U.S. patent application number 11/913495 was filed with the patent office on 2008-08-14 for use of liquid colorant preparations for dyeing composite cellulose/polymer materials.
This patent application is currently assigned to Basf Aktiengesellschaft. Invention is credited to Andres Carlos Garcia Espino, Juliane Krusemann, Werner Peter.
Application Number | 20080189879 11/913495 |
Document ID | / |
Family ID | 36011742 |
Filed Date | 2008-08-14 |
United States Patent
Application |
20080189879 |
Kind Code |
A1 |
Garcia Espino; Andres Carlos ;
et al. |
August 14, 2008 |
Use Of Liquid Colorant Preparations For Dyeing Composite
Cellulose/Polymer Materials
Abstract
Liquid colorant preparations comprising at least one pigment and
at least one dye are useful for coloring cellulose polymer
compounds or composites.
Inventors: |
Garcia Espino; Andres Carlos;
(Mannheim, DE) ; Krusemann; Juliane;
(Ludwigshafen, DE) ; Peter; Werner; (Hackettstown,
NJ) |
Correspondence
Address: |
OBLON, SPIVAK, MCCLELLAND MAIER & NEUSTADT, P.C.
1940 DUKE STREET
ALEXANDRIA
VA
22314
US
|
Assignee: |
Basf Aktiengesellschaft
Ludwigshafen
DE
|
Family ID: |
36011742 |
Appl. No.: |
11/913495 |
Filed: |
April 28, 2006 |
PCT Filed: |
April 28, 2006 |
PCT NO: |
PCT/EP06/61923 |
371 Date: |
November 2, 2007 |
Current U.S.
Class: |
8/506 |
Current CPC
Class: |
B27N 3/00 20130101; C08J
5/045 20130101; C08J 5/06 20130101; B27N 3/002 20130101 |
Class at
Publication: |
8/506 |
International
Class: |
D06P 5/00 20060101
D06P005/00 |
Foreign Application Data
Date |
Code |
Application Number |
May 2, 2005 |
DE |
102005020741.3 |
Claims
1-12. (canceled)
13. A method of coloring cellulose polymer compounds or composites
comprising applying liquid colorant preparations comprising at
least one pigment and at least one dye.
14. The method of coloring cellulose polymer compounds or
composites according to claim 13 wherein the colorant preparations
comprise 0.5% to 10% by weight of dye, based on the pigment.
15. The method of coloring cellulose polymer compounds or
composites according to claim 13 wherein the colorant preparations
comprise (A) 10% to 70% by weight of at least one pigment, (B)
0.05% to 7% by weight of at least one dye, (C) 1% to 50% by weight
of at least one dispersant, (D) 10% to 88.95% by weight of water or
of a mixture of water and at least one water-retaining agent, and
(E) 0% to 5% by weight of further constituents customary for
colorant preparations.
16. The method of coloring cellulose polymer compounds or
composites according to claim 15 wherein component (B) comprises at
least one dye selected from the group consisting of anionic dyes,
cationic dyes and disperse dyes.
17. The method of coloring cellulose polymer compounds or
composites according to claim 15 wherein component (C) comprises at
least one water-soluble surface-active additive selected from the
group consisting of nonionic additives based on polyethers (C1),
anionic additives based on polymers of ethylenically unsaturated
carboxylic acids (C2), anionic additives based on polyurethanes
(C3) and anionic additives based on acidic phosphoric, phosphonic,
sulfuric and/or sulfonic esters of polyethers (C4).
18. A process for producing colored cellulose polymer compounds or
composites, which comprises utilizing cellulose particles colored
with liquid colorant preparations according to claim 17.
19. The process according to claim 18 wherein the cellulose
particles utilized are at least one selected from the group
consisting of colored wood shavings, moist wood fibers, dry wood
fibers, wood dusts, and mixtures thereof.
20. The process according to claim 19 wherein wood-chopping chips
serving as starting material to produce the wood shavings, wood
fibers and wood dusts are contacted with the colorant
preparations.
21. The process according to claim 19 wherein the moist wood fibers
obtained by cooking and grinding, are contacted with the liquid
colorant preparations.
22. The process according to claim 19 wherein the moist wood fibers
obtained by cooking and grinding, together with further auxiliaries
for composite or compound production are contacted with the liquid
colorant preparations
23. The process according to claim 19 wherein the dry wood fibers
are sprayed with the liquid colorant preparations.
24. The process according to claim 18 wherein a polymer matrix is
additionally colored.
25. Cellulose polymer composites or compounds colored with liquid
colorant preparations according to claim 13.
26. Cellulose polymer composites or compounds colored with liquid
colorant preparations according to claim 14.
27. Cellulose polymer composites or compounds colored with liquid
colorant preparations according to claim 15.
Description
[0001] The present invention relates to the use of liquid colorant
preparations comprising at least one pigment and at least one dye
for coloring cellulose polymer compounds or composites.
[0002] Cellulose polymer compounds or composites, in particular
lignocellulose polymer or wood polymer or plastic compounds or
composites (WPCs) have the properties of both wood and plastic.
They are further advantageous because they can be produced on the
basis of raw materials from recycling. They are of interest for a
multiplicity of applications. An example is their use as a
structural element in the building construction industry, for
example as a dividing wall, as a roof, as a floor, as a window
frame and as lining, and also as packaging material.
[0003] The cellulose particles used in the compounds or composites
may have different morphologies and accordingly different largest
particle diameters ranging from about 1 to 10 mm (shavings) to 0.1
to 1 mm for fibers to 0.01 to 0.1 mm (dust). The finer the
cellulose particles, the greater the holding capacity of the
polymer matrix for these particles, but the tensile strength of the
compound or composite decreases in the same direction.
[0004] Wood is currently the preferred cellulose material, not only
softwoods, examples being pinewood and cedarwood, but also
hardwoods, examples being oak and maple. Other vegetable materials
are similarly useful, examples being fibers of sisal, flax, hemp,
jute, cotton and other cereals, bamboo, straw, reed, coir, banana
fibers, flax shives, rice-hulls and peanut shells.
[0005] Thermoplastic polymers are used in general. Preferred
polymers in particular are polyethylene, polypropylene and
polyvinyl chloride, but it will be appreciated that other polymers
are similarly useful, 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 copolymers) and PU
(polyurethanes).
[0006] The mixing ratio is generally 40% to 95% by weight of
cellulose particles and 5% to 60% by weight of polymer.
[0007] The cellulose polymer compounds or composites are generally
produced by first producing a mixed granulate to equalize the
density difference between polymer and cellulose particles. To
produce the mixed granulate, polymer and cellulose particles are
first metered into a heated mixer, in which the polymer is melted
and mixed with the cellulose particles. This mixture is then
granulated in a cooling mixer. The granulate is subsequently
extruded and can be brought into the desired form by injection
molding.
[0008] In general, additives are used to increase the compatibility
between the cellulose component and the polymer component and/or
the interphase adhesion (examples being maleic acid modified
polyolefins or isocyanates) or enhance the processibility for
extrusion (examples being resins, waxes).
[0009] It is further customary to employ additives to modify the
technical properties of the compounds or composites (tensile
strength, density, flexibility, impact sensitivity, thermal
stability), for their mechanical or chemical protection, to extend
their useful lives and to enhance their esthetic appeal. Such
additives may be for example foaming agents to expand the polymer
matrix, flow additives, thermal stabilizers, biocides,
insecticides, antioxidants, UV absorbers, antistats, flame
retardants, fillers and colorants.
[0010] Various ways are known to color cellulose polymer compounds
or composites.
[0011] DE-A-20 42 496 describes granular colorant concentrates
comprising 20% by weight of a 1:1 mixture of C.I. Pigment Blue 15
and a blue reactive dye or 20% by weight of just the pigment or dye
and 80% by weight of a polyethylene wax. The concentrates are mixed
with wood flour and polymer component and then jointly
extruded.
[0012] WO-A-02/103113 has composites based on wood flour which
confer the impression of a wood grain at the surface being produced
by adding a combination of pigment-olefin masterbatch and
unspecified liquid colorant at extrusion.
[0013] US-A-2004/0076847 discloses composites based on polyvinyl
chloride and wood flour which has been colored with an aqueous
dispersion of a pigment. Pigments identified as preferred include
metal oxide pigments, such as iron(III) oxide and manganese
antimony titanate, and also copper phthalocyanine. The possibility
of dyeing with an aqueous solution of the dye is also
mentioned.
[0014] EP-A-888 870 describes packaging materials based on
transparent composites having a low fraction of wood fiber. It is
mentioned that the transparent polymer can be colored with dye
solutions or the wood fibers can be coated with colored
material.
[0015] Finally, US-A-2002/0040557 discloses construction panels for
shingling based on cellulose polymer composites produced by
pressing a mixture of cellulose fibers, polymer, maleic acid
grafted polyolefin as a coupling agent, UV absorber, thermal
stabilizer, iron oxide pigment, fungicide and flame retardant.
[0016] None of the known ways to produce colored cellulose polymer
compounds or composites utilizes a liquid colorant preparation
comprising both pigment and dye.
[0017] It is an object of the present invention to provide colorant
formulations for advantageous coloration of cellulose polymer
compounds or composites.
[0018] We have found that this object is achieved by the use of
liquid colorant preparations comprising at least one pigment and at
least one dye for coloring cellulose polymer compounds or
composites.
[0019] Such colorant preparations are known from WO-A-0435276 and
35277 where they are used for coloring chipboard, MDF and OSB
panels.
[0020] The advantageous properties of these colorant preparations
also come to the fore in the coloration of the cellulose particles
in cellulose polymer compounds or composites. The cellulose
particles are readily through-colored regardless of their size,
including even comparatively large wood shavings, and acquire
strong, bright and lightfast colors. A more efficient coloration of
cellulose polymer compounds or composites is possible in this way,
since, in the cellulose particles, the main constituent of these
compounds or composites is colored and not just the quantitatively
subordinate polymer matrix.
[0021] The liquid colorant preparations to be used according to the
present invention preferably comprise 0.5% to 10% by weight of dye,
based on the pigment.
[0022] More preferably, the colorant preparations to be used
according to the present invention comprise (A) 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-retaining
agent.
[0023] Component (A) in the colorant preparations to be used
according to the present invention may comprise organic or
inorganic pigments. It will be appreciated that the colorant
preparations may also comprise mixtures of various organic or
various inorganic pigments or mixtures of organic and inorganic
pigments.
[0024] The pigments are preferably present in finely divided form.
Accordingly, the pigments typically have average particle sizes
from 0.1 to 5 .mu.m, in particular from 0.1 to 3 .mu.m and
especially from 0.1 to 1 .mu.m.
[0025] Depending on the effect desired, the pigments may be used in
transparent or hiding form.
[0026] The organic pigments are typically organic chromatic and
black pigments. Inorganic pigments can likewise be color pigments
(chromatic, black and white pigments) and also luster pigments.
[0027] There now follow examples of suitable organic color
pigments:
TABLE-US-00001 monoazo pigments: 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 1, 3, 62, 65, 73, 74, 97, 120, 151, 154, 168,
181, 183 and 191; C.I. Pigment Violet 32; disazo pigments: 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 and 188;
condensed disazo C.I. Pigment Yellow 93, 95 and 128; pigments: C.I.
Pigment Red 144, 166, 214, 220, 221, 242 and 262; C.I. Pigment
Brown 23 and 41; anthanthrone C.I. Pigment Red 168; pigments:
anthraquinone C.I. Pigment Yellow 147, 177 and 199; pigments: C.I.
Pigment Violet 31, anthrapyrimidine C.I. Pigment Yellow 108;
pigments: quinacridone C.I. Pigment Orange 48 and 49; pigments:
C.I. Pigment Red 122, 202, 206 and 209; C.I. Pigment Violet 19;
quinophthalone C.I. Pigment Yellow 138; pigments:
diketopyrrolopyrrole C.I. Pigment Orange 71, 73 and 81; pigments:
C.I. Pigment Red 254, 255, 264, 270 and 272; dioxazine pigments:
C.I. Pigment Violet 23 and 37; C.I. Pigment Blue 80; flavanthrone
C.I. Pigment Yellow 24; pigments: indanthrone C.I. Pigment Blue 60
and 64; pigments: isoindoline C.I. Pigments Orange 61 and 69;
pigments: C.I. Pigment Red 260; C.I. Pigment Yellow 139 and 185;
isoindolinone C.I. Pigment Yellow 109, 110 and 173; pigments:
isoviolanthrone C.I. Pigment Violet 31; pigments: metal complex
C.I. Pigment Red 257; pigments: C.I. Pigment Yellow 117, 129, 150,
153 and 177; C.I. Pigment Green 8; perinone pigments: C.I. Pigment
Orange 43; C.I. Pigment Red 194; perylene pigments: C.I. Pigment
Black 31 and 32; C.I. Pigment Red 123, 149, 178, 179, 190 and 224;
C.I. Pigment Violet 29; phthalocyanine C.I. Pigment Blue 15, 15:1,
15:2, 15:3, 15:4, 15:6 pigments: and 16; C.I. Pigment Green 7 and
36; pyranthrone C.I. Pigment Orange 51; pigments: C.I. Pigment Red
216; pyrazoloquinazolone C.I. Pigment Orange 67; pigments: C.I.
Pigment Red 251; thioindigo pigments: C.I. Pigment Red 88 and 181;
C.I. Pigment Violet 38; triaryloarbonium C.I. Pigment Blue 1, 61
and 62; pigments: C.I. Pigment Green 1; C.I. Pigment Red 81, 81:1
and 169; C.I. Pigment Violet 1, 2, 3 and 27; C.I. Pigment Black 1
(aniline black); C.I. Pigment Yellow 101 (aldazine yellow); C.I.
Pigment Brown 22.
[0028] Examples of suitable inorganic color pigments are:
TABLE-US-00002 [0028] white titanium dioxide (C.I. Pigment White
6), zinc white, pigments: pigment grade zinc oxide; zinc sulfide,
lithopone; black iron oxide black (C.I. Pigment Black 11), iron
manganese pigments: black, spinel black (C.I. Pigment Black 27);
carbon black (C.I. Pigment Black 7); chromatic chromium oxide,
chromium oxide hydrate green; chrome pigments: 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 blue; ultramarine violet; cobalt violet
and manganese violet; red iron oxide (C.I. Pigment Red 101);
cadmium sulfoselenide (C.I. Pigment Red 108); cerium sulfide (C.I.
Pigment Red 265); molybdate red (C.I. Pigment Red 104); ultramarine
red; brown iron oxide (C.I. Pigment Brown 6 and 7), mixed brown,
spinel phases and corundum phases (C.I. Pigment Brown 29, 31, 33,
34, 35, 37, 39 and 40), chromium titanium yellow (C.I. Pigment
Brown 24), chrome orange; cerium sulfide (C.I. Pigment Orange 75);
yellow iron oxide (C.I. Pigment Yellow 42); nickel titanium yellow
(C.I. Pigment Yellow 53; C.I. Pigment Yellow 157, 158, 159, 160,
161, 162, 163, 164 and 189); chromium titanium yellow; spinel
phases (C.I. Pigment Yellow 119); cadmium sulfide and cadmium zinc
sulfide (C.I. Pigment Yellow 37 and 35); chrome yellow (C.I.
Pigment Yellow 34); bismuth vanadate (C.I. Pigment Yellow 184).
[0029] Luster pigments are platelet-shaped pigments having a
monophasic or polyphasic construction whose color play is marked by
the interplay of interference, reflection and absorption phenomena.
Examples are aluminum platelets and aluminum, iron oxide and mica
platelets bearing one or more coats, especially of metal
oxides.
[0030] The pigments will be chosen specifically in line with the
planned application for the compound or composite. For example,
high-lightfastness pigments, such as inorganic pigments and organic
pigments from the perylene, indanthrone and copper phthalocyanine
series, are useful for exterior applications. By using conductive
carbon black it is possible to obtain conductive compounds or
composites which are of interest for antistatic liners.
[0031] The amount of pigment (A) included in the colorant
preparations to be used according to this invention is generally in
the range from 10% to 70% by weight and preferably in the range
from 10% to 60% by weight.
[0032] Component (B) in the colorant preparations to be used
according to this invention is at least one dye. Dyes which are
suitable are in particular dyes which are soluble in water or in a
water-miscible or water-soluble organic solvent. Preferably, the
dyes (B) used have in each case a hue which is comparable to the
pigments (A), since this is a way of achieving a particularly
intensive coloration of the woodbase materials. However, it is also
possible to use dyes (B) which differ in hue, thereby enabling the
coloration to be shaded.
[0033] Suitable dyes are in particular cationic dyes, anionic dyes
and disperse dyes.
[0034] Suitable cationic dyes (B) belong in particular to the di-
and triarylmethane, xanthene, azo, cyanine, azacyanine, methine,
acridine, safranine, oxazine, induline, nigrosine and phenazine
range, and dyes of the azo, triarylmethane and xanthene range are
preferred.
[0035] Specific examples which may be recited are: C.I. Basic
Yellow 1, 2 and 37; C.I. Basic Orange 2; C.I. Basic Red 1 and 108;
C.I. Basic Blue 1, 7 and 26; C.I. Basic Violet 1, 3, 4, 10, 11 and
49; C.I. Basic Green 1 and 4; C.I. Basic Brown 1 and 4.
[0036] Cationic dyes (B) may also be colorants comprising external
basic groups. Suitable examples here are C.I. Basic Blue 15 and
161.
[0037] Useful cationic dyes (B) further include the corresponding
dyebases used in the presence of solubilizing acidic agents. As
examples there may be mentioned: C.I. Solvent Yellow 34; C.I.
Solvent Orange 3; C.I. Solvent Red 49; C.I. Solvent Violet 8 and 9;
C.I. Solvent Blue 2 and 4; C.I. Solvent Black 7.
[0038] Suitable anionic dyes are in particular sulfonated compounds
from the range of the azo, anthraquinone, metal complex,
triarylmethane, xanthene and stilbene range, and dyes of the
triarylmethane, azo and metal complex (especially copper, chromium
and cobalt complex) range are preferred.
[0039] Specific examples which may be mentioned are: C.I. Acid
Yellow 3, 19, 36 and 204; C.I. Acid Orange 7, 8 and 142; C.I. Acid
Red 52, 88, 351 and 357; C.I. Acid Violet 17 and 90; C.I. Acid Blue
9, 193 and 199; C.I. Acid Black 194; anionic chromium complex dyes
such as C.I. Acid Violet 46, 56, 58 and 65; C.I. Acid Yellow 59;
C.I. Acid Orange 44, 74 and 92; C.I. Acid Red 195; C.I. Acid Brown
355 and C.I. Acid Black 52; anionic cobalt complex dyes such as
C.I. Acid Yellow 119 and 204; C.I. Direct Yellow 4 and 11; C.I.
Direct Red 80, 81 and 254 and C.I. Direct Blue 199
[0040] These dyes are water-soluble in particular when they are
present as an alkali metal salt, in particular as a lithium, sodium
or potassium salt, or as a substituted or unsubstituted ammonium
salt, in particular alkanolammonium salt.
[0041] Disperse dyes are preferably used in the form of
commercially available, aqueous dispersions and develop their
coloring effect in the manufacturing operation of the cellulose
polymer compounds or composites through diffusion at high
temperatures.
[0042] Disperse dyes from the series of the quinophthalones and
anthraquinones are particularly suitable for example.
[0043] The dye (B) is generally present in the colorant
preparations to be used according to the present invention in
amounts from 0.5% to 10% by weight and preferably from 1% to 8% by
weight, all based on the pigment (A). Based on the total weight of
the preparation, this corresponds to amounts of generally 0.05% to
7% by weight and in particular 0.1% to 5.6% by weight.
[0044] Preferred pigment-dye combinations are for example: C.I.
Pigment Blue 15:1 and C.I. Basic Violet 4; C.I. Pigment Green 7 and
C.I. Basic Green 4; C.I. Pigment Green 7 and C.I. Direct Blue 199;
C.I. Pigment Red 48:2 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 74 and C.I. Direct Yellow 4; C.I.
Pigment Black 7 and C.I. Basic Violet 3.
[0045] Component (C) in the colorant preparations to be used
according to this invention is at least one dispersant.
[0046] Particularly suitable dispersants (C) are nonionic and
anionic water-soluble surface-active additives.
[0047] Particularly suitable nonionic additives (C) are based on
polyethers (additives (C1)).
[0048] As well as unmixed polyalkylene oxides, preferably
C.sub.2-C.sub.4-alkylene oxides and phenyl-substituted
C.sub.2-C.sub.4-alkylene oxides, especially polyethylene oxides,
polypropylene oxides and poly(phenylethylene oxide)s, it is in
particular block copolymers, especially polymers which contain
polypropylene oxide and polyethylene oxide blocks or
poly(phenylethylene oxide) and polyethylene oxide blocks, and also
random copolymers of these alkylene oxides which are suitable.
[0049] These polyalkylene oxides are preparable by polyaddition of
the alkylene oxides to starter molecules, such as to saturated or
unsaturated aliphatic and aromatic alcohols, to phenol or naphthol,
which may each be substituted by alkyl, especially
C.sub.1-C.sub.12-alkyl, preferably C.sub.4-C.sub.12-alkyl and
C.sub.1-C.sub.4-alkyl respectively, to saturated or unsaturated
aliphatic and aromatic amines and to saturated or unsaturated
aliphatic carboxylic acids and carboxamides. It is customary to use
from 1 to 300 mol and preferably from 3 to 150 mol of alkylene
oxide per mole of starter molecule.
[0050] Suitable aliphatic alcohols comprise in general from 6 to 26
carbon atoms and preferably from 8 to 18 carbon atoms and can have
an unbranched, branched or cyclic structure. Examples 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 and also
mixtures of these alcohols, such as C.sub.8/C.sub.10,
C.sub.13/C.sub.15 and C.sub.16/C.sub.18 alcohols, and cyclopentanol
and cyclohexanol. Of particular interest are the saturated or
unsaturated fatty alcohols obtained from natural raw materials by
fat hydrolysis and reduction and the synthetic fatty alcohols from
the oxo process. The alkylene oxide adducts with these alcohols
typically have average molecular weights M.sub.n from 200 to
5000.
[0051] Examples of the abovementioned aromatic alcohols include not
only unsubstituted phenol and .alpha.- and .beta.-naphthol but also
hexylphenol, heptylphenol, octylphenol, nonylphenol,
isononylphenol, undecylphenol, dodecylphenol, di- and
tributylphenol and dinonylphenol.
[0052] Suitable aliphatic amines correspond to the abovementioned
aliphatic alcohols. Again of particular importance here are the
saturated and unsaturated fatty amines which preferably have from
14 to 20 carbon atoms. Examples of suitable aromatic amines are
aniline and its derivatives.
[0053] Useful aliphatic carboxylic acids include especially
saturated and unsaturated fatty acids which preferably comprise
from 14 to 20 carbon atoms and fully hydrogenated, partially
hydrogenated and unhydrogenated resin acids and also polyfunctional
carboxylic acids, for example dicarboxylic acids, such as maleic
acid.
[0054] Suitable carboxamides are derived from these carboxylic
acids.
[0055] As well as alkylene oxide adducts with monofunctional amines
and alcohols it is alkylene oxide adducts with at least
bifunctional amines and alcohols which are of very particular
interest.
[0056] The at least bifunctional amines preferably have from 2 to 5
amine groups and conform in particular to the formula
H.sub.2N--(R.sup.1--NR.sup.2).sub.n--H (R.sup.1:
C.sub.2-C.sub.6-alkylene; R.sup.2: hydrogen or
C.sub.1-C.sub.6-alkyl; n: 1-5). Specific examples are:
ethylenediamine, diethylenetriamine, triethylenetetramine,
tetraethylenepentamine, 1,3-propylenediamine, dipropylene-triamine,
3-amino-1-ethyleneaminopropane, hexamethylenediamine,
dihexamethylene-triamine, 1,6-bis(3-aminopropylamino)hexane and
N-methyidipropylenetriamine, of which hexamethylenediamine and
diethylenetriamine are more preferable and ethylenediamine is most
preferable.
[0057] These amines are preferably reacted first with propylene
oxide and then with ethylene oxide. The ethylene oxide content of
the block copolymers is typically about 10-90% by weight.
[0058] The average molecular weights M.sub.n of the block
copolymers based on polyamines are generally in the range from 1000
to 40 000 and preferably in the range from 1500 to 30 000.
[0059] The at least bifunctional alcohols preferably have from two
to five hydroxyl groups. Examples are C.sub.2-C.sub.6-alkylene
glycols and the corresponding di- and polyalkylene glycols, such as
ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol,
1,2-butylene glycol, 1,4-butylene glycol, 1,6-hexylene glycol,
dipropylene glycol and polyethylene glycol, glycerol and
pentaerythritol, of which ethylene glycol and polyethylene glycol
are more preferable and propylene glycol and dipropylene glycol are
most preferable.
[0060] Particularly preferred alkylene oxide adducts with at least
bifunctional alcohols have a central polypropylene oxide block,
i.e., are based on a propylene glycol or polypropylene glycol which
is initially reacted with further propylene oxide and then with
ethylene oxide. The ethylene oxide content of the block copolymers
is typically in the range from 10% to 90% by weight.
[0061] The average molecular weights M.sub.n of the block
copolymers based on polyhydric alcohols are generally in the range
from 1000 to 20 000 and preferably in the range from 1000 to 15
000.
[0062] Such alkylene oxide block copolymers are known and
commercially obtainable, for example under the names Tetronic.RTM.
and Pluronic.RTM. (BASF).
[0063] Examples of the water-soluble anionic surface-active agents
particularly suitable for use 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, phosphonic, sulfuric and/or sulfonic esters of the
abovementioned polyethers (C3).
[0064] Mixtures of a plurality of additives (C) can also be used of
course, i.e., not only mixtures of various nonionic additives but
also mixtures of various anionic additives and also mixtures of
nonionic and anionic additives.
[0065] Useful anionic water-soluble surface-active additives based
on polymers of unsaturated carboxylic acids (C2) include in
particular additives from the group of the homo- and copolymers of
ethylenically unsaturated monocarboxylic acids and/or ethylenically
unsaturated dicarboxylic acids, which may further comprise
interpolymerized vinyl monomers without acid function, the
alkoxylation products of these homo- and copolymers and the salts
of these homo- and copolymers and their alkoxylation products.
[0066] Examples which may be mentioned of the carboxyl-containing
monomers and the vinyl monomers are: [0067] acrylic acid,
methacrylic acid and crotonic acid; [0068] maleic acid, maleic
anhydride, maleic monoesters, maleic monoamides, reaction products
of maleic acid with diamines that may have been oxidized to
derivatives containing amine oxide groups, and fumaric acid, of
which maleic acid, maleic anhydride and maleic monoamides are
preferred; [0069] vinylaromatics, 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)acrylates and also phenyl, naphthyl
and benzyl (meth)acrylates; 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 maleates and fumarates;
vinylpyrrolidone; acrylonitrile and methacrylonitrile, of which
styrene, isobutene, diisobutene, acrylic esters and polyethylene
glycol monovinyl ether are preferred.
[0070] Polyacrylic acids in particular are to be mentioned as
examples of preferred homopolymers of these monomers.
[0071] The copolymers of the monomers mentioned may be constructed
from two or more and in particular three different monomers. The
copolymers 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
which may each comprise acrylic esters and/or maleic esters as
additional monomeric constituents.
[0072] Preferably, the carboxyl groups of the nonalkoxylated homo-
and copolymers are at least partly present in salt form in order
that solubility in water may be ensured.
[0073] Suitable examples are alkali metal salts, such as sodium and
potassium salts, and ammonium salts.
[0074] The average molecular weight M.sub.w of the nonalkoxylated
polymeric additives (C2) is typically in the range from 900 to 250
000. The molecular weight ranges particularly suitable for the
individual polymers are naturally dependent on their composition.
Exemplary molecular weight ranges for various polymers are as
follows: polyacrylic acids: M.sub.w from 900 to 250 000;
styrene-acrylic acid copolymers: M.sub.w from 1000 to 50 000;
acrylic acid-methacrylic acid copolymers: M.sub.w from 1000 to 250
000; acrylic acid-maleic acid copolymers: Mw from 2000 to 70
000.
[0075] As well as these homo- and copolymers themselves, their
alkoxylation products are also of particular interest for use as
additives (C2).
[0076] Alkoxylation products here refers according to the invention
in particular to the partial to (insofar as possible) complete
esterification products of these polymers with polyether alcohols.
The degree of esterification of these polymers is generally in the
range from 30 to 80 mol %.
[0077] Useful esterifying agents include in particular the
polyether alcohols themselves, preferably polyethylene glycols and
polypropylene glycols, and also their singlesidedly end group
capped derivatives, especially the corresponding monoethers, such
as monoaryl ethers, for example monophenyl ethers, and in
particular mono-C.sub.1-C.sub.26-alkyl ethers, for example glycols
of ethylene and propylene which are etherified with fatty alcohols,
and the polyether amines which are preparable for example by
converting 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 polyetheramines are preferred here. The average
molecular weights M.sub.n of the employed polyether alcohols and
their derivatives are typically in the range from 200 to 10
000.
[0078] Specific surface-active properties can be achieved for the
additives (C2) via the ratio of polar to apolar groups.
[0079] Such anionic surface-active additives (C2) are likewise
known and commercially available for example under the names of
Sokalan.RTM. (BASF), Joncryl.RTM. (Johnson Polymer),
Alcosperse.RTM. (Alco), Geropon.RTM. (Rhodia), Good-Rite.RTM.
(Goodrich), Neoresin.RTM. (Avecia), Orotan.RTM. and Morez.RTM.
(Rohm & Haas), Disperbyk.RTM. (Byk) and also Tegospers.RTM.
(Goldschmidt).
[0080] Useful anionic surface-active additives for the pigment
preparations of the present invention further include
polyurethane-based additives (C3).
[0081] For the purposes of the present invention, polyurethane
shall be understood as referring not just to the pure reaction
products of polyfunctional isocyanates (C3a) with
isocyanate-reactive hydroxyl-comprising organic compounds (C3b),
but also reaction products which have been additionally
functionalized by the addition of further isocyanate-reactive
compounds, for example by the addition of carboxylic acids bearing
primary or secondary amino groups.
[0082] These additives are distinguished from other surface-active
additives by their low ionic conductivity and their neutral pH.
[0083] Useful polyfunctional isocyanates (C3a) for the preparation
of the additives (C3) include in particular diisocyanates, but it
is also possible to use compounds having three or four isocyanate
groups. Not only aromatic but also aliphatic isocyanates can be
used.
[0084] As examples of preferred di- and triisocyanates there may be
recited: 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, 2,4,4- and 2,2,4-trimethylhexamethylene diisocyanates,
2,4'-methylene bis(cyclohexyl)diisocyanate, cis-cyclohexane
1,4-diisocyanate, transcyclohexane 1,4-diisocyanate and
4-methylcyclohexane 1,3-diisocyanate (H-TDI).
[0085] It will be appreciated that mixtures of isocyanates (C3a)
can be used as well. As examples there may be mentioned here:
mixtures of structural isomers of 2,4-tolylene diisocyanate and
triisocyanatotoluene, for example mixtures of 80 mol % of
2,4-tolylene diisocyanate and 20 mol % of 2,6-tolylene
diisocyanate; mixtures of cis- and trans-cyclohexane
1,4-diisocyanates; mixtures of 2,4- or 2,6-tolylene diisocyanate
with aliphatic diisocyanates, such as hexamethylene diisocyanate
and isophorone diisocyanate.
[0086] Preferred isocyanate-reactive organic compounds (C3b) are
compounds having at least two isocyanate-reactive hydroxyl groups
per molecule. However, useful C3b compounds further include
compounds which have only one isocyanate-reactive hydroxyl group
per molecule. These monofunctionalized compounds may partly or else
wholly replace the compounds comprising at least two
isocyanate-reactive hydroxyl groups per molecule in the reaction
with the polyisocyanate (C3a).
[0087] Examples of particularly preferred isocyanate-reactive
compounds (C3b) having at least two isocyanate-reactive hydroxyl
groups per molecule will now be recited.
[0088] They are polyether diols, polyester diols, polyester diols
based on lactone, diols and triols having up to 12 carbon atoms,
dihydroxy carboxylic acids, dihydroxy sulfonic acids, dihydroxy
phosphonic acids, polycarbonate diols, polyhydroxy olefins and
polysiloxanes having on average at least two hydroxyl groups per
molecule.
[0089] Useful polyether diols (C3b) include for example homo- and
copolymers of C.sub.2-C.sub.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. Useful
polyether diols are further obtainable by (co)polymerization of
these compounds in the presence of a starter having at least two
acidic hydrogen atoms, examples of starters being 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.
[0090] Examples of particularly suitable polyether diols (C3b) are
polyethylene glycol, polypropylene glycol, polybutylene glycol and
polytetrahydrofuran and also copolymers thereof.
[0091] The molecular weight M.sub.n of the polyether diols is
preferably in the range from 250 to 5000 and more preferably in the
range from 500 to 2500.
[0092] Polyester diols (hydroxy polyesters) useful as an
isocyanate-reactive compound (C3b) are common knowledge.
[0093] Preferred polyester diols (C3b) are the reaction products of
diols with dicarboxylic acids or their reactive derivatives,
examples being anhydrides or dimethyl esters.
[0094] Useful dicarboxylic acids are saturated and unsaturated
aliphatic and also aromatic dicarboxylic acids, which may bear
additional substituents, such as halogen.
[0095] Preferred aliphatic dicarboxylic acids are saturated
unbranched .alpha.,.omega.-dicarboxylic acids comprising 3 to 22
and especially 4 to 12 carbon atoms.
[0096] Examples of particularly suitable dicarboxylic acids are:
succinic acid, glutaric acid, adipic acid, suberic acid, azelaic
acid, sebacic acid, 1,12-dodecanedicarboyxlic acid, maleic acid,
maleic anhydride, fumaric acid, itaconic acid, phthalic acid,
isophthalic acid, phthalic anhydride, tetrahydrophthalic anhydride,
hexahydrophthalic anhydride, tetrachlorophthalic anhydride,
endomethylenetetrahydrophthalic anhydride, terephthalic acid,
dimethyl terephthalate and dimethyl isophthalate.
[0097] Useful diols include in particular saturated and unsaturated
aliphatic and cycloaliphatic diols. The particularly preferred
aliphatic .alpha.,.omega.-diols are unbranched and have 2 to 12, in
particular 2 to 8, especially 2 to 4 carbon atoms. Preferred
cycloaliphatic diols are derived from cyclohexane.
[0098] 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-but-2-ene-1,4-diol, trans-but-2-ene-1,4-diol,
2-butyne-1,4-diol, cis-1,4-di(hydroxymethyl)-cyclohexane and
trans-1,4-di(hydroxymethyl)cyclohexane.
[0099] The molecular weight M.sub.n of the polyester diols is
preferably in the range from 300 to 5000.
[0100] Lactone-based polyester diols useful as an
isocyanate-reactive compound (C3b) are based in particular on
aliphatic saturated unbranched .omega.-hydroxy carboxylic acids
having 4 to 22 and preferably 4 to 8 carbon atoms. It is also
possible to use branched .omega.-hydroxy carboxylic acids wherein
one or more --CH.sub.2-- groups in the alkylene chain are replaced
by --CH(C.sub.1-C.sub.4-alkyl)-.
[0101] Examples of preferred .omega.-hydroxy carboxylic acids are
.gamma.-hydroxybutyric acid and .delta.-hydroxyvaleric acid.
[0102] It will be appreciated that the abovementioned diols may
likewise be used as isocyanate-reactive compounds (C3b), in which
case the same preferences as above apply.
[0103] Triols, in particular triols having 3 to 12 and especially 3
to 8 carbon atoms, are likewise useful as isocyanate-reactive
compounds (C3b). Trimethylolpropane is an example of a particularly
suitable triol.
[0104] Dihydroxy carboxylic acids useful as isocyanate compounds
(C3b) are in particular aliphatic saturated dihydroxy carboxylic
acids which preferably comprise 4 to 14 carbon atoms. Dihydroxy
carboxylic acids of the formula
##STR00001##
[0105] where A.sup.1 and A.sup.2 represent identical or different
C.sub.1-C.sub.4-alkylene radicals and R represents hydrogen or
C.sub.1-C.sub.4-alkyl, are very particularly suitable.
[0106] Dimethylolpropionic acid (DMPA) is a particularly preferred
example of these dihydroxy carboxylic acids.
[0107] Useful isocyanate-reactive compounds (C3b) further include
the corresponding dihydroxy sulfonic acids and dihydroxy phosphonic
acids, such as 2,3-dihydroxy-propanephosphonic acid.
[0108] Dihydroxy carboxylic acid as used herein shall also comprise
compounds comprising more than one carboxyl function (or as the
case may be anhydride or ester function). Such compounds are
obtainable by reaction of dihydroxy compounds with tetracarboxylic
dianhydrides, such as pyromellitic dianhydride or
cyclopentane-tetracarboxylic dianhydride, in a molar ratio from 2:1
to 1.05:1 in a polyaddition reaction, and preferably have an
average molecular weight M.sub.n in the range from 500 to 10
000.
[0109] Examples of useful polycarbonate diols (C3b) are the
reaction products of phosgene with an excess of diols, in
particular unbranched saturated aliphatic .alpha.,.omega.-diols
having 2 to 12, in particular 2 to 8 and especially 2 to 4 carbon
atoms.
[0110] Polyhydroxyolefins useful as an isocyanate-reactive compound
(C3b) are in particular .alpha.,.omega.-dihydroxyolefins, and
.alpha.,.omega.-dihydroxybutadienes are preferred.
[0111] The polysiloxanes useful as an isocyanate-reactive compound
(C3b) comprise on average at least two hydroxyl groups per
molecule. Particularly suitable polysiloxanes comprise on average 5
to 200 silicon atoms (number average) and are in particular
substituted by C.sub.1-C.sub.12-alkyl groups, in particular methyl
groups.
[0112] Examples of isocyanate-reactive compounds (C3b) comprising
just one isocyanate-reactive hydroxyl group are in particular
aliphatic, cycloaliphatic, araliphatic or aromatic monohydroxy
carboxylic acids and monohydroxy sulfonic acids.
[0113] The polyurethane-based additives (C3) are prepared by
reaction of the compounds (C3a) and (C3b) in a molar ratio of (C3a)
to (C3b) which is generally in the range from 2:1 to 1:1 and
preferably in the range from 1.2:1 to 1:1.2.
[0114] It is possible in this connection, as well as the
aforementioned isocyanate-reactive compounds (C3b), to add further
compounds having isocyanate-reactive groups, for example dithiols,
thio alcohols, such as thioethanol, amino alcohols, such as
ethanolamine and N-methylethanolamine, or diamines, such as
ethylenediamine, to thereby prepare polyurethanes which, as well as
the urethane groups, additionally bear 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 bear at least two primary
and/or secondary amino groups.
[0115] It will be appreciated that it is also possible to add
corresponding compounds having just one isocyanate-reactive group,
examples being monoalcohols, primary and secondary monoamines,
monoamino carboxylic acid and sulfonic acids and mercaptans.
Customary use levels range up to 10 mol %, based on (C3a).
[0116] Preferably, some or all of the carboxyl groups of the
reaction products (C3) are in salt form in order their solubility
in water may be ensured. Useful salts include for example alkali
metal salts, such as sodium and potassium salts, and ammonium
salts.
[0117] Typically, the additives (C3) have average molecular weights
M.sub.w in the range from 500 to 250 000.
[0118] Specific surface-active properties can be achieved for the
additives (C3) via the ratio of polar to apolar groups.
[0119] Such anionic surface-active additives (C3) are known and
commercially available, for example under the name of Borchi.RTM.
GEN SN95 (Borchers).
[0120] Water-soluble anionic surface-active additives based on
acidic phosphoric, phosphonic, sulfuric and/or sulfonic esters of
polyethers (C4) are based in particular on the reaction products of
the above-recited polyethers (C1) with phosphoric acid, phosphorus
pentoxide and phosphonic acid or sulfuric acid and sulfonic acid.
The reaction converts the polyethers into the corresponding
phosphoric mono- and diesters and phosphonic esters or sulfuric
monoesters and sulfonic esters. These acidic esters are preferably
present in the form of water-soluble salts, in particular as alkali
metal salts, especially sodium salts, and ammonium salts, but they
can also be used in the form of the free acids.
[0121] Preferred phosphates and phosphonates are derived in
particular from alkoxylated, especially ethoxylated, fatty and oxo
process 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 including polyfunctional amines, such as
hexamethylenediamine.
[0122] Such anionic surface-active additives are known and
commercially available, for example under the names of Nekal.RTM.
(BASF), Tamol.RTM. (BASF), Crodafos.RTM. (Croda), Rhodafac.RTM.
(Rhodia), Maphos.RTM. (BASF), Texapon.RTM. (Cognis), Empicol.RTM.
(Albright & Wilson), Matexil.RTM. (ICI), Soprophor.RTM.
(Rhodia) and Lutensit.RTM. (BASF).
[0123] The amount of dispersant (C) in the colorant preparations to
be used according to this invention is typically in the range from
1% to 50% by weight and especially in the range from 1% to 40% by
weight.
[0124] Water forms the liquid vehicle for the colorant preparations
to be used according to this invention.
[0125] The liquid phase of the colorant preparations is preferably
a mixture of water and a water-retaining agent. The water-retaining
agents used are in particular organic solvents which are high
boiling (i.e., generally have a boiling point >100.degree. C.)
and hence have a water-retaining action and are soluble in or
miscible with water.
[0126] Examples of suitable water-retaining agents are polyhydric
alcohols, preferably unbranched and branched polyhydric alcohols
containing from 2 to 8 and especially from 3 to 6 carbon atoms,
such as ethylene glycol, 1,2-propylene glycol, 1,3-propylene
glycol, glycerol, erythritol, pentaerythritol, pentitols, such as
arabitol, adonitol and xylitol and hexitols such as sorbitol,
mannitol and dulcitol. Useful water-retaining agents further
include for example di-, tri- and tetraalkylene glycols and their
monoalkyl (especially C.sub.1-C.sub.6-alkyl and in particular
C.sub.1-C.sub.4-alkyl) ethers. Examples which may be mentioned are
di-, tri- and tetraethylene glycol, diethylene glycol monomethyl,
monoethyl, monopropyl and monobutyl ethers, triethylene glycol
monomethyl, monoethyl, monopropyl and monobutyl 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, monoethyl,
monopropyl and monobutyl ethers.
[0127] The amount of liquid phase (D) present in the colorant
preparations to be used according to this invention is generally in
the range from 10% to 88.95% by weight and preferably in the range
from 10% to 80% by weight. When water is present in a mixture with
a water-retaining organic solvent, this solvent will account for a
proportion of phase (D) which is generally in the range from 1% to
80% by weight and preferably in the range from 1% to 60% by
weight.
[0128] The colorant preparations may further comprise customary
addition agents, such as biocides, defoamers, antisettling agents
and rheological modifiers, and their fraction may generally be up
to 5% by weight.
[0129] The colorant preparations to be used according to this
invention are obtainable in various ways. It is preferable first to
prepare a pigment dispersion which is then admixed with the dye as
a solid or especially in dissolved form or as a dispersion in a
liquid, in particular aqueous, phase.
[0130] The colorant preparations to be used according to present
invention are very useful for coloring the cellulose particles used
in cellulose polymer compounds or composites. The particles in
question may consist of any naturally occurring cellulose variety
and may be finely to coarsely divided. Preferred examples of these
materials are wood shavings, wood fibers and wood dust.
[0131] The cellulose particles can be colored at various production
stages. The chopping chips serving as starting material can be
colored, but the cellulose particles can also be colored after
their fabrication in the moist or dry state.
[0132] This will now be more particularly described by way of
example with reference to wood fibers. As well as coloration of the
chopping chips serving as a starting material, it is similarly
possible for the moist wood fibers obtained after comminution by
cooking and grinding to be contacted with the colorant
preparations. The colorant preparations may here be applied to the
wood fiber together with further auxiliaries for compound or
composite production if desired. Finally, the wood fibers can be
sprayed with the colorant preparations after drying.
[0133] The colored particles of cellulose, as usual for the
manufacture of cellulose polymer compounds or composites, can then
be mixed with the matrix polymer and jointly extruded.
[0134] When the polymer matrix is to be colored as well, this is
simple to accomplish by additional incorporation of commonly known
polymeric concentrates of pigment known as masterbatches in the
extrusion operation.
* * * * *