example dithiols, thioalcohols, such as thioethanol, amino alcohols, such as ethanolamine and N-methylethanolamine, or diamines, such as ethylenediamine, and thereby produce polyurethanes which, in addition to the urethane groups, also carry isocyanurate groups, allophanate groups, urea groups, biuret groups, uretdione groups or carbodiimide groups. Further examples of such isocyanate-reactive compounds are aliphatic, cycloaliphatic, araliphatic or aromatic carboxylic acids and sulfonic acids which carry at least two primary and / or secondary amino groups.
Selbstverständlich können auch entsprechende nur eine isocyanatreaktive Gruppe aufweisende Verbindungen, beispielsweise Monoalkohole, primäre und sekundäre Monoamine, Monoaminocarbon- und -suifonsäuren und Mercaptane, zugesetzt werden. Übliche Einsatzmengen liegen bei bis zu 10 mol-%, bezogen auf (C3a).Of course, it is also possible to add corresponding compounds having only one isocyanate-reactive group, for example monoalcohols, primary and secondary monoamines, monoaminocarboxylic acids and succinic acids and mercaptans. Usual amounts are up to 10 mol%, based on (C3a).
Vorzugsweise liegen die Carboxyigruppen der Umsetzungsprodukte (C3) zumindest teilweise in Salzform vor, um Wasserlösfichkeit zu gewährleisten. Geeignet sind beispielsweise Alkalimetallsalze, wie Natrium- und Kaliumsaize, und Ammoniumsaize.Preferably, the carboxy groups of the reaction products (C3) are at least partially in salt form to ensure water solubility. Suitable examples are alkali metal salts, such as sodium and potassium salts, and ammonium salts.
Üblicherweise weisen die Additive (C3) mittlere Molekulargewichte Mw von 500 bis 250 000 auf.Usually, the additives (C3) have average molecular weights M w of 500 to 250,000.
Durch Steuerung des Verhältnisses von polaren zu unpolaren Gruppen können die oberflächenaktiven Eigenschaften der Additive (C3) gezielt eingestellt werden.By controlling the ratio of polar to non-polar groups, the surface-active properties of the additives (C3) can be adjusted in a targeted manner.
Derartige anionische oberflächenaktive Additive (C3) sind bekannt und im Handel z.B. unter den Namen Borchi® GEN SN95 (Borchers) erhältlich. Wasserlösliche anionische oberflächenaktive Additive auf der Basis von sauren Phosphorsäure-, Phosphonsäure-, Schwefelsäure- und/oder Sulfonsäureestem von Poiye- thern (C4) basieren insbesondere auf den Umsetzungsprodukten der oben aufgeführten Polyether (C1) mit Phosphorsäure, Phosphorpentoxid und Phosphonsäure bzw. Schwefelsäure und Sulfonsäure, Hierbei werden die Polyether in die entsprechenden Phosphorsäuremono- oder -diester und Phosphonsaureester bzw. die Schwefelsäuremonoester und Suifonsäureester überführt. Diese sauren Ester liegen bevorzugt in Form wasserlöslicher Salze, insbesondere als Alkafimetallsalze, vor allem Natriumsai- ze, und Ammoniumsalze vor, sie können jedoch auch in Form der freien Säuren einge- setzt werden.Such anionic surface-active additives (C3) are known and commercially available, for example under the name Borchi ® GEN SN95 (Borchers). Water-soluble anionic surface-active additives based on acidic phosphoric acid, phosphonic acid, sulfuric acid and / or sulfonic acid esters of polyesters (C4) are based in particular on the reaction products of the abovementioned polyethers (C1) 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 suifonic acid esters. These acidic 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.
Bevorzugte Phosphate und Phosphonate leiten sich vor allem von alkoxylierten, insbesondere ethoxylierten, Fett- und Oxoalkoholen, Aikylphenolen, Fettaminen, Fettsäuren und Harzsäuren ab, bevorzugte Sulfate und Sulfonate basieren insbesondere auf alko- xylierten, vor allem ethoxylierten, Fettalkoholen, Aikylphenolen und Aminen, auch mehrwertigen Aminen, wie Hexamethylendiamin.Preferred phosphates and phosphonates are derived primarily from alkoxylated, in particular ethoxylated, fatty and oxo alcohols, Aikylphenolen, fatty amines, fatty acids and resin acids, preferred sulfates and sulfonates are based in particular on alko- xylierten, especially ethoxylated, fatty alcohols, Aikylphenolen and amines, also polyhydric amines, such as hexamethylenediamine.
Derartige anionische oberflächenaktive Additive sind bekannt und im Handel z.B. unter den Namen Nekal® (BASF), Tamol® (BASF), Crodafos® (Croda), Rhodafac® (Rhodia), Maphos® (BASF), Texapon® (Cognis), Empicol® (Albright & Wilson), Matextl® (ICI), Soprophor® (Rhodia) und Lutensit® (BASF) erhältlich.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), Matextl ® (ICI), Soprophor ® (Rhodia) and Lutensit ® (BASF).
Die Farbmitteizubereitungen weisen üblicherweise einen Gehalt an Dispergiermittel (C) von 1 bis 50 Gew.-%, insbesondere von 1 bis 40 Gew.-%, auf.The colorant preparations usually have a content of dispersant (C) of from 1 to 50% by weight, in particular from 1 to 40% by weight.
Wasser bildet das flüssige Trägermaterial der Farbmittelzubereitungen.Water forms the liquid carrier material of the colorant preparations.
Vorzugsweise enthalten die Farbmittelzubereitungen ein Gemisch von Wasser und einem Wasserrückhaltemittel als flüssige Phase. Als Wasserrückhaltemittel dienen insbesondere organische Lösungsmittel, die schwer verdampfbar sind (d. h. in der Regel einen Siedepunkt > 1000C haben), daher wasserrückhaltend wirken, und in Wasser löslich oder mit Wasser mischbar sind.Preferably, the colorant formulations contain a mixture of water and a water retention agent as the liquid phase. As water-retaining agents in particular organic solvents have high boiling points are used (ie usually a boiling point> 100 0 C have), therefore water back reserved, and are miscible in water soluble or water.
Beispiele für geeignete Wasserrückhaltemittel sind mehrwertige Alkohole, bevorzugt unverzweigte und verzweigte mehrwertige Alkohole mit 2 bis 8, insbesondere 3 bis 6, C-Atomen, wie Ethylengiykol, 1,2- und 1,3-Propylenglykol, Glycerin, Erythrit, Penta- erythrit, Pentite, wie Arabit, Adonit und Xylit, und Hexite, wie Sorbit, Mannit und Dulctt. Weiterhin eignen sich z.B. auch Di-, Tri- und Tetraalkyienglykole und deren Mono- (vor allem Ci-Ce-, insbesondere Ci-C4-)alkylether. Beispielhaft seien Di-, Tri- und Tetraethy- lengiykol, Diethyienglykoimonomethyh -ethyl-, -propyl- und -butylether, Triethylengly- kolmonomethyl-, -ethyl-, -propyl- und -butylether, Di-, Tri- und Tetra-1 ,2- und -1 ,3-propyienglykol und Di-, Tri- und Tetra-1 ,2- und -1 ,3-propylenglykolmonomethyl-, -ethyi-, -propyl- und -butyiether genannt.Examples of suitable water retention agents are polyhydric alcohols, preferably unbranched and branched polyhydric alcohols having 2 to 8, in particular 3 to 6, carbon atoms, such as ethylene glycol, 1,2- and 1,3-propylene glycol, glycerol, erythritol, pentaerythritol, Pentites such as arabitol, adonite and xylitol, and hexites such as sorbitol, mannitol and dulctt. Also suitable, for example, are di-, tri- and tetraalkylene glycols and their mono- (especially C 1 -C 6, in particular C 1 -C 4 ) -alkyl ethers. Examples of these are di-, tri- and tetraethylene glycol, diethylene glycol monomethyl ethyl, propyl and butyl ethers, triethylene glycol monomethyl, ethyl, propyl and butyl ethers, di-, tri- and tetra-1, 2- and -1, 3-propylene glycol and di-, tri- and tetra-1, 2- and -1, 3-propylene glycol monomethyl, called -ethyi-, -propyl- and -butyiether.
in der Reget enthatten die Farbmitteizubereitungen 10 bis 88,95 Gew.-%, vorzugsweise 10 bis 80 Gew.-%, flüssige Phase (D). Liegt Wasser im Gemisch mit einem wasser- rückhaitenden organischen Lösungsmittel vor, so macht dieses Lösungsmittel im allgemeinen 1 bis 80 Gew.-%, bevorzugt 1 bis 60 Gew.-%, der Phase (D) aus.The colorant preparations generally contain from 10 to 88.95% by weight, preferably from 10 to 80% by weight, of liquid phase (D). If water is present in a mixture with a water-retaining organic solvent, this solvent generally constitutes from 1 to 80% by weight, preferably from 1 to 60% by weight, of phase (D).
Weiterhin können die Farbmitteizubereitungen als Komponente (E) noch übliche Zusatzstoffe, wie Biozide, Entschäumer, Antiabsetzmittei und Rheoiogiemodifizierer, ent- halten, deren Anteil im allgemeinen bis zu 5 Gew.-% betragen kann.Furthermore, the colorant preparations as component (E) may contain conventional additives, such as biocides, defoamers, anti-settling agents and rheology modifiers, the proportion of which may generally be up to 5% by weight.
Die Farbmitteizubereitungen können auf verschiedene Weise erhalten werden. Vorzugsweise wird zunächst eine Pigmentdispersion hergestellt, der der Farbstoff dann als Feststoff oder insbesondere in gelöster oder in flüssiger, insbesondere wäßriger, Phase dispergierter Form zugegeben wird.The colorant preparations can be obtained in various ways. Preferably, a pigment dispersion is first prepared, to which the dye is then added as a solid or in particular in dissolved or in liquid, in particular aqueous, phase-dispersed form.
Die Farbmitteizubereitungen können dem als Basis für die erfindungsgemäßen Holzwerkstoffplatten dienenden Gemisch aus Holzfasern bzw. -spänen und Bindemittel auf verschiedene Weise und an verschiedenen Stellen des Fabrikationsprozesses zuge- setzt werden. Im Fall der bevorzugten MDF-/HDF-PIatten werden sie vorteilhaft über die Blowline, getrennt von oder zusammen mit dem Leim, direkt in den Plattenherstellungsprozeß eingebracht.The colorant preparations can be added to the mixture of wood fibers or chips and binder used as a basis for the wood-based panels according to the invention in various ways and at different points in the fabrication process. In the case of the preferred MDF / HDF sheets, they are advantageously introduced directly into the plate making process via the blowline, separate from or together with the glue.
BeispieleExamples
Herstellung von erfindungsgemäßen MDF-PfattenProduction of MDF boards according to the invention
Beispiel 1example 1
a) Bieichunga) Bieichung
In einem 5I-Gefäß mit Ankerrührer und thermostatgeführter Heizung wurden 70 g Holzfasern (Fichte) und 1 g Ethylendiamintetraessigsäure (Trtlon® B, BASF) in 3 I Wasser unter Rühren auf 700C erhitzt. Nach Zugabe von 7 g Natriumpercarbonat wurde 1 h bei 70-750C gerührt. Dann wurden 7 g Natriumdithionit zugegeben und abschließend weitere 30 min bei 70-750C gerührt.5I in a vessel with an anchor stirrer and thermostat-compensating heating 70 g wood fibers (spruce) and 1 g of ethylenediaminetetraacetic acid (Trtlon ® B, BASF) were heated in 3 liters of water with stirring to 70 0 C. After addition of 7 g of sodium percarbonate was stirred at 70-75 0 C for 1 h. Then 7 g of sodium dithionite were added and finally stirred at 70-75 0 C for a further 30 min.
Die Holzstoffmaische wurde nach Abkühlen auf Raumtemperatur über ein Sieb der Maschenweite 1 mm von den flüssigen Bestandteilen abgetrennt und unter laufendem Wasser kurz ausgewaschen und durchgewalgt. Das ausgebreitete Fiitergut wurde dann bei 600C im Umlufttrockenschrank 3 Tage getrocknet. b) FärbungThe wood pulp mash was separated after cooling to room temperature over a sieve of mesh size 1 mm from the liquid components and washed out briefly under running water and durchgewalgt. The spread Fiitergut was then dried at 60 0 C in a convection oven for 3 days. b) staining
Die gebleichten Holzfasern wurden in einem Schaufelmischer durchmischt und mit dem in der folgenden Tabelle aufgeführten Leimansatz besprüht, der eine graue Pig- mentzubereitung der dort ebenfalls angegebenen Zusammensetzung enthielt.The bleached wood fibers were mixed in a paddle mixer and sprayed with the glue formulation listed in the following table, which contained a gray pigment preparation of the composition likewise indicated there.
Tabelletable
Die beleimten Fasern wurden anschließend zu einer Matte geschüttet, kalt vorverdichtet und bei 19O0C zu einer Platte gepreßt.The glued fibers were then poured into a mat, precompressed cold and pressed at 19O 0 C to a plate.
Zum Vergleich wurde bei ansonsten unveränderter Vorgehensweise eine MDF-Platte aus ungebleichten Holzfasern hergestellt.For comparison, an MDF board was made of unbleached wood fibers with an otherwise unchanged procedure.
In beiden Fällen wurde eine hellgraue MDF-Piatte erhalten. Die zum Vergleich hergestellte MDF-Platte wies jedoch einen gelblich-bräunlichen Grauton auf, während die erfindungsgemäße MDF-Platte aus gebleichten Holzfasern einen reinen helleren Grauton (Heliigkeitsdifferenz ΔL* gegenüber dem Vergleich: 2) zeigte. Beispiel 2In both cases, a light gray MDF board was obtained. However, the MDF board prepared for comparison had a yellowish-brownish gray tone, while the bleached wood fiber MDF board according to the present invention showed a pure lighter gray tone (difference in brightness ΔL * over the comparison: 2). Example 2
Eine MDF-Technikυmsanlage wurde mit Hackschnitzeln aus Fichtenholz beschickt und der MDF-Herstellungsprozeß mit einem Durchsatz von 21 kg/h gestartet. Unmittelbar vor dem Refiner wurde eine 20 gew.-%ige wäßrige Natriumdithionitlösung, entsprechend 5% Natπumdithionit atro Fasern, in den Prozeß gepumpt.An MDF plant was fed with wood chips from spruce and the MDF production process was started at a rate of 21 kg / h. Immediately before the refiner a 20 wt .-% aqueous sodium dithionite, corresponding to 5% Natπumdithionit atro fibers, was pumped into the process.
Die resultierenden gebleichten Holzfasern wurden durch die Blowline kontinuierlich mit dem in Tabelle 2 aufgeführten Leinansatz besprüht, der eine graue Pigmentzuberei- tung der dort ebenfalls angegebenen Zusammensetzung enthielt.The resulting bleached wood fibers were continuously sprayed by the blowline with the flax formulation listed in Table 2, which contained a gray pigment preparation of the composition also indicated there.
Tabelle 2Table 2
Die beieimten Holzfasern wurden in dem sich anschließenden kontinuierlichen Trockner auf eine Restfeuchte von etwa 9 Gew.-% getrocknet und dann diskontinuierlich zu einer Matte geschüttet, kaft vorverdichtet und bei 19O0C mit einem Preßzeitfaktor von 15 s/mm zu einer 16 mm dicken Platte gepreßt.The beimimten wood fibers were dried in the subsequent continuous dryer to a residual moisture content of about 9 wt .-% and then poured discontinuously into a mat kaft precompressed and at 19O 0 C with a pressing time factor of 15 s / mm to a 16 mm thick plate pressed.
Gegenüber einer ohne Bleichung, aber bei ansonsten unveränderter Vorgehensweise hergestellten MDF-Platte ergab sich eine Heiligkeitsdifferenz ΔL* von 3 Einheiten. Compared with a MDF board produced without bleaching, but with an otherwise unchanged procedure, a difference in the degree of dignity ΔL * of 3 units resulted.

Claims

Patentansprüche claims
1. Hellfarbige Holzwerkstoff platten, die aus Holzfasern hergestellt sind, die gebleicht und mit flüssigen Farbmitteϊzubereitungen, enthaltend mindestens ein Pigment und mindestens einen im sichtbaren Bereich des elektromagnetischen1. Light-colored wood-based panels, which are made of wood fibers, bleached and with liquid Farbmitteϊzubereitungen containing at least one pigment and at least one in the visible range of the electromagnetic
Spektrums absorbierenden Farbstoff, gefärbt sind.Spectrum absorbing dye, dyed.
2. Holzwerkstoffplatten nach Anspruch 1 , bei denen die Holzfasern zunächst oxida- tiv und dann reduktiv gebleicht sind.2. wood-based panels according to claim 1, wherein the wood fibers are first bleach oxidative and then reductive.
3. Holzwerkstoffplatten nach Anspruch 1 oder 2, bei denen die Holzfasern mit Farbmittelzubereitungen gefärbt sind, die 0,01 bis 10 Gew.-% Farbstoff, bezogen auf das Pigment, enthalten.3. wood-based panels according to claim 1 or 2, wherein the wood fibers are dyed with colorant preparations containing 0.01 to 10 wt .-% of the dye, based on the pigment.
4. Holzwerkstoffplatten nach den Ansprüchen 1 bis 3, bei denen die Holzfasern mit Farbmittelzubereitungen, die4. wood-based panels according to claims 1 to 3, wherein the wood fibers with colorant preparations, the
(A) 10 bis 70 Gew.-% mindenstens eines Pigments,(A) 10 to 70% by weight of at least one pigment,
(B) 0,05 bis 7 Gew.-% mindestens eines im sichtbaren Bereich des elektromagnetischen Spektrums absorbierenden Farbstoffs,(B) 0.05 to 7% by weight of at least one dye which absorbs in the visible region of the electromagnetic spectrum,
(C) 1 bis 50 Gew.-% mindestens eines Dispergiermittels,(C) 1 to 50% by weight of at least one dispersing agent,
(D) 10 bis 88,95 Gew.-% Wasser oder eines Gemisches von Wasser und mindestens einem Wasserrückhaltemittel und(D) 10 to 88.95% by weight of water or a mixture of water and at least one water retention agent and
(E) 0 bis 5 Gew.-% weitere für Farbmittelzubereitungen übliche Bestandteile(E) 0 to 5 wt .-% further common for colorant preparations ingredients
enthalten, gefärbt sind.contain, are colored.
5. Holzwerkstoffplatten nach den Ansprüchen 1 bis 4, bei denen die Holzfasern in einer Standardfarbtiefe von < 1/9 mit den Farbmittelzubereitungen gefärbt sind.5. wood-based panels according to claims 1 to 4, wherein the wood fibers are dyed in a standard color depth of <1/9 with the colorant preparations.
6. Holzwerkstoffplatten nach den Ansprüchen 1 bis 4, bei denen die Holfasern mit Farbmittelzubereitungen gefärbt sind, die einen CiELAB-Helligkeitswert L* > 75 aufweisen.6. wood-based panels according to claims 1 to 4, wherein the Holfasern are dyed with colorant preparations having a CiELAB brightness value L * > 75.
7. Holzwerkstoffplatten nach den Ansprüchen 1 bis 6, dadurch gekennzeichnet, daß es sich um MDF-, HDF- oder Spanplatten handelt. 7. wood-based panels according to claims 1 to 6, characterized in that it is MDF, HDF or chipboard.
8. Verwendung der Holzwerkstoffen gemäß den Ansprüchen 1 bis 7 zur Herstellung von Einrichtungsgegenständen.8. Use of the wood-based materials according to claims 1 to 7 for the production of furnishings.
9. Einrichtungsgegenstände, enthaltend Holzwerkstoffpiatten gemäß den Ansprü- chen 1 bis 7. 9. Furnishings, comprising Holzwerkstoffpiatten according to the claims 1 to 7.
EP06777443A 2005-06-29 2006-06-23 Light-colored engineered wood boards Withdrawn EP1899427A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE200510030788 DE102005030788A1 (en) 2005-06-29 2005-06-29 Light-colored engineered wood board, useful for producing furnishing, produced from wood fiber that is bleached and dyed with liquid dye preparation comprising pigment and dye that absorbs light in visible range of electromagnetic spectrum
DE200610009479 DE102006009479A1 (en) 2006-02-27 2006-02-27 Light-colored engineered wood board, useful for producing furnishing, produced from wood fiber that is bleached and dyed with liquid dye preparation comprising pigment and dye that absorbs light in visible range of electromagnetic spectrum
PCT/EP2006/063499 WO2007000418A1 (en) 2005-06-29 2006-06-23 Light-colored engineered wood boards

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EP1899427A1 true EP1899427A1 (en) 2008-03-19

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JP2009500189A (en) 2009-01-08
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