EP1831460B1 - Method for colouring substrates containing cellulose - Google Patents

Description

1. a) Dispergieren von mindestens einem Pigment in partikulärer Form mit mindestens einem nicht-ionischen oberflächenaktiven Stoff,
2. b) Vermischen der so erhältlichen Dispersion von Pigment in partikulärer Form und nicht-ionischem oberflächenaktiven Stoff mit wässrigem Medium,
3. c) Polymerisieren mindestens eines ersten Monomers oder Copolymerisation einer ersten Mischung von Comonomeren in Gegenwart einer Mischung nach b), wobei wasserunlösliches Polymer oder Copolymer an der Oberfläche von Pigment in partikulärer Form gebildet wird,
4. d) Hinzufügen mindestens eines zweiten Monomers oder einer zweiten Mischung von Comonomeren und Polymerisation oder Copolymerisation,

mit der Maßgabe, dass Verfahren zum Bedrucken nicht umfasst sind.The present invention relates to a method for coloring cellulosic substrates, which comprises contacting substrates to be colored or their precursors contacted with at least one treated pigment in particulate form which is at least partially coated with at least one cationic copolymer prepared by a process, comprising the following steps:

1. a) dispersing at least one pigment in particulate form with at least one nonionic surfactant,
2. b) mixing the thus obtainable dispersion of pigment in particulate form and nonionic surfactant with aqueous medium,
3. c) polymerizing at least one first monomer or copolymerizing a first mixture of comonomers in the presence of a mixture according to b), wherein water-insoluble polymer or copolymer is formed on the surface of pigment in particulate form,
4. d) adding at least one second monomer or a second mixture of comonomers and polymerization or copolymerization,

with the proviso that methods for printing are not included.

Demanding requirements are imposed on colorant preparations which are to be used in modern methods of coloring cellulosic substrates. Colored substrates should have a high brilliance of the colors, the coloration should be permanent, ie. have high fastness properties, such as rub fastness and light fastness. Furthermore, colorants are, when it comes to wood-containing cellulose-containing substrates, penetrate into the wood during incorporation in certain proportions and not just remain on the surface. Following incorporation, the colorants should no longer migrate.

Pure pigments, which by definition are not or only poorly soluble in the medium in question, often remain on the surface of wood to be colored.

There are attempts to treat pigments by coating them with a polymer. US 3,133,893 discloses the coating of pigments treated with a surfactant with polyacrylonitrile prepared in a polymerization step which is synthesized in the presence of the pigment. The so wrapped

Pigments can be incorporated into fibers but are not good for coloring cellulosic substrates.

US 4,608,401 discloses a process for encapsulating pigments for latex paints, in which pigment particles are dispersed with water-insoluble monomers and a detergent under non-shear conditions in water and then subjected to emulsion polymerization conditions. The so coated pigments can not be used well to colorize cellulosic substrates.

The older registration WO 2004/113454 teach cationically encapsulated pigments in particulate form prepared by a two-stage emulsion polymerization process in the presence of pigment, and their use for printing on surfaces.

The older registration WO 2005/037930 describes formulations containing these pigments in particulate form and at least one radiation-curable component for dyeing leather.

US 4,680,200 discloses a process for the encapsulation of non-pretreated pigments in which pigment particles with styrene and the oligomer Polywet KX-3 from Uniroyal are dispersed in water and then subjected to the conditions of an emulsion polymerization. However, the results in the colorization of cellulosic substrates are unsatisfactory.

It was therefore the object to provide a process for the coloration of cellulose-containing substrates, which avoids the disadvantages of the prior art and provides particularly well dyed or solid-colored cellulosic substrates. It was a further object to provide colored cellulose-containing substrates.

Accordingly, the method defined above was found.

In the following, coloring is understood to mean processes for coloring which not only produce a superficial coloring, but also at least partially cause, at a certain depth of the relevant substrate, a coloring which can be just as intense or slightly less intense as the coloring on the surface. Methods for printing are not included below.

Cellulosic substrates are understood below to mean wood-containing and so-called wood-free papers, cardboard, cardboard, furthermore wood in any dimensions, for example wood blanks such as boards, rods, blocks, furthermore wood wool, wood-containing composite materials, wood blanks, plywood, chipboard, MDF boards (medium density fiberboard) , Oriented Strand Board (OSB), annual woody yearlong, straw and fibrous materials such as flax, linen, hemp, jute, cotton, bamboo, paper mulberry or wood pulp fibers. Cellulose-containing substrates For the purposes of the present invention may be configured, for example, flat or as a shaped body.

In the context of the present invention, precursors are to be understood as meaning in particular paper precursors, for example bleached and unbleached pulps and wood pulp, pulp and wood chips.

According to the invention, substrates to be colored or their precursors are contacted with at least one treated pigment in particulate form, which is at least partially coated with at least one cationic copolymer.

For carrying out the process according to the invention, the starting material is specifically treated pigment. By treated pigment is meant pigment which is at least partially coated with at least one cationic copolymer. Treated pigment may also be completely coated with cationic copolymer. Preferably treated pigment in the context of the present invention is at least 10% up to 99% coated with cationic copolymer, preferably 40 to 70%, wherein the percentages can be determined by, for example, microscopic methods.

By partially encased, in one embodiment of the present invention, it can be understood that a certain percentage of the pigment particles are coated with cationic copolymer and the remainder of the pigment particles are not enveloped by cationic copolymer.

In another embodiment of the present invention, it can be partially understood that all pigment particles are partially enveloped.

The cationic copolymer coating is usually so thin that even completely coated pigment particles are colored.

Pigment partially coated with cationic copolymer is prepared by synthesizing the corresponding cationic copolymer in the presence of pigment. In a preferred embodiment of the present invention, cationic copolymer is synthesized in the presence of pigment according to an emulsion polymerization process of at least two stages in which the composition of comonomers is changed at least once, for example by changing the comonomer feed.

Cationic copolymers in the context of the present invention are copolymers of free-radically polymerizable ethylenically unsaturated compounds, of which at least one carries a protonatable group, for example nitrogen-atom nitrogen atoms, or cationic groups such as, for example, quaternary nitrogen atoms, incorporated in the polymer chain.

In one embodiment of the present invention cationic copolymers are present in acidic conditions, for example at pH values of 6 or less, in at least partially protonated form. Cationic copolymers may, for example, be understood as meaning those copolymers which carry free amino groups, for example NH ₂ groups, NH (C ₁ -C ₄ -alkyl) groups or N (C ₁ -C ₄ -alkyl) ₂ groups.

In one embodiment of the present invention, cationic copolymers may be understood as meaning those copolymers which comprise as one of the comonomers one or more amides of at least one ethylenically unsaturated carboxylic acid, for example (meth) acrylamide in copolymerized form.

In one embodiment of the present invention, cationic copolymers have a molecular weight M _w in the range of 10,000 to 10,000,000 g / mol, preferably 100,000 to 5,000,000 g / mol.

In one embodiment of the present invention, cationic copolymers are copolymers which are composed of at least one nonionic comonomer, for example a vinyl aromatic compound such as, for example, Example, styrene or at least one C ₁ -C ₂₀ alkyl ester of at least one ethylenically unsaturated carboxylic acid, and at least one comonomer having at least one protonatable or quaternized nitrogen atom per molecule.

Cationic copolymers in the context of the present invention may also contain one or more anionic comonomers, such as, for example, (meth) acrylic acid or crotonic acid in copolymerized form. If cationic copolymers also contain at least one anionic monomer in copolymerized form, the molar fraction of cationic comonomers is always higher than the molar fraction of anionic comonomers, for example by 0.5 mol%, based on the total cationic copolymer, preferably at least 1 mol% , particularly preferably 1.5 to 20 mol%.

Preferably cationic copolymer is synthetic cationic copolymer.

For carrying out the process according to the invention, it is furthermore assumed that pigments are used in preferably particulate form. For the purposes of the present invention, pigments are to be understood as meaning virtually insoluble finely divided, organic or inorganic colorants as defined in DIN 55944.

Pigments can be selected from inorganic and preferably organic pigments.

• Zinkoxid, Zinksulfid, Lithopone, Bleiweiß, Bleisulfat, Kreide, Titandioxid, Calziumcarbonat, Kaolin;
• Eisenoxidgelb, Cadmiumgelb, Nickeltitangelb, Chromtitangelb, Chromgelb, Bleichromat, Bismutvanadat, Neapelgelb oder Zinkgelb
• Ultramarinblau, Kobaltblau, Manganblau, Eisenblau,
• Ultramaringrün, Kobaltgrün, Chromoxid (Chromoxidgrün);
• Ultramarinviolett, Kobaltviolett, Manganviolett;
• Ultramarinrot, Molybdatrot, Chromrot, Cadmiumrot;
• Eisenoxidbraun, Chromeisenbraun, Zinkeisenbraun, Mangantitanbraun;
• Eisenoxidschwarz, Eisen-Mangan-Schwarz, Spinellschwarz, Ruß;
• orangefarbene Spinelle und Korunde, Cadmiumorange, Chromorange, Bleimolybdat; Aluminium oder Cu/Zn-Legierung.

Exemplary selected inorganic pigments are

• Zinc oxide, zinc sulfide, lithopone, lead white, lead sulfate, chalk, titanium dioxide, calcium carbonate, kaolin;
• Iron oxide yellow, cadmium yellow, nickel titanium yellow, chrome titanium yellow, chrome yellow, lead chromate, bismuth vanadate, Naples yellow or zinc yellow
• Ultramarine blue, cobalt blue, manganese blue, iron blue,
• Ultramarine green, cobalt green, chrome oxide (chrome oxide green);
• Ultramarine violet, cobalt violet, manganese violet;
• Ultramarine red, molybdenum red, chrome red, cadmium red;
• Iron oxide brown, chrome iron brown, zinc iron brown, mangantite brown;
• Iron oxide black, iron manganese black, spinel black, carbon black;
• orange spinels and corundum, cadmium orange, chrome orange, lead molybdate; Aluminum or Cu / Zn alloy.

Preferred are carbon black, carbon black, calcium carbonate, kaolin, iron oxide pigments such as iron oxide yellow, iron oxide brown and iron oxide black, zinc oxide and titanium dioxide.

As carbon blacks, mention may be made in particular of those which are prepared by the gas black process, the flame black process or the furnace carbon black process.

The BET surface area of carbon black used in accordance with the invention can be, for example, in the range from 20 to 2000 m ² / g, determined according to DIN 66131/2 or ISO 4652.

Carbon black used according to the invention can be surface-modified, for example by oxidation. Carbon black used according to the invention can have acidic and / or basic groups, for example carboxyl groups, lactol groups, phenol groups, quinone groups, basic oxides with, for example, pyrone-like structures.

Examples of selected organic pigments, which are also counted below vat dyes, are

Monoazo pigments such as CI Pigment Brown 25;
CI Pigment Orange 5, 13, 36 and 67; CI Pigment Red 1, 2, 3, 5, 8, 9, 12, 17, 22, 23, 31, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 52: 1 , 52: 2, 53, 53: 1, 53: 3, 57: 1, 63, 112, 146, 170, 184, 210, 245 and 251; CI Pigment Yellow 1, 3, 73, 74, 65, 97, 151 and 183; Disazo pigments such as CI Pigment Orange 16, 34 and 44;
CI Pigment Red 144, 166, 214 and 242; CI Pigment Yellow 12, 13, 14, 16, 17, 81, 83, 106, 113, 126, 127, 155, 174, 176 and 188;
Anthanthrone pigments such as CI Pigment Red 168 and CI Vat Orange 3; Anthrachinonpigmente such as CI Pigment Yellow 147 and 177;
CI Pigment Violet 31;
Anthrapyrimidine pigments such as CI Pigment Yellow 108,
CI Vat Yellow 20;
Quinacridone pigments such as CI Pigment Red 122, 202 and 206;
CI Pigment Violet 19;
Quinophthalone pigments such as CI Pigment Yellow 138;
Diketopyrrolopyrrole pigments such as CI Pigment Orange 71, 73 and 81;
CI Pigment Red 254, 255, 264, 270 and 272,
Dioxazine pigments such as CI Pigment Violet 23 and 37;
Flavanthrone pigments such as CI Pigment Yellow 24, CI Vat Yellow 1;
Indanthrone pigments such as CI Pigment Blue 60 and 64, CI Vat Blue 4 and 6;
Isoindoline pigments such as CI Pigment Orange 69; CI Pigment Red 260; CI Pigment Yellow 139 and 185;
Isoindolinone pigments such as CI Pigment Orange 61;
CI Pigment Red 257 and 260; CI Pigment Yellow 109, 110, 173 and 185;
Isoviolanthrone pigments such as CI Pigment Violet 31 and CI Vat Violet 1; Metal complex pigments such as CI Pigment Yellow 117, 150 and 153;
CI Pigment Green 8;
Perinone pigments such as CI Pigment Orange 43, CI Vat Orange 7,
CI Pigment Red 194, CI Vat Red 15;
Perylene pigments such as CI Pigment Black 31 and 32; CI Pigment Red 123, 149, 178, 179, CI Vat Red 23, 190, 29 and 224; CI Pigment Violet 29;
Phthalocyanine pigments such as CI Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6 and 16; CI Pigment Green 7 and 36;
Pyranthrone pigments such as CI Pigment Orange 51;
CI Pigment Red 216 and CI Vat Orange 4;
Thioindigo pigments such as CI Pigment Red 88 and 181, CI Vat Red 1;
CI Pigment Violet 38 and CI Vat Violet 3;
Triaryl carbonium pigments such as CI Pigment Blue 1, 61 and 62;
CI Pigment Green 1; CI Pigment Red 81, 81: 1 and 169; CI Pigment Violet 1, 2, 3 and 27; CI Pigment Black 1 (aniline black);
CI Pigment Yellow 101 (aldazine yellow);
CI Pigment Brown 22.

Examples of particularly preferred organic pigments are: C.I. Pigment Yellow 138, C.I. Pigment Red 122, C.I. Pigment Violet 19, C.I. Pigment Blue 15: 3 and 15: 4, C.I. Pigment Black 7, C.I. Pigment Orange 5, 38 and 43 and C.I. Pigment Green 7.

According to the invention, mixtures of two or more different pigments can also be used.

It is assumed that pigments are present in particulate form, i. in the form of particles. For example, it is possible to start from so-called crude pigments, which are untreated pigments, as obtained after pigment synthesis. The particles may be regular or irregular in shape, for example, the particles may be in spherical or approximately spherical or needle shape. One can do this step (a) so that a wet comminution takes place.

In one embodiment of the present invention, one starts from pre-milled pigment.

In one embodiment of the present invention, pre-milled pigment is based on having been coated with at least one pigment derivative, for example a pigment sulfonic acid, a pigment amidosulfonic acid or a methyleneamine derivative of a pigment.

The pigment or pigments in particulate form are dispersed in step a) with at least one nonionic surfactant.

Examples of suitable nonionic surface-active substances are, for example, ethoxylated mono-, di- and tri-alkylphenols (degree of ethoxylation: from 3 to 50, alkyl radical: C ₃ -C ₁₂ ) and also ethoxylated fatty alcohols (EO degree: from 3 to 80; ₈ -C ₃₆ ). Examples are the Lutensol ^® grades from BASF AG or the Triton ^® grades from Union Carbide. Particular preference is given to ethoxylated linear fatty alcohols of the general formula III

nC _× H _{2x + 1} -O (CH ₂ CH ₂ O) _y -H, III

where x are integers in the range of 10 to 24, preferably in the range of 12 to 20. The variable y preferably stands for integers in the range of 5 to 50, more preferably 8 to 40.

Ethoxylated linear fatty alcohols of the general formula III are usually present as a mixture of different ethoxylated fatty alcohols with different degrees of ethoxylation. The variable y in the context of the present invention stands for the mean value (number average).

The dispersion of pigment in particulate form and at least one nonionic surfactant takes place in devices suitable for dispersing, preferably in mills such as ball mills or stirred ball mills. Particularly suitable is the ball mill Drais Superflow DCP SF 12.

By way of example, ½ hour to 48 hours have proven to be a suitable period for dispersing, although a longer period of time is also conceivable. Preferred is a period for dispersing from 5 to 24 hours.

Pressure and temperature conditions during dispersion are generally not critical, for example, normal pressure has proven to be suitable. As temperatures, for example, temperatures in the range of 10 ° C to 100 ° C have proven to be suitable.

The amount ratio of pigment to non-ionic surfactant can be chosen within wide limits, for example in the range from 10: 1 to 2: 1.

During the performance of step a) one can add water. Also you can enforce conventional non-ionic grinding aids.

The mean diameter (number average) of the pigments after step a) is usually in the range from 10 nm to 5 μm, preferably in the range from 50 nm to 3 μm.

When the pigment is carbon black, the average diameter (number average) of the primary particles may be, for example, in the range of 5 to 200 nm.

To determine the mean diameter, common methods are suitable, for example electron microspheres.

In step b), the dispersion of pigment in particulate form and nonionic surfactant with aqueous medium obtainable after step a) is mixed. For dispersion, one can use any devices, for example stirred vessels or stirred flasks.

For the purposes of the present invention, aqueous media are understood as meaning those liquid media which contain water as an important component, for example at least 40% by weight, preferably at least 55% by weight.

In step b), the weight ratio dispersion of pigment in particulate form and nonionic surfactant to aqueous medium is generally in the range of 1: 1.5 to 1:15, preferably 1: 2.5 to 1: 9.

Pressure and temperature conditions for step b) are generally not critical, for example, temperatures in the range of 5 to 100 ° C are suitable, preferably 20 to 85 ° C and pressures in the range of atmospheric pressure to 10 bar.

Mixing after step b) gives a mixture.

In step c), at least one first monomer is polymerized or copolymerized a first mixture of comonomer in the presence of a mixture obtainable according to b), wherein water-insoluble polymer or copolymer is formed on the surface of pigment in particulate form.

To carry out step c), at least one monomer or at least one mixture of comonomers is added to a mixture obtainable according to b). The addition can be done, for example, in one portion, in several portions or continuously. If you want to copolymerize at least different monomers together, you can first add a comonomer and then the second and optionally further comonomers. In another embodiment, all comonomers are added in one portion.

Monomer or comonomers can be added in bulk or in aqueous dispersion.

As monomers or comonomers in step c) are selected such monomers or comonomers which are sparingly soluble in water. Under poorly water-soluble monomers or comonomers are understood to mean those monomers or comonomers whose solubility in water at 50 ° C 1 x 10 ^-1 mol / l or less.

Preferred examples of monomers or comonomers in step c) are vinylaromatic compounds and poorly water-soluble α, β-unsaturated carboxylic acid derivatives.

in der R⁷ und R⁸ unabhängig voneinander jeweils für Wasserstoff, Methyl oder Ethyl stehen, R⁹ Methyl oder Ethyl bedeutet und k eine ganze Zahl von 0 bis 2 bedeutet; ganz besonders bevorzugt sind R⁷ und R⁸ jeweils Wasserstoff, und ganz besonders bevorzugt gilt k = 0.Preferably, at least one compound of general formula IV is chosen as the vinylaromatic compound,

in which R ⁷ and R ⁸ are each independently hydrogen, methyl or ethyl, R ^{9 is} methyl or ethyl and k is an integer from 0 to 2; Most preferably, R ⁷ and R ^{8 are} each hydrogen, and most preferably k = 0.

in der die Variablen wie folgt definiert sind:

R¹

gewählt aus

• unverzweigtem oder verzweigtem C₁-C₁₀-Alkyl, wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl, tert.-Butyl, n-Pentyl, iso-Pentyl, sec.-Pentyl, neo-Pentyl, 1,2-Dimethylpropyl, iso-Amyl, n-Hexyl, iso-Hexyl, sec.-Hexyl, n-Heptyl, n-Octyl, 2-Ethylhexyl, n-Nonyl, n-Decyl; besonders bevorzugt C₁-C₄-Alkyl wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl und tert.-Butyl;
• oder Wasserstoff,
• ganz besonders bevorzugt sind Wasserstoff und Methyl;

R²

gewählt aus

• unverzweigtem oder verzweigtem C₁-C₁₀-Alkyl, wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl, tert.-Butyl, n-Pentyl, iso-Pentyl, sec-Pentyl, neo-Pentyl, 1,2-Dimethylpropyl, iso-Amyl, n-Hexyl, iso-Hexyl, sec.-Hexyl, n-Hep-tyl, n-Octyl, 2-Ethylhexyl, n-Nonyl, n-Decyl; besonders bevorzugt C₁-C₄-Alkyl wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl und tert.-Butyl;
• oder ganz besonders bevorzugt Wasserstoff.

R³

gewählt aus unverzweigtem oder verzweigtem C₄-C₁₀-Alkyl, wie n-Butyl, iso-Butyl, sec.-Butyl, tert.-Butyl, n-Pentyl, iso-Pentyl, sec.-Pentyl, neo-Pentyl, 1,2-Dimethylpropyl, iso-Amyl, n-Hexyl, iso-Hexyl, sec.-Hexyl, n-Heptyl, n-Octyl, 2-Ethylhexyl, n-Nonyl, n-Decyl; ganz besonders n-Butyl und 2-Ethylhexyl.

Preferably, a compound of general formula I is chosen as poorly soluble in water-soluble α, β-unsaturated carboxylic acid derivative,

where the variables are defined as follows:

R ¹

chosen out

• unbranched or branched C ₁ -C ₁₀ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n- decyl; particularly preferably C ₁ -C ₄ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl;
• or hydrogen,
• very particular preference is given to hydrogen and methyl;

R ²

chosen out

• unbranched or branched C ₁ -C ₁₀ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso -hexyl, sec-hexyl, n-hep-tyl, n-octyl, 2-ethylhexyl, n-nonyl, n decyl; particularly preferably C ₁ -C ₄ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl;
• or very particularly preferably hydrogen.

R ³

selected from straight-chain or branched C ₄ -C ₁₀ -alkyl, such as n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neo-pentyl, 1 , 2-dimethylpropyl, iso-amyl, n-hexyl, iso -hexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl; especially n-butyl and 2-ethylhexyl.

In one embodiment of the present invention, the ratio of pigment to amount of monomer or comonomer in step c) in the range of 3: 1 to 1: 2, preferably in the range 2: 1 to 1: 1.5.

It is possible to use mixtures of the abovementioned monomers in step c). For example, mixtures of styrene and n-butyl acrylate are very well suited, the mixing ratio being arbitrary.

It is preferred to polymerize under the conditions of an emulsion polymerization. Very particular preference is given to so-called "starved conditions", ie, little or preferably no wetting agent is added. That's how you get no measurable levels of stabilized droplets of the first monomer or mixture of comonomers, and the proportion of wetting agent serves to network the pigment surface and to transport the first monomer or first mixture of comonomers through the continuous aqueous phase. Suitable wetting agents are, for example, organic sulfur compounds, for example alkyl sulfates, alkyl sulfonates, alkylaryl sulfonates, alkyl ether sulfates, alkylaryl ether sulfates, sulfosuccinates, such as sulfosuccinic monoesters and sulfosuccinic diesters; Furthermore, organic phosphorus compounds such as alkyl ether phosphates are suitable.

Usually, polymerization is carried out using at least one initiator. At least one initiator may be a peroxide. Examples of suitable peroxides are alkali metal peroxodisulfates, e.g. Sodium peroxodisulfate, ammonium peroxodisulfate, hydrogen peroxide, organic peroxides such as diacetyl peroxide, di-tert-butyl peroxide, diamyl peroxide, dioctanoyl peroxide, didecanoyl peroxide, dilauroyl peroxide, dibenzoyl peroxide, bis (o-toloyl) peroxide, succinyl peroxide, tert-butyl peracetate, tert-butyl permalate, tert Butyl perisobutyrate, tert-butyl perpivalate, tert-butyl peroctoate, tert-Butylperneodecanoat, tert-butyl perbenzoate, tert-butyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, tert-butyl peroxy-2-ethylhexanoate and Diisopropylperoxidicarbamat. Also suitable are azo compounds such as azobisisobutyronitrile, azobis (2-amidopropane) dihydrochloride and 2,2'-azobis (2-methylbutyronitrile) and 2,2'-azobis (2-amidinopropane) dihydrochloride.

Redox initiators are also suitable, for example, peroxides and oxidizable sulfur compound. Very particularly preferred are systems of acetone bisulfite and organic peroxide such as tert-C ₄ H ₉ -OOH, Na ₂ S ₂ O ₅ (sodium disulfite) and organic peroxide such as tert-C ₄ H ₉ -OOH or a combination of alkali metal salt of HO -CH ₂ SO ₂ H and organic peroxide such as tert-C ₄ H ₉ -OOH. Also, systems such as ascorbic acid / H ₂ O _{2 are} particularly preferred.

Temperatures in the range from 20 to 100.degree. C., preferably from 50 to 85.degree. C., can be chosen as the polymerization temperature. The selected temperature depends on the decay characteristic of the initiator used.

The pressure conditions are generally not critical, suitable, for example, pressures in the range of atmospheric pressure to 10 bar.

As time duration for step c), for example, 1 to 30 minutes have proven to be suitable, preferably 2 to 20 minutes and more preferably 3 to 15 minutes.

Of course, you can add to the reaction mixture other additives that are common in emulsion polymerization, for example, glycols, polyethylene glycols, Protective colloids, buffer / pH regulators, molecular weight regulators and chain transfer inhibitors.
Obtained after step c) with polymer or copolymer coated pigment in particulate form, which is obtained in the form of isolated particles. It is observed no measurable or very low levels of agglomerates, for example, less than 2 wt .-%, preferably less than 0.2 wt .-%.

The polymer or copolymer formed in step c) on the surface of the pigment in particulate form is water-insoluble.

In a further step, it is possible to isolate the dispersed polymer or copolymer-coated pigments obtainable in accordance with c) in a particulate form by purification operations, for example filtering, decanting or washing, and redispersing them to carry out step d). However, it is preferable to further process in situ the blended pigments coated with polymer or copolymer according to c) in particulate form.

In step d), at least one second monomer or a second mixture of comonomers is added to the dispersion from step c) or the worked-up and redispersed coated pigments in particulate form and polymerized or copolymerized. In this case, the second monomer or at least one comonomer of the second mixture of comonomers is cationic.

In this context, in connection with the present invention, a second mixture of comonomers is also used in step d) if a monomer has been used in step c) and a mixture of two comonomers is added in step d). Likewise, in connection with the present invention, a second monomer is also used in step d) if a mixture of comonomers has been used in step c) and a monomer is added in step d).

If it is desired to add a second mixture of comonomers, add at least one comonomer other than the monomer or comonomers of step c).

In one embodiment of the present invention, in step c) a vinyl aromatic compound is used as the monomer and in step d) at least one monomer or comonomer which can swell polymer or copolymer from step c). By swelling it is meant that under normal conditions at least 5% by weight of monomer or comonomer can be physically incorporated into the polymer or copolymer from step c).

wobei die Variablen wie folgt definiert sind:

R⁴

gewählt aus

• unverzweigtem oder verzweigtem C₁-C₁₀-Alkyl, wie Methyl, Ethyl, n-Propyl,
  iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl, tert.-Butyl, n-Pentyl, iso-Pentyl, sec.-Pentyl, neo-Pentyl, 1,2-Dimethylpropyl, iso-Amyl, n-Hexyl, iso-Hexyl,
  sec.-Hexyl, n-Heptyl, n-Octyl, 2-Ethylhexyl, n-Nonyl, n-Decyl; besonders bevorzugt C₁-C₄-Alkyl wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl und tert.-Butyl;
• oder Wasserstoff;

ganz besonders bevorzugt sind Wasserstoff und Methyl;

R⁵

gewählt aus

• unverzweigtem oder verzweigtem C₁-C₁₀-Alkyl, wie Methyl, Ethyl, n-Propyl, so-Propyl, n-Butyl, iso-Butyl, sec.-Butyl, tert.-Butyl, n-Pentyl, iso-Pentyl, sec.-Pentyl, neo-Pentyl, 1,2-Dimethylpropyl, iso-Amyl, n-Hexyl, iso-Hexyl, sec.-Hexyl, n-Heptyl, n-Octyl, 2-Ethylhexyl, n-Nonyl, n-Decyl; besonders bevorzugt C₁-C₄-Alkyl wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl und tert.-Butyl;
• oder ganz besonders bevorzugt Wasserstoff.

R⁶

wird gewählt aus unverzweigtem oder verzweigtem C₁-C₁₀-Alkyl, wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl, tert.-Butyl, n-Pentyl, iso-Pentyl, sec.-Pentyl, neo-Pentyl, 1,2-Dimethylpropyl, iso-Amyl, n-Hexyl, iso-Hexyl, sec.-Hexyl, n-Heptyl, n-Octyl, 2-Ethylhexyl, n-Nonyl, n-Decyl; besonders bevorzugt C₁-C₄-Alkyl wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl und tert.-Butyl.

Very particular preference is given to adding at least one comonomer of the general formula II,

where the variables are defined as follows:

R ⁴

chosen out

• unbranched or branched C ₁ -C ₁₀ -alkyl, such as methyl, ethyl, n-propyl,
  iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n Hexyl, iso-hexyl,
  sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl; particularly preferably C ₁ -C ₄ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl;
• or hydrogen;

very particular preference is given to hydrogen and methyl;

R ⁵

chosen out

• unbranched or branched C ₁ -C ₁₀ -alkyl, such as methyl, ethyl, n-propyl, so-propyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n- decyl; particularly preferably C ₁ -C ₄ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl;
• or very particularly preferably hydrogen.

R ⁶

is selected from linear or branched C ₁ -C ₁₀ -alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso Pentyl, sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl , n-decyl; particularly preferably C ₁ -C ₄ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl.

If it is desired to add a mixture of comonomers in step d), it is sufficient if at least one comonomer is different from the monomer or comonomer from step c). For example, it is possible to use styrene in step c) and in step d) to use a mixture of methacrylamide and styrene.

In one embodiment of the present invention, the weight ratio of the second monomer or second mixture of comonomers from step d) to pigment from step a) is in the range from 0.1: 1 to 10: 1, preferably 0.5: 1 to 7: 1, more preferably 2: 1 to 5: 1.

Overall, one chooses the amount of monomers or comonomers from step c) and d) so that the ratio of polymer or copolymer to pigment in the range of 1: 2 to 5: 1, preferably in the range of 2: 1 to 4: 1 lies.

In step d), polymerization or copolymerization is preferably carried out under the conditions of an emulsion polymerization. It is customary to use at least one initiator, it being possible for the initiator (s) to be selected from the abovementioned ones.

It is possible to use at least one emulsifier, which may be cationic or non-ionic.

Suitable nonionic emulsifiers are, for example, ethoxylated mono-, di- and tri-alkylphenols (degree of ethoxylation: 3 to 50, alkyl radical: C ₄ -C ₁₂ ) and ethoxylated fatty alcohols (degree of ethoxylation: 3 to 80, alkyl radical: C ₈ -C ₃₆ ). Examples are the Lutensol ^® brands from BASF Aktiengesellschaft and the Triton ^® grades from Union Carbide.

Suitable cationic emulsifiers are generally C ₆ -C ₁₈ -alkyl-, aralkyl- or heterocyclic radical-containing primary, secondary, tertiary or quaternary ammonium salts, alkanolammonium salts, pyridinium salts, imidazolinium salts, oxazolinium salts, morpholinium salts, thiazolinium salts and salts of amine oxides, quinolinium salts , Isoquinolinium salts, tropylium salts, sulfonium salts and phosphonium salts. Examples which may be mentioned dodecylammonium acetate or the corresponding hydrochloride, the chlorides or acetates of the various 2- (N, N, N-trimethyl ammonium) ethylparaffinsäureester, N -Cetylpyridiniumchlorid, N-cetyl N Laurylpyridiniumsulfat and N, N, N trimethylammonium bromide, N - Dodecyl- N , N , N- trimethylammonium bromide, N , N -distearyl- N , N -dimethylammonium chloride and the gemini-surfactant N , N '- (lauryldimethyl) ethylenediamine dibromide. Numerous other examples can be found in H. Stache, Tensid-Taschenbuch, Carl-Hanser-Verlag, Munich, Vienna, 1981 and in McCutcheon's, Emulsifiers & Detergents, MC Publishing Company, Glen Rock, 1989 ,

In one embodiment of the present invention, the amount of emulsifier is chosen so that the mass ratio between the second monomer or second mixture of comonomers on the one hand and emulsifier on the other hand is greater than 1, preferably greater than 10 and more preferably greater than 15.

The order of addition of the reactants from step d) is not critical per se.

In one embodiment of the present invention, the initiator is added when a milky-looking emulsion has been produced by, for example, stirring.

Temperatures in the range from 20 to 100.degree. C., preferably from 50 to 85.degree. C., can be chosen as the polymerization temperature. The selected temperature depends on the decay characteristic of the initiator used.

The pressure conditions are generally not critical, suitable, for example, pressures in the range of atmospheric pressure to 10 bar.

The period of time for the polymerization or copolymerization in step d) can be chosen to be in the range from 30 minutes to 12 hours, preferably from 2 to 3 hours.

zusetzen, in denen die Variablen wie folgt definiert sind:

R¹⁰

gewählt aus

• unverzweigtem oder verzweigtem C₁-C₁₀-Alkyl, wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl, tert.-Butyl, n-Pentyl, iso-Pentyl, sec.-Pentyl, neo-Pentyl, 1,2-Dimethylpropyl, iso-Amyl, n-Hexyl, iso-Hexyl, sec.-Hexyl, n-Hep-tyl, n-Octyl, 2-Ethylhexyl, n-Nonyl, n-Decyl; besonders bevorzugt C₁-C₄-Alkyl wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl und tert.-Butyl;
• oder Wasserstoff;

ganz besonders bevorzugt sind Wasserstoff und Methyl;

R¹¹

gewählt aus

• unverzweigtem oder verzweigtem C₁-C₁₀-Alkyl, wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl, tert.-Butyl, n-Pentyl, iso-Pentyl, sec.-Pentyl, neo-Pentyl, 1,2-Dimethylpropyl, iso-Amyl, n-Hexyl, iso-Hexyl, sec.-Hexyl, n-Hep-tyl, n-Octyl, 2-Ethylhexyl, n-Nonyl, n-Decyl; besonders bevorzugt C₁-C₄-Alkyl wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl und tert.-Butyl;
• oder ganz besonders bevorzugt Wasserstoff.

R¹²

wird gewählt aus unverzweigtem oder verzweigtem C₁-C₁₀-Alkyl, wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl, tert.-Butyl, n-Pentyl, iso-Pentyl, sec.-Pentyl, neo-Pentyl, 1,2-Dimethylpropyl, iso-Amyl, n-Hexyl, iso-Hexyl, sec.-Hexyl, n-Heptyl, n-Octyl, 2-Ethylhexyl, n-Nonyl, n-Decyl; besonders bevorzugt C₁-C₄-Alkyl wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl und tert.-Butyl,

• oder ganz besonders bevorzugt Wasserstoff.

X

gewählt aus

• Wasserstoff,
• Glycidyl
  
• Gruppen mit tertiären Aminogruppen, beispielsweise NH(CH₂)_b-N(CH₃)₂, wobei b eine ganze Zahl im Bereich von 2 bis 6 ist,
• enolisierbaren Gruppen mit 1 bis 20 C-Atomen, beispielsweise Acetoacetyl
  

wobei

R¹³

wird gewählt aus unverzweigtem oder verzweigtem C₁-C₁₀-Alkyl, wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl, tert.-Butyl, n-Pentyl, iso-Pentyl, sec.-Pentyl, neo-Pentyl, 1,2-Dimethylpropyl, iso-Amyl, n-Hexyl, iso-Hexyl, sec.-Hexyl, n-Heptyl, n-Octyl, 2-Ethylhexyl, n-Nonyl, n-Decyl; besonders bevorzugt C₁-C₄-Alkyl wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl und tert.-Butyl.

In one embodiment of the present invention, in step d) as comonomer, up to 20% by weight, preferably from 2 to 10% by weight, based on monomers or comonomers from step d), of at least one compound of general formula V a to Vb

in which the variables are defined as follows:

R ¹⁰

chosen out

• unbranched or branched C ₁ -C ₁₀ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-hep-tyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl; particularly preferably C ₁ -C ₄ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl;
• or hydrogen;

very particular preference is given to hydrogen and methyl;

R ¹¹

chosen out

• unbranched or branched C ₁ -C ₁₀ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-hep-tyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl; particularly preferably C ₁ -C ₄ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl;
• or very particularly preferably hydrogen.

R ¹²

is selected from linear or branched C ₁ -C ₁₀ -alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso Pentyl, sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl , n-decyl; particularly preferably C ₁ -C ₄ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl,

• or very particularly preferably hydrogen.

X

chosen out

• Hydrogen,
• glycidyl
  
• Groups having tertiary amino groups, for example NH (CH ₂ ) _b -N (CH ₃ ) ₂ , where b is an integer in the range from 2 to 6,
• enolizable groups having 1 to 20 carbon atoms, for example acetoacetyl
  

in which

R ¹³

is selected from linear or branched C ₁ -C ₁₀ -alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso Pentyl, sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl , n-decyl; especially preferably C ₁ -C ₄ -alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and tert-butyl.

Very particular preference in formula V a or V b R ^{10 is} selected from hydrogen and methyl and R ¹¹ and R ¹² are each hydrogen.

In a further embodiment of the present invention, comonomers can be used in step d): in each case 1 to 20, preferably up to 5% by weight of (meth) acrylonitrile, (meth) acrylamide, ureido (meth) acrylate, 2 Hydroxyethyl (meth) acrylate, 2- (N, N-dimethylamino) ethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 3- (N, N-dimethylamino) propyl (meth) acrylate, acrylamidopropanesulfonic acid, branched or unbranched, Alkali metal salt and in particular sodium salt of vinylsulfonic acid.

enthält, wobei in Formel VI die Variablen wie oben stehend definiert sind.In one embodiment of the present invention, the second mixture of comonomers is selected to range from 0.1 to 3% by weight, based on the amount of pigment in particulate form, of one or more unsaturated carboxylic acids of formula VI

In Formula VI, the variables are defined as above.

In one embodiment of the present invention, the second monomer or mixture of comonomers is selected by preparing in step d) a polymer or copolymer having a glass transition temperature T _g of -30 ° C.

In a preferred embodiment of the present invention, treated pigment is used in admixture with polymer or copolymer which is derived from monomers or mixtures of comonomers from step d). The polymer or copolymer derived from monomers or mixtures of comonomers from step d) is preferably in the form of spherical particles. The particles thus characterized are also referred to below as pigment-free polymer particles.

In a preferred embodiment, the weight ratio (A) to pigment-free polymer particles is in the range from 10: 0.1 to 10: 20, preferably from 10: 0.5 to 10: 4.

kann beispielsweise im Bereich von 1,2 bis 10 liegen, bevorzugt im Bereich von 1,5 bis 5.In a preferred embodiment, the mean radii r (pigment-free polymer particles) are smaller than the average radii r (A), in each case based on the number average. The radii ratio $$\frac{\mathrm{r}\left(\mathrm{A}\right)}{\mathrm{r}\left(\mathrm{pigment}\mathrm{-}\mathrm{free\; polymer\; particles}\right)}$$

may for example be in the range of 1.2 to 10, preferably in the range of 1.5 to 5.

The process according to the invention for coloring cellulosic substrates can be carried out by methods known per se. If, for example, one wishes to color paper, cardboard or cardboard, the process according to the invention can be carried out by contacting a non-aqueous or preferably aqueous formulation comprising at least one treated pigment in particulate form with paper, cardboard or cardboard, for example Painting, spraying, dipping or watering.

In a preferred embodiment of the present invention, at least one treated pigment in particulate form is added to a paper precursor, for example the pulp.

For example, pulp may contain from 2 to 10% by weight of preferably bleached pulp and from 90 to 98% by weight of water, and preferably no further auxiliaries.

Treated pigment can be added to the pulp, for example in amounts of from 0.001 to 1% by weight, based on the total pulp, and then processed into paper by methods known per se.

If, for example, it is desired to color wood or wood-containing substrates, then it is possible to operate at atmospheric pressure, for example at 1.1 to 20 bar, preferably at 10 bar, or at reduced pressure, for example at 50 to 800 mbar, preferably 100 to 650 mbar, or combinations of different pressure conditions. Examples of suitable normal pressure processes are immersion and impregnation processes such as, for example, the trough suction method, the trough-pressure-suction method, the tray impregnation, the hot-cold impregnation method and the adjustment method. Examples of methods at elevated pressure are the boiler pressure method. Examples of reduced pressure methods are the vacuum method, the double vacuum method, and the Boucherie method. Examples of working with combinations of different pressure conditions are the alternating pressure method, the Rüping method and the boiler pressure suction method. When looking at combinations of one wishes to operate under oscillating conditions, which in the context of the present invention are understood to mean multiple pressure changes from reduced pressure in the abovementioned ranges to increased pressure in the abovementioned ranges. The number of pressure changes is not critical per se, for example you can change the pressure conditions twice up to 500 times.

As a temperature for carrying out the method for coloring wood according to the invention, for example 10 to 20 ° C and preferably room temperature are suitable.

In one embodiment of the present invention, about 0.1 to 50 kg of treated pigment / m ³ , preferably up to 30 kg of treated pigment / m ^{3 of} wood are applied. This embodiment is preferred if, for example, one would like to work according to printing methods.

In one embodiment of the present invention, 0.01 to 20 g of treated pigment / m ^{2 of} wood surface is applied. This embodiment is preferred if, for example, one would like to work by dipping.

In one embodiment of the present invention, treated pigment in particulate form which is at least partially coated with at least one cationic copolymer is brought together with one or more wood preservatives. Suitable wood preservatives, for example, as in EP-A 0 316 602 are disclosed. You can apply 200 to 600 g of wood preservative per m ² wood surface on the surface, for example in the form of a dipping process. In the processes in which pressure is applied, as in the vacuum-pressure process, it is possible to use, for example, 1500 to 7000 kg of wood preservative per m ^{3 of} wood.

As a period for the contact can be chosen for example 10 seconds to 48 hours, preferably 20 seconds to 24 hours.

Another object of the present invention are colored cellulosic substrates obtainable by the process according to the invention. They are characterized by particular brilliance of the colors, low tendency to bleed and in the case of colored wood according to the invention by good light fastness and weather resistance.

The invention will be explained by working examples.

General preliminary remarks:

• 242 g n-Octadecanol und 0,1 mol KOH-Schuppen wurden bei einer Temperatur von 100°C und einem Druck von 1 mbar in einer Zeit von 2 Stunden im Autoklaven entwässert, mit Stickstoff anschließend entspannt und 3 mal mit Stickstoff gespült und anschließend auf 130°C im Autoklaven erhitzt. Nach Erreichen der Temperatur wurden innerhalb von 3 h 20 min 1100 g Ethylenoxid kontinuierlich zudosiert bei einem Druck von bis zu 6,1 bar. Nach vollständiger Zugabe ließ man abreagieren, bis Druckkonstanz erreicht war. Anschließend wurde auf 100°C abgekühlt und im Autoklaven bei 1 mbar 60 min entgast und das Reaktionsprodukt bei 70°C ausgefüllt. Die Ausbeute betrug 1337 g.

NC ₁₈ H ₃₇ - (OCH ₂ CH ₂ ) ₂₅ -OH is ethoxylated with ethylene oxide n-octadecanol, prepared according to the following procedure:

• 242 g of n-octadecanol and 0.1 mol KOH flakes were dewatered in a autoclave at a temperature of 100 ° C and a pressure of 1 mbar in a period of 2 hours, then expanded with nitrogen and purged 3 times with nitrogen and then on Heated to 130 ° C in an autoclave. After reaching the temperature 1100 g of ethylene oxide were metered in continuously within 3 h 20 min at a pressure of up to 6.1 bar. After complete addition, it was allowed to react until pressure constancy was reached. It was then cooled to 100 ° C and degassed in an autoclave at 1 mbar for 60 min and the reaction product was filled at 70 ° C. The yield was 1337 g.

The glass transition temperature was determined using a DSC822 (TA8200 series) from Mettler-Toledo with an autosampler TSO 801RO. The DSC device was equipped with a temperature sensor FSR5. It was worked according to DIN 53765.

I. Treatment of pigment in particulate form I a) dispersing pigment with nonionic surfactant I: 1a) dispersing a blue pigment with a nonionic surfactant

In a stirred ball mill of the type Drais Superflow DCP SF 12 were ground together: 1800 g Pigment Blue 15: 3 450 g nC ₁₈ H ₃₇ O (CH ₂ CH ₂ O) ₂₅ H 24 g glutaraldehyde 30 g tetramethylolacetylenediurea 3696 g distilled water

The milling was continued until the pigment particles had an average diameter of 130 nm.

Dispersion I 1a) of pigment in particulate form and nonionic surfactant was obtained.

I. 2a) dispersing a yellow pigment with a non-ionic surfactant

In a stirred ball mill of the type Drais Superflow DCP SF 12 were ground together: 1800 g Pigment Yellow 138 450 g nC ₁₈ H ₃₇ O (CH ₂ CH ₂ O) ₂₅ H 24 g glutaraldehyde 30 g tetramethylolacetylenediurea 3696 g distilled water

The milling was continued until the pigment particles had an average diameter of 130 nm.

Dispersion I 2a) of pigment in particulate form and nonionic surfactant was obtained.

I. 3a) dispersing a black pigment with a nonionic surfactant

In a stirred ball mill of the type Drais Superflow DCP SF 12 were ground together:

Black pigment

1800g Pigment Black 7 450g nC ₁₈ H ₃₇ O (CH ₂ CH ₂ O) ₂₅ H 3696 g distilled water

The milling was continued until the pigment particles had a mean diameter of 150 nm (number average). Dispersion I 3a) of pigment in particulate form and nonionic surfactant was obtained.

I b) mixing with water I. 1 b) mixing I 1a) with water

In a 1 liter vessel with stirrer, nitrogen inlet and three metering devices, 213.3 g of the dispersion from I. 1a) were mixed with 262.2 g of demineralized water with stirring. 5.8 g of 40% by weight aqueous solution of ethoxylated (mean 5 ethylene oxide units per molecule) methyl quaternized oleylammonium sulfate and 32 g of styrene were added and the pH was adjusted to 4 with formic acid.

This gave mixture I. 1b) of pigment in particulate form in an aqueous medium.

I. 2b) mixing I 2a) with water

In a 1 l kettle with stirrer, nitrogen inlet and three metering devices, 213.3 g of the dispersion from I. 2a) were mixed with 262.2 g of demineralized water with stirring. 5.8 g of 40% by weight aqueous solution of ethoxylated (on average 5 ethylene oxide units per molecule) methyl quaternized oleylammonium sulfate and 32 g of styrene were added and the pH was adjusted to 3, 1 with formic acid.

This gave mixture I 2b) of pigment in particulate form in aqueous medium

I. 3b) mixing I 3a) with water

In a 1 l kettle with stirrer, nitrogen inlet and three metering devices, 213.3 g of the dispersion from I. 3a) were mixed with 262.2 g of demineralized water with stirring. 5.8 g of 40% by weight aqueous solution of ethoxylated (mean 5 ethylene oxide units per molecule) methyl quaternized oleylammonium sulfate and 32 g of styrene were added and the pH was adjusted to 4 with formic acid.

This gave mixture I 3b) of pigment in particulate form in an aqueous medium

I c) polymerization I. 1c) Polymerization of I 1b)

The mixture from step I. 1b) was passed over a period of 1 hour nitrogen. It was then heated to 85 ° C. Thereafter, 1.6 g of tert-butyl hydroperoxide (10 wt .-% in water) and 1.6 g of HOCH ₂ SO ₂ Na was added.

The formation of a water-insoluble polymer on the blue pigment in particulate form is observed.

I. 2c) Polymerization of I 2b)

The mixture from step I. 2b) was passed over a period of 1 hour nitrogen. It was then heated to 85 ° C. Thereafter, 1.6 g of tert-butyl hydroperoxide (10 wt .-% in water) and 1.6 g of HOCH ₂ SO ₂ Na was added.

The formation of a water-insoluble polymer on the yellow pigment in particulate form is observed.

I. 3c) Polymerization of I 3b)

The mixture from step I. 3b) was passed over a period of 1 hour nitrogen. It was then heated to 85 ° C. Thereafter, 1.6 g of tert-butyl hydroperoxide (10 wt .-% in water) and 1.6 g of HOCH ₂ SO ₂ Na was added.

The formation of a water-insoluble polymer on the black pigment in particulate form is observed.

I d) adding an emulsion of comonomers and further copolymerization I. 1d) addition of an emulsion of comonomers and further copolymerization to I. 1c)

• 224 g vollentsalztes Wasser
• 12 g wässrige Lösung von ethoxyliertem (im Mittel 5 Ethylenoxid-Einheiten pro Mole kül) Methyl-quaternisiertem Oleylammoniumsulfat (40 Gew.-%)
• 3,2 g Acrylsäure
• 14,4 g Dimethylaminopropylmethacrylamid
• 24 g n-Butylacrylat
• 44,8 g Ethylacrylat
• 73,6 g Methylmethacrylat

Gleichzeitig wurde mit der Zugabe einer Lösung von 3,2g 2,2'-Azobis (2-amidinopropan)dihydrochlorid in 133,3 g Wasser begonnen, und die Zugabe wurde über einen Zeitraum von 105 Minuten durchgeführt. Während der Zugabe wurde die Temperatur bei 85°C gehalten.15 minutes after the addition of tert-butyl hydroperoxide and H ₂ SO ₂ Na according to step I. 1c), a mixture was added over a period of 90 minutes, which was composed as follows:

• 224 g of demineralized water
• 12 g of aqueous solution of ethoxylated (average of 5 ethylene oxide units per mole of molecule) methyl quaternized oleylammonium sulfate (40 wt .-%)
• 3.2 g of acrylic acid
• 14.4 g of dimethylaminopropylmethacrylamide
• 24 g of n-butyl acrylate
• 44.8 g of ethyl acrylate
• 73.6 g of methyl methacrylate

At the same time, the addition of a solution of 3.2 g of 2,2'-azobis (2-amidinopropane) dihydrochloride in 133.3 g of water was started and the addition was carried out over a period of 105 minutes. During the addition, the temperature was maintained at 85 ° C.

After completion of the addition, the mixture was stirred for 30 minutes at 85 ° C and then for deodorization simultaneously a solution of 5.5 g of tert-butyl hydroperoxide (70% in water) in 18 g of deionized water and a solution of 3.5 g of H 2 O ₂ SO ₂ Na dosed in 20 g of demineralized water over a period of 90 minutes.

Thereafter, it was cooled to room temperature.

Subsequently, the aqueous dispersion thus obtained was filtered through a 125 μm mesh. Dispersion D.1.1 was obtained. The solids content of the dispersion D.1.1 was 25%. The particle diameter distribution was determined using an Autosizer IIC from Malvern to ISO 13321 and gave maxima at 133 and 120 nm. The glass transition temperature T _g was determined to be 17 ° C.

I. 2d) addition of an emulsion of comonomers and further copolymerization to I. 2c)

• 224 g vollentsalztes Wasser
• 12 g wässrige Lösung von ethoxyliertem (im Mittel 5 Ethylenoxid-Einheiten pro Molekül) Methyl-quaternisiertem Oleylammoniumsulfat (40 Gew.-%)
• 3,2 g Acrylsäure
• 14,4 g Dimethylaminopropylmethacrylamid
• 24 g n-Butylacrylat
• 44,8 g Ethylacrylat
• 73,6 g Methylmethacrylat.

15 minutes after the addition of tert-butyl hydroperoxide and H ₂ SO ₂ Na according to step I. 2c), a mixture was added over a period of 90 minutes, which was composed as follows:

• 224 g of demineralized water
• 12 g of aqueous solution of ethoxylated (average of 5 ethylene oxide units per molecule) methyl quaternized oleylammonium sulfate (40% by weight)
• 3.2 g of acrylic acid
• 14.4 g of dimethylaminopropylmethacrylamide
• 24 g of n-butyl acrylate
• 44.8 g of ethyl acrylate
• 73.6 g of methyl methacrylate.

At the same time, the addition of a solution of 3.2 g of 2,2'-azobis (2-amidinopropane) dihydrochloride in 133.3 g of water was begun and the addition was carried out over a period of 105 minutes. During the addition, the temperature was maintained at 85 ° C.

After completion of the addition, the mixture was stirred for another 30 minutes at 85 ° C and then for deodorization simultaneously a solution of 5.5 g of tert-butyl hydroperoxide (70 wt .-% in water) in 18 g of deionized water and a solution of 3, 5 g H ₂ SO ₂ Na in 20 g deionized water over a period of 90 minutes added.

Thereafter, it was cooled to room temperature.

Subsequently, the aqueous dispersion thus obtained was filtered through a 125 μm mesh. Dispersion D.2.1 was obtained. The solids content of the dispersion D.2.1 was 25.6%. The particle diameter distribution was determined using an Autosizer IIC from Malvern according to ISO 13321 and gave maxima at 147 and 128 nm. The glass transition temperature was determined to be 17 ° C.

I. 3d) addition of an emulsion of comonomers and further copolymerization to I. 3c)

• 224 g vollentsalztes Wasser
• 12 g wässrige Lösung von ethoxyliertem (im Mittel 5 Ethylenoxid-Einheiten pro Molekül) Methyl-quaternisiertem Oleylammoniumsulfat (40 Gew.-%)
• 3,2 g Acrylsäure
• 14,4 g Dimethylaminopropylmethacrylamid
• 24 g n-Butylacrylat
• 44,8 g Ethylacrylat
• 73,6 g Methylmethacrylat.

15 minutes after the addition of tert-butyl hydroperoxide and H ₂ SO ₂ Na according to step I. 3c), a mixture was added over a period of 90 minutes, which was composed as follows:

• 224 g of demineralized water
• 12 g of aqueous solution of ethoxylated (average of 5 ethylene oxide units per molecule) methyl quaternized oleylammonium sulfate (40% by weight)
• 3.2 g of acrylic acid
• 14.4 g of dimethylaminopropylmethacrylamide
• 24 g of n-butyl acrylate
• 44.8 g of ethyl acrylate
• 73.6 g of methyl methacrylate.

At the same time, the addition of a solution of 3.2 g of 2,2'-azobis (2-amidinopropane) dihydrochloride in 133.3 g of water was begun and the addition was carried out over a period of 105 minutes. During the addition, the temperature was maintained at 85 ° C.

After completion of the addition, the mixture was stirred for another 30 minutes at 85 ° C and then for deodorization simultaneously a solution of 5.5 g of tert-butyl hydroperoxide (70 wt .-% in water) in 18 g of deionized water and a solution of 3, 5 g H ₂ SO ₂ Na in 20 g deionized water over a period of 90 minutes added.

Thereafter, it was cooled to room temperature.

Subsequently, the aqueous dispersion thus obtained was filtered through a 125 μm mesh.
Dispersion D.3.1 was obtained. The solids content of the dispersion D.3.1 was 25.6%. The particle diameter distribution was determined using an Autosizer IIC from Malvern according to ISO 13321 and gave maxima at 143 and 382 nm. The glass transition temperature was determined to be 13 ° C.

II. Production of colored wood II.1 Preparation of a formulation

• 50 g n-Dodecyldimethylamin
• 10 g 2-Ethylhexansäure
• 15 g Phosphonsäure
• 25 g Propylenglykol

A formulation was made by mixing in a jar:

• 50 g of n-dodecyldimethylamine
• 10 g of 2-ethylhexanoic acid
• 15 g of phosphonic acid
• 25 g of propylene glycol

Formulation F-1 was obtained.

II.2 Preparation of impregnation solutions II.2.1 Preparation of a blue impregnation solution

An aqueous impregnation solution T-1 was prepared by mixing 30 liters of water with 303 grams of dispersion D.1.1 and 303 grams of F-1.

II.2.2 Preparation of a yellow impregnation solution

An aqueous impregnation solution T-2 was prepared by mixing 30 liters of water with 303 grams of dispersion D.2.1 and 303 grams of F-1.

II.2.3 Preparation of a black impregnation solution

An aqueous impregnation solution T-3 was prepared by mixing 30 liters of water with 303 grams of dispersion D.3.1 and 303 grams of F-1.

II.2.4 Preparation of comparative solution solutions

In a stirred ball mill of the type Drais Superflow DCP SF 12, 500 g of Pigment Green 36 were mixed
200 g of a 90 wt .-% solution of an average of 10 equivalents of ethylene oxide ethoxylated isotridecanol
100 g of propylene glycol
200 g of water.
90 g of the pigment dispersion thus obtainable were mixed with 303 g of F-1 and 30 liters of water. Comparative solution VT-4 was obtained.

II.3 Coloring of pine wood, general rule using the example of a blue coloration

• eine Stunde Vorvakuum (200 mbar),
• zwei Stunden Druck (8 bar)

Anschließend entspannte man, spülte mit Wasser und trocknete zwei Tage bei Zimmertemperatur. Man erhielt erfindungsgemäßes koloriertes Holz H-T-1.0.02 m ^{3 of} wood (pine, lath-shaped, planed, length / width / thickness 50 cm / 20 cm 3 cm) was impregnated with 30 l of impregnation solution T-1 in the boiler pressure method at room temperature according to the following parameters:

• one hour pre-vacuum (200 mbar),
• two hours pressure (8 bar)

Then one relaxed, rinsed with water and dried for two days at room temperature. This gave colored wood according to the invention HT-1.

The compatibility with the wood preservative solution, the staining of the wood, the penetration of the impregnation solution into the wood, the behavior of the coloration of existing dyes, the stability of the impregnation solution during coloration (impregnation) and the decrease of staining on weathering were examined. The results are summarized in Table 1.

To investigate the decrease in staining on weathering stored according to the invention colorized wood or reference wood in the open at an angle of 45 °, directed to the southwest, one summer month long (July).

In further experiments, the procedure was analogous, but impregnation solution T-1 replaced by T-2, T-3 and VT-4. Colored wood according to the invention was obtained HT-2 (yellow), HT-3 (black) or reference wood VHT-4. Table 1: Results of the colorization experiments (with comments on the visual impression) HT-1 VHT-4 Compatibility, storage stability [Note] 5 (practically no settling of the pigment particles) 4 (slight settling of the pigment particles) Wood staining [Note] 5 (uniformly covering) 3 (slightly cloudy, not uniformly covering) Penetration Behavior [Note] 4 (visible) 2 (pigment lies on and clogs the pores) Stability on coloring [note] 4 (impregnation solution remains stable) 3-4 (impregnation solution remains almost stable) Decrease in staining on weathering 4 (good color coverage) 2 (inconsistent color coverage, in less covering areas wood shimmers gray) Scores: 5 (very good), 4 (good), 3 (sufficient), 2 (poor), 1 (insufficient)

III. Production of colored paper

• Ein Gemisch aus 70 Gew.-% gebleichtem Kiefernsulfatzellstoff und 30 Gew.-% gebleichtem Birkensulfatzellstoff wurde in einem Laborrefiner auf einen Mahlgrad von 22° nach Schopper-Riegler gemahlen. Man erhielt ein gemahlenes Zellstoffgemisch mit einem Trockengehalt von 10,3 Gew.-%, ermittelt durch Ofentrocknung.

The production of dyed paper was carried out according to the following general procedure (using example of D.1.1):

• A mixture of 70% by weight bleached pine sulfate pulp and 30% by weight bleached birch sulphate pulp was ground in a laboratory refiner to a 22 ° buffle according to Schopper-Riegler. This gave a ground pulp mixture with a solids content of 10.3 wt .-%, determined by oven drying.

48.5 g of ground pulp mixture (corresponding to 5 g dry mass) were placed in a beaker and suspended in a total of 250 ml of drinking water. 0.5 g of dispersion D1.1 were added to the pulp suspension obtainable in this way. The mixture was stirred for 5 minutes and diluted with drinking water to a total of 3 l. Thereafter, a sheet of paper was made with a sheet former from Rapid-Köthen (grammage: 150 g / m ² ). The sheet was pressed and dried between two filter papers at 85 ° C on a steel cylinder. The obtained color was visually evaluated and evaluated by CIE-LAB. The filtrate was collected and visually assessed. This gave colored paper P1 according to the invention.

In further experiments, the procedure was analogous, but replaced dispersion D.1.1 by D.2.1, D.3.1 or a comparative dispersion V-D4. Inventive colored paper P2 (yellow), P3 (black) or comparative paper V-P4 was obtained according to the invention.

• Man vermischte in einer Rührwerkskugelmühle des Typs Drais Superflow DCP SF 12 400 g Pigment Blau 15:1
• 80 g n-C₁₈H₃₇O(CH₂CH₂O)₂₅H
• 70 g Diethylenglykol
• 450 g vollentsalztes Wasser

To carry out the comparative test for paper coloration, instead of a dispersion of treated pigment used according to the invention, 0.05 g of a comparative dispersion V-D4 which had been obtained as follows:

• In a stirred ball mill of the type Drais Superflow DCP SF 12, 400 g of Pigment Blue 15: 1 were mixed
• 80 g of nC ₁₈ H ₃₇ O (CH ₂ CH ₂ O) ₂₅ H
• 70 g of diethylene glycol
• 450 g of demineralized water

The procedure was as described above, except that D.1.1 was replaced by comparative dispersion V-D4. It was observed that despite the lower amount of colorant in the comparative experiment, the filtrate was intensely colored. Higher amounts of colorant did not increase the absorption of colorant. Table 2: Evaluation of papers according to the invention and the efficiency of dyeing colorants L a * b * Staining filtrate P1 62.1 -21.3 36.0 Weak P2 92.8 -10.7 66.4 Weak P3 47.6 0.7 2.4 Weak V-P4 59.7 -21.0 -27.6 Very strong

The colors are characterized by their brilliance, high bleeding fastness and high light fastness.

The dispersions D.1.1, D.2.1 or D.3.1 are mutually readily miscible. For example, the mixture of yellow and blue can produce intense, brilliant shades of green.
For example, the dispersions D.1.1, D.2.1 and D.3.1 are stable over a period of 10 weeks at temperatures such as 4 ° C and 50 ° C.

Claims (15)

1. A process for colouring cellulosic substrates, which comprises substrates to be coloured, or precursors thereof, being contacted with at least one treated pigment in particulate form that is at least partially enveloped by at least one cationic copolymer, prepared according to a process comprising the steps of:

   a) dispersing at least one pigment in particulate form with at least one nonionic surface-active material,

   b) mixing the thus obtainable dispersion of pigment in particulate form and nonionic surface-active material with aqueous medium,

   c) addition polymerizing at least one first monomer or addition copolymerization of a first mixture of comonomers in the presence of a mixture according to b) to form water-insoluble polymer or copolymer on the surface of pigment in particulate form,

   d) adding at least one second monomer or a second mixture of comonomers and addition polymerization or copolymerization,

   with the proviso that processes for printing are not comprised.
2. The process according to Claim 1 wherein cationic copolymers comprise copolymers constructed of at least one nonionic comonomer and at least one comonomer having at least one protonatable nitrogen atom per molecule.
3. The process according to Claim 1 or 2 wherein step d) produces a polymer or copolymer having a glass transition temperature T_g of -30°C or higher.
4. The process according to any one of Claims 1 to 3 wherein pigments in particulate form are selected from carbon black, calcium carbonate, kaolin and organic pigments.
5. The process according to any one of Claims 1 to 4 wherein the first monomer in step c) comprises a vinylaromatic compound or a compound of the general formula I

   

   where

   R¹ is selected from hydrogen, branched C₁-C₁₀-alkyl or unbranched C₁-C₁₀-alkyl,

   R² is selected from hydrogen, branched C₁-C₁₀-alkyl or unbranched C₁-C₁₀-alkyl,

   R³ is selected from branched C₄-C₁₀-alkyl or unbranched C₄-C₁₀-alkyl.
6. The process according to any one of Claims 1 to 5 wherein the first mixture of comonomers comprises a mixture of at least one vinylaromatic compound and at least one compound of the general formula I.
7. The process according to any one of Claims 1 to 6 wherein R¹ and R² are both hydrogen in one compound of the general formula I.
8. The process according to any one of Claims 1 to 7 wherein the second monomer added is a monomer of the general formula II

   

   where

   R⁴ is selected from hydrogen, branched C₁-C₁₀-alkyl or unbranched C₁-C₁₀-alkyl,

   R⁵ is selected from hydrogen, branched C₁-C₁₀-alkyl or unbranched C₁-C₁₀-alkyl,

   R⁶ is selected from branched C₁-C₁₀-alkyl or unbranched C₁-C₁₀-alkyl.
9. The process according to any one of Claims 1 to 8 wherein the second mixture of comonomers comprises at least one monomer of the general formula II.
10. The process according to any one of Claims 1 to 9 wherein R⁴ is hydrogen or methyl and R⁵ is hydrogen in one compound of the general formula II.
11. The process according to any one of Claims 1 to 10 wherein the second mixture of comonomers comprises at least one comonomer selected from vinylaromatic compound and a compound of the general formula I.
12. The process according to any one of Claims 1 to 11 wherein step d) comprises up to 20% by weight, based on the second mixture of comonomers, of at least one compound of the formula V a or V b

    

    where

    R¹⁰ to R¹² are the same or different and are each selected from hydrogen, branched C₁-C₁₀-alkyl and unbranched C₁-C₁₀-alkyl,

    X is selected from hydrogen, glycidyl, protonatable groups having tertiary amino groups and enolizable groups having 1 to 20 carbon atoms.
13. The process according to any one of Claims 1 to 12 wherein cellulosic substrates comprise wood.
14. The process according to any one of Claims 1 to 12 wherein cellulosic substrates comprise woody or so-called wood-free paper and the paper precursor comprises paper stock.
15. Coloured cellulosic substrates obtainable by a process according to Claim 1 to 12.