EP1888700A2 - Utilisation de preparations colorantes liquides pour colorer des materiaux composites a base de cellulose et de polymere - Google Patents

Utilisation de preparations colorantes liquides pour colorer des materiaux composites a base de cellulose et de polymere

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Publication number
EP1888700A2
EP1888700A2 EP06763064A EP06763064A EP1888700A2 EP 1888700 A2 EP1888700 A2 EP 1888700A2 EP 06763064 A EP06763064 A EP 06763064A EP 06763064 A EP06763064 A EP 06763064A EP 1888700 A2 EP1888700 A2 EP 1888700A2
Authority
EP
European Patent Office
Prior art keywords
pigment
colorant preparations
acid
wood
cellulose
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Withdrawn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
EP06763064A
Other languages
German (de)
English (en)
Inventor
Andres Carlos Garcia Espino
Juliane Krüsemann
Werner Peter
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
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Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP1888700A2 publication Critical patent/EP1888700A2/fr
Withdrawn legal-status Critical Current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
    • B27N3/00—Manufacture of substantially flat articles, e.g. boards, from particles or fibres
    • B27N3/002—Manufacture of substantially flat articles, e.g. boards, from particles or fibres characterised by the type of binder
    • 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
    • B27N3/00—Manufacture of substantially flat articles, e.g. boards, from particles or fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/045—Reinforcing macromolecular compounds with loose or coherent fibrous material with vegetable or animal fibrous material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials

Definitions

  • the present invention relates to the use of liquid colorant formulations containing at least one pigment and at least one dye for coloring cellulose / polymer composites.
  • Cellulose / polymer composites in particular lignocellulose / polymer or wood / polymer composites (WPC: Wood Polymer Compound or Wood Plastic Composite) are characterized by having both the properties of wood and the properties of plastic. Furthermore, it is advantageous that they can be produced based on raw materials from recycling. They are of interest for a variety of applications. As an example, the use as a structural element in the construction industry, e.g. as a partition, roof, floor, window frame and cladding, as well as packaging material.
  • WPC Wood Polymer Compound or Wood Plastic Composite
  • the cellulose particles used in the composites may have different morphology and correspondingly different largest particle diameters of about 1 to 10 mm (chips) over 0.1 to 1 mm (fibers) to 0.01 to 0.1 mm (dust).
  • chips 1 to 10 mm
  • fibers 0.1 to 1 mm
  • dust 0.01 to 0.1 mm
  • Wood is the currently preferred cellulosic material, with both softwoods, e.g. Pine and cedar, as well as hardwoods, e.g. Oak and maple, usable.
  • other vegetable materials are also suitable, e.g. Fibers of sisal, flax, hemp, jute, cotton and other cereals, bamboo, straw, reeds, coconut fibers, banana fibers, flax shives, rice husks and peanut shells.
  • thermoplastic polymers As a polymer component usually thermoplastic polymers are used. However, other polymers, such as ABS (graft copolymers of acrylonitrile and styrene on butadiene rubbers), ASA (graft copolymers of styrene and acrylonitrile on polyalkyl acrylate rubbers), SAN (styrene-acrylonitrile-co-polymers), are of course also preferred polymers. polymers) and PU (polyurethanes).
  • the mixing ratio is 40 to 95 wt .-% cellulose particles and 5 to 60 wt .-% polymer.
  • the preparation of the cellulose / polymer composites is generally carried out in such a way that initially to compensate for the density difference between polymer and cellulose.
  • a mixed granules is produced.
  • the polymer and cellulose particles are first metered into a heating mixer, in which the polymer is melted and mixed with the cellulose particles. This mixture is then granulated in a cooling mixer. The granules are then extruded and can be brought by injection into the desired shape.
  • additives are added which increase the compatibility of the cellulose component and the polymer component and / or the interphase adhesion (for example maleic acid-modified polyolefins or isocyanates) or favor the processability of the extrusion (for example resins, waxes).
  • additives are usually used to modify the technical properties of the composites (tensile strength, density, flexibility, shock sensitivity, heat resistance), their mechanical or chemical protection, to increase their lifetime and their aesthetic design.
  • additives may e.g. Foaming agents for foaming the polymer matrix, flow additives, thermal stabilizers, biocides, insecticides, antioxidants, UV light stabilizers, antistatics, flame retardants, fillers and colorants.
  • EP-A-888 870 describes packaging materials based on transparent low-fiber-content composites. It is mentioned that the transparent polymer can be dyed with dye solutions or the wood fibers can be coated with colored material.
  • the object of the invention was to provide colorant preparations with which cellulose / polymer composite materials can advantageously be dyed.
  • liquid colorant formulations containing at least one pigment and at least one dye has been found to color cellulose / polymer composites.
  • Such colorant preparations are known from WO-A-04/35276 and 35277 where they are used for coloring particleboard, MDF and OSB boards.
  • the liquid colorant preparations to be used according to the invention preferably contain from 0.5 to 10% by weight of dye, based on the pigment.
  • the colorant preparations (A) to be used according to the invention particularly preferably comprise at least one pigment, (B) at least one dye, (C) at least one dispersant and (D) water or a mixture of water and at least one water retention agent.
  • component (A) organic or inorganic pigments may be present in the colorant preparations to be used according to the invention.
  • the colorant formulations may 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 pigments can be used in transparent or opaque form.
  • 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.
  • Disazo condensation pigments Cl. Pigment Yellow 93, 95 and 128;
  • Anthanthrone pigments Cl. Pigment Red 168; 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;
  • Dioxazine pigments Cl. Pigment Violet 23 and 37; Cl. Pigment Blue 80;
  • Flavanthrone pigments Cl. Pigment Yellow 24;
  • Isoindoline pigments Cl. Pigments orange 61 and 69;
  • Isoviolanthrone pigments Cl. Pigment Violet 31;
  • Phthalocyanine pigments Cl. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6 and 16;
  • Triaryl carbonium pigments Cl. Pigment Blue 1, 61 and 62; Cl. Pigment Green 1; Cl. Pigment Red 81, 81: 1 and 169; Cl. Pigment Violet 1, 2, 3 and 27;
  • Suitable inorganic color pigments are, for example:
  • titanium dioxide CI Pigment White 6
  • zinc white colored zinc oxide
  • Zinc sulfide lithopone
  • Black pigments iron oxide black (CI Pigment Black 11), iron manganese black, spinel black (CI Pigment Black 27); Carbon black (Cl.
  • chromium oxide chromium oxide hydrate green
  • Chrome green CI Pigment Green 48
  • Cobalt green CI Pigment Green 50
  • Ultramarine green chromium oxide, chromium oxide hydrate green
  • Chrome green CI Pigment Green 48
  • Cobalt green CI Pigment Green 50
  • Cobalt blue (CI Pigment Blue 28 and 36; CI Pigment Blue 72); Ultramarine blue; Manganese blue;
  • Iron oxide brown (CI Pigment Brown 6 and 7), mixed brown
  • Iron oxide yellow (CI Pigment Yellow 42); Nickel titanium yellow (CI Pigment Yellow 53, CI Pigment Yellow 157, 158, 159, 160, 161, 162, 163, 164 and 189); Chromium titanium yellow; Spinel phases (CI Pigment Yellow 119); Cadmium sulfide and cadmium zinc sulfide (CI Pigment Yellow 37 and 35); Chrome yellow (CI Pigment Yellow 34); Bismuth vanadate (CI Pigment Yellow 184).
  • the luster pigments are single-phase or multi-phase platelet-shaped pigments whose color play is characterized by the interplay of interference, reflection and absorption phenomena. Examples which may be mentioned aluminum platelets and one or more times, in particular coated with metal oxides aluminum, iron oxide and mica platelets.
  • the pigments specifically.
  • high-lightfast pigments such as inorganic pigments and organic pigments from the perylene, indanthrone and copper phthalocyanine series.
  • conductive carbon black provides conductive composites of interest for antistatic liners.
  • the colorant preparations to be used according to the invention contain from 10 to 70% by weight, preferably from 10 to 60% by weight, of pigment (A).
  • the colorant preparations to be used according to the invention contain at least one dye.
  • Particularly suitable dyes are those which are soluble in water or in a water-miscible or water-soluble organic solvent.
  • the dyes (B) used preferably have a color which can be compared to the pigments (A), since in this way a particularly intensive coloring of the wood-based materials can be achieved.
  • colorants (B) which deviate in color, as a result of which nuances of the coloration are possible.
  • Particularly suitable are cationic dyes, anionic dyes and disperse dyes.
  • Suitable cationic dyes (B) are derived in particular from the di- and triarylmethane, 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 Cl. 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 include: 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, Metallkopmplex-, triarylmethane, xanthene and stilbene series, wherein dyes from the triarylmethane, azo and metal complex (especially copper, chromium) and cobalt complex) series 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.
  • Disperse dyes are preferably used in the form of commercially available, aqueous dispersions and develop their coloring effect in the production process of cellulose / polymer composites by diffusion at high temperatures.
  • disperse dyes from the series of quinophthalones and anthraquinones are particularly suitable.
  • the colorant preparations to be used according to the invention generally comprise the dye (B) in amounts of from 0.5 to 10% by weight, preferably from 1 to 8% by weight, based in each case 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 are, for example: Cl. Pigment Blue 15: 1 and Cl. Basic Violet 4; Cl. Pigment Green 7 and Cl. Basic Green 4; Cl. Pigment Green 7 and Cl. Direct Blue 199; Cl. Pigment Red 48: 2 and Cl. Direct Red 80; Cl. Pigment Red 112 and Cl. Direct Red 254; Cl. Pigment Orange 34 and Cl. Direct Yellow 11; C I. Pigment Yellow 74 and Cl. Direct Yellow 4; Cl. Pigment Black 7 and Cl. Basic Violet 3.
  • Component (C) comprises at least one dispersing agent in the colorant preparations to be used according to the invention.
  • Particularly suitable dispersants (C) are nonionic and anionic water-soluble surface-active additives.
  • nonionic additives (C) are based on polyethers (additives (C1)).
  • polyalkylene oxides preferably C 2 -C 4 -alkylene oxides and phenyl-substituted C 2 -C 4 -alkylene oxides, in particular polyethylene oxides, polypropylene oxides and poly (phenylethyleneoxides), block copolymers, in particular polypropylene oxide and polyethylene oxide blocks or poly (Phenylethylene oxide) - and polyethylene oxide blocks having polymers, and also random copolymers of these alkylene oxides suitable.
  • polyethylene oxides preferably polypropylene oxides and poly (phenylethyleneoxides)
  • block copolymers in particular polypropylene oxide and polyethylene oxide blocks or poly (Phenylethylene oxide) - and polyethylene oxide blocks having polymers, and also random copolymers of these alkylene oxides suitable.
  • polyalkylene oxides by polyaddition of alkylene oxides to Startermolekü- Ie as to saturated or unsaturated aliphatic and aromatic alcohols, phenol or naphthol, which in each case, preferably by alkyl, in particular Ci-C 12 alkyl C 4 - C 12 - or -C 4 Alkyl, substituted or unsaturated aliphatic and aromatic amines, saturated or unsaturated aliphatic carboxylic acids and carboxylic acid amides can be prepared.
  • alkyl in particular Ci-C 12 alkyl C 4 - C 12 - or -C 4 Alkyl
  • substituted or unsaturated aliphatic and aromatic amines saturated or unsaturated aliphatic carboxylic acids and carboxylic acid amides
  • 1 to 300 mol, preferably 3 to 150 mol, of alkylene oxide are used per mole of starter molecule.
  • Suitable aliphatic alcohols generally contain 6 to 26 C atoms, preferably 8 to 18 C atoms, and may be unbranched, branched or cyclic. Examples which may be mentioned are octanol, nonanol, decanol, isodecanol, undecanol, dodecanol, 2-butyloctanol, tridecanol, isotridecanol, tetradecanol, pentadecanol, hexadecanol (cetyl alcohol), 2-hexyldecanol, heptadecanol, octadecanol (stearyl alcohol), 2-heptylundecanol , 2-octyldecanol, 2-nonyltridecanol, 2-decyltetradecanol, oleyl alcohol and 9-octadecenol, as well as mixtures of these alcohols, such as C 8 / Ci
  • 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 ⁇ - and ⁇ -naphthol, hexylphenol, heptylphenol, octylphenol, nonylphenol, isononylphenol, undecylphenol, dodecylphenol, di- and tributylphenol and dinonylphenol.
  • Suitable aliphatic amines correspond to the abovementioned aliphatic alcohols. Of particular importance here are the saturated and unsaturated fatty amines, which preferably have 14 to 20 carbon atoms. Examples of aromatic amines are aniline and its derivatives.
  • Particularly suitable aliphatic carboxylic acids are 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 particular interest.
  • divalent to pentavalent amines are preferred which in particular of the formula H 2 N- (R 1 -NR 2 ) n -H (R 1 : C 2 -C 6 -alkylene; R 2 : hydrogen or d-Ce Alkyl; n: 1 to 5).
  • ethylenediamine diethylenetriamine, triethylenetetramine, tetraethylenepentamine, propylenediamine-1,3-dipropylenetriamine, 3-amino-1-ethyleneaminopropane, hexamethylenediamine, dihemamethylenetriamine, 1,6-bis (3-aminopropylamino) hexane and N-methyldipropylene triamine, with hexamethylenediamine and diethylenetriamine being particularly preferred and ethylenediamine being most preferred.
  • these amines are first reacted with propylene oxide and then with ethylene oxide.
  • the content of the block copolymers of ethylene oxide is usually about 10 to 90% by weight.
  • 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.
  • Suitable compounds 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 mentioned, with ethylene glycol and polyethylene glycol are particularly preferred and propylene glycol and dipropylene glycol are very particularly preferred.
  • Particularly preferred alkylene oxide adducts with at least bifunctional alcohols have a central polypropylene oxide block, that is to say they start from a propylene glycol or polypropylene glycol which is reacted first with further 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 block copolymers based on polyhydric alcohols generally have average molecular weights M n of from 1 000 to 20 000, preferably from 1 000 to 15 000.
  • alkylene oxide are known and commercially available eg 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 sulfonic acid esters of the above polyether (C3) called.
  • 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 may additionally contain copolymerized vinyl monomers containing no acid function, the alkoxylation products of these homopolymers and copolymers and the salts of these homopolymers and copolymers and their alkoxylation products.
  • 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 especially acrylic and methacrylic esters, such as methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, 2-ethylhexyl, nonyl, lauryl and hydroxyethyl (meth ) acrylate and phenyl, naphthyl and benzyl (meth) acrylate
  • Dialkyl esters of ethylenically unsaturated dicarboxylic acids such as dimethyl, diethyl, dipropyl, diisopropyl, dibutyl, dipentyl, dihexyl, di-2-ethylhexyl, dinonyl, dilauryl and di-2-hydroxyethyl maleate and
  • 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. There 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 / maleic acid copolymers, in each case as additional monomer constituents may contain acrylic acid esters and / or maleic acid esters.
  • the carboxyl groups of the non-alkoxylated homo- and copolymers are present at least partially in salt form in order to ensure water solubility.
  • Suitable examples are the alkali metal salts, such as sodium and potassium salts, and the ammonium salts.
  • the non-alkoxylated polymeric additives (C2) usually 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 this is possible) to be understood as meaning polymers completely esterified with polyether alcohols.
  • the degree of esterification of these polymers is 30 to 80 mol%.
  • polyether alcohols themselves, preferably polyethylene glycols and polypropylene glycols as well as their one side end-group-terminated derivatives, especially the corresponding monoethers, such as mono- aryl ethers, such as monophenyl ether, and especially mono-CrC ⁇ ⁇ -alkyl ether, for example with fatty alcohols etherified ethylene and propylene glycols, and the polyetheramines which can be prepared, for example, by conversion of a terminal OH group of the corresponding polyether alcohols or by polyaddition of alkylene oxides onto preferably primary aliphatic amines.
  • Polyethylene glycols, polyethylene glycol monoethers and polyether amines are preferred.
  • the average molecular weights M n of the polyether alcohols and their derivatives used are usually 200 to 10,000.
  • 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), Alcosperse ® (Alco), Geropon ® (Rhodia), Good-Rite ® (Goodrich), Neoresin ® (Avecia), Orotan ® and Morez ® (Rohm & Haas), Disperbyk ® (Byk) and Tegospers ® (Goldschmidt) available.
  • the pigment preparations of the invention may further contain polyurethane-based additives (C3).
  • polyurethane is to be understood not only to mean the pure reaction products of polyfunctional isocyanates (C3a) with isocyanate-reactive organic compounds (C3b) containing organic compounds, 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 , Tetramethylxylylene diisocyanate (TMXDI), 2,4'-diphenylmethane diisocyanate (2,4'-MDI) and triisocyanatotoluene and also isophorone diisocyanate (IPDI), 2-butyl-2-ethylpentamethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, 2,2- Bis (4-isocyanatocyclohexyl) propane, trimethylhexane diisocyanate, 2-isocyanatopropylcyclohexyl isocyanate,
  • mixtures of isocyanates C3a
  • isocyanates C3a
  • examples which may be mentioned here are: mixtures of structural isomers of 2,4-toluene diisocyanate and triisocyanatotoluene, for example mixtures of 80 mol% 2,4-tolylene diisocyanate and 20 mol% 2,6-tolylene diisocyanate; Mixtures of cis- and trans-cyclohexane-1,4-diisocyanate; Mixtures of 2,4- or 2,6-toluene 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 monofunctionalized compounds can partially or completely replace the compounds containing at least two isocyanate-reactive hydroxyl groups per molecule in the reaction with the polyisocyanate (C3a).
  • C3b particularly preferred isocyanate-reactive compounds having at least two isocyanate-reactive hydroxyl groups per molecule are listed below.
  • polyetherdiols polyetherdiols, polyesterdiols, lactone-based polyesterdiols, diols and triols having up to 12 carbon atoms, dihydroxycarboxylic acids, dihydroxysulphonic acids, dihydroxyphosphonic acids, polycarbonatediols, polyhydroxyolefins and polysiloxanes having on average at least two hydroxyl groups per molecule.
  • Suitable polyether diols (C3b) are, for example, homo- 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 obtainable in the presence of a suitable catalyst, for example boron trifluoride.
  • a suitable catalyst for example boron trifluoride.
  • polyether diols are by (co) polymerization of these compounds in the presence of a starter having at least two acidic hydrogen atoms, for example 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-hydroxyphenyl) propane, to obtain.
  • a starter having at least two acidic hydrogen atoms for example 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-hydroxyphenyl) propane, to obtain.
  • polyether diols (C3b) examples include 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 diols (C3b) are the reaction products of diols with dicarboxylic acids or their reactive derivatives, e.g. Anhydrides or dimethyl esters.
  • 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 from 3 to 22, especially 4 to 12, carbon atoms.
  • dicarboxylic acids examples include: succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, 1,1'-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 dimethyl isophthalate.
  • Particularly suitable diols are saturated and unsaturated aliphatic and cycloaliphatic diols.
  • the particularly preferred aliphatic ⁇ , ⁇ -diols are unbranched and have 2 to 12, in particular 2 to 8, especially 2 to 4 C-atoms.
  • Preferred cycloaliphatic diols are derived from cyclohexane.
  • 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-diol and cis- and trans-1 , 4-di (hydroxymethyl) cyclohexane.
  • the molecular weight M n of the polyester diols is preferably from 300 to 5,000.
  • Lactone-based polyesterdiols 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 co-hydroxycarboxylic acids in which one or more -CH 2 groups in the alkylene chain have been replaced by -CH (C r C 4 -alkyl) -.
  • Examples of preferred ⁇ -hydroxycarboxylic acids are ⁇ -hydroxybutyric acid and ⁇ -hydroxyvaleric acid.
  • diols are also suitable as isocyanate-reactive compounds (C3b), the same preferences apply as above.
  • isocyanate-reactive compounds C3b
  • triols which have, in particular, 3 to 12, in particular 3 to 8, C atoms.
  • An example of a particularly suitable triol is trimethylolpropane.
  • Dihydroxycarboxylic acids suitable as isocyanate-reactive compounds (C3b) are, in particular, aliphatic saturated dihydroxycarboxylic acids, which are preferably 4 to 14 Contain C atoms, particularly suitable. Dihydroxycarboxylic acids of the formula are very particularly suitable
  • 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 pyromellitic dianhydride or cyclopentanetetracarboxylic dianhydride, in a molar ratio of 2: 1 to 1.05: 1 in a polyaddition reaction and preferably have an average molecular weight M n of 500 to 10,000.
  • tetracarboxylic dianhydrides such as pyromellitic 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, in particular 2 to 8, especially 2 to 4 carbon atoms.
  • Polyhydroxyolefins suitable as isocyanate-reactive compound (C3b) are especially ⁇ , ⁇ -dihydroxyolefins, with ⁇ , ⁇ -dihydroxybutadienes being preferred.
  • the polysiloxanes which are furthermore suitable as isocyanate-reactive compound (C3b) contain on average at least two hydroxyl groups per molecule.
  • Particularly suitable polysiloxanes have on average 5 to 200 Si atoms (number average) and are especially substituted with C 1 -C 12 -alkyl groups, in particular 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, is.
  • 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 carboxyl 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 C3 are known and commercially available, for example under the name Borchi ® GEN SN95 (Borchers).
  • Water-soluble anionic surface-active additives based on acid phosphorous acid, phosphonic acid, sulfuric acid and / or sulfonic acid esters of polyethers (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.
  • the polyethers are converted into the corresponding phosphoric acid mono- or diesters and phosphonic acid esters or the sulfuric acid monoesters and sulfonic acid esters.
  • These acidic esters are preferably in the form of water-soluble salts, especially as alkali metal salts, especially sodium salts. ze, 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, alkylphenols, fatty amines, fatty acids and resin acids, preferred sulfates and sulfonates are based in particular on alkoxylated, especially ethoxylated, fatty alcohols, alkylphenols and amines, also 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), Matexil ® (ICI), Soprophor ® (Rhodia) and Lutensit ® (BASF).
  • Nekal ® BASF
  • Tamol ® BASF
  • Crodafos ® Crodafos ® (Croda)
  • Rhodafac ® Rhodia
  • Maphos ® BASF
  • Texapon ® Cognis
  • Empicol ® Albright & Wilson
  • Matexil ® ICI
  • Soprophor ® Rosit ®
  • Lutensit ® BASF
  • the colorant preparations to be used according to the invention 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 to be used according to the invention.
  • 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 xyNt, and hexites such as sorbitol, mannitol and dulcitol.
  • suitable are, for example, di-, tri- and tetraalkylene glycols and their mono- (especially C 1 -C 6 -, in particular C r C 4 -) alkyl ethers.
  • Examples which may be mentioned 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, -ethyl, propyl and -butylether called.
  • the colorant preparations to be used according to the invention contain from 10 to 88.95% by weight, preferably from 10 to 80% by weight, of liquid phase (D).
  • D liquid phase
  • this solvent generally makes 1 to 80 wt .-%, preferably 1 to 60 wt .-%, of the phase (D).
  • the colorant preparations 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 to be used according to the invention 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 to be used according to the invention are outstandingly suitable for coloring the cellulose particles used in cellulose / polymer composites.
  • the particles can consist of all naturally occurring celluloses and can be finely divided to coarse. Wood chips, wood fibers and wood dust are mentioned as preferred examples of these materials.
  • the cellulose particles can be colored at different stages of production.
  • the wood chips serving as starting material can be dyed, but the cellulose particles can also be dyed only after their production in a moist or dry state.
  • wood fibers In addition to the coloration of the wood chips serving as starting material, it is likewise possible to bring the moist wood fibers obtained after comminution by boiling and grinding into contact with the colorant preparations. If desired, the colorant preparations can be applied to the wood fiber together with further aids for composite production. Finally, the wood fibers can also be sprayed with the colorant preparations after drying.
  • the colored cellulose particles may then be mixed with the matrix polymer and coextruded, as is customary for the fabrication of cellulosic / polymer composites.
  • the polymer matrix is also to be colored, this can be done in a simple manner by additionally introducing generally known polymer-containing pigment concentrates, so-called masterbatches, into the extrusion process.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Wood Science & Technology (AREA)
  • Forests & Forestry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Coloring (AREA)
  • Paints Or Removers (AREA)

Abstract

L'invention concerne l'utilisation de préparations colorantes liquides contenant au moins un pigment et au moins un colorant pour colorer des matériaux composites à base de cellulose et de polymère.
EP06763064A 2005-05-02 2006-04-28 Utilisation de preparations colorantes liquides pour colorer des materiaux composites a base de cellulose et de polymere Withdrawn EP1888700A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102005020741A DE102005020741A1 (de) 2005-05-02 2005-05-02 Verwendung von flüssigen Farbmittelzubereitungen zur Einfärbung von Cellulose/Polymer-Verbundwerkstoffen
PCT/EP2006/061923 WO2006117341A2 (fr) 2005-05-02 2006-04-28 Utilisation de preparations colorantes liquides pour colorer des materiaux composites a base de cellulose et de polymere

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EP1888700A2 true EP1888700A2 (fr) 2008-02-20

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US (1) US20080189879A1 (fr)
EP (1) EP1888700A2 (fr)
CN (1) CN101184814A (fr)
CA (1) CA2606802A1 (fr)
DE (1) DE102005020741A1 (fr)
WO (1) WO2006117341A2 (fr)

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DE102005020742A1 (de) * 2005-05-02 2006-03-30 Basf Ag Verwendung von festen Pigmentzubereitungen zur Einfärbung von Cellulose/Polymer-Verbundwerkstoffen
DE102006037416A1 (de) * 2006-08-10 2008-02-14 Basf Ag Fußbodenpaneel aus MDF oder HDF
CN101657508A (zh) * 2007-04-13 2010-02-24 巴斯夫欧洲公司 形成有机颜料的方法
CN102161837A (zh) * 2011-02-25 2011-08-24 陈华 一种适用于合成革干法和后段的环保型液体染料
CN102286800B (zh) * 2011-05-30 2013-05-29 上海瑞贝卡纤维材料科技有限公司 一种功能性改性腈纶发用纤维及其制备方法
JPWO2013190777A1 (ja) * 2012-06-19 2016-02-08 パナソニックＩｐマネジメント株式会社 バガス成形体
US9718944B2 (en) 2015-04-02 2017-08-01 Cnh Industrial Canada, Ltd. Method of coloring biocomposite materials
WO2017029291A1 (fr) * 2015-08-20 2017-02-23 Basf Se Préparations pigmentaires universelles pour une utilisation sur point de vente
IT201600109323A1 (it) * 2016-10-28 2018-04-28 Giovanni Broggi Preparazioni pigmentarie universali per colorare e rinforzare materie plastiche
US20210163774A1 (en) * 2019-01-09 2021-06-03 Hewlett-Packard Development Company, L.P. Fluid sets
CN110437536A (zh) * 2019-08-13 2019-11-12 深圳市前海幸运色彩科技有限公司 一种用于pp基料的染色材料及其制备、染色工艺
CN112518933A (zh) * 2020-07-31 2021-03-19 老木匠木业有限公司 一种不褪色的木材染色方法
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CA2606802A1 (fr) 2006-11-09
DE102005020741A1 (de) 2006-03-30
CN101184814A (zh) 2008-05-21
WO2006117341A2 (fr) 2006-11-09
US20080189879A1 (en) 2008-08-14
WO2006117341A3 (fr) 2007-02-15

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