CN101184814A - Use of liquid colorant preparations for dyeing composite cellulose/polymer materials - Google Patents

Abstract

The present invention discloses use of liquid coloring agent preparation comprising at least one pigment and at least one dye, for the coloring of cellulose/polymer composite materials.

Description

Liquid colorant preparations is used for the painted purposes of composite cellulose/polymer materials

The liquid colorant preparations that the present invention relates to comprise at least a pigment and at least a dyestuff is used for cellulose polymer compound compound or the painted purposes of matrix material.

Cellulose polymer compound compound or matrix material, particularly ligno-cellulose polymkeric substance or wood polymers or plastics compound or matrix material (WPCs) have the two performance of timber and plastics.They are also because they can be favourable with the raw material production of retrieving.They can be used for multiple application.Example be they as the structural element in the Architectural Construction industry, for example as dividing wall, as the roof, as the floor, as window frame with as wadding, and as the purposes of wrapping material.

Therefore used cellulose particulates can have different forms and has from about 1-10 millimeter (bits) to the different maximum particle diameter of 0.1-1 millimeter (fiber) to 0.01-0.1 millimeter (powder) in compound or the matrix material.Cellulose particulates is thin more, and the verify hold facility (holdingcapacity) of these particles of polymer-based carbon is big more, but this compound or matrix material tensile strength in the same direction reduces.

Timber is at present preferred cellulose materials, is not only cork, and for example pine and China fir also comprise hardwood, for example oak and maple.Other vegetable material is available equally, for example the fiber of sisal hemp, flax, hemp, jute, cotton and other cereal, bamboo, straw, reed, coir, banana fiber, flax fragment, rice husk and Pericarppium arachidis hypogaeae.

The general thermoplastic polymer that uses.Preferred polymkeric substance is polyethylene, polypropylene and polyvinyl chloride particularly, but recognize, other polymkeric substance is available equally, for example ABS (vinyl cyanide and vinylbenzene are at the graft copolymer on the divinyl rubber), ASA (vinylbenzene and the vinyl cyanide graft copolymer on polyalkyl acrylate rubber), SAN (styrene-acrylonitrile copolymer) and PU (urethane).

Ratio of mixture is generally 40 weight % to 95 weight % cellulose particulates and 5 weight % to 60 weight % polymkeric substance.

Cellulose polymer compound compound or matrix material are produced with the density difference between balance polymer and the cellulose particulates by at first producing composite grain usually.In order to produce composite grain, at first polymkeric substance and cellulose particulates are metered in the mixing tank of heating, mix with polymer melt and with cellulose particulates at this.Then with this mixture granulation in the cooling mixing device.Extrude particle subsequently and can make it have desired shape by injection moulding.

Generally speaking, use additive to improve consistency and/or the alternate binding property (for example polyolefine of toxilic acid modification or isocyanic ester) between cellulosic component and the polymeric constituent or strengthen the workability extruded (for example resin, wax).

Usually the processing performance (tensile strength, density, flexible, impact sensitivity, thermostability) of using this compound of additive improved or matrix material in addition to be carrying out machinery or chemoproection to it, thereby prolongs their useful life and improve their eye appeal.This class additive can be for example to make polymeric matrix expansible whipping agent, flowing additive, thermo-stabilizer, biocides, sterilant, antioxidant, UV light absorber, static inhibitor, fire retardant, filler and colorant.

Known multiple with cellulose polymer compound compound or matrix material method of colouring.

DE-A-20 42 496 has described 1: 1 mixture or the only described pigment of 20 weight % or the granular colorant enriched material of dyestuff and 80 weight % polyethylene waxs of the C.I. pigment Blue 15 that comprises 20 weight % and blue active dye.This enriched material is mixed with wood powder and polymeric constituent, extrude jointly then.

WO-A-02/103113 has the matrix material based on the wood powder of giving the wood grain trace from the teeth outwards, and it is made by the combination of adding pigment-alkene masterbatch and unspecified liquid colorant when extruding.

US-A-2004/0076847 discloses based on polyvinyl chloride and has used the matrix material of the painted wood powder of pigment water dispersion.The pigment of preferably pointing out comprises metal oxide pigment, for example ferric oxide (III) and manganese titanate antimony, and copper phthalocyanine.Also mention with the painted feasibility of aqueous dye solutions.

EP-A-888 870 has described the wrapping material based on the transparent composite with low ratio xylon.It is mentioned, this transparent polymer can be with dye solution painted or xylon can apply with colored materials.

At last, US-A-2002/0040557 discloses the building panel that is used to take repeatedly (shingle) based on the cellulose polymer compound matrix material, and it is by compressed fibre cellulose fiber, polymkeric substance, produce as the mixture of toxilic acid graft polyolefin, UV light absorber, thermo-stabilizer, iron oxide pigment, mycocide and the fire retardant of coupling agent.

The known way of producing colored cellulose polymer composition or matrix material all not have employing not only to contain pigment but also contains the liquid colorant preparations of dyestuff.

The purpose of this invention is to provide the favourable painted colorant preparations that is used for cellulose polymer compound compound or matrix material.

We have found that the liquid colorant preparations that comprises at least a pigment and at least a dyestuff by use is painted with cellulose polymer compound compound or matrix material, has realized this purpose.

Know this class colorant preparations from WO-A-0435276 and 35277, wherein they are used for shaving board, MDF and OSB plate painted.

In fibrous particle in cellulose polymer compound compound or matrix material painted, the advantageous property of these colorant preparations also arouses attention.Irrelevant with its size, even comprise relatively large wood chip, cellulose particulates is " thoroughly painted (through-colored) " easily, and obtains strong, bright and fast to light color.Cellulose polymer compound compound or matrix material can be more effective painted thus, because in cellulose particulates, the main component of these compounds or matrix material is colored and is not only quantitatively accessory polymeric matrix.

It is the dyestuff of 0.5 weight % to 10 weight % that liquid colorant preparations used according to the invention preferably comprises based on pigment.

More preferably, colorant preparations used according to the invention comprises (A) at least a pigment, (B) at least a dyestuff, (C) at least a dispersion agent and (D) mixture of water or water and at least a water-holding agent.

Component in the colorant preparations used according to the invention (A) can comprise organic or mineral dye.It being understood that this colorant preparations can also comprise the mixture or organic and mixture mineral dye of various organic or various mineral dyes.

Pigment optimization exists with form in small, broken bits.Therefore, pigment has 0.1 to 5 micron usually, and particularly 0.1 to 3 micron, 0.1 to 1 micron mean particle size especially.

Depend on required effect, pigment can use with transparent or covering form.

Normally organic colour of pigment dyestuff and black pigment.Mineral dye can be colored pigment (colored, black and white pigment) and spangles equally.

Provide the example of suitable organic colored pigment below:

-monoazo pigment: C.I. pigment brown 25;

C.I. pigment orange 5,13,36,38,64 and 67;

C.I. Pigment red 1,2,3,4,5,8,9,12,17,

22、23、31、48:1、48:2、48:3、48:4、49、

49:1、51:1、52:1、52:2、53、53:1、53:3、

57:1、58:2、58:4、63、112、146、148、170、

175、184、185、187、191:1、208、210、245、

247 and 251;

C.I. Pigment Yellow 73 1,3,62,65,73,74,97,120,

151,154,168,181,183 and 191;

C.I. pigment violet 32;

-disazo pigment: C.I. pigment orange 16,34,44 and 72;

C.I. pigment Yellow 12,13,14,16,17,81,83,

106、113、126、127、155、174、176、180

With 188;

-condensed type disazo pigment: C.I. Pigment Yellow 73 93,95 and 128;

C.I. Pigment red 144,166,214,220,221,242

With 262;

C.I. pigment brown 23 and 41;

-three benzos [cd, jk] pyrene-5,10-two

Ketone pigment: C.I. Pigment red 168;

-anthraquinone pigment: C.I. pigment yellow 147,177 and 199;

C.I. pigment violet 31;

-anthrapyrimidine pigment: C.I. Pigment Yellow 73 108;

-quinacridone pigment: C.I. pigment orange 48 and 49;

C.I. pigment red 122,202,206 and 209;

C.I. pigment violet 19;

-quinolinone pigment: C.I. pigment yellow 13 8;

Diketopyrrolo-pyrrole pigment: C.I. pigment orange 71,73 and 81;

C.I. Pigment red 254,255,264,270 and 272;

-two  piperazine pigment: C.I. pigment Violet 23 and 37;

C.I. Pigment blue 80;

-flavanthrone pigment: C.I. Pigment Yellow 73 24;

-indanthrone pigment: C.I. pigment blue 60 and 64;

-xylylenimine pigment: C.I. pigment orange 61 and 69;

C.I. Pigment red 260;

C.I. pigment yellow 13 9 and 185;

-isoindolinone pigment: C.I. Pigment Yellow 73 109,110 and 173;

-isoviolanthrone pigment: C.I. pigment violet 31;

-metal complex pigments: C.I. Pigment red 257;

C.I. Pigment Yellow 73 117,129,150,153 and 177;

C.I. Pigment green 8;

-purple cyclic ketones (perinone) pigment: C.I. pigment orange 43;

C.I. Pigment red 194;

-perylene pigmentss: C.I. Pigment black 31 and 32;

C.I. pigment red 123,149,178,179,190 and 224;

C.I. pigment violet 29;

-phthalocyanine pigment: C.I. pigment Blue 15,15:1,15:2,15:3,15:4,15:6

With 16;

C.I. pigment Green 7 and 36;

-pyranthrone pigments: C.I. pigment orange 51;

C.I. pigment red 21 6;

-pyrazoles quinazolone pigment: C.I. pigment orange 67;

C.I. Pigment red 251;

-thioindigo color: C.I. pigment Red 88 and 181;

C.I. pigment violet 38;

-triaryl carbon  pigment: C.I. pigment blue 1,61 and 62;

C.I. Pigment green 1;

C.I. pigment red 81,81:1 and 169;

C.I. pigment violet 1,2,3 and 27;

C.I. Pigment black 1 (nigrosine);

C.I. Pigment Yellow 73 101 (aldazine Huang);

C.I. pigment brown 22.

The example of suitable inorganic colored pigment is:

-white pigment: titanium dioxide (C.I. Pigment white 6), zinc white, pigment-level oxidation

Zinc; Zinc sulphide, lithopone;

-black pigment: iron oxide black (C.I. Pigment black 11), black, the spinel of ferrimanganic

Black (C.I. Pigment black 27); Carbon black (C.I. Pigment black 7);

-coloured pigment: chromic oxide, transparent vert emeraude; Chrome green (C.I. Pigment green

48); Cobalt green (C.I. Pigment green 50); Ultramarine green;

Cobalt blue (C.I. Pigment blue 28 and 36; C.I. Pigment blue 72);

Ultramarine blue; Manganese indigo plant;

Ultramarine violet; Cobalt violet and manganese violet;

Red iron oxide (C.I. Pigment red 101); Cadmium sulfoselenide pigment

(C.I. Pigment red 108); Cerium sulphide (C.I. Pigment red 265);

Molybdenum orange (C.I. Pigment red 104); Ultramarine is red;

Iron oxide brown (C.I. pigment brown 6 and 7), mixing palm fibre, point crystalline substance

Stone mutually with corundum mutually (C.I. pigment brown 29,31,33,34,

35,37,39 and 40), chromium titan yellow (C.I. pigment brown 24),

Chrome orange;

Cerium sulphide (C.I. pigment orange 75);

Iron oxide yellow (C.I. Pigment Yellow 73 42); Nickel titanium yellow (C.I. pigment

Yellow 53; C.I. Pigment Yellow 73 157,158,159,160,161,

162,163,164 and 189); The chromium titan yellow; The spinel phase

(C.I. Pigment Yellow 73 119); Cadmium Sulfide and Cadmium Sulfide zinc (C.I. face

Material yellow 37 and 35); Chrome yellow (C.I. pigment yellow 34); Vanadic acid

Bismuth (C.I. Pigment Yellow 73 184).

Spangles is the lamellar pigment with single-phase or heterogeneous structure, and its color performance is a feature with the interaction of interference, reflection and absorbing phenomenon.Example is aluminium flake and aluminium, ferric oxide and the sheet mica that has one or more coatings, especially coating of metal oxides.

Specifically select pigment according to the desired use of this compound or matrix material.For example, high fast light pigment can be used for applications as the pigment dyestuff of mineral dye and Lai Zi perylene system, indanthrone and copper phthalocyanine system.By using graphitized carbon black, can obtain to have the conduction compound or the matrix material that are used in antistatic wadding.

The amount of the pigment that comprises in the colorant preparations used according to the invention (A) is generally 10 weight % to 70 weight %, preferred 10 weight % to 60 weight %.

Component in the colorant preparations used according to the invention (B) is at least a dyestuff.The dyestuff that is fit to is the dyestuff of water soluble or water-soluble miscibility or water-miscible organic solvent particularly.Preferably, used dyestuff (B) all has and the suitable tone of pigment (A) in each case, because this is the strong especially painted mode that realizes wood based material.But, can also use the different dyestuff of tone (B), can make painted gradual change thus.

Suitable dyestuff is cationic dyes, anionic dyestuff and dispersed dye particularly.

Suitable cationic dyes (B) belongs to two especially-and triarylmethane, xanthene, azo, cyanine, azacyanine, methyne, acridine, safranine,  piperazine, indulines, nigrosine and azophenlyene scope, the dyestuff of preferred azo, triarylmethane and xanthene scope.

The specific examples that can mention is: C.I. basic yellow 1,2 and 37; C.I. Basic Orange 2; C.I. alkali red 1:1 and 108; C.I. alkali blue 1,7 and 26; C.I. alkaline purple 1,3,4,10,11 and 49; C.I. alkali green 1 and 4; C.I. vesuvine 1 and 4.

Cationic dyes (B) also can be the colorant that comprises outside basic group.Suitable example is C.I. alkali blue 15 and 161 at this.

Available cationic dyes (B) also is included in acid solubilizing agent and has the corresponding dyeing alkali that uses down.As an example, can mention: C.I. solvent yellow 34; C.I. the solvent orange 3; C.I. solvent red 49; C.I. solvent purple 8 and 9; C.I. solvent blue 2 and 4; C.I. solvent black 7.

Suitable anionic dyestuff particularly is selected from azo, anthraquinone, metal complexes, triarylmethane, xanthene and 1, the sulfonated compound of 2-two-vinylbenzene scope, the preferably dyestuff of triarylmethane, azo and metal complexes (especially copper, chromium and cobalt complex) scope.

The specific examples that can mention is: C.I. quinoline yellow, 19,36 and 204; C.I. acid orange 7,8 and 142; C.I. Xylene Red 52,88,351 and 357; C.I. acid violet 17 and 90; C.I. acid blue 9,193 and 199; C.I. Acid Black 1 94; The negatively charged ion chromium complex dyes, for example the C.I. acid violet 46,56,58 and 65; C.I. acid yellow 59; C.I. von Muller's indicator 44,74 and 92; C.I. azogeramine 95; C.I. ACID BROWN 355 and C.I. erie black 52; Negatively charged ion cobalt complex dyestuff, for example C.I. acid yellow 11 9 and 204; C.I. direct yellow 4 and 11; C.I. directly red 80,81 and 254 and C.I. sun blue 199.

These dyestuffs are water miscible, particularly work as them as an alkali metal salt, particularly as lithium, sodium or sylvite, or as replacement or unsubstituting ammonium salt, when particularly alkanol ammonium salts exists.

Dispersed dye preferably use with commercially available water dispersion form and bring into play its coloring effect by diffusion at high temperature in the manufacturing operations of cellulose polymer compound compound or matrix material.

For example, the dispersed dye of quinolinone system and anthraquinone system are particularly suitable for.

Dyestuff (B) usually in colorant preparations used according to the invention with 0.5 weight % to 10 weight %, the amount of preferred 1 weight % to 8 weight % exists, entirely based on pigment (A).Based on the gross weight of preparation, this is equivalent to common 0.05 weight % to 7 weight %, the particularly amount of 0.1 weight % to 5.6 weight %.

Preferred pigment-dye combinations is, for example: the C.I. pigment Blue 15: 1 and C.I. alkalescence purple 4; C.I. pigment Green 7 and C.I. alkali green 4; C.I. pigment Green 7 and C.I. sun blue 199; C.I. pigment red 4 8:2 and C.I. direct red 80; C.I. Pigment Red 112 and C.I. direct red 254; C.I. pigment orange 34 and C.I. direct yellow 11; C.I. Pigment Yellow 73 74 and C.I. direct yellow 4; C.1. Pigment black 7 and C.I. alkaline purple 3.

Component in the colorant preparations used according to the invention (C) is at least a dispersion agent.

Specially suitable dispersion agent (C) is non-ionic type and anionic water-soluble surface-active additives.

Specially suitable non-ionic type additive (C) is based on polyethers (additive (C1)).

Except unmixing polyoxyalkylene, preferred C ₂-C ₄The C that oxyalkylene and phenyl replace ₂-C ₄Oxyalkylene, especially outside polyoxyethylene, polyoxytrimethylene and poly-(Styrene oxide 98min.), suitable segmented copolymer especially in addition, especially the polymkeric substance that contains polyoxytrimethylene and polyoxyethylene block or poly-(Styrene oxide 98min.) and polyoxyethylene block, and the random copolymers of these oxyalkylenes.

These polyoxyalkylenes can be by preparing the oxyalkylene addition polymerization on starter molecules, for example addition polymerization on saturated or unsaturated aliphatic and aromatic alcohol, addition polymerization is to separately can be respectively by alkyl, C especially ₁-C ₁₂Alkyl, preferred C ₄-C ₁₂Alkyl and C ₁-C ₄On the phenol or naphthols that alkyl replaces, addition polymerization on saturated or unsaturated aliphatic and aromatic amine and addition polymerization on saturated or unsaturated aliphatic carboxylic acid and carboxylic acid amides.Common every mole of starter molecules is used 1 to 300 mole, preferred 3 to 150 moles oxyalkylene.

Suitable fatty alcohol comprises 6 to 26 carbon atoms usually, preferred 8 to 18 carbon atoms, and can have not branching, branching or ring texture.Example is octanol, nonyl alcohol, decyl alcohol, isodecyl alcohol, hendecanol, dodecanol, 2-butyl octanol, tridecyl alcohol, different tridecyl alcohol, tetradecanol, pentadecylic alcohol, cetyl alcohol (hexadecanol), 2-hexyl decyl alcohol, heptadecanol, Stearyl alcohol (stearyl alcohol), 2-heptyl hendecanol, 2-octyl group decyl alcohol, 2-nonyl tridecyl alcohol, 2-decyl tetradecanol, oleyl alcohol and 9-Stearyl alcohol, and these pure mixture, for example C ₈/ C ₁₀, C ₁₃/ C ₁₅And C ₁₆/ C ₁₈Alcohol and cyclopentanol and hexalin.Particularly advantageous is the saturated or pure and mild synthetic fatty alcohol from oxo synthesis of unsaturated fatty acids that is obtained by fat splitting and reduction by natural matter.Oxyalkylene and these pure adductss have 200 to 5000 molecular-weight average M usually _n

The example of above-mentioned aromatic alcohol not only comprises unsubstituting phenenyl phenol and α-and 2-Naphthol, also comprises hexyl phenol, heptyl phenol, octyl phenol, nonyl phenol, different nonyl phenol, undecyl phenol, 4-dodecylphenol, two-and tributyl phenol and binonylphenol.

Suitable aliphatic amine is corresponding to above-mentioned fatty alcohol.Also particularly importantly preferably has the saturated and unsaturated fatty acids amine of 14 to 20 carbon atoms at this.The example of suitable aromatic amine is aniline and derivative thereof.

The available aliphatic carboxylic acid especially comprises saturated and unsaturated fatty acids and hydrogenation fully, partial hydrogenation and unhydrided resinous acid and polyfunctional carboxylic acids, for example dicarboxylic acid, for example toxilic acid that preferably contains 14 to 20 carbon atoms.

Suitable carboxylic acid amides is derived from these carboxylic acids.

Except the adducts of oxyalkylene and monofunctional amines and alcohol, very particularly advantageous is oxyalkylene and the adducts of bifunctional amine and alcohol at least.

Described bifunctional amine at least preferably has 2 to 5 amidos and meets formula H especially ₂N-(R ¹-NR ²) _n-H (R ¹: C ₂-C ₆Alkylidene group; R ²: hydrogen or C ₁-C ₆Alkyl; N:1-5).Specific examples is: quadrol, diethylenetriamine, Triethylenetetramine (TETA), tetren, 1,3-propylene diamine, dipropylenetriamine, 3-amino-1-ethyleneimino propane, hexamethylene-diamine, bis hexamethylene triamine, 1,6-two (amino third amino of 3-) hexane and N-methyl dipropylenetriamine, wherein more preferably hexamethylene-diamine and diethylenetriamine, most preferably quadrol.

These amine preferably at first react with propylene oxide, react with ethylene oxide then.The ethylene oxide content of segmented copolymer is typically about 10-90 weight %.

Molecular-weight average M based on the segmented copolymer of polyamines _nBe generally 1000 to 40000, be preferably 1500 to 30000.

Described difunctional alcohol at least preferably has 2 to 5 hydroxyls.Example is C ₂-C ₆Aklylene glycol and corresponding two-and multi alkylidene diol, ethylene glycol, 1 for example, 2-propylene glycol, 1, ammediol, 1,2-butyleneglycol, 1,4-butyleneglycol, 1,6-hexylene glycol, dipropylene glycol and polyoxyethylene glycol, glycerol and tetramethylolmethane, wherein more preferably ethylene glycol and polyoxyethylene glycol, most preferably propylene glycol and dipropylene glycol.

Particularly preferred oxyalkylene has center polyoxytrimethylene block with the adducts of difunctional alcohol at least, promptly based at first with another propylene oxide reaction then with the propylene glycol or the polypropylene glycol of ethylene oxide reaction.The ethylene oxide content of this segmented copolymer is generally 10 weight % to 90 weight %.

Molecular-weight average M based on the segmented copolymer of polyvalent alcohol _nBe generally 1000 to 20000, be preferably 1000 to 15000.

This class oxyalkylene segmented copolymer is known and for example can be with Tetronic ^And Pluronic ^(BASF) run after fame and buy.

The example that is especially suitable for use as the water soluble anion type tensio-active agent of component (C) is: based on the additive (C2) of the polymkeric substance of ethylenically unsaturated carboxylic acids, based on the additive (C3) of urethane with based on the additive (C3) of the ester of acid phosphatase, phosphonic acids, sulfuric acid and/or the sulfonic acid of above-mentioned polyethers.

Can certainly use the mixture of multiple additives (C), that is, and the mixture of not only various non-ionic type additives, and the mixture of various anionic additives, the mixture of non-ionic type and anionic additive in addition.

Available based on the anionic water-soluble surface-active additives (C2) of the polymkeric substance of unsaturated carboxylic acid particularly including being selected from following additive: alkoxylated polymerization product and the salt of these homopolymer and multipolymer and their alkoxylated polymerization product of the homopolymer of olefinic unsaturated monocarboxylic and/or ethylenically unsaturated dicarboxylic and multipolymer (it can further comprise does not have sour functional copolyethylene monomer), these homopolymer and multipolymer.

The carboxylic monomer that can mention and the example of vinyl monomer are:

-vinylformic acid, methacrylic acid and Ba Dousuan;

The reaction product and the fumaric acid of-toxilic acid, maleic anhydride, toxilic acid monoesters, toxilic acid monoamide, toxilic acid and diamines (it can be oxidized to the derivative that comprises the amine oxide group), wherein preferred toxilic acid, maleic anhydride and toxilic acid monoamide;

-vinyl aromatic compounds, for example vinylbenzene, vinyl toluene and Vinyl toluene; Ethene, propylene, iso-butylene, diisobutylene and divinyl; Vinyl ether, for example polyoxyethylene glycol mono vinyl ether; The vinyl ester of straight chain or branching monocarboxylic acid, for example vinyl-acetic ester and propionate; The alkyl ester of olefinic unsaturated monocarboxylic and aryl ester, especially acrylate and methacrylic ester, for example (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) isopropyl acrylate, (methyl) butyl acrylate, (methyl) vinylformic acid pentyl ester, (methyl) Ethyl acrylate, (methyl) 2-EHA, (methyl) vinylformic acid ester in the ninth of the ten Heavenly Stems, (methyl) lauryl acrylate and (methyl) Hydroxyethyl acrylate and (methyl) phenyl acrylate, (methyl) vinylformic acid naphthalene ester and (methyl) benzyl acrylate; The dialkyl of ethylenically unsaturated dicarboxylic, for example the dimethyl ester of toxilic acid and fumaric acid, diethyl ester, dipropyl, diisopropyl ester, dibutylester, diamyl ester, dihexyl, two 2-ethylhexyls, two the ninth of the ten Heavenly Stems ester, two lauryls and two 2-hydroxyl ethyl esters; Vinyl pyrrolidone; Vinyl cyanide and methacrylonitrile; Wherein optimization styrene, iso-butylene, diisobutylene, acrylate and polyoxyethylene glycol mono vinyl ether.

Mention the example of polyacrylic acid especially as these monomeric preferred homopolymer.

The monomeric multipolymer of mentioning can be by two or more, and particularly three kinds of different monomers constitute.Multipolymer can be random copolymers, alternating copolymer, segmented copolymer and graft copolymer.Preferred copolymer is styrene-propene acid, vinylformic acid-toxilic acid, vinylformic acid-methacrylic acid, butadiene-acrylic acid, iso-butylene-toxilic acid, diisobutylene-toxilic acid and styrene-maleic acid copolymer, they can each self-contained acrylate and/or maleic acid ester as extra monomer component.

Preferably, the carboxyl of not oxyalkylated homopolymer and multipolymer to small part exists to guarantee the solubleness in water with salt form.

Suitable example is an an alkali metal salt, for example sodium salt and sylvite, and ammonium salt.

The molecular-weight average M of alkoxylate polymeric additive (C2) not _wBe generally 900 to 250000.The molecular weight ranges that is particularly suitable for each polymkeric substance depends on its composition naturally.The example molecule weight range of various polymkeric substance is as follows: polyacrylic acid: M _wBe 900 to 250000; Styrene-propene acid copolymer: M _wBe 1000 to 50000; Vinylformic acid-Sipacril 2739OF: M _wBe 1000 to 250000; Vinylformic acid-maleic acid: M _wBe 2000 to 70000.

Except these homopolymer and multipolymer itself, their alkoxylated polymerization product also particularly advantageously can be used as additive (C2).

Alkoxylated polymerization product this be meant especially according to the present invention these polymkeric substance with Aethoxy Sklerol part to (if possible) product of esterification fully.The degree of esterification of these polymkeric substance is generally 30-80 mole %.

The available esterifying agent is particularly including Aethoxy Sklerol itself, preferred polyoxyethylene glycol and polypropylene glycol, and their one-sided end group capped derivatives, especially corresponding monoether, for example single aryl oxide, monophenyl ether for example, particularly single C ₁-C ₂₆Alkyl oxide, for example use the Fatty Alcohol(C12-C14 and C12-C18) etherificate the pure and mild trimethylene glycol of ethylene and can be for example terminal OH groups converted or polyetheramine by making corresponding Aethoxy Sklerol by the oxyalkylene addition polymerization is prepared to the preferred aliphatic series primary amine.At this preferably polyoxyethylene glycol, polyoxyethylene glycol monoether and polyetheramine.The molecular-weight average M of used Aethoxy Sklerol and derivative thereof _nBe generally 200 to 10000.

For additive (C2), can realize the particular surface activity performance via the ratio of polarity and non-polar group.

This anionoid type surfactant additive (C2) is known equally and can be for example with Sokalan ^(BASF), Joncryl ^(Johnson Polymer), Alcosperse ^(Alco), Geropon ^(Rhodia), Good-Rite ^(Goodrich), Neoresin ^(Avecia), Orotan ^And Morez ^(Rohm﹠amp; Haas), Disperbyk ^(Byk) and Tegospers ^(Goldschmidt) run after fame and buy.

The anionic surface activity additive that can be used for pigment preparation of the present invention also comprises polyurethane-base additive (C3).

For the present invention, urethane is construed as the pure reaction product that not only is meant polyfunctional isocyanate (C3a) and contains the organic compound (C3b) of isocyanate-reactive hydroxyl, also has the extra functionalized reaction product by adding other isocyanate-reactive compound (carboxylic acid that for example has primary amino or secondary amino group by interpolation).

The difference of these additives and other surfactant additive is their low ionic conductivity and their pH neutral.

The polyfunctional isocyanate (C3a) who can be used for preparing additive (C3) is particularly including vulcabond, but also can use the compound with three or four isocyanate groups.Not only aromatic isocyanate can be used, aliphatic isocyanate can also be used.

As preferred two-and the example of triisocyanate, can mention: 2,4-tolylene diisocyanate (2,4-TDI), 4,4 '-'-diphenylmethane diisocyanate (4,4 '-MDI), the terephthalylidene vulcabond, 1, the 4-phenylene diisocyanate, tetramethyl xylylene diisocyanate (TMXDI), 2,4 '-'-diphenylmethane diisocyanate (2,4 '-MDI) and the toluene triisocyanate, and isophorone diisocyanate (IPDI), 2-butyl-2-ethyl pentamethylene diisocyanate, tetramethylene diisocyanate, 1, hexamethylene-diisocyanate, ten dimethylene diisocyanates, 2, two (the 4-isocyanato-cyclohexyl) propane of 2-, the trimethyl cyclohexane vulcabond, 2-propyl isocyanate basic ring hexyl isocyanic ester, 2,4,4-and 2,2, the 4-trimethyl hexamethylene diisocyanate, 2,4 '-methylene-bis (cyclohexyl) vulcabond, cis hexanaphthene 1, the 4-vulcabond, trans cyclohexane 1,4-vulcabond and 4-methylcyclohexane 1,3-vulcabond (H-TDI).

It being understood that the mixture that also can use isocyanic ester (C3a).Can mention as an example: 2, the mixture of the constitutional isomer of the mixture of the constitutional isomer of 4-tolylene diisocyanate and toluene triisocyanate, 80 moles of %2 for example, 4-tolylene diisocyanate and 20 moles of %2, the mixture of 6-tolylene diisocyanate; Cis and trans-hexanaphthene 1, the mixture of 4-vulcabond; 2,4-or 2, the mixture of 6-tolylene diisocyanate and aliphatic vulcabond (for example hexamethylene diisocyanate and isophorone diisocyanate).

Preferred isocyanate-reactive organic compound (C3b) is the compound that per molecule contains at least two isocyanate-reactive hydroxyls.But available C3b compound comprises that also per molecule only contains the compound of an isocyanate-reactive hydroxyl.These monofunctional compounds can with the reaction of polyisocyanates (C3a) in partially or completely substitute the compound that per molecule comprises at least two isocyanate-reactive hydroxyls.

The example that particularly preferred per molecule has the isocyanate-reactive compound (C3b) of at least two isocyanate-reactive hydroxyls is described now.

They are polyether glycol, polyester glycol, on average contain the polysiloxane of at least 2 hydroxyls based on the polyester glycol of lactone, the two pure and mild triols, dihydroxy carboxylic acids, dihydroxyl sulfonic acid, dihydroxyl phosphonic acids, polycarbonate diol, poly-hydroxy alkene and the per molecule that contain maximum 12 carbon atoms.

Available polyether glycol (C3b) for example comprises, can be in appropriate catalyst, and for example there is the C that obtains down in boron trifluoride ₂-C ₄The homopolymer and the multipolymer of oxyalkylene (for example ethylene oxide, propylene oxide and oxybutylene), tetrahydrofuran (THF), Styrene oxide 98min. and/or Epicholorohydrin.The available polyether glycol also can obtain in (being total to) polymerization that has in the presence of the initiator of at least two acid hydrogen atoms by these compounds, the example of initiator is water, ethylene glycol, THIOGLYCOL (thioglycol), mercaptoethanol, 1, ammediol, 1,4-butyleneglycol, 1,6-hexylene glycol, 1,12-dodecanediol, quadrol, aniline or 1,2-two (4-hydroxyphenyl) propane.

The example of specially suitable polyether glycol (C3b) is polyoxyethylene glycol, polypropylene glycol, polytetramethylene glycol and polytetrahydrofuran and multipolymer thereof.

The molecular weight M of polyether glycol _nBe preferably 250 to 5000, more preferably 500 to 2500.

The polyester glycol (hydroxyl polyester) that can be used as isocyanate-reactive compound (C3b) is a general knowledge.

Preferred polyester glycol (C3b) is glycol and dicarboxylic acid or its reactive derivatives, for example reaction product of acid anhydride or dimethyl ester.

The available dicarboxylic acid is saturated and unsaturated aliphatic and aromatic dicarboxylic acid, and it can have extra substituting group, for example halogen.

Preferred aliphatic dicarboxylic acid is to comprise 3 to 22, especially the saturated not branching alpha, omega-dicarboxylic acid of 4 to 12 carbon atoms.

The example of specially suitable dicarboxylic acid is: succsinic acid, pentanedioic acid, hexanodioic acid, suberic acid, nonane diacid, sebacic acid, 1,12-dodecane dioctyl phthalate, toxilic acid, maleic anhydride, fumaric acid, methylene-succinic acid, phthalic acid, m-phthalic acid, Tetra hydro Phthalic anhydride, Tetra Hydro Phthalic Anhydride, hexahydrophthalic anhydride, tetrachlorophthalic tetrachlorophthalic anhydrid, interior methylene radical Tetra Hydro Phthalic Anhydride, terephthalic acid, dimethyl terephthalate (DMT) and dimethyl isophthalate.

The available glycol is particularly including saturated and unsaturated aliphatic and alicyclic diol.Particularly preferred aliphatic α, omega-diol be nonbranched and have 2 to 12, particularly 2 to 8, and 2 to 4 carbon atoms especially.Preferred alicyclic diol is derived from hexanaphthene.

The example of specially suitable glycol is: ethylene glycol, propylene glycol, 1, ammediol, 1,4-butyleneglycol, 2-methylpropane-1,3-glycol, 1,5-pentanediol, neopentyl glycol, 1,6-hexylene glycol, 1,8-ethohexadiol, 1,10-decanediol, 1,12-dodecanediol, cis-but-2-ene-1,4-glycol, trans-but-2-ene-1,4-glycol, 2-butyne-1,4-glycol, cis-1,4-two (methylol) hexanaphthene and anti-form-1,4-two (methylol) hexanaphthene.

The molecular weight M of polyester glycol _nBe preferably 300 to 5000.

The lactone polyester glycol that can be used as isocyanate-reactive compound (C3b) is especially based on having 4 to 22, the aliphatic saturated not branching 'omega '-hydroxy carboxylic acid of preferred 4 to 8 carbon atoms.Can also use the one or more-CH in the alkylidene chain wherein ₂-group quilt-CH (C ₁-C ₄Alkyl)-alternate branching 'omega '-hydroxy carboxylic acid.

The example of preferred 'omega '-hydroxy carboxylic acid is gamma-hydroxybutyric acid and δ-hydroxypentanoic acid.

It being understood that above-mentioned glycol can be used as isocyanate-reactive compound (C3b) equally, be suitable for preferred version same as above in this case.

Triol particularly has 3 to 12, and especially the triol of 3 to 8 carbon atoms can be used as isocyanate-reactive compound (C3b) equally.TriMethylolPropane(TMP) is the example of specially suitable triol.

The dihydroxy carboxylic acids that can be used as isocyanate-reactive compound (C3b) particularly preferably comprises the aliphatic saturated dihydroxy carboxylic acids of 4 to 14 carbon atoms.The dihydroxy carboxylic acids of following formula is suitable very especially:

A wherein ¹And A ²Represent identical or different C ₁-C ₄Alkylidene group, R are represented hydrogen or C ₁-C ₄Alkyl.

Dimethylol propionic acid (DMPA) is the particularly preferred example of these dihydroxy carboxylic acids.

Available isocyanate-reactive compound (C3b) also comprises corresponding dihydroxyl sulfonic acid and dihydroxyl phosphonic acids, for example 2, and 3-dihydroxypropane phosphonic acids.

Dihydroxy carboxylic acids used herein also should comprise and contains the compound that surpasses a carboxyl-functional (or depend on the circumstances, can be acid anhydride or ester official can).This compounds can be by dihydroxy compound and tetracarboxylic dianhydride, and for example pyromellitic dianhydride or cyclopentane tetracarboxylic acid dianhydride react with polyaddition reaction with 2: 1 to 1.05: 1 mol ratio and obtain, and preferably have 500 to 10000 average molecular mass Mn.

The example of available polycarbonate diol (C3b) is phosgene and excess diol, particularly contains 2 to 12, particularly 2 to 8, and the not branching radical of saturated aliphatic α of 2 to 4 carbon atoms especially, the reaction product of omega-diol.

The poly-hydroxy alkene that can be used as isocyanate-reactive compound (C3b) is α particularly, alpha, omega-dihydroxy alkene, and preferred α, alpha, omega-dihydroxy divinyl.

The polysiloxane per molecule that can be used as isocyanate-reactive compound (C3b) on average comprises at least two hydroxyls.Specially suitable polysiloxane on average comprises 5 to 200 Siliciumatoms (number average), and especially by C ₁-C ₁₂Alkyl, particularly methyl substituted.

The example of isocyanate-reactive compound (C3b) that only contains an isocyanate-reactive hydroxyl is particularly aliphatic, alicyclic, araliphatic or aromatics monohydroxy carboxylic acid and monohydroxy sulfonic acid.

Polyurethane-base additive (C3) by compound (C3a) and (C3b) with usually at 2: 1 to 1: 1, interior (C3a)/(C3b) molar ratio reaction of preferred 1.2: 1 to 1: 1.2 scopes prepares.

Thus, except above-mentioned isocyanate-reactive compound (C3b), can also add other compound with isocyanate-reactive group, two mercaptan for example, mercaptan such as sulfo-ethanol, amino alcohol such as thanomin and N-Mono Methyl Ethanol Amine, or diamines such as quadrol, thereby preparation also has the urethane of isocyanurate group, allophanate groups, urea groups, biuret group, urea diketone (uretidione) group or carbodiimide group except urethane groups.Other example of this kind isocyanate reactive compounds is the aliphatic series that has at least two primary aminos and/or secondary amino group, alicyclic, araliphatic or aromatic carboxylic acid and sulfonic acid.

It being understood that also and can add the respective compound that only has an isocyanate-reactive group, for example single alcohol, primary and secondary monoamine, mono amino carboxylic acid and sulfonic acid and mercaptan.Usual amounts is maximum 10 moles of % based on (C3a).

Preferably, the part or all of carboxyl of reaction product (C3) is that salt form is to guarantee its solubleness in water.Available salt comprises, for example, an alkali metal salt, as sodium and sylvite, and ammonium salt.

Usually, additive (C3) has 500 to 250 000 molecular-weight average M _w

For additive (C3), can via polarity and nonpolar group because of ratio realize the particular surface activity performance.

This anionoid type surfactant additive (C3) is known and can be for example with Borchi ^GENSN95 (Borchers) runs after fame and buys.

Based on the water soluble anion type surfactant additive (C4) of the ester of acid phosphatase, phosphonic acids, sulfuric acid and/or the sulfonic acid of polyethers especially based on the reaction product of above-mentioned polyethers (C1) with phosphoric acid, Vanadium Pentoxide in FLAKES and phosphonic acids or sulfuric acid and sulfonic acid.This reaction changes into corresponding mono phosphoric acid ester-and diester and phosphonic acid ester or sulfuric acid monoester and sulphonate with polyethers.These acid esters are preferably with water-soluble salt, and particularly the form of an alkali metal salt, especially sodium salt and ammonium salt exists, but they also can use with free acid form.

Preferred phosphoric acid ester and phosphonic acid ester are derived from alkoxylate especially, especially the Fatty Alcohol(C12-C14 and C12-C18) of ethoxylation and oxo alcohol, alkylphenol, aliphatic amide, lipid acid and resinous acid, preferred sulfuric ester and sulphonate are especially based on alkoxylate, especially the Fatty Alcohol(C12-C14 and C12-C18) of ethoxylation, alkylphenol and amine, comprise polyfunctional amine, for example hexamethylene-diamine.

This anionoid type surfactant additive is known and can buys, for example with Nekal ^(BASF), Tamol ^(BASF), Crodafos ^(Croda), Rhodafac ^(Rhodia), Maphos ^(BASF), Texapon ^(Cognis), Empicol ^(Albright﹠amp; Wilson), Matexil ^(ICI), Soprophor ^(Rhodia) and Lutensit ^(BASF) run after fame and buy.

Amount according to the dispersion agent (C) in the colorant preparations of this method use is generally 1 weight % to 50 weight %, especially 1 weight % to 40 weight %.

Water constitutes the liquid vehicle of colorant preparations used according to the invention.

The liquid phase of colorant preparations is the mixture of water and water-holding agent preferably.Used water-holding agent particularly high boiling point (promptly have usually＞100 ℃ boiling point) and therefore have water retention and water soluble or with water-soluble mixed organic solvent.

The example of suitable water-holding agent is a polyvalent alcohol, preferably contain 2 to 8, especially the not branching of 3 to 6 carbon atoms and branching polyvalent alcohol, ethylene glycol, 1 for example, 2-propylene glycol, 1, ammediol, glycerol, tetrahydroxybutane, tetramethylolmethane, pentitol (as arabitol, adonitol and Xylitol) and hexitol (as Sorbitol Powder, N.F,USP MANNITOL and galactitol).The available water-holding agent also comprises, for example, two-, three-and four aklylene glycols and their monoalkyl (C especially ₁-C ₆Alkyl, particularly C ₁-C ₄-alkyl) ether.The example that can mention is two-, three-and TEG, diethylene glycol monomethyl ether, single ethyl ether, single propyl ether and single-butyl ether, triethylene glycol monomethyl ether, single ethyl ether, single propyl ether and single-butyl ether, two-, three-and four-1,2-and-1, ammediol and two-, three-and four-1,2-and-1, ammediol monomethyl ether, single ethyl ether, single propyl ether and single-butyl ether.

The amount of the liquid phase that exists in the colorant preparations used according to the invention (D) is generally 10 weight % to 88.95 weight %, is preferably 10 weight % to 80 weight %.When water was present in the mixture with the water conservation organic solvent, the ratio that this solvent accounts for phase (D) was generally 1 weight % to 80 weight %, preferred 1 weight % to 60 weight %.

Colorant preparations can further comprise conventional additives, biological example kill agent, defoamer, anti-sedimentation agent and rheology modifiers, and their ratio is generally maximum 5 weight %.

Colorant preparations used according to the invention can obtain in every way.Preferably at first prepare pigment dispersion, subsequently its dyestuff is mixed, dyestuff is solid or especially solubilized form or as in liquid phase, particularly the dispersion of aqueous phase.

Colorant preparations used according to the invention can be used for cellulose particulates used in cellulose polymer compound compound or the matrix material painted very much.Described particle can be made of the Mierocrystalline cellulose kind of any natural appearance and can be in small, broken bits to rough segmentation.The preferred embodiment of these materials is wood chip, xylon and wood powder.

Cellulose particulates can be painted in each production phase.Can the smear metal (choppingchip) as raw material is painted, but also can cellulose particulates is painted under moistening or drying regime after it is made.

For example this is described more specifically referring now to xylon.Except make as the smear metal of raw material painted, can make similarly and pulverize the wet xylon that the back obtains by boiling and grinding and contact with colorant preparations.At this colorant preparations,, can put on xylon with other auxiliary agent that is used for compound or matrix material production if need.At last, xylon can spray with colorant preparations after drying.

According to the manufacturing convention of cellulose polymer compound compound or matrix material, painted cellulose particulates can be mixed with matrix polymer subsequently also and extrude jointly.

When polymeric matrix also wanted painted, this realized by additionally mix the known polymeric pigment enriched material that is known as masterbatch in extruding operation simply.

Claims (12)

1. the liquid colorant preparations that comprises at least a pigment and at least a dyestuff is used for cellulose polymer compound compound or the painted purposes of matrix material.

2. according to the purposes of claim 1, wherein to comprise based on pigment be the dyestuff of 0.5 weight % to 10 weight % to colorant preparations.

3. according to the purposes of claim 1 or 2, wherein colorant preparations comprises:

(A) at least a pigment of 10 weight % to 70 weight %,

(B) at least a dyestuff of 0.05 weight % to 7 weight %,

(C) at least a dispersion agent of 1 weight % to 50 weight %,

(D) mixture of the water of 10 weight % to 88.95 weight % or water and at least a water-holding agent and

(E) routine of 0 weight % to 5 weight % is used for other composition of colorant preparations.

4. according to each purposes in the claim 1 to 3, wherein component (B) comprises at least a dyestuff that is selected from anionic dyestuff, cationic dyes and dispersed dye.

5. according to each purposes in the claim 1 to 4, wherein component (C) comprises at least a following water-soluble surface-active additives that is selected from: based on the non-ionic type additive (C1) of polyethers, based on the anionic additive (C2) of the polymkeric substance of ethylenically unsaturated carboxylic acids, based on the anionic additive (C3) of urethane with based on the anionic additive (C4) of the ester of acid phosphatase, phosphonic acids, sulfuric acid and/or the sulfonic acid of polyethers.

6. produce the method for colored cellulose polymer composition or matrix material, it comprises uses according to the painted cellulose particulates of each liquid colorant preparations in the claim 1 to 5.

7. according to the method for claim 6, wherein used cellulose particulates comprises painted wood chip, xylon and/or wood powder.

8. according to the method for claim 7, the wooden smear metal as the raw material of producing wood chip, xylon and wood powder is contacted with colorant preparations.

9. according to the method for claim 7, wherein make the wet xylon that obtains by boiling and grinding, if the words that need contact with liquid colorant preparations with being used for other auxiliary agent that matrix material or compound are produced.

10. according to the method for claim 7, wherein xylon sprays with liquid colorant preparations after drying.

11. it is, wherein additionally that polymeric matrix is painted according to the method for claim 6.

12. use according to each liquid colorant preparations in the claim 1 to 5 painted cellulose polymer compound matrix material or compound.