Dispersant for the production of aqueous pigment pastes

The invention relates to polymethacrylic acid esters which are transesterified with polyether diols or amidated with polyether diamines and then end-functionalized, and to their use as dispersants for the preparation of aqueous pigment preparations.

In order to facilitate and improve the dispersion of solids in liquid media, it is customary to use dispersants which, at the same time, are also said to have a stabilizing effect on the dispersions obtained and are intended to prevent reagglomeration or flocculation of the solid particles. As surface-active agents, the dispersants promote the wetting of the solid particles to be dispersed and facilitate the breaking up of agglomerates.

They are of particular importance, for example, for the dispersion of pigments in the production of printing inks, paints and varnishes and in the pigmentation of plastics.

In addition, special dispersants as compatibilizers can increase the compatibility between chemically different types of polymers. This is e.g. B. of particular importance for the production of SMC or BMC molding materials.

Wetting and dispersing agents facilitate the incorporation of pigments and fillers in the manufacture of paints and varnishes, which, as important formulation components, significantly determine the visual appearance and the physicochemical properties of coatings. For optimal utilization, these solids must be distributed evenly in lacquers and paints, on the one hand, and the distribution once achieved must be stabilized. Numerous problems can now arise during the production and processing of aqueous pigment pastes:<ul id="ul0001" list-style="bullet" compact="compact"><li>difficult incorporation of the pigments, poor wetting</li><li>high viscosities of color pastes, paints and varnishes</li><li>Sediment formation</li><li>vertical floating of pigments (flooding)</li><li>horizontal floating of pigments (floating)</li><li>low degree of gloss</li><li>low hiding power</li><li>insufficient color strength</li><li>poorly reproducible color tones, color shift</li><li>lacquers are too prone to run off</li></ul>

There is therefore no shortage of attempts to provide effective dispersing additives for solids, in particular pigments. For example, water-soluble, hydrophilic polyether chain polyisocyanate addition products (EP-A-0 731 148), acidic poly (meth) acrylates (US-A-3 980 602, WO-A-94/21701), phosphate esters of polyalkylene oxide block -Polyesters (WO-A-97/19948) or alternating copolymers of vinyl monomers and dicarboxylic acid diesters (WO-A-96/14347, EP-A-0 791 024), in particular copolymers based on maleic acid derivatives and vinyl monomers, are described for this purpose.

However, there are a number of disadvantages associated with the use of such products. Thus, high levels of dispersing additive additives are often required, the achievable pigmentation levels of the pastes are unsatisfactorily low, the stability of the pastes and thus their viscosity constancy is insufficient, flocculation and aggregation cannot always be avoided; in many cases there is also a lack of color consistency after the pastes have been stored and their compatibility with various binders. In many cases, the use of known dispersing additives also negatively influences the water resistance or light resistance of coatings, and the undesirable foam which arises during production and processing is additionally stabilized. The gloss is also undesirably impaired in many cases, owing to the poor compatibility of the dispersing resins in many products.

In particular, the phosphoric acid esters of amphiphilic block copolymers are characterized by inadequate hydrolysis stability of the phosphoric ester grouping. The water resistance of coatings produced with this is also adversely affected. In addition, these acidic phosphoric acid esters generally require an undesirable amine-based additive in the required amount, in order to e.g. B. adjust the optimized pH of a paint system.

The present invention is therefore based on the object of overcoming a large number of the disadvantages mentioned, the viscosity stability of the pastes important for processability, the extensive avoidance of flocculation and aggregation, the color constancy after storage of the pastes and the water resistance of coatings produced therefrom being positively influenced should.

In addition, these products are intended to improve the compatibility of chemically incompatible substances.

The object is surprisingly achieved according to the invention by dispersants based on block-polymethacrylic acid ester-block-polyalkylene oxide copolymers with terminal carboxylic acid of the general formula I<chemistry id="chem0001" num="0001"><img file="EP0979844A2_D0001.tif" /></chemistry> in which<dl id="dl0001" compact="compact"><dt>R¹</dt><dd>is the rest of a chain regulator or initiator known per se which is free of active hydrogen atoms,</dd><dt>R²</dt><dd>are identical or different and are alkyl radicals having 1 to 22 carbon atoms or optionally also substituted aryl radicals, perfluoroalkyl or dialkylamino radicals,</dd><dt>R³</dt><dd>are identical or different and are alkyl radicals having 1 to 4 carbon atoms or phenyl radicals,</dd><dt>R⁴</dt><dd>represents an organic radical with at least one carboxylic acid or carboxylate function,</dd><dt>X</dt><dd>Is oxygen or NH</dd><dt>a</dt><dd>a value from 4 to 20,</dd><dt>b</dt><dd>a value from 20 to 100 and</dd><dt>c</dt><dd>has a value from 0 to 20, the ratio <maths id="math0001" num=""><math display="inline"><mrow><mtext>b / c&gt; = 4</mtext></mrow></math><img file="EP0979844A2_D0002.tif" /></maths> is.</dd></dl>

The rest R¹ is a chain regulator or initiator known per se. Azo compounds or peroxides may be mentioned as examples of the prior art. Examples of chain regulators are mercaptans, chloroform, isopropylbenzene or isopropanol. Preferred for R¹ the rest is -SC₁₂H₂₅. Further examples of residues resulting from the chain regulator are the residue derived from tert-dodecyl mercaptan and the octadecyl and tetradecyl mercaptan residue.

R² is preferably a methyl or butyl radical. Examples of suitable perfluoroalkyl radicals are the trifluoroethyl, pentafluoropropyl, nonafluorohexyl and the tridecafluorooctyl radical.

X is an oxygen atom when using α, ω-polyalkoxy ether diols and an NH group when using α, ω-polyether diamines.

R³ is an alkyl or aryl group, preferably a methyl or phenyl group.

The indices b and c can be the same or different and are usually b in the range from 20 to 100 and c in the range from 0 to 20. The ratio of b: c is preferably ≥ 4. The different alkoxy units can be blockwise or else also be statistically incorporated in the polyalkoxy chain. Examples of suitable alkoxylating agents are ethylene carbonate, propylene carbonate, styrene oxide, butylene oxide, especially propylene oxide and in particular ethylene oxide and mixtures thereof.

The rest R⁴ contains at least one carboxylic acid or at least one carboxylate unit. Examples of R⁴ are all products that result from the reaction of an alcohol with anhydrides. Preferred anhydrides are succinic anhydride, maleic anhydride, phthalic anhydride or trimellitic anhydride. Analogously form for the case<maths id="math0002" num=""><math display="inline"><mrow><mtext>X = NH</mtext></mrow></math><img file="EP0979844A2_D0003.tif" /></maths> the analog half amide compounds.

Examples of R

4

:

<chemistry id="chem0002" num="0002"><img file="EP0979844A2_D0004.tif" /></chemistry>

Z is a cation. Z is preferably an alkali or ammonium radical, which can optionally be alkyl-substituted. Examples of such substituted ammonium radicals are the NH (CH₃)₃-, NH (C₂H₅)₃- and NH (CH₂-C₆H₅) (CH₃)₂. In addition, the cations known from the prior art for carboxylic acid groups can be selected (eg neutralization with amines or amino alcohols, such as triethanolamine, aminomethylpropanol or dimethylethanolamine).

Examples of block copolymers according to the invention are:

<chemistry id="chem0003" num="0003"><img file="EP0979844A2_D0005.tif" /></chemistry>

To produce such block copolymers with terminal carboxylic acid, the block-polymethacrylic acid ester-block polyalkylene oxide copolymer with terminal hydroxyl or amino group is first prepared and then anionically end-functionalized.

The production of polymethacrylate block polyalkylene oxide with a terminal hydroxyl group is known from the literature. For example, in Macromolecules (1992), 25 (25), 6733-6738, Polym. J. (1980), 12 (3), 183-192, in the patent literature (DD-C-0 221 742) or in Makromol. Chem., Rapid Commun. (1984), 5 (9), 615-618 describes the preparation of such block copolymers via anionic polymerization of methyl methacrylate and ethylene oxide using organolithium initiators. Such processes are hardly feasible on an industrial scale. On the one hand, there is an extremely high requirement for the purity of the reactants and any solvents used, on the other hand, very low reaction temperatures (around -78 ° C) are usually required. The use of special, sensitive alkali metal initiators (potassium naphthalide or diphenylmethyl potassium) makes the reaction even more difficult.

Alternatively, block copolymers based on polyalkylene oxide and methacrylate monomers can be produced by redox polymerization based on Ce4 +. A variety of examples are listed in the literature, such as. B. in Angew. Macromol. Chem. (1997) 245, 9-22. The main disadvantage of this reaction is that cerium (IV) ammonium nitrate is very expensive and must be used in equimolar amounts. In addition, it has a very high molecular weight (MW 548.23), which means that about 1.1 kg of cerium (IV) ammonium nitrate would have to be used for one mole of PEG3000.

The simplest way to prepare block-polymethacrylic acid ester-block-polyalkylene oxide copolymers is described in EP-A-0 613 910. There the end group transesterification of polymethacrylic acid esters with a wide variety of alcohols is described. In principle, this method is not only limited to monoalcohols, but dihydroxy-functional compounds can also be used, as already described in EP-A-0 622 378.

However, none of these patents describes a further reaction of the terminal hydroxyl groups with anhydrides to form polymethacrylic acid ester block polyalkylene oxide compounds with a terminal carboxy function. It has surprisingly been found that the desired end-functionalized block copolymers can be prepared in a very simple manner by a one-pot reaction.

Here, a polymethacrylic acid ester obtained by free-radical polymerization in the presence of a chain regulator is transesterified with α, ω-difunctional polyethers at temperatures of 70 to 150 ° C., preferably 100 to 120 ° C. The reaction can be carried out with or without a solvent. As a rule, to remove any traces of moisture that may be present, residues of water are removed from the system with an inert solvent, such as, for example, toluene or xylene. In order to remove the alcohol released in the transesterification reaction (depending on the polymethacrylate used, e.g. methanol or butanol) more easily from the reaction mixture, the addition of an inert solvent such as toluene, xylene or a gasoline fraction with a boiling range of 70 to 140 ° C recommendable. State-of-the-art Lewis transesterification catalysts, such as alkyl titanate, alkyl zirconate, dialkyltin acetate halide or dialkyltin dialkyl ester, can be used in amounts of 0.1 to 3% by weight, based on the polymethacrylic acid ester. Particularly suitable catalysts are isopropyl titanate, dibutyltin acetate chloride or dibutyltin oxide. The molar ratio of polymethacrylic acid ester to polyalkylene oxide can be 1: 0.5 to 1: 3, preferably 1: 1. The main side reaction is the formation of the triblock copolymer polymethacrylic acid ester block polyalkylene oxide block polymethacrylic acid ester, which is not removed from the reaction mixture. The proportion of the by-product is strongly influenced by the polymethacrylic acid ester / polyalkylene oxide ratio. The turnover can be tracked, among other things, by determining the OH number.

After complete conversion, the anionic modification can be carried out in a manner known per se. For this purpose, the corresponding anhydride is added and the reaction mixture is heated at a temperature of 70 to 150 ° C., preferably 100 to 120 ° C. The molar ratio of anhydride to hydroxy groups present can be 2: 1 to 1:10, preferably 1: 1. All commercially available anhydrides can be used. Suitable anhydrides are e.g. B. Succinic anhydride, maleic anhydride, phthalic anhydride or trimellitic anhydride. The end of the reaction can be determined from the disappearing OH and acid number. Other prior art acylating agents such as acid halides or esters can also be used.

The preparation of the block polymethacrylic acid ester block polyalkylene oxide copolymers with terminal carboxylic acid for use as a dispersant for aqueous pigment pastes is explained in more detail in the examples below.

Example 1A

Production of polymethyl methacrylate by radical polymerization (not according to the invention)

180 g of toluene are heated in a reactor to 100 ° C. under a nitrogen atmosphere. A solution of 4.2 g of azodiisobutyronitrile, 202.4 g of n-dodecyl mercaptan (1 mol) and 1198 g (approx. 12 mol) of methyl methacrylate in 170 g of toluene is added dropwise over a period of 3 hours at 100 ° C. at a constant rate. After the reaction has ended, 2.8 g of azodiisobutyronitrile are added to initiate the reaction over the course of 1 hour and the mixture is then left to react for 1 hour. Residual monomers and solvents are removed at 150 ° C. in an oil pump vacuum (1 torr) and the clear, viscous product is diluted to a solids content of 70% by adding toluene. From the gel chromatographic examination, an M is obtained for the polymer obtained_nValue (calibration against PMMA / THF) of 1710 for an M_w/ M_nRatio of 1.56. The residual monomer content is &lt;0.1%.

Examples 2A and 3A

Production of polymethyl methacrylates with different molecular weights by radical polymerization (not according to the invention)

The procedure is basically as in Example 1A, with the difference that, as can be seen from Table 1, the amount of n-dodecyl mercaptan and the amount of initiator vary. <tables id="tabl0001" num="0001"><table frame="all"><title>Table 1</title><tgroup cols="6" colsep="1" rowsep="1"><colspec colnum="1" colname="col1" colwidth="26.25mm" /><colspec colnum="2" colname="col2" colwidth="26.25mm" /><colspec colnum="3" colname="col3" colwidth="26.25mm" /><colspec colnum="4" colname="col4" colwidth="26.25mm" /><colspec colnum="5" colname="col5" colwidth="26.25mm" /><colspec colnum="6" colname="col6" colwidth="26.25mm" /><thead valign="top"><row><entry namest="col1" nameend="col1" align="center">Polymethyl methacrylate ex.no.</entry><entry namest="col2" nameend="col2" align="center">Methacrylate [g] / [mol]</entry><entry namest="col3" nameend="col3" align="center">n-dodecyl mercaptan [g]</entry><entry namest="col4" nameend="col4" align="center">Initiator quantity [g]</entry><entry namest="col5" nameend="col5" align="center">Molecular weight (GPC) M_n</entry><entry namest="col6" nameend="col6" align="center">Inconsistency factor</entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="center">2nd A</entry><entry namest="col2" nameend="col2" align="center">898 / 9</entry><entry namest="col3" nameend="col3" align="center">202</entry><entry namest="col4" nameend="col4" align="char" char=",">3,3</entry><entry namest="col5" nameend="col5" align="center">1345</entry><entry namest="col6" nameend="col6" align="char" char=",">1,50</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="center">3rd A</entry><entry namest="col2" nameend="col2" align="center">598 / 6</entry><entry namest="col3" nameend="col3" align="center">202</entry><entry namest="col4" nameend="col4" align="char" char=",">2,4</entry><entry namest="col5" nameend="col5" align="center">945</entry><entry namest="col6" nameend="col6" align="char" char=",">1,45</entry></row></tbody></tgroup></table></tables>

Example 4 A

Production of poly-n-butyl methacrylate by radical polymerization (not according to the invention)

The procedure is basically as in Example 1A, with the difference that instead of 12 molar equivalents of methyl methacrylate, 10 molar equivalents of n-butyl methacrylate are used per 1 mol of n-dodecyl mercaptan.

From the gel chromatographic examination, an M is obtained for the polymer obtained_nValue (calibration against PMMA / THF) of 2150 for an M_w/ M_nRatio of 1.78. The residual monomer content is &lt;0.1%.

Example 5 A

Preparation of a polystyrene block-polyalkylene oxide copolymer (not according to the invention; analogous to DE-A-41 34 967)

100 g of xylene are heated to 120 ° C. in a reactor equipped with a stirrer under a nitrogen atmosphere. For this purpose, a mixture of 2288 g (about 22 mol) of styrene, 78 g (1 mol) of 2-mercaptoethanol, 4.1 g of azodiisobutyronitrile and 310 g of xylene is added within 3 hours while maintaining the temperature of 120 ° C. After the addition has ended, there is an after-reaction of about 15 minutes; 0.16 g of methyl hydroquinone are then added.

Excess monomer, xylene and residual amounts of 2-mercaptoethanol are removed by distillation in vacuo, and the remaining colorless, viscous product is finally diluted with xylene to a solids content of approximately 80%.

A molecular weight M results from the determination of the hydroxyl number_n of 1100 g / mol. A value of 1200 g / mol is obtained from the vapor pressure osmometric molecular weight determination. From the gel chromatographic examination, an M is obtained for the polymer obtained_nValue (calibration against polystyrene / THF) of 1175 for an M_w/ M_nRatio of 1.75. The residual monomer content is &lt;0.1%.

The solution of 1100 g (about 1 mole) of the ω-hydroxy-functional polystyrene in 200 g of xylene and 35.0 g of potassium methylate (about 0.5 mole) are placed in a well-dried stainless steel reactor which is additionally provided with a stirrer. Azeotropic distillation removes both traces of water and methanol along with xylene. The temperature is then adjusted to 80 ° C. and about 3000 g of ethylene oxide (about 70 mol) are added with stirring so rapidly that the internal temperature of the reactor does not exceed 85 ° C. After the introduction is complete, 100 g of water are added and the pH is then brought to 6 to 7 with 30% phosphoric acid. The water is removed by azeotropic distillation in vacuo and that of the precipitated salt by filtration.

The molecular weight determined from the determination of the hydroxyl number with an assumed functionality of 1 is 13.8 mg KOH / g polymer; the gel permeation chromatogram shows only one maximum and gives for M_n (Calibration against polystyrene) a value of 2880, for the ratio M_w/ M_n you get 1.21.

Examples 1 B to 4 B

(not according to the invention)

The polyether diols used in the examples according to the invention and not according to the invention are, starting from ethylene glycol as starting alcohol, by alkaline-catalyzed homopolymerization of 70 or 55 mol of ethylene oxide or, starting from propylene oxide, by block-wise, likewise alkaline-catalyzed copolymerization of propylene oxide (12 or 17 mol ) and ethylene oxide (55 or 23 moles). <tables id="tabl0002" num="0002"><table frame="all"><title>Table 2</title><tgroup cols="3" colsep="1" rowsep="1"><colspec colnum="1" colname="col1" colwidth="52.50mm" /><colspec colnum="2" colname="col2" colwidth="52.50mm" /><colspec colnum="3" colname="col3" colwidth="52.50mm" /><thead valign="top"><row><entry namest="col1" nameend="col1" align="center">Example No.</entry><entry namest="col2" nameend="col2" align="center">PEG molecular weight</entry><entry namest="col3" nameend="col3" align="center">EO / PO</entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="center">1 B</entry><entry namest="col2" nameend="col2" align="center">3000</entry><entry namest="col3" nameend="col3" align="center">purely EO</entry></row><row><entry namest="col1" nameend="col1" align="center">2nd B</entry><entry namest="col2" nameend="col2" align="center">2200</entry><entry namest="col3" nameend="col3" align="center">purely EO</entry></row><row><entry namest="col1" nameend="col1" align="center">3rd B</entry><entry namest="col2" nameend="col2" align="center">3100</entry><entry namest="col3" nameend="col3" align="center">55/12</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="center">4th B</entry><entry namest="col2" nameend="col2" align="center">2000</entry><entry namest="col3" nameend="col3" align="center">23/17</entry></row></tbody></tgroup></table></tables>

Example 1 C

Production of block-polymethacrylic acid ester-block-polyalkylene oxide copolymers (not according to the invention)

1400 g (approx. 1 mol) of the polymethyl methacrylate from Example 1A (70% solution in toluene), 3000 g (approx. 1 mol) of the polyether from Example 1B are heated to 120 ° C. in a reactor under a nitrogen atmosphere and the Distilled off solvent with simultaneous removal of traces of water. Then 22 g (0.5% by weight) of isopropyl titanate are added at 100 ° C. and the methanol formed in the onset of the reaction is distilled off at 120 ° C. and 2 mm Hg for several hours. The course of the reaction can be followed by gas chromatographic examination of the distillate with regard to the amount of methanol contained, but also by determining the OH number. After about 8 hours the conversion is quantitative and a yellow product is obtained which is solid at room temperature. The OH number is 12.9 mg KOH / g polymer. From the gel chromatographic examination, an M is obtained for the polymer obtained_nValue (calibration against PMMA / THF) of 8730 for an M_w/ M_nRatio of 1.15.

Table 3 shows further examples of the synthesis of block-polymethacrylic acid ester-block-polyalkylene oxide copolymers as obtained by the above production process. <tables id="tabl0003" num="0003"><table frame="all"><title>Table 3</title><tgroup cols="6" colsep="1" rowsep="1"><colspec colnum="1" colname="col1" colwidth="26.25mm" /><colspec colnum="2" colname="col2" colwidth="26.25mm" /><colspec colnum="3" colname="col3" colwidth="26.25mm" /><colspec colnum="4" colname="col4" colwidth="26.25mm" /><colspec colnum="5" colname="col5" colwidth="26.25mm" /><colspec colnum="6" colname="col6" colwidth="26.25mm" /><thead valign="top"><row><entry namest="col1" nameend="col1" align="center">Ex. No.</entry><entry namest="col2" nameend="col2" align="center">Polymethacrylate ex. / [g]</entry><entry namest="col3" nameend="col3" align="center">PEG Ex. / [g]</entry><entry namest="col4" nameend="col4" align="center">Molecular weight (GPC) M_n</entry><entry namest="col5" nameend="col5" align="center">Inconsistency factor</entry><entry namest="col6" nameend="col6" align="center">mg KOH / g polymer</entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="center">2nd C.</entry><entry namest="col2" nameend="col2" align="center">2nd A / 1100</entry><entry namest="col3" nameend="col3" align="center">1 B / 3000</entry><entry namest="col4" nameend="col4" align="center">8150</entry><entry namest="col5" nameend="col5" align="char" char=",">1,21</entry><entry namest="col6" nameend="col6" align="char" char=",">13,9</entry></row><row><entry namest="col1" nameend="col1" align="center">3rd C.</entry><entry namest="col2" nameend="col2" align="center">3rd A / 800</entry><entry namest="col3" nameend="col3" align="center">2nd B / 2200</entry><entry namest="col4" nameend="col4" align="center">7440</entry><entry namest="col5" nameend="col5" align="char" char=",">1,25</entry><entry namest="col6" nameend="col6" align="char" char=",">19,0</entry></row><row><entry namest="col1" nameend="col1" align="center">4th C.</entry><entry namest="col2" nameend="col2" align="center">4th A / 1600</entry><entry namest="col3" nameend="col3" align="center">1 B / 3000</entry><entry namest="col4" nameend="col4" align="center">8900</entry><entry namest="col5" nameend="col5" align="char" char=",">1,31</entry><entry namest="col6" nameend="col6" align="char" char=",">12,3</entry></row><row><entry namest="col1" nameend="col1" align="center">5 C.</entry><entry namest="col2" nameend="col2" align="center">2nd A / 1100</entry><entry namest="col3" nameend="col3" align="center">3rd B / 3100</entry><entry namest="col4" nameend="col4" align="center">7910</entry><entry namest="col5" nameend="col5" align="char" char=",">1,35</entry><entry namest="col6" nameend="col6" align="char" char=",">13,5</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="center">6 C.</entry><entry namest="col2" nameend="col2" align="center">1 A / 1400</entry><entry namest="col3" nameend="col3" align="center">4th B / 2000</entry><entry namest="col4" nameend="col4" align="center">7690</entry><entry namest="col5" nameend="col5" align="char" char=",">1,27</entry><entry namest="col6" nameend="col6" align="char" char=",">16,8</entry></row></tbody></tgroup></table></tables>

Example 1 D

Production of block-polymethacrylic acid ester-block-polyalkylene oxide copolymers with terminal carboxy group (according to the invention)

Immediately following the synthesis of the block polymethacrylic acid ester block polyalkylene oxide 1 C, 98 g (about 1 mol) of maleic anhydride are added at 120 ° C. The reaction is complete after about 2 hours. The acid number of the material obtained is 12.4 mg KOH / g polymer.

Table 4 shows further examples of the reaction of block-polymethacrylic acid ester-block-polyalkylene oxide copolymers with a wide variety of anhydrides, as are obtained by the above production process. <tables id="tabl0004" num="0004"><table frame="all"><title>Table 4</title><tgroup cols="5" colsep="1" rowsep="1"><colspec colnum="1" colname="col1" colwidth="31.50mm" /><colspec colnum="2" colname="col2" colwidth="31.50mm" /><colspec colnum="3" colname="col3" colwidth="31.50mm" /><colspec colnum="4" colname="col4" colwidth="31.50mm" /><colspec colnum="5" colname="col5" colwidth="31.50mm" /><thead valign="top"><row><entry namest="col1" nameend="col1" align="center">Ex. No.</entry><entry namest="col2" nameend="col2" align="center">Polymethacrylate ex. / [g]</entry><entry namest="col3" nameend="col3" align="center">PEG Ex. / [g]</entry><entry namest="col4" nameend="col4" align="center">anhydride</entry><entry namest="col5" nameend="col5" align="center">SZ mg KOH / g polymer</entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="center">2nd D</entry><entry namest="col2" nameend="col2" align="center">2nd A / 1100</entry><entry namest="col3" nameend="col3" align="center">1 B / 3000</entry><entry namest="col4" nameend="col4" align="left">BSA</entry><entry namest="col5" nameend="col5" align="char" char=",">13,5</entry></row><row><entry namest="col1" nameend="col1" align="center">3rd D</entry><entry namest="col2" nameend="col2" align="center">3rd A / 800</entry><entry namest="col3" nameend="col3" align="center">2nd B / 2200</entry><entry namest="col4" nameend="col4" align="left">TSA</entry><entry namest="col5" nameend="col5" align="char" char=",">17,2</entry></row><row><entry namest="col1" nameend="col1" align="center">4th D</entry><entry namest="col2" nameend="col2" align="center">4th A / 1600</entry><entry namest="col3" nameend="col3" align="center">1 B / 3000</entry><entry namest="col4" nameend="col4" align="left">BSA</entry><entry namest="col5" nameend="col5" align="char" char=",">12,1</entry></row><row><entry namest="col1" nameend="col1" align="center">5 D</entry><entry namest="col2" nameend="col2" align="center">2nd A / 1100</entry><entry namest="col3" nameend="col3" align="center">3rd B / 3100</entry><entry namest="col4" nameend="col4" align="left">BSA</entry><entry namest="col5" nameend="col5" align="char" char=",">12,5</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="center">6 D</entry><entry namest="col2" nameend="col2" align="center">1 A / 1400</entry><entry namest="col3" nameend="col3" align="center">4th B / 2000</entry><entry namest="col4" nameend="col4" align="left">BSA</entry><entry namest="col5" nameend="col5" align="char" char=",">15,5</entry></row></tbody></tgroup></table></tables>

Example 7 D

Reaction of succinic anhydride (BSA) with polystyrene block-polyalkylene oxide copolymers 5 A (not according to the invention)

The anionic modification is carried out analogously to 1 D, except that this time directly after the synthesis of 5 A, 1 molar equivalent of succinic anhydride is added. After a reaction time of 2 hours at 120 ° C., the end of the reaction can be determined from the acid number of 12.8 mg KOH / g polymer.

Example 8 D

Production of the phosphoric acid ester of polystyrene block-polyalkylene oxide copolymers 5 A (not according to the invention)

4100 g (corresponds to 1 OH equivalent) of the block copolymer 5 A are placed in the reactor and, after addition of about 200 ml of toluene, heated to 120.degree. By applying a vacuum, all volatile constituents, in particular any water possibly present in the product, are removed from the reaction space by distillation. After venting with nitrogen, the temperature is raised to 80 ° C. and 85 g of the liquid polyphosphoric acid (0.25 mol P₄O₁₀; Manufacturer: Merck, salary as P₄O₁₀ calculated: approx. 85%). The reaction is complete after 2 hours. The acid number of the material obtained is 25.8 mg KOH / g. in the¹H-NMR spectrum no longer shows an aliphatic hydroxyl group.

Example 9 D

Production of the phosphoric acid ester of the polymethacrylic acid ester block-polyalkylene oxide copolymer 1 C (not according to the invention)

The reaction with polyphosphoric acid is carried out analogously to 8 D, except that this time directly after the synthesis of 1 C instead of an anhydride, 0.25 mol of P₄O₁₀ adds. The end of the reaction can be seen from the acid number of 25 mg KOH / g polymer.

For the preparation of aqueous pigment pastes, 0.1 to 100% by weight of the block-polymethacrylic acid ester-block-polyalkylene oxide copolymers with terminal carboxylic acid, preferably 0.5 to 50% by weight (based on the weight of the pigments), are used. The copolymers according to the invention can either be mixed beforehand with the pigments to be dispersed or can be dissolved directly in the dispersing medium (water, any glycol ether additives) before or simultaneously with the addition of the pigments and any other solids.

To prepare aqueous, highly concentrated, pumpable and flowable pigment preparations, the polymer to be used according to the invention, optionally in combination with at least one further component, is mixed with water, the pigment is sprinkled into this mixture with stirring and until the desired fineness and consistency of the suspension is achieved dispersed.

Another method for producing the pigment preparations according to the invention is to first dry-mix a pigment with the copolymers according to the invention, which results in a powdered pigment preparation. If necessary, this can be dispersed in water, the pigment preparation according to the invention being obtained.

A third method for producing aqueous, highly concentrated, pumpable and flowable pigment suspensions and pastes is to add an aqueous-moist pigment filter cake with the copolymer according to the invention and, for example, to incorporate it into the pigment filter cake with a dissolver, which liquefies.

Examples of pigments to be dispersed are:<dl id="dl0002"><dt>- monoazo pigments:</dt><dd>CI Pigment Brown 25; CI Pigment Orange 5, 36 and 67; CI Pigment Red 1, 2, 3, 48: 4, 49, 52: 2, 53, 57: 1, 251, 112, 170 and 184; CI Pigment Yellow 1, 3, 73, 74, 65, 97, 151 and 183;</dd><dt>- diazo pigments:</dt><dd>CI Pigment Orange 34; CI Pigment Red 144 and 166 CI Pigment Yellow 12, 13, 17, 83, 113 and 126;</dd><dt>- Anthraquinone pigments:</dt><dd>CI Pigment Yellow 147 and 177; CI Pigment Violet 31;</dd><dt>- anthrapyrimidine pigments:</dt><dd>CI Pigment Yellow 108;</dd><dt>- Quinacridone pigments:</dt><dd>CIPigment Red 122, 202 and 20; CIPigment Violet 19;</dd><dt>- Quinophthalone pigments:</dt><dd>CIPigment Yellow 138;</dd><dt>- Dioxazine pigments:</dt><dd>CIPigment Violet 23 and 27;</dd><dt>- Flavanthrone pigments:</dt><dd>CI Pigment Yellow 24;</dd><dt>- Indanthrone pigments:</dt><dd>CI Pigment Blue 60 and 64;</dd><dt>- Isoindoline pigments:</dt><dd>CI Pigment Orange 69; CI Pigment Red 260; CI Pigment Yellow 139;</dd><dt>- Isoindolinone pigments:</dt><dd>CI Pigment Orange 61; CI Pigment Red 257 and 260 CI Pigment Yellow 109, 110, 173 and 185;</dd><dt>- Metal complex pigments:</dt><dd>CI Pigment Yellow 117 and 153;</dd><dt>- Perinone pigments:</dt><dd>CI Pigment Orange 43; CI Pigment Red 194;</dd><dt>- Perylene pigments:</dt><dd>CI Pigment Black 31 and 32; CI Pigment Red 123, 149, 178, 179, 190 and 224; CI Pigment Violet 29;</dd><dt>- phthalocyanine pigments:</dt><dd>CI Pigment Blue 15, 15: 1, 15: 2.15: 3, 15: 4, 15: 6 and 16; CI Pigment Green 7 and 36;</dd><dt>- Pyranthrone pigments:</dt><dd>CI Pigment Orange 51; CI Pigment Red 216;</dd><dt>- Thioindigo pigments:</dt><dd>CI Pigment Red 88;</dd><dt>- Triphenylmethane pigments:</dt><dd>CI Pigment Blue 1.61, and 62; CI Pigment Green 1; CI Pigment Rad 81 and 169; CI Pigment Violet 2 and 3;</dd><dt>- CI Pigment Black 1 (aniline black)</dt>&lt;dd /&gt;<dt>- CIPigment Yellow 101 (Aldazine Yellow)</dt>&lt;dd /&gt;<dt>- Inorganic pigments:</dt>&lt;dd /&gt;<dt>- white pigments:</dt><dd>Titanium dioxide (CI Pigment White 6), zinc white, colored zinc oxide; Zinc sulfide, lithopone; Lead white;</dd><dt>- black pigments:</dt><dd>Iron oxide black (CI Pigment Black 11), iron-manganese black, spinel black (CIPigment Black 27); Carbon black (CI Pigment Black 7);</dd><dt>- Colored pigments:</dt><dd>Chromium oxide, chromium oxide hydrate green; Chrome green (CI Pigment Green 48); Cobalt green (CIPigment Green 50); Ultramarine green; Cobalt blue (CI Pigment Plus 28 and 36); Ultramarine blue; Iron blue (CI Pigment Blue 27); Manganese blue; Ultramarine violet; Cobalt and manganese violet; Iron oxide red (CI Pigment Red 101); Cadmium sulfoselenide (CI Pigment Red 108); Molybdate red (CI Pigment Red 104); Ultramarine red; Iron oxide brown, mixed brown, spinel and corundum phases (CI Pigment Brown 24, 29 and 31), Chrome orange; Iron oxide yellow (CI Pigment Yellow 42); Nickel titanium yellow (CI Pigment Yellow 53; CI Pigment Yellow 157 and 164); Chromium titanium yellow, cadmium sulfide and cadmium zinc sulfide, (CI Pigment Yellow 37 and 35); Chrome yellow (CI Pigment Yellow 34), zinc yellow, alkaline earth metal chromates, Naples yellow, bismuth vanadate (CI Pigment Yellow 184);</dd><dt>- gloss pigments:</dt><dd>Metallic effect pigments based on metal oxide coated metal flakes; Pearlescent pigments based on mica flakes coated with metal oxide.</dd></dl>

Fillers that can be dispersed, for example, in aqueous paints are e.g. B. those based on kaolin, talc, other silicates, chalk, glass fibers, glass beads or metal powders.

Any aqueous 1-component or 2-component coatings can be used as coating systems in which the pigment preparations according to the invention can be coated. Examples include aqueous 1-component paints, such as those based on alkyd, acrylate, epoxy, polyvinyl acetate, polyester or polyurethane resins, or aqueous 2-component paints, for example those based on hydroxyl-containing polyacrylate or polyester resins with melamine resins or optionally blocked polyisocyanate resins as crosslinkers. Polyepoxy resin systems may also be mentioned in the same way.

Water is the preferred solvent for the copolymers of the invention. However, organic solvents such as glycol ethers or esters can also be used alone or in a mixture with water. The addition of solvents is particularly advantageous for the drying behavior of the pigment pastes produced by means of the copolymers according to the invention.

To prepare the pigment preparations according to the invention, it is also possible to add other non-inventive, water-dispersible polymers, such as, for example, polyacrylate, polyurethane or polysiloxane derivatives.

In the preparation of the pigment preparations according to the invention, further auxiliaries, such as defoamers, preservatives, wetting agents, deaerators or anti-settling agents, waxes or rheology additives corresponding to the prior art can be used.

The block polymethacrylic acid ester block polyalkylene oxide carboxylic acids used as dispersants for aqueous pigment pastes are described according to general formula I. The indices a, b and c and the radicals R¹ to R⁴ and X has the meanings or values ​​shown in the table below. <tables id="tabl0005" num="0005"><table frame="all"><tgroup cols="9" colsep="1" rowsep="1"><colspec colnum="1" colname="col1" colwidth="17.50mm" /><colspec colnum="2" colname="col2" colwidth="17.50mm" /><colspec colnum="3" colname="col3" colwidth="17.50mm" /><colspec colnum="4" colname="col4" colwidth="17.50mm" /><colspec colnum="5" colname="col5" colwidth="17.50mm" /><colspec colnum="6" colname="col6" colwidth="17.50mm" /><colspec colnum="7" colname="col7" colwidth="17.50mm" /><colspec colnum="8" colname="col8" colwidth="17.50mm" /><colspec colnum="9" colname="col9" colwidth="17.50mm" /><thead valign="top"><row><entry namest="col1" nameend="col1" align="center">No.</entry><entry namest="col2" nameend="col2" align="center">a</entry><entry namest="col3" nameend="col3" align="center">B</entry><entry namest="col4" nameend="col4" align="center">c</entry><entry namest="col5" nameend="col5" align="center">R¹</entry><entry namest="col6" nameend="col6" align="center">R²</entry><entry namest="col7" nameend="col7" align="center">R³</entry><entry namest="col8" nameend="col8" align="center">R⁴</entry><entry namest="col9" nameend="col9" align="center">X</entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="center">1</entry><entry namest="col2" nameend="col2" align="center">12</entry><entry namest="col3" nameend="col3" align="center">70</entry><entry namest="col4" nameend="col4" align="left">0</entry><entry namest="col5" nameend="col5" align="left">C.₁₂H₂₅S</entry><entry namest="col6" nameend="col6" align="center">Me</entry><entry namest="col7" nameend="col7" align="left">-</entry><entry namest="col8" nameend="col8" align="left">MSA</entry><entry namest="col9" nameend="col9" align="left">O</entry></row><row><entry namest="col1" nameend="col1" align="center">2</entry><entry namest="col2" nameend="col2" align="center">9</entry><entry namest="col3" nameend="col3" align="center">70</entry><entry namest="col4" nameend="col4" align="left">0</entry><entry namest="col5" nameend="col5" align="left">C.₁₂H₂₅S</entry><entry namest="col6" nameend="col6" align="center">Me</entry><entry namest="col7" nameend="col7" align="left">-</entry><entry namest="col8" nameend="col8" align="left">BSA</entry><entry namest="col9" nameend="col9" align="left">O</entry></row><row><entry namest="col1" nameend="col1" align="center">3</entry><entry namest="col2" nameend="col2" align="center">6</entry><entry namest="col3" nameend="col3" align="center">50</entry><entry namest="col4" nameend="col4" align="left">0</entry><entry namest="col5" nameend="col5" align="left">C.₁₂H₂₅S</entry><entry namest="col6" nameend="col6" align="center">Me</entry><entry namest="col7" nameend="col7" align="left">-</entry><entry namest="col8" nameend="col8" align="left">TSA</entry><entry namest="col9" nameend="col9" align="left">O</entry></row><row><entry namest="col1" nameend="col1" align="center">4</entry><entry namest="col2" nameend="col2" align="center">10</entry><entry namest="col3" nameend="col3" align="center">70</entry><entry namest="col4" nameend="col4" align="left">0</entry><entry namest="col5" nameend="col5" align="left">C.₁₂H₂₅S</entry><entry namest="col6" nameend="col6" align="center">Bu</entry><entry namest="col7" nameend="col7" align="left">-</entry><entry namest="col8" nameend="col8" align="left">BSA</entry><entry namest="col9" nameend="col9" align="left">O</entry></row><row><entry namest="col1" nameend="col1" align="center">5</entry><entry namest="col2" nameend="col2" align="center">9</entry><entry namest="col3" nameend="col3" align="center">55</entry><entry namest="col4" nameend="col4" align="left">12</entry><entry namest="col5" nameend="col5" align="left">C.₁₂H₂₅S</entry><entry namest="col6" nameend="col6" align="center">Me</entry><entry namest="col7" nameend="col7" align="left">Me</entry><entry namest="col8" nameend="col8" align="left">BSA</entry><entry namest="col9" nameend="col9" align="left">O</entry></row><row><entry namest="col1" nameend="col1" align="center"> </entry><entry namest="col2" nameend="col2" /><entry namest="col3" nameend="col3" /><entry namest="col4" nameend="col4" /><entry namest="col5" nameend="col5" /><entry namest="col6" nameend="col6" /><entry namest="col7" nameend="col7" /><entry namest="col8" nameend="col8" /><entry namest="col9" nameend="col9" /></row><row><entry namest="col1" nameend="col1" align="center">6</entry><entry namest="col2" nameend="col2" align="center">12</entry><entry namest="col3" nameend="col3" align="center">70</entry><entry namest="col4" nameend="col4" align="left">0</entry><entry namest="col5" nameend="col5" align="left">C.₁₂H₂₅S</entry><entry namest="col6" nameend="col6" align="center">Me</entry><entry namest="col7" nameend="col7" align="left">-</entry><entry namest="col8" nameend="col8" align="left">H</entry><entry namest="col9" nameend="col9" align="left">O</entry></row><row><entry namest="col1" nameend="col1" align="center">7</entry><entry namest="col2" nameend="col2" align="center">12</entry><entry namest="col3" nameend="col3" align="center">70</entry><entry namest="col4" nameend="col4" align="left">0</entry><entry namest="col5" nameend="col5" align="left">C.₁₂H₂₅S</entry><entry namest="col6" nameend="col6" align="center">Me</entry><entry namest="col7" nameend="col7" align="left">-</entry><entry namest="col8" nameend="col8" align="left">POx</entry><entry namest="col9" nameend="col9" align="left">O</entry></row><row><entry namest="col1" nameend="col1" align="center">8</entry><entry namest="col2" nameend="col2" align="center">10</entry><entry namest="col3" nameend="col3" align="center">70</entry><entry namest="col4" nameend="col4" align="left">0</entry><entry namest="col5" nameend="col5" /><entry namest="col6" nameend="col6" align="center">Styrene!</entry><entry namest="col7" nameend="col7" align="left">-</entry><entry namest="col8" nameend="col8" align="left">POx</entry><entry namest="col9" nameend="col9" align="left">O</entry></row><row><entry namest="col1" nameend="col1" align="center">9</entry><entry namest="col2" nameend="col2" align="center">10</entry><entry namest="col3" nameend="col3" align="center">70</entry><entry namest="col4" nameend="col4" align="left">0</entry><entry namest="col5" nameend="col5" /><entry namest="col6" nameend="col6" align="center">Styrene!</entry><entry namest="col7" nameend="col7" align="left">-</entry><entry namest="col8" nameend="col8" align="left">BSA</entry><entry namest="col9" nameend="col9" align="left">O</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="center">10</entry><entry namest="col2" nameend="col2" align="center">12</entry><entry namest="col3" nameend="col3" align="center">23</entry><entry namest="col4" nameend="col4" align="left">17</entry><entry namest="col5" nameend="col5" align="left">C.₁₂H₂₅S</entry><entry namest="col6" nameend="col6" align="center">Me</entry><entry namest="col7" nameend="col7" align="left">Me</entry><entry namest="col8" nameend="col8" align="left">BSA</entry><entry namest="col9" nameend="col9" align="left">O</entry></row></tbody></tgroup></table></tables>

Production of pigment pastes

To prepare the pigment pastes, the (1 to 5) and non-inventive (6 to 10) dispersion additives according to the invention are 40% pre-dissolved in water, mixed with water and auxiliaries, and the pigments are then added. Dispersion takes place after adding grinding media (glass balls 2 to 3 mm, same volume as the pigment paste) 1 (titanium dioxide) or 2 h (other pigments) in a Skandex vibrator with air cooling.

Formulation of the white pastes

The white pastes are formulated as follows (data in% by weight):<dl id="dl0003" compact="compact"><dt>16,4</dt><dd>water</dd><dt>12,3</dt><dd>Additive solution, 40%</dd><dt>1,0</dt><dd>Defoamer (e.g. Tego Foamex 810, Tego Chemie Service GmbH)</dd><dt>70,0</dt><dd>Titanium dioxide 2160 (Kronos)</dd><dt>0,3</dt><dd>Aerosil A 200 (Degussa)</dd></dl>

Formulation of the black pastes

The black pastes are formulated as follows (figures in% by weight):<dl id="dl0004" compact="compact"><dt>60,3</dt><dd>water</dd><dt>22,3</dt><dd>Additive solution, 40%</dd><dt>1,0</dt><dd>Defoamer (e.g. Tego Foamex 810, Tego Chemie Service GmbH)</dd><dt>1,4</dt><dd>AMP 90 (Angus)</dd><dt>15,0</dt><dd>Color black FW 200 (Degussa)</dd></dl>

Test paints

Stoving clear lacquer based on a modified alkyd resin (figures in% by weight)<dl id="dl0005" compact="compact"><dt>70,88</dt><dd>Resydrol VWA 5477, 40% (Hoechst)</dd><dt>0,14</dt><dd>Defoamer (e.g. Byk 020, Byk-Chemie)</dd><dt>0,68</dt><dd>Bentone SD 1 (Rheox)</dd><dt>8,24</dt><dd>Maprenal MF 900 (Hoechst)</dd><dt>0,14</dt><dd>Triethanolamine</dd><dt>19,10</dt><dd>water</dd><dt>0,68</dt><dd>Additol XW 395 (Hoechst)</dd><dt>0,14</dt><dd>Additol XW 329</dd></dl> Place position 1 and add the other components while stirring.

Dispersion clear coat

<dl id="dl0006" compact="compact"><dt>97,0</dt><dd>Neocryl XK 90 (Zeneca)</dd><dt>3,0</dt><dd>Texanol</dd></dl>

To produce gray pigmented lacquers, 40.0 g of clear lacquer are placed in each case, 14.2 g of white paste and 2.65 g of black paste are added and the mixture is homogenized at 1500 rpm for 5 min. The samples are knife-coated onto aluminum sheets with a wet film thickness of 100 μm and either baked for 15 minutes at 150 ° C. after baking time of 20 minutes (baking varnish) or dried at room temperature (dispersion varnish).

Paste stability test

To determine the paste stabilities, the achievable initial viscosities and the viscosities after four weeks of storage at 50 ° C. are determined at two different shear rates (20 1 / s and 1000 1 / s).

White pastes

<tables id="tabl0006" num="0006"><table frame="all"><tgroup cols="5" colsep="1" rowsep="1"><colspec colnum="1" colname="col1" colwidth="31.50mm" /><colspec colnum="2" colname="col2" colwidth="31.50mm" /><colspec colnum="3" colname="col3" colwidth="31.50mm" /><colspec colnum="4" colname="col4" colwidth="31.50mm" /><colspec colnum="5" colname="col5" colwidth="31.50mm" /><thead valign="top"><row><entry namest="col1" nameend="col1" align="center">sample</entry><entry namest="col2" nameend="col2" align="center">Viscosity / Pas immediately at 20 1 / s</entry><entry namest="col3" nameend="col3" align="center">Viscosity / Pas immediately at 1000 1 / s</entry><entry namest="col4" nameend="col4" align="center">Viscosity / Pas after 4 weeks 50 ° C at 20 1 / s</entry><entry namest="col5" nameend="col5" align="center">Viscosity / Pas after 4 weeks 50 ° C at 1000 1 / s</entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="center">1</entry><entry namest="col2" nameend="col2" align="char" char=",">3,0</entry><entry namest="col3" nameend="col3" align="char" char=",">0,6</entry><entry namest="col4" nameend="col4" align="center">3,4</entry><entry namest="col5" nameend="col5" align="center">0,7</entry></row><row><entry namest="col1" nameend="col1" align="center">2</entry><entry namest="col2" nameend="col2" align="char" char=",">2,8</entry><entry namest="col3" nameend="col3" align="char" char=",">0,5</entry><entry namest="col4" nameend="col4" align="center">3,2</entry><entry namest="col5" nameend="col5" align="center">0,7</entry></row><row><entry namest="col1" nameend="col1" align="center">3</entry><entry namest="col2" nameend="col2" align="char" char=",">2,7</entry><entry namest="col3" nameend="col3" align="char" char=",">0,5</entry><entry namest="col4" nameend="col4" align="center">3,0</entry><entry namest="col5" nameend="col5" align="center">0,6</entry></row><row><entry namest="col1" nameend="col1" align="center">4</entry><entry namest="col2" nameend="col2" align="char" char=",">3,2</entry><entry namest="col3" nameend="col3" align="char" char=",">0,5</entry><entry namest="col4" nameend="col4" align="center">3,7</entry><entry namest="col5" nameend="col5" align="center">0,5</entry></row><row><entry namest="col1" nameend="col1" align="center">5</entry><entry namest="col2" nameend="col2" align="char" char=",">2,5</entry><entry namest="col3" nameend="col3" align="char" char=",">0,6</entry><entry namest="col4" nameend="col4" align="center">3,0</entry><entry namest="col5" nameend="col5" align="center">0,7</entry></row><row><entry namest="col1" nameend="col1" align="center">6</entry><entry namest="col2" nameend="col2" align="char" char=",">2,9</entry><entry namest="col3" nameend="col3" align="char" char=",">0,7</entry><entry namest="col4" nameend="col4" align="center">5,0</entry><entry namest="col5" nameend="col5" align="center">1,1</entry></row><row><entry namest="col1" nameend="col1" align="center">7</entry><entry namest="col2" nameend="col2" align="char" char=",">1,9</entry><entry namest="col3" nameend="col3" align="char" char=",">0,4</entry><entry namest="col4" nameend="col4" align="center">2,5</entry><entry namest="col5" nameend="col5" align="center">0,7</entry></row><row><entry namest="col1" nameend="col1" align="center">8</entry><entry namest="col2" nameend="col2" align="char" char=",">2,1</entry><entry namest="col3" nameend="col3" align="char" char=",">0,4</entry><entry namest="col4" nameend="col4" align="center">2,6</entry><entry namest="col5" nameend="col5" align="center">0,6</entry></row><row><entry namest="col1" nameend="col1" align="center">9</entry><entry namest="col2" nameend="col2" align="char" char=",">2,6</entry><entry namest="col3" nameend="col3" align="char" char=",">0,5</entry><entry namest="col4" nameend="col4" align="center">3,8</entry><entry namest="col5" nameend="col5" align="center">0,8</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="center">10</entry><entry namest="col2" nameend="col2" align="char" char=",">4,0</entry><entry namest="col3" nameend="col3" align="char" char=",">0,8</entry><entry namest="col4" nameend="col4" align="center">sedimented</entry><entry namest="col5" nameend="col5" align="center">sedimented</entry></row></tbody></tgroup></table></tables>

Black pastes

<tables id="tabl0007" num="0007"><table frame="all"><tgroup cols="5" colsep="1" rowsep="1"><colspec colnum="1" colname="col1" colwidth="31.50mm" /><colspec colnum="2" colname="col2" colwidth="31.50mm" /><colspec colnum="3" colname="col3" colwidth="31.50mm" /><colspec colnum="4" colname="col4" colwidth="31.50mm" /><colspec colnum="5" colname="col5" colwidth="31.50mm" /><thead valign="top"><row><entry namest="col1" nameend="col1" align="center">sample</entry><entry namest="col2" nameend="col2" align="center">Viscosity / dPas immediately at 20 1 / s</entry><entry namest="col3" nameend="col3" align="center">Viscosity / dPas immediately at 1000 1 / s</entry><entry namest="col4" nameend="col4" align="center">Viscosity / dPas after 4 weeks 50 ° C at 20 1 / s</entry><entry namest="col5" nameend="col5" align="center">Viscosity / dPas after 4 weeks 50 ° C at 1000 1 / s</entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="center">1</entry><entry namest="col2" nameend="col2" align="char" char=",">2,2</entry><entry namest="col3" nameend="col3" align="char" char=",">0,6</entry><entry namest="col4" nameend="col4" align="center">2,3</entry><entry namest="col5" nameend="col5" align="center">0,6</entry></row><row><entry namest="col1" nameend="col1" align="center">2</entry><entry namest="col2" nameend="col2" align="char" char=",">2,0</entry><entry namest="col3" nameend="col3" align="char" char=",">0,6</entry><entry namest="col4" nameend="col4" align="center">2,2</entry><entry namest="col5" nameend="col5" align="center">0,7</entry></row><row><entry namest="col1" nameend="col1" align="center">3</entry><entry namest="col2" nameend="col2" align="char" char=",">2,1</entry><entry namest="col3" nameend="col3" align="char" char=",">0,6</entry><entry namest="col4" nameend="col4" align="center">2,3</entry><entry namest="col5" nameend="col5" align="center">0,6</entry></row><row><entry namest="col1" nameend="col1" align="center">4</entry><entry namest="col2" nameend="col2" align="char" char=",">2,5</entry><entry namest="col3" nameend="col3" align="char" char=",">0,5</entry><entry namest="col4" nameend="col4" align="center">2,7</entry><entry namest="col5" nameend="col5" align="center">0,6</entry></row><row><entry namest="col1" nameend="col1" align="center">5</entry><entry namest="col2" nameend="col2" align="char" char=",">2,3</entry><entry namest="col3" nameend="col3" align="char" char=",">0,7</entry><entry namest="col4" nameend="col4" align="center">2,4</entry><entry namest="col5" nameend="col5" align="center">0,7</entry></row><row><entry namest="col1" nameend="col1" align="center">6</entry><entry namest="col2" nameend="col2" align="char" char=",">2,3</entry><entry namest="col3" nameend="col3" align="char" char=",">0,5</entry><entry namest="col4" nameend="col4" align="center">3,5</entry><entry namest="col5" nameend="col5" align="center">0,8</entry></row><row><entry namest="col1" nameend="col1" align="center">7</entry><entry namest="col2" nameend="col2" align="char" char=",">2,2</entry><entry namest="col3" nameend="col3" align="char" char=",">0,6</entry><entry namest="col4" nameend="col4" align="center">2,3</entry><entry namest="col5" nameend="col5" align="center">0,6</entry></row><row><entry namest="col1" nameend="col1" align="center">8</entry><entry namest="col2" nameend="col2" align="char" char=",">2,2</entry><entry namest="col3" nameend="col3" align="char" char=",">0,6</entry><entry namest="col4" nameend="col4" align="center">2,5</entry><entry namest="col5" nameend="col5" align="center">0,8</entry></row><row><entry namest="col1" nameend="col1" align="center">9</entry><entry namest="col2" nameend="col2" align="char" char=",">2,3</entry><entry namest="col3" nameend="col3" align="char" char=",">0,5</entry><entry namest="col4" nameend="col4" align="center">2,8</entry><entry namest="col5" nameend="col5" align="center">0,7</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="center">10</entry><entry namest="col2" nameend="col2" align="char" char=",">3,0</entry><entry namest="col3" nameend="col3" align="char" char=",">0,7</entry><entry namest="col4" nameend="col4" align="center">sedimented</entry><entry namest="col5" nameend="col5" align="center">sedimented</entry></row></tbody></tgroup></table></tables>

The good stability of the pigment pastes according to the invention can easily be seen from the only slight increase in viscosity. When the block copolymer 10 according to the invention was not used, no storage-stable pigment concentrates could be formulated.

Dispersion test

The test formulations are applied with a 100 µm wet film thickness; After drying for six minutes, a rub-out test is carried out on 1/3 of the coated surface. After baking or drying overnight, the colorimetric measurement of the elevators is carried out after 24 hours using a type XP 68 spectrophotometer from X-Rite. The degree of gloss and haze are determined using the Haze-Gloss device from Byk-Gardner.

Stoving varnish based on Resydrol VWA 5477

<tables id="tabl0008" num="0008"><table frame="all"><tgroup cols="4" colsep="1" rowsep="1"><colspec colnum="1" colname="col1" colwidth="39.37mm" /><colspec colnum="2" colname="col2" colwidth="39.37mm" /><colspec colnum="3" colname="col3" colwidth="39.37mm" /><colspec colnum="4" colname="col4" colwidth="39.37mm" /><thead valign="top"><row><entry namest="col1" nameend="col1" align="center">sample</entry><entry namest="col2" nameend="col2" align="center">Brightness L</entry><entry namest="col3" nameend="col3" align="center">Delta E after rub-out</entry><entry namest="col4" nameend="col4" align="center">Degree of gloss (60 ° angle)</entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="center">1</entry><entry namest="col2" nameend="col2" align="char" char=",">44,0</entry><entry namest="col3" nameend="col3" align="char" char=",">0,4</entry><entry namest="col4" nameend="col4" align="center">53</entry></row><row><entry namest="col1" nameend="col1" align="center">2</entry><entry namest="col2" nameend="col2" align="char" char=",">43,6</entry><entry namest="col3" nameend="col3" align="char" char=",">0,2</entry><entry namest="col4" nameend="col4" align="center">57</entry></row><row><entry namest="col1" nameend="col1" align="center">3</entry><entry namest="col2" nameend="col2" align="char" char=",">44,2</entry><entry namest="col3" nameend="col3" align="char" char=",">0,2</entry><entry namest="col4" nameend="col4" align="center">58</entry></row><row><entry namest="col1" nameend="col1" align="center">4</entry><entry namest="col2" nameend="col2" align="char" char=",">44,8</entry><entry namest="col3" nameend="col3" align="char" char=",">0,5</entry><entry namest="col4" nameend="col4" align="center">57</entry></row><row><entry namest="col1" nameend="col1" align="center">5</entry><entry namest="col2" nameend="col2" align="char" char=",">43,8</entry><entry namest="col3" nameend="col3" align="char" char=",">0,5</entry><entry namest="col4" nameend="col4" align="center">54</entry></row><row><entry namest="col1" nameend="col1" align="center">6</entry><entry namest="col2" nameend="col2" align="char" char=",">44,0</entry><entry namest="col3" nameend="col3" align="char" char=",">1,1</entry><entry namest="col4" nameend="col4" align="center">47</entry></row><row><entry namest="col1" nameend="col1" align="center">7</entry><entry namest="col2" nameend="col2" align="char" char=",">44,2</entry><entry namest="col3" nameend="col3" align="char" char=",">0,9</entry><entry namest="col4" nameend="col4" align="center">50</entry></row><row><entry namest="col1" nameend="col1" align="center">8</entry><entry namest="col2" nameend="col2" align="char" char=",">44,3</entry><entry namest="col3" nameend="col3" align="char" char=",">2,6</entry><entry namest="col4" nameend="col4" align="center">60</entry></row><row><entry namest="col1" nameend="col1" align="center">9</entry><entry namest="col2" nameend="col2" align="char" char=",">43,9</entry><entry namest="col3" nameend="col3" align="char" char=",">2,1</entry><entry namest="col4" nameend="col4" align="center">53</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="center">10</entry><entry namest="col2" nameend="col2" align="char" char=",">41,9</entry><entry namest="col3" nameend="col3" align="char" char=",">4,6</entry><entry namest="col4" nameend="col4" align="center">41</entry></row></tbody></tgroup></table></tables>

Dispersion varnish based on Neocryl XK 90

<tables id="tabl0009" num="0009"><table frame="all"><tgroup cols="5" colsep="1" rowsep="1"><colspec colnum="1" colname="col1" colwidth="31.50mm" /><colspec colnum="2" colname="col2" colwidth="31.50mm" /><colspec colnum="3" colname="col3" colwidth="31.50mm" /><colspec colnum="4" colname="col4" colwidth="31.50mm" /><colspec colnum="5" colname="col5" colwidth="31.50mm" /><thead valign="top"><row><entry namest="col1" nameend="col1" align="center">sample</entry><entry namest="col2" nameend="col2" align="center">Brightness L</entry><entry namest="col3" nameend="col3" align="center">Delta E after rub-out</entry><entry namest="col4" nameend="col4" align="center">Degree of gloss (60 ° angle)</entry><entry namest="col5" nameend="col5" align="center">Haze</entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="center">1</entry><entry namest="col2" nameend="col2" align="char" char=",">48,5</entry><entry namest="col3" nameend="col3" align="char" char=",">0,3</entry><entry namest="col4" nameend="col4" align="center">40</entry><entry namest="col5" nameend="col5" align="center">110</entry></row><row><entry namest="col1" nameend="col1" align="center">2</entry><entry namest="col2" nameend="col2" align="char" char=",">49,0</entry><entry namest="col3" nameend="col3" align="char" char=",">0,1</entry><entry namest="col4" nameend="col4" align="center">41</entry><entry namest="col5" nameend="col5" align="center">108</entry></row><row><entry namest="col1" nameend="col1" align="center">3</entry><entry namest="col2" nameend="col2" align="char" char=",">49,1</entry><entry namest="col3" nameend="col3" align="char" char=",">0,3</entry><entry namest="col4" nameend="col4" align="center">40</entry><entry namest="col5" nameend="col5" align="center">107</entry></row><row><entry namest="col1" nameend="col1" align="center">4</entry><entry namest="col2" nameend="col2" align="char" char=",">49,5</entry><entry namest="col3" nameend="col3" align="char" char=",">0,5</entry><entry namest="col4" nameend="col4" align="center">41</entry><entry namest="col5" nameend="col5" align="center">110</entry></row><row><entry namest="col1" nameend="col1" align="center">5</entry><entry namest="col2" nameend="col2" align="char" char=",">49,3</entry><entry namest="col3" nameend="col3" align="char" char=",">0,5</entry><entry namest="col4" nameend="col4" align="center">38</entry><entry namest="col5" nameend="col5" align="center">106</entry></row><row><entry namest="col1" nameend="col1" align="center">6</entry><entry namest="col2" nameend="col2" align="char" char=",">47,8</entry><entry namest="col3" nameend="col3" align="char" char=",">0,8</entry><entry namest="col4" nameend="col4" align="center">37</entry><entry namest="col5" nameend="col5" align="center">110</entry></row><row><entry namest="col1" nameend="col1" align="center">7</entry><entry namest="col2" nameend="col2" align="char" char=",">48,4</entry><entry namest="col3" nameend="col3" align="char" char=",">0,8</entry><entry namest="col4" nameend="col4" align="center">43</entry><entry namest="col5" nameend="col5" align="center">105</entry></row><row><entry namest="col1" nameend="col1" align="center">8</entry><entry namest="col2" nameend="col2" align="char" char=",">49,5</entry><entry namest="col3" nameend="col3" align="char" char=",">0,7</entry><entry namest="col4" nameend="col4" align="center">45</entry><entry namest="col5" nameend="col5" align="center">103</entry></row><row><entry namest="col1" nameend="col1" align="center">9</entry><entry namest="col2" nameend="col2" align="char" char=",">49,0</entry><entry namest="col3" nameend="col3" align="char" char=",">0,9</entry><entry namest="col4" nameend="col4" align="center">40</entry><entry namest="col5" nameend="col5" align="center">110</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="center">10</entry><entry namest="col2" nameend="col2" align="char" char=",">47,0</entry><entry namest="col3" nameend="col3" align="char" char=",">2,0</entry><entry namest="col4" nameend="col4" align="center">37</entry><entry namest="col5" nameend="col5" align="center">100</entry></row></tbody></tgroup></table></tables>

One can see the favorable color strength development which can be achieved by using the dispersion additives according to the invention and the rub-out test which is favorable in all cases.

Water resistance test

The baked (Resydrol system) or gray pigmented lacquer films (System Neocryl) air-dried for 7 days at room temperature are exposed to standing water for 20 hours and then assessed for surface defects (blistering / color shift) and softening. <tables id="tabl0010" num="0010"><table frame="all"><tgroup cols="3" colsep="1" rowsep="1"><colspec colnum="1" colname="col1" colwidth="52.50mm" /><colspec colnum="2" colname="col2" colwidth="52.50mm" /><colspec colnum="3" colname="col3" colwidth="52.50mm" /><thead valign="top"><row><entry namest="col1" nameend="col1" align="center">sample</entry><entry namest="col2" nameend="col2" align="center">Surface defects</entry><entry namest="col3" nameend="col3" align="center">softening</entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="center">1</entry><entry namest="col2" nameend="col2" align="center">no</entry><entry namest="col3" nameend="col3" align="center">minimal</entry></row><row><entry namest="col1" nameend="col1" align="center">2</entry><entry namest="col2" nameend="col2" align="center">no</entry><entry namest="col3" nameend="col3" align="center">minimal</entry></row><row><entry namest="col1" nameend="col1" align="center">3</entry><entry namest="col2" nameend="col2" align="center">no</entry><entry namest="col3" nameend="col3" align="center">minimal</entry></row><row><entry namest="col1" nameend="col1" align="center">4</entry><entry namest="col2" nameend="col2" align="center">no</entry><entry namest="col3" nameend="col3" align="center">minimal</entry></row><row><entry namest="col1" nameend="col1" align="center">5</entry><entry namest="col2" nameend="col2" align="center">no</entry><entry namest="col3" nameend="col3" align="center">minimal</entry></row><row><entry namest="col1" nameend="col1" align="center">6</entry><entry namest="col2" nameend="col2" align="center">no</entry><entry namest="col3" nameend="col3" align="center">minimal</entry></row><row><entry namest="col1" nameend="col1" align="center">7</entry><entry namest="col2" nameend="col2" align="center">clear</entry><entry namest="col3" nameend="col3" align="center">clear</entry></row><row><entry namest="col1" nameend="col1" align="center">8</entry><entry namest="col2" nameend="col2" align="center">clear</entry><entry namest="col3" nameend="col3" align="center">clear</entry></row><row><entry namest="col1" nameend="col1" align="center">9</entry><entry namest="col2" nameend="col2" align="center">no</entry><entry namest="col3" nameend="col3" align="center">minimal</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="center">10</entry><entry namest="col2" nameend="col2" align="center">no</entry><entry namest="col3" nameend="col3" align="center">minimal</entry></row></tbody></tgroup></table></tables>

The active compounds according to the invention do not impair the water resistance of the paint films, especially when compared to analog phosphoric acid esters.

As can be seen from the previous comparisons, the compounds to be used according to the invention are notable for their universal applicability, the ease of manufacture of stable pigment pastes, achievable pigmentation levels, achievable color stability and achievable improvements in the water resistance of lacquered coatings.