POLYURETHANE TWO-COMPONENT OR MULTI-COMPONENT SYSTEMS HAVING A LATENT THICKENING TENDENCY

Abstract

The invention relates to a two-component or multi-component system comprising: at least one polyol component 1 that has i) at least one polyol, ii) at least one inorganic thickener (a1), and iii) at least one wetting and dispersing agent (a2) which inhibits the thickening effect of said inorganic thickener (a1); as well as at least one polyisocyanate component 2 that comprises i) at least one polyisocyanate; where (A) either the polyisocyanate component 2 comprises at least one component (b1) that at least partially cancels the inhibition of the thickening effect of the inorganic thickener (a1); and/or (B) at least one isocyanate-free component 3 comprises at least one component (b1) that at least partially cancels the inhibition of the thickening effect of the inorganic thickener (a1); said wetting and dispersing agent (a2) being non-reactive to the at least one polyol, and the polyisocyanate component 2 being reactive to the polyol component 1. The invention also relates to a substrate coated with a system according to the invention, and to the use of at least one inorganic thickener (a1) and at least one wetting and dispersing agent (a2) which inhibits the thickening effect of said inorganic thickener (a1), in order to provide a latent thickening effect for a composition that contains at least one polyol.

Claims

1. A two-component or multicomponent system comprising at least one polyol component 1 which comprises i. at least one polyol, ii. at least one inorganic thickener (a1), and iii. at least one wetting and dispersing agent (a2) which inhibits the thickening effect of the inorganic thickener (a1); and at least one polyisocyanate component 2 which comprises i. at least one polyisocyanate; and (A) either the polyisocyanate component 2 comprising at least one component (b1) which at least partly eliminates the inhibition of the thickening effect of the inorganic thickener (a1); and/or (B) at least one isocyanate-free component 3 comprising at least one component (b1) which at least partly eliminates the inhibition of the thickening action of the inorganic thickener (a1); and the wetting and dispersing agent (a2) being nonreactive toward the at least one polyol and the polyisocyanate component 2 being reactive toward the polyol component 1.

2. The two-component or multicomponent system as claimed in claim 1, the inorganic thickener (a1) being selected from the group consisting of phyllosilicates, precipitated silicas, and fumed silicas.

3. The two-component or multicomponent system as claimed in claim 1, the inorganic thickener (a1) being non-organically modified fumed silica or hydrophobically modified fumed silica.

4. The two-component or multicomponent system as claimed in claim 1, the inorganic thickener (a1) being a phyllosilicate mixture which has been surface-treated with quaternary alkylammonium salts and which comprises 50 to 95 wt %, based on the phyllosilicate mixture, of a clay mineral selected from the group consisting of sepiolite and palygorskite or mixtures thereof and less than 50 wt %, based on the phyllosilicate mixture, of at least one smectite.

5. The two-component or multicomponent system as claimed in claim 1, the polyol of the polyol component 1 being selected from the group of the polyester polyols, polyether polyols and monomeric molecularly uniform polyols.

6. The two-component or multicomponent system as claimed in claim 1, the polyisocyanate component 2 comprising a polyisocyanate which is selected from the group consisting of aromatic diisocyanates, cycloaliphatic diisocyanates, araliphatic diisocyanates, aliphatic diisocyanates, mixtures thereof, and uretdiones, isocyanurates and/or biurets of the diisocyanates or the mixtures of the diisocyanates.

7. The two-component or multicomponent system as claimed in claim 1, the wetting and dispersing agent (a2) and the component (b1) being selected such that they comprise one or more of the following functional groups selected from group 1: consisting of imidazolyl groups, with the structural element N-CN, amino groups with the structural elements N for tertiary amines, NH for secondary amines, and NH.sub.2 for primary amines, and ammonium groups with the structural element NH.sup.+X.sup. for ammonium salts of tertiary amines, with the structural element NH.sub.2.sup.+X.sup. for ammonium salts of secondary amines, and NH.sub.3.sup.+X.sup. for ammonium salts of primary amines, X.sup. in each case being the anion of an acid; and/or group 2: consisting of hydroxyl groups with the structural element OH, urea groups with the structural element HNC(O)CNH for ureas of primary amines and NC(O)CN for ureas of secondary amines, amide groups, with the structural element C(O)N for amides of secondary amines, C(O)NH for amides of primary amines, and C(O)NH.sub.2 for amides of ammonia, carboxylic acid groups with the structural element COOH, and organic phosphoric ester groups with the structural element OP(O)(OH).sub.2, and (A) the weight percentage fraction of structural elements in the wetting and dispersing agent (a2), selected from the functional groups of groups 1 and 2, based on the weight of the wetting and dispersing agent (a2), being lower than the weight percentage fraction of structural elements in component (b1), selected from the functional groups of groups 1 and 2, based on the weight of the component (b1); and/or (B) component (b1) comprising a higher weight percentage fraction of structural elements from the functional groups selected from group 1, based on the weight of component (b1), than that of the structural elements from the functional groups selected from group 1 in the wetting and dispersing agent (a2), based on the weight of the wetting and dispersing agent (a2).

8. The two-component or multicomponent system as claimed in claim 7, (A) the weight percentage fraction of structural elements selected from the functional groups of groups 1 and 2, based on the weight of the wetting and dispersing agent (a2), being less than 11 wt %, and the weight percentage fraction of structural elements selected from the functional groups of groups 1 and 2, based on the weight of component (b1), being greater than or equal to 11 wt %.

9. The two-component or multicomponent system as claimed in claim 7, the difference in the weight percentage fractions of structural elements between the wetting and dispersing agent (a2) and component (b1) being at least 2 wt %.

10. The two-component or multicomponent system as claimed in claim 1, the weight ratio of wetting and dispersing agent (a2) to component (b1) being 15:1 to 1:5.

11. The two-component or multicomponent system as claimed in claim 1, the wetting and dispersing agent (a2) binding reversibly to the surface of the inorganic thickener (a1).

12. The two-component or multicomponent system as claimed in claim 1, the polymer (b1) being able to bind to the surface of the inorganic thickener (a1) with at least partial displacement of (a2).

13. The two-component or multicomponent system as claimed in claim 1, being an adhesive, sealant, a coating material or a molding compound.

14. A substrate coated with a two-component or multicomponent system of claim 1.

15. A method of utilizing at least one inorganic thickener (a1) and at least one wetting and dispersing agent (a2) which inhibits the thickening effect of the inorganic thickener (a1) to provide a formulation comprising at least one polyol with a latent thickening effect.

Description

EXAMPLES

Preparation Examples

[0141] In the case of molecularly nonuniform substances, the stated molecular weightsbelow and in the foregoing descriptionrepresent average values of the numerical average. The molecular weights, or number-average molecular weights M.sub.n, are determinedwhere there are determinable functional end groups present such as hydroxyl, NCO, amino or acid groupsby end group determination via ascertainment of OH number, NCO number, amine number or acid number by titration, respectively. In the case of compounds for which end group determination is not applicable, the number-average molecular weight is determined by gel permeation chromography against a polystyrene standard. Molecular weights reported for the polyamines are number averages M.sub.n determined by ebullioscopy.

[0142] Unless otherwise stated, amounts in parts are parts by weight and amounts in percent are percentages by weight.

Viscosity Measurements

[0143] The viscosities of the base components and of the mixtures of the base components were determinedunless otherwise specifiedon a Stresstech instrument from Rheologica via a plate-cone method (cone diameter 25 mm; cone angle: 1; cone-plate gap: 35 m; temperature: 23 C.; shear rate 1 s.sup.1; number of data points: 21; compensation time 10 s; measuring time per data point: delay time+integration time; delay time: 5-8 s; integration time: 3 s; control strength (sensitivity): 60%).

[0144] The measurements on two-, three- and multicomponent systems were carried out 2 minutes after their preparation.

[0145] The viscosities of the base components and of the mixtures of the base components were determinedwhere the Brookfield method is reportedon a Brookfield DV-II+viscometer from Brookfield via spindle method (spindle 3; 5 rpm, temperature: 23 C.; measuring time per data point: 1 min). The measurements on two-, three- and multicomponent systems were carried out 2 minutes after their preparation.

Determination of Tertiary Nitrogen Content

[0146] The tertiary nitrogen content indicates the percentage content of bound tertiary basic nitrogen in a sample under analysis. The method of determination uses the fact that tertiary amino groupsin contrast to primary and secondary amino groupsdo not react with anhydrides to form amides. When primary and secondary amino groups are acetylated with acetic anhydride, the tertiary amino groups can be subsequently titrated quantitatively with perchloric acid. For determining the tertiary nitrogen content of a sample, a quantity of a sample under analysis is weighed to a precision of 0.1 mg on an analytical balance into an 80 ml glass beaker. The quantity to be weighed out of the amount to be analyzed is guided by the anticipated tertiary nitrogen content and is taken from the table below:

TABLE-US-00002 Anticipated tertiary Sample quantity to be nitrogen content [%] weighed out [g] 0-0.3 3-5 0.3-0.6 1.5-3 0.6-0.9 1.0-1.5 0.9-1.5 0.6-1.0 1.5-2.0 0.45-0.6 2.0-3.0 0.30-0.45 3-5 0.15-0.30 5-10 0.08-0.15 10-20 0.06-0.08

[0147] The sample is dissolved in 20 ml of acetic acid (99.8% strength) and 30 ml of acetic anhydride (98.5% strength). The resulting sample solution is then fitted with a ground glass lid and heated in a thermoblock or waterbath at 70 C. for a time of 30 minutes. When the sample solution has cooled, it is placed on a magnetic stirrer and an Ag/AgCl combination electrode is immersed into the sample solution. The combination electrode is part of a microprocessor-controlled analytical apparatus (Titrator DL77, DL70 ES or DL67) from Mettler. The sample solution is titrated with perchloric acid (0.1 N in acetic acid, anhydride-free). The tertiary nitrogen content is determined by the analytical apparatus used. The tertiary nitrogen content is calculated as follows:

[00001]$\mathrm{Tertiary}.Math..Math.N.Math..Math.\mathrm{content}.Math..Math.\left(\mathrm{wt}.Math..Math.\%\right)=\frac{\mathrm{consumption}.Math..Math.\mathrm{ml}Nf1.4008}{\mathrm{initial}.Math..Math.\mathrm{mass}.Math..Math..Math.\mathrm{in}.Math..Math.g}$

[0148] N=normality of the titrant

[0149] f=factor of the titrant

[0150] The factor f here takes account where appropriate of any deviation in the titrant used from a normality of 0.1 N.

Inorganic Thickeners (a1)

[0151] Inorganic thickeners used were two different kinds of commercially available fumed silica (available from Evonik Industries) which differ in their BET surface area, namely:

[0152] (a1.1)=Aerosil 200 (BET 200) and

[0153] (a1.2)=Aerosil 380 (BET 380).

[0154] Also used were three different modified phyllosilicate mixtures, available commercially from Byk Chemie GmbH under the brand name Garamite, namely:

[0155] (a1.3)=Garamite 7305 (mixture of different bentonites, modified with quaternary ammonium compounds)

[0156] (a1.4)=Garamite 1210 (mixture of different bentonites, modified with quaternary ammonium compounds)

[0157] (a1.5)=Garamite 1958 (mixture of different bentonites, modified with quaternary ammonium compounds)

Wetting and Dispersing Agents (a2)

Preparation of (a2.1)

Precursor A

[0158] 30 g of Epomin SP-018 (from Nippon Shokubai) are heated to 80 C. Over a period of two hours, 70 g of 2-ethylhexyl acrylate are added dropwise, after which reaction is allowed to continue for six hours.

Precursor B

[0159] 92% of polyether (butanol-started EO/PO polyether (about 1:1), Mw about 1100 Da) is heated to 60 C. 7.6 g of polyphosphoric acid are slowly added dropwise. The reaction mixture is stirred for six hours until there is no further rise in the acid number (acid number as per DIN EN ISO 2114) in the flask.

Synthesis of the Compound from Precursors A and B

[0160] 20 g of precursor A are introduced at 60 C. and 80 g of precursor B are metered in slowly over a period of two hours. The reaction mixture is stirred at 60 C. for five hours.

[0161] The product obtained has an active substance content of 100%.

Preparation of (a2.2)

[0162] A reaction vessel was charged with 205 g of tetrahydrofuran, and 0.11 ml of 1M tetrabutylammonium 3-chlorobenzoate in acetonitrile and 1.94 g of 1-methoxy-1-trimethylsiloxy-2-methylpropane are added. The reaction vessel was cooled to 10 C. In parallel to an addition over 40 minutes of a mixture consisting of 39.6 g of 2-ethylhexyl methacrylate, 20 g of methyl methacrylate and 2.84 g of butyl methacrylate, a dilution of 0.22 ml of 1M tetrabutylammonium 3-chlorobenzoate in acetonitrile in 5 ml of tetrahydrofuran was added over a period of one hour. At no point did the reaction temperature exceed the temperature of 25 C.

[0163] Then 20.9 g of N,N-dimethylaminoethyl methacrylate were added dropwise over a period of 10 minutes, and in parallel a further 0.11 ml of 1M tetrabutylammonium 3-chlorobenzoate in acetonitrile was metered in over a period of 10 minutes. After a further three hours of stirring at a temperature (23 C.), 5 ml of methanol were added. Following addition of 6.7 g of benzyl chloride, stirring is carried out at 60 C. for a further six hours.

[0164] Methoxypropyl acetate is then added to the product, and the tetrahydrofuran present is removed by distillation, and the fraction of nonvolatiles (2.00.1 g test substance, duplicate determination, 10 minutes, 150 C.; EN ISO 3251) is adjusted to 40%.

Preparation of (a2.3)

Precursor A

[0165] 100 g of dimethylolpropionic acid (from Perstorp), 255.26 g of -caprolactone and 74.64 g of -valerolactone were admixed with dibutyltin dilaurate (200 ppm) and stirred under inert gas at 170 C. until the fraction of nonvolatiles (2.00.1 g test substance, duplicate determination, 10 minutes, 150 C.; EN ISO 3251) exceeded a figure of 98%.

Precursor B

[0166] 435 g of Desmodur T100 (from Bayer) are introduced under nitrogen and 1100 g of the dry (Karl Fischer water content <0.1%) polyether (butanol-started PO polyether, Mw about 1100 Da) are added slowly dropwise such that the reaction temperature does not exceed 60 C. After the end of the addition, stirring is continued at 60 C. until the NCO number of the product shows no significant change over a period of 30 minutes.

[0167] Then the remaining excess of Desmodur T100 is removed by distillation using a thin-film or short-path evaporator.

Synthesis of the Compound from Precursors A and B

[0168] 1.2 g of Epomin SP200 (from Nippon Shokubai) are heated together with 59.0 g of precursor A to 180 C. under nitrogen. The batch was stirred at this temperature until the acid number (AN as per DIN 53402) reached a figure of 8.4 mg KOH/g substance. During the reaction, the water of reaction formed was distilled off at the reaction temperature selected and was collected in a water separator. Then the hydroxyl number (as per DIN/ISO 4629) of the resulting product was determined, and 50% of the hydroxyl groups were reacted at a temperature at 60 C. by addition of precursor B and four-hour stirring under nitrogen.

[0169] The product is obtained as a brown oil of high viscosity, the active substance concentration being 100%.

Preparation of (a2.4)

Precursor A

[0170] 100 g of dimethylolpropionic acid (from Perstorp), 255.26 g of -caprolactone and 74.64 g of -valerolactone were admixed with dibutyltin dilaurate (200 ppm) and stirred under inert gas at 170 C. until the fraction of nonvolatiles (2.00.1 g test substance, duplicate determination, 10 minutes, 150 C.; EN ISO 3251) exceeded a figure of 98%.

Precursor B

[0171] 435 g of Desmodur T100 (from Bayer) are introduced under nitrogen and 1100 g of the dry (Karl Fischer water content <0.1%) polyether (butanol-started PO polyether, Mw about 1100 Da) are added slowly dropwise such that the reaction temperature does not exceed 60 C. After the end of the addition, stirring is continued at 60 C. until the NCO number of the product shows no significant change over a period of 30 minutes.

[0172] Then the remaining excess of Desmodur T100 is removed by distillation using a thin-film or short-path evaporator.

Synthesis of the Compound from Precursors A and B

[0173] 1.2 g of Epomin SP200 (from Nippon Shokubai) are heated together with 59.0 g of precursor A to 180 C. under nitrogen. The batch was stirred at this temperature until the acid number (AN as per DIN 53402) reached a figure of 7.8 mg KOH/g substance. During the reaction, the water of reaction formed was distilled off at the reaction temperature selected and was collected in a water separator. Then the hydroxyl number (as per DIN/ISO 4629) of the resulting product was determined, and 50% of the hydroxyl groups were reacted at a temperature at 60 C. by addition of precursor B and four-hour stirring under nitrogen.

[0174] The resulting product is subsequently diluted for further use to 80% in methoxypropyl acetate.

Preparation of (a2.5)

Precursor A

[0175] 134 g of dimethylolpropionic acid (from Perstorp), 342 g of -caprolactone and 100 g of -valerolactone were admixed with dibutyltin dilaurate (200 ppm) and stirred under inert gas at 170 C. until the fraction of nonvolatiles (2.00.1 g test substance, duplicate determination, 10 minutes, 150 C.; EN ISO 3251) exceeded a figure of 98%.

Precursor B

[0176] 435 g of Desmodur T100 (from Bayer) are introduced under nitrogen and 1100 g of the dry (Karl Fischer water content <0.1%) polyether (butanol-started PO polyether, Mw about 1100 Da) are added slowly dropwise such that the reaction temperature does not exceed 60 C. After the end of the addition, stirring is continued at 60 C. until the NCO number of the product shows no significant change over a period of 30 minutes.

[0177] Then the remaining excess of Desmodur T100 is removed by distillation using a thin-film or short-path evaporator.

Synthesis of the Compound from Precursors A and B

[0178] 10 g of Epomin SP006 (from Nippon Shokubai) are heated together with 550 g of precursor A to 180 C. under nitrogen. The batch was stirred at this temperature until the acid number (AN as per DIN 53402) reached a figure of 10.3 mg KOH/g substance. During the reaction, the water of reaction formed was distilled off at the reaction temperature selected and was collected in a water separator. Then the hydroxyl number (as per DIN/ISO 4629) of the resulting product was determined, and 50% of the hydroxyl groups were reacted at a temperature at 60 C. by addition of precursor B and four-hour stirring under nitrogen.

[0179] The resulting product is subsequently diluted for further use to 80% in benzyl alcohol.

Preparation of (a2.6)

[0180] 250 g of polyether (methanol-started EO polyether, Mw about 500 Da) are admixed with 181 g of -caprolactone and heated to 80 C. Then 1000 ppm of toluenesulfonic acid are added. The reaction mixture is stirred until the fraction of nonvolatiles (2.00.1 g test substance, duplicate determination, 10 minutes, 150 C.; EN ISO 3251) exceeds a figure of 98%. then 650 ppm of dibutylethanolamine are added and the reaction mixture is stirred for 10 minutes more.

[0181] 51 g of polyphosphoric acid are metered in. The reaction mixture is stirred for three hours until the acid number (acid number as per DIN EN ISO 2114) in the flask shows no further increase. Then 5 g of water, 900 g of methoxypropyl acetate and 19 g of magnesium oxide are added and the reaction mixture is homogenized at 100 C. for an hour. Excess water is removed under reduced pressure until the Karl-Fischer water content (as per DIN 51777) reaches a figure <0.2%.

[0182] The active substance content is subsequently adjusted to a level of 40%, by determination of the fraction of nonvolatiles (2.00.1 g test substance, duplicate determination, 10 minutes, 150 C.; EN ISO 3251).

Preparation of (a2.7)

[0183] 30 g of Epomin SP-018 (from Nippon Shokubai) are heated to 80 C. Over a period of two hours, 70 g of 2-ethylhexyl acrylate are added dropwise, after which reaction is allowed to continue for six hours.

[0184] The resulting product has an active substance concentration of 100%.

Preparation of (a2.8)

[0185] 65 g of synthetic resin SMA 2000 (styrene-maleic anhydride copolymer, 187 mmol of anhydride groups, from Cray Valley) are diluted in 100 g of methoxypropyl acetate and admixed slowly with a mixture of 105 g of Jeffamin M2070 (amine-terminated EO/PO polyether, from Huntsman) and 10.2 g of N,N-dimethylaminopropylamine and heated at 170 C. for four hours. During this time the methoxypropyl acetate present is removed by distillation. Then 8.9 g of benzyl chloride are added at 70 C. and the batch is reacted for eight hours.

[0186] The product obtained is admixed with a mixture of methoxypropyl acetate and butyl glycol (ratio 1:1, by weight) until the active substance content is 40%.

Preparation of (a2.9)

[0187] 65 g of synthetic resin SMA 2000 (styrene-maleic anhydride copolymer, 187 mmol of anhydride groups, from Cray Valley) are diluted in 100 g of methoxypropyl acetate and admixed slowly with a mixture of 105 g of Jeffamin M2070 (amine-terminated EO/PO polyether, from Huntsman) and 10.2 g of N,N-dimethylaminopropylamine and heated at 170 C. for four hours. During this time the methoxypropyl acetate present is removed by distillation.

[0188] The product obtained is admixed with a mixture of methoxypropyl acetate and butyl glycol (ratio 1:1, by weight) until the active substance content is 40%.

Preparation of (a2.10)

Precursor A

[0189] A reaction vessel was charged with 205 g of tetrahydrofuran, and 0.11 ml of 1M tetrabutylammonium 3-chlorobenzoate in acetonitrile and 1.94 g of 1-methoxy-1-trimethylsiloxy-2-methylpropane were added. The reaction mixture was cooled to 10 C. In parallel to an addition over 40 minutes of a mixture consisting of 39.6 g of 2-ethylhexyl methacrylate, 20 g of methyl methacrylate and 2.84 g of butyl methacrylate, a dilution of 0.22 ml of 1M tetrabutylammonium 3-chlorobenzoate in acetonitrile in 5 ml of tetrahydrofuran was added over a period of one hour. At no point did the reaction temperature exceed the temperature of 25 C.

[0190] Then 20.9 g of N,N-dimethylaminoethyl methacrylate were added dropwise over a period of 10 minutes, and in parallel a further 0.11 ml of 1M tetrabutylammonium 3-chlorobenzoate in acetonitrile was metered in over a period of 10 minutes.

[0191] After a further three hours of stirring at room temperature (23 C.), 5 ml of methanol were added.

Precursor B

[0192] 87 g of polyether (butanol-started PO polyether, Mw about 700 Da) is heated to 60 C. 13 g of polyphosphoric acid are slowly added dropwise. The reaction mixture is stirred for six hours until there is no further rise in the acid number (acid number as per DIN EN ISO 2114) in the flask.

Synthesis of the Compound from Precursors A and B

[0193] 120 g of precursor A are admixed with 50 g of polyether (methanol-started EO polyether, Mw about 350) and the solvent present is distilled off under reduced pressure. The remaining batch is then heated to 60 C., 14 g of precursor B are added, and the mixture is stirred at this temperature for eight hours.

[0194] The product obtained has an active substance concentration of 50%.

Preparation of (a2.11)

[0195] 15.2 g of alpha-methylstyrene dimer are introduced in 120 g of methoxypropyl acetate and heated to 120 C. 100 g of dimethylaminoethyl methacrylate and 1.5 g of AlBN in solution in 10 g of methoxypropyl acetate are metered in parallel over a period of 60 minutes, after which reaction is allowed to continue for 30 minutes. Then a mixture of 60 g of methyl methacrylate, 20 g of 2-ethylhexyl methacrylate, 50 g of 2-ethylhexyl acrylate and 230 g of butyl acrylate is metered in parallel to a solution of 37.2 g of AlBN in 240 g of methoxypropyl acetate over a period of 150 minutes, after which reaction is allowed to continue for 30 minutes.

[0196] Then 100 g of dimethylaminoethyl methacrylate and, in parallel, 1.2 g of AlBN in solution in 10 g of methoxypropyl acetate are metered in over a period of 60 minutes, after which reaction is allowed to continue for 30 minutes.

[0197] After a further addition of 0.4 g of AlBN in solution in 5 g of methoxypropyl acetate, over a period of 15 minutes, reaction is allowed to continue for 60 minutes.

[0198] The product obtained has an active substance content of 60%.

Preparation of (a2.12)

Precursor A

[0199] 15 g of tall oil fatty acid (acid number: 186 mg KOH/g substance) and 10 g of polyethylene glycol 200 are heated together slowly at 200 C. until water which forms can no longer be collected. Reduced pressure (beginning at atmospheric pressure, slow reduction to 60 mbar) is applied for 2 hours. Then 4 g of maleic anhydride are added. Reaction is allowed to take place for an hour at 200 C.

Precursor B

[0200] 17 g of tall oil fatty acid (acid number: 186 mg KOH/g substance) and 3.0 g of diethylenetriamine are combined and heated at 170 C. for four hours. Water of reaction produced is removed by distillation, followed by stirring under reduced pressure (60 mbar) for a further two hours.

[0201] Then 2 g of water are added and the mixture is stirred at 95 C. for 30 minutes until the tertiary nitrogen content (see description of method) is no longer detectable. Then again reduced pressure (60 mbar) is applied and excess water is removed by distillation until the Karl-Fischer water content (as per DIN 51777) reaches a figure <0.4%.

Synthesis of the Compound from Precursors A and B

[0202] 25 g of precursor A and 20 g of precursor B are stirred homogeneously together with 45 g of Isopar G (hydrogenated C10-C12 isoalkanes, <2% aromatic content) at 80 C. for an hour.

[0203] The product obtained has an active substance content of 50%.

Preparation of (a2.13)

Precursor A

[0204] 88 g of Lutensol A011 (fatty alcohol-started EO polyether from BASF SE) are admixed with 0.05 g of potassium carbonate and heated to 100 C. Subsequently, 12 g of maleic anhydride are added and the mixture is stirred at this temperature for three hours.

Precursor B

[0205] 270 g of methoxypropyl acetate and 18 g of alpha-methylstyrene are heated to 120 C. In parallel, 300 g of butyl methacrylate and a solution of 7.2 g of AlBN in 40.8 g of methoxypropyl acetate are metered in over a period of two hours. After further reaction for a period of 30 minutes, in parallel, 163 g of N,N-dimethylaminoethyl methacrylate and a solution of 1.43 g of AlBN in 8.2 g of methoxypropyl acetate are metered in over a period of one hour. After further reaction for a period of 30 minutes, a solution of 1.4 g of AlBN in 8 g of methoxypropyl acetate is metered in over a period of 15 minutes and the mixture is stirred for a further hour.

Synthesis of the Compound from Precursors A and B

[0206] 40 g of precursor B, 20 g of precursor A and 13.3 g of methoxypropyl acetate are stirred together at 120 C. for five hours.

[0207] The product obtained has an active substance content of 60%.

Preparation of (a2.14)

Precursor A

[0208] 100 g of dimethylolpropionic acid (from Perstorp), 255.26 g of -caprolactone and 74.64 g of -valerolactone were admixed with dibutyltin dilaurate (200 ppm) and stirred under inert gas at 170 C. until the fraction of nonvolatiles (2.00.1 g test substance, duplicate determination, 10 minutes, 150 C.; EN ISO 3251) exceeded a figure of 98%.

Precursor B

[0209] 435 g of Desmodur T100 (from Bayer) are introduced under nitrogen and 1100 g of the dry (Karl Fischer water content <0.1%) polyether (butanol-started PO polyether, Mw about 1100 Da) are added slowly dropwise such that the reaction temperature does not exceed 60 C. After the end of the addition, stirring is continued at 60 C. until the NCO number of the product shows no significant change over a period of 30 minutes.

[0210] Then the remaining excess of Desmodur T100 is removed by distillation using a thin-film or short-path evaporator.

Synthesis of the Compound from Precursors A and B

[0211] 1.2 g of Epomin SP200 (from Nippon Shokubai) are heated together with 59.0 g of precursor A to 180 C. under nitrogen. The batch was stirred at this temperature until the acid number (AN as per DIN 53402) reached a figure of 9.6 mg KOH/g substance. During the reaction, the water of reaction formed was distilled off at the reaction temperature selected and was collected in a water separator. Then the hydroxyl number (as per DIN/ISO 4629) of the resulting product was determined, and 50% of the hydroxyl groups were reacted at a temperature at 60 C. by addition of precursor B and four-hour stirring under nitrogen. The resulting product is subsequently diluted for further use to 80% in benzyl alcohol.

Component (b1)

Preparation of (b1.1)

[0212] 881 g of a mixture of polymerized fatty acids having a trimerized fatty acid fraction of >75 wt %, based in each case on the total weight of the mixture, with an acid number of 191 mg KOH/g substance (Pripol 1040, from Croda) are admixed with 438 g of triethylenetetramine (CAS No.: 112-24-3) and 400 ml of solvent naphtha (aromatic hydrocarbon fraction, boiling range of 150 C. to 210 C.) and heated to 150 C. until the stream of distillate which occurs subsides significantly. This is followed by heating at 190 C. for 6 hours and application at reduced pressure (about 500 mbar) until a total of 108 g of water have separated out.

[0213] The resulting product is admixed with benzyl alcohol until the nonvolatiles fraction obtained (2.00.1 g test substance, duplicate determination, 20 minutes, 150 C.; EN ISO 3251) is 70-75 wt %.

Preparation of (b1.2)

[0214] 400 g of Lupasol P (polyethyleneimine from BASF SE, 50% form) are admixed with 600 g of benzyl alcohol and then freed from the water by distillation at 100 C. under reduced pressure (slow reduction of the pressure from atmospheric pressure to 30 mbar) until distillate is no longer obtained. Then, under an inert gas atmosphere, 200 g of tall oil fatty acid (acid number: 186 mg KOH/g substance) are added and the batch is reacted at 140 C. for three hours.

[0215] A pale yellow product having an active substance content of 40% is obtained.

Preparation of (b1.3)

[0216] According to patent specification DE3706860A1, example 8 referred to therein is synthesized. In deviation from the protocol there, dilution takes place not to 50% in cyclohexanone but instead to 50% in solvent naphtha (aromatic hydrocarbon fraction, boiling range of 150 C. to 210 C.)

Preparation of (b1.4)

[0217] 800 g of Lupasol P (polyethyleneimine from BASF SE, 50% form) are admixed with 400 g of benzyl alcohol and then freed from the water by distillation at 100 C. under reduced pressure (slow reduction of the pressure from atmospheric pressure to 30 mbar) until distillate is no longer obtained. Then, under an inert gas atmosphere, 200 g of tall oil fatty acid (acid number: 186 mg KOH/g substance) are added and the batch is reacted at 140 C. for three hours.

[0218] A pale yellow product having an active substance content of 60% is obtained.

Preparation of (b1.5)

[0219] 600 g of Lupasol P (polyethyleneimine from BASF SE, 50% form) are admixed with 300 g of benzyl alcohol and then freed from the water by distillation at 100 C. under reduced pressure (slow reduction of the pressure from atmospheric pressure to 30 mbar) until distillate is no longer obtained. Then, under an inert gas atmosphere, 120 g of tall oil fatty acid (acid number: 186 mg KOH/g substance) are added and the batch is reacted at 140 C. for three hours.

[0220] A pale yellow product having an active substance content of 58% is obtained.

Components (b1.x) Below are Available Commercially:

Component (b1.6)

[0221] Lupasol P, polyethyleneimine from BASF SE, Mw about 750 000 Da (active substance content: 50 wt %)

Component (b1.7)

[0222] Tween 20, polyoxyethylene(20)-sorbitan monolaurate

Component (b1.8)

[0223] Triethylenetetramine

Component (b1.9)

[0224] Isophoronediamine, isomer mixture

Component (b1.10)

[0225] Diglycolamine

Component (b1.11)

[0226] Jeffamine T-403, polyetheramine from Huntsman

USE EXAMPLES

[0227] Described below is the production of inventive two-component systems obtained from in each case two base components by mixingas indicated below. Unless indicated otherwise, not only the commercial products but also the inorganic thickeners (a1.x), the wetting and dispersing agents (a2.x), and the components (b1.x) are used in the form of the commercial product or synthesis product. The quantities (in g) therefore relate to the respective commercial and synthesis products, including any solvents present and/or including any auxiliaries present as a result of the production process and not removed.

List of Commercial Products Used in the Use Examples

[0228] Setathane D 1150: solvent-free, liquid, branched polyol based on castor oil, from Nuplex. [0229] Setathane D 1145: solvent-free, liquid, branched polyol based on castor oil, from Nuplex. [0230] Desmodur VL: aromatic polyisocyanate based on diphenylmethanediisocyanate, from Bayer. [0231] BYK-088: silicone- and polymer-containing deaerating agent from BYK-Chemie GmbH. [0232] Bayferrox 318M: micronized black iron oxide pigment from Lanxess Deutschland GmbH. [0233] MOLSIV: UOP L paste, preparation of 50% castor oil and 50% L powder, from UOP CH Sarl. [0234] EWO: heavy spar from Sachtleben Chemie GmbH.

Polyol-Polyisocyanate Systems

[0235] Described below is the production of inventive two-component polyurethane systems obtained from in each case two base components by mixingas indicated below.

Preparation of Respective Base Components SK.UA, SK.UC and SK.UE

[0236] The individual constituents of the base components SK.UA, SK.UC and SK.UE are added successively in the quantities indicated in tables 1 to 10 with stirring at room temperature (23 C.) using the Pendraulik TD 100 dissolver with a toothed disk at 2 m/s and then stirred for homogenization for 1 minute at 5 m/s, 1 minute at m/s, and 1 minute at 15 m/s. The viscosity of these systems is subsequently measured at room temperature (23 C.)

Preparation of Base Component SK.UG

[0237] Sedathane D1150, MOLSIV and BYK-088 are mixed in the quantities stated in table 11 with stirring at room temperature (23 C.) using the Pendraulik TD 100 dissolver with a toothed disk of 5 m/s for one minute. Then EWO is added and mixing is continued for 2 minutes at 5 m/s. Thereafter the Garamite 7305 is added and the mixture is stirred for 1 minute at 5 m/s, 1 minute at m/s, and 1 minute at 15 m/s. The viscosity of these systems is subsequently measured at room temperature (23 C.)

Preparation of the Intermediates by Combination of Base Components SK.UA and SK.UB, SK.UC and SK.UD, SK.UE and SK.UF, and SK.UG and SK.UH

[0238] The two base components SK.A and SK.B (or SK.C and SK.D; SK.E and SK.F; and SK.G and SK.H) are combined and homogenized with the Pendraulik TD 100 dissolver with a toothed disk at 5 m/s for 1 minute. Viscosity is measured after 2 minutes.

TABLE-US-00003 TABLE 1 (quantities in g) Comp. ex. Comp. ex. Comp. ex. VU1 VU2 VU3 Constituents SK.UA SK.UB SK.UA SK.UB SK.UA SK.UB Setathane D 94.5 94.5 94.5 1150 BYK-088 0.5 0.5 0.5 (a1.1) 6.0 6.0 6.0 (a2.11) 0.0 0.0 2.4 Desmodur VL 37.0 37.0 37.0 (b1.3) 0.0 1.2 1.2

TABLE-US-00004 TABLE 2 (quantities in g) Ex. U1 Ex. U2 Ex. U3 Ex. U4 Ex. U5 Ex. U6 SK. SK. SK. SK. SK. SK. SK. SK. SK. SK. SK. SK. Constituents UA UB UA UB UA UB UA UB UA UB UA UB Setathane D 94.5 94.5 94.5 94.5 94.5 94.5 1150 BYK-088 0.5 0.5 0.5 0.5 0.5 0.5 (a1.1) 6.0 6.0 6.0 6.0 6.0 6.0 (a2.x) 2.4.sup.1 2.4.sup.1 2.4.sup.2 2.4.sup.2 3.6.sup.3 3.6.sup.3 Desmodur VL 37.0 37.0 37.0 37.0 37.0 37.0 (b1.x) 1.2* 1.2** 1.2* 1.2** 1.2* 1.2** .sup.1= (a2.11); .sup.2= (a2.1); .sup.3= (a2.13); *= (b1.1); **=(b1.2)

TABLE-US-00005 TABLE 3 (quantities in g) Ex. U7 Ex U8 Ex. U9 Ex. U10 Constituents SK. UA SK. UB SK. UA SK. UB SK. UA SK. UB SK. UA SK. UB Setathane D 94.5 94.5 94.5 94.5 1150 BYK-088 0.5 0.5 0.5 0.5 (a1.1) 6.0 6.0 6.0 6.0 (a2.11) 2.4 2.4 2.4 2.4 Desmodur VL 37.0 37.0 37.0 37.0 (b1.x) 1.2* 1.2** 1.2*** 1.2**** *= (b1.11); **= (b1.8); ***= (b1.9); ****= (b1.10)

TABLE-US-00006 TABLE 4 (quantities in g) Ex. U11 Ex. U12 Ex.U13 SK. SK. SK. SK. SK. SK. Constituents UA UB UA UB UA UB Setathane D 94.5 94.5 94.5 1150 BYK-088 0.5 0.5 0.5 (a1.1) 6.0 6.0 6.0 (a2.1) 2.4 2.4 2.4 Desmodur VL 37.0 37.0 37.0 (b1.x) 1.2* 1.2** 1.2*** *= (b1.11); **= (b1.8); ***= (b1.9)

TABLE-US-00007 TABLE 5 (quantities in g) Ex. U14 Ex. U15 Ex. U16 Ex. U17 Constituents SK.UA SK.UB SK.UA SK.UB SK.UA SK.UB SK.UA SK.UB Setathane D 94.5 94.5 94.5 94.5 1150 BYK-088 0.5 0.5 0.5 0.5 (a1.1) 6.0 6.0 6.0 6.0 (a2.13) 3.6 3.6 3.6 3.6 Desmodur VL 37.0 37.0 37.0 37.0 (b1.x) 1.2* 1.2** 1.2*** 1.2**** *= (b1.11); **= (b1.8); ***= (b1.9); ****= (b1.10)

TABLE-US-00008 TABLE 6 (quantities in g) Ex. U18 Ex. U19 Ex. U20 Ex. U21 Ex. U22 Ex. U23 SK. SK. SK. SK. SK. SK. SK. SK. SK. SK. SK. SK. Constituents UC UD UC UD UC UD UC UD UC UD UC UD Setathane D 94.5 94.5 94.5 94.5 94.5 94.5 1150 BYK-088 0.5 0.5 0.5 0.5 0.5 0.5 (a1.2) 5.0 5.0 5.0 5.0 5.0 5.0 (a2.x) 3.0.sup.1 3.0.sup.1 3.0.sup.2 3.0.sup.2 5.0.sup.3 5.0.sup.3 Desmodur VL 37.0 37.0 37.0 37.0 37.0 37.0 (b1.x) 1.0* 1.0** 1.0* 1.0** 1.0* 1.0** .sup.1= (a2.11); .sup.2= (a2.1); .sup.3= (a2.13); *= (b1.l); **= (b1.2)

TABLE-US-00009 TABLE 7 (quantities in g) Ex. U24 Ex. U25 Ex. U26 Ex. U27 Ex. U28 SK. SK. SK. SK. SK. SK. SK. SK. SK. SK. Constituents UC UD UC UD UC UD UC UD UC UD Setathane D 94.5 94.5 94.5 94.5 94.5 1150 BYK-088 0.5 0.5 0.5 0.5 0.5 (a1.2) 5.0 5.0 5.0 5.0 5.0 (a2.11) 3.0 3.0 3.0 3.0 3.0 Desmodur VL 37.0 37.0 37.0 37.0 37.0 (b1.x) 1.0* 0.5** 1.0** 1.0*** 1**** *= (b1.11); **= (b1.8); ***= (b1.9); ****= (b1.10)

TABLE-US-00010 TABLE 8 (quantities in g) Ex. U29 Ex. U30 Ex. U31 Ex. U32 Constituents SK.UC SK.UD SK.UC SK.UD SK.UC SK.UD SK.UC SK.UD Setathane D 94.5 94.5 94.5 94.5 1150 BYK-088 0.5 0.5 0.5 0.5 (a1.2) 5.0 5.0 5.0 5.0 (a2.1) 2.0 2.0 2.0 2.0 Desmodur VL 37.0 37.0 37.0 37.0 (b1.x) 0.5* 1.0* 1.0** 1.0*** *= (b1.8); **= (b1.9); ***= (b1.10)

TABLE-US-00011 TABLE 9 (quantities in g) Ex. U33 Ex. U34 Ex. U35 Constituents SK.UC SK.UD SK.UC SK.UD SK.UC SK.UD Setathane D 94.5 94.5 94.5 1150 BYK-088 0.5 0.5 0.5 (a1.2) 5.0 5.0 5.0 (a2.13) 5.0 5.0 5.0 Desmodur VL 37.0 37.0 37.0 (b1.x) 1.0* 0.5** 1.0*** *= (b1.11); **= (b1.8); ***= (b1.9)

TABLE-US-00012 TABLE 10 (quantities in g) Ex. U36 Ex. U37 Ex. U38 Ex. U39 Ex. U40 Ex. U41 SK. SK. SK. SK. SK. SK. SK. SK. SK. SK. SK. SK. Constituents UE UF UE UF UE UF UE UF UE UF UE UF Setathane D 13.5 13.5 13.5 13.5 13.5 13.5 1150 Setathane D 16.0 16.0 16.0 16.0 16.0 16.0 1145 BYK-088 0.5 0.5 0.5 0.5 0.5 0.5 EWO 38.5 38.5 38.5 38.5 38.5 38.5 MOLSIV 7.4 7.4 7.4 7.4 7.4 7.4 Bayferrox 5.0 5.0 5.0 5.0 5.0 5.0 318M-paste (50% strength in Setathane D 1150) (a1.1) 2.0 2.0 2.0 2.0 2.0 2.0 (a2.x) 0.8.sup.1 0.8.sup.1 0.4.sup.2 0.4.sup.2 0.4.sup.2 0.4.sup.2 Desmodur VL 17.1 17.1 17.1 17.1 17.1 17.1 (b1.x) 0.4* 0.8* 0.4* 0.8* 0.2** 0.4** .sup.1= (a2.11); .sup.2= (a2.1); *= (b1.1); **= (b1.2)

TABLE-US-00013 TABLE 11 (quantities in g) Ex. U42 Ex. U43 Ex. U44 Constituents SK.UG SK.UH SK.UG SK.UH SK.UG SK.UH Setathane D 54.0 54.0 54.0 1150 MOLSIV 6.0 6.0 6.0 BYK-088 1.0 1.0 1.0 EWO 37.5 37.5 37.5 (a1.3) 1.5 1.5 1.5 (a2.x) 0.9.sup.1 0.9.sup.2 0.9.sup.3 Desmodur VL 37.0 37.0 37.0 (b1.x) 0.3* 0.3* 0.3* .sup.1= (a2.11); .sup.2= (a2.9); .sup.3= (a2.13); *= (b1.1)

TABLE-US-00014 TABLE 12 Viscosity* SK.UA Viscosity Viscosity Comp. without Viscosity* loss Viscosity* Viscosity* increase.sup.1 ex. (a2.x) SK.UA in % SK.UB SK.UA + SK.UB in % VU1 56.8 ./. ./. 0.09 12.5 ./. VU2 56.8 ./. ./. 0.09 292.8 ./. VU3 56.8 18.3 68 0.09 7.9 Viscosity* SK.UA Viscosity Viscosity without Viscosity* loss Viscosity* Viscosity* increase.sup.1 Ex. (a2.x) SK.UA in % SK.UB SK.UA + SK.UB in % U1 56.8 18.3 68 0.09 493.1 2595 U2 56.8 18.3 68 0.09 285.6 1461 U3 56.8 6.2 89 0.09 302.9 4785 U4 56.8 6.2 89 0.09 188.4 2939 U5 56.8 19.0 67 0.09 90.8 378 U6 56.8 19.0 67 0.09 241.2 1169 U7 56.8 18.3 68 0.09 113.9 522 U8 56.8 18.3 68 0.09 650.2 3453 U9 56.8 18.3 68 0.09 130.7 614 U10 56.8 18.3 68 0.09 205.1 1021 U11 56.8 6.2 89 0.09 43.9 608 U12 56.8 6.2 89 0.09 716.1 11 450 U13 56.8 6.2 89 0.09 71.4 1051 U14 56.8 19.0 67 0.09 31.0 63 U15 56.8 19.0 67 0.09 777.0 3989 U16 56.8 19.0 67 0.09 53.8 183 U17 56.8 19.0 67 0.09 143.6 656 Viscosity* SK.UC Viscosity Viscosity without Viscosity* loss Viscosity* Viscosity* increase.sup.2 Ex. (a2.x) SK.UC in % SK.UD SK.UC + SK.UD in % U18 65.8 11.8 82 0.09 238.7 1923 U19 65.8 11.8 82 0.09 338.4 2768 U20 65.8 11.4 83 0.09 60.1 427 U21 65.8 11.4 83 0.09 14.9 31 U22 65.8 6.1 91 0.09 70.7 1059 U23 65.8 6.1 91 0.09 13.4 120 U24 65.8 11.8 82 0.09 98.3 733 U25 65.8 11.8 82 0.09 168.1 1325 U26 65.8 11.8 82 0.09 427.5 3523 U27 65.8 11.8 82 0.09 646.8 5381 U28 65.8 11.8 82 0.09 716.3 5970 U29 65.8 11.4 83 0.09 19.0 67 U30 65.8 11.4 83 0.09 243.7 2038 U31 65.8 11.4 83 0.09 65.7 476 U32 65.8 11.4 83 0.09 37.3 227 U33 65.8 6.1 91 0.09 17.1 180 U34 65.8 6.1 91 0.09 25.7 321 U35 65.8 6.1 91 0.09 28.1 361 Viscosity* SK.UE Viscosity Viscosity without Viscosity* loss Viscosity* Viscosity* increase.sup.3 Ex. (a2.x) SK.UE in % SK.UF SK.UE + SK.UF in % U36 227 135.9 40 0.09 583.0 329 U37 227 135.9 40 0.09 869.0 539 U38 227 45.1 80 0.09 850.1 1785 U39 227 45.1 80 0.09 7215.0 15 898 U40 227 45.1 80 0.09 246.0 445 U41 227 45.1 80 0.09 768.2 1603 Viscosity* SK.UG Viscosity Viscosity without Viscosity* loss Viscosity* Viscosity* increase.sup.4 Ex. (a2.x) SK.UG in % SK.UH SK.UG + SK.UH in % U42** 9.7 9.0 7 0.09 11.9 32 U43** 9.7 9.3 4 0.09 12.2 131 U44** 9.7 8.4 13.4 0.09 12.5 49 *in pascal-seconds; **variant: viscosity determined with a Brookfield viscometer at 23 C. with spindle 3 at a shear rate of 5 rpm; .sup.1relative to SK.UA; .sup.2relative to SK.UC; .sup.3relative to SK.UE; .sup.4relative to SK.UG

[0239] In comparative example VU1, the base components SK.UA and SK.UB were prepared without the compounds (a2) and (b1). It is found that the viscosity of the thixotroped base component SK.UA is very high and the viscosity when the curing agent (base component SK.B) is added to the resin collapses considerably.

[0240] In comparative example VU2, the base component SK.UA was prepared without wetting and dispersing agent (a2), and base component SK.UB was prepared with 1.2 g of the polymer (b1) (here: (b1.3)). It is found that the viscosity of the base component SK.UA is very high and the addition of the polymer (b1) not only prevents the collapse of the viscosity of the mixture of base components SK.A and SK.B as in comparative example VU1, but rather the viscosity of this mixture is very high.

[0241] In comparative example VU3, the base component SK.UA was prepared with the wetting and dispersing agent (a2) (here: (a2.11)) and the base component SK.UB was prepared with 1.2 g of the polymer (b1) (here: (b1.3)). It is found that, despite the addition of a compound (b1), structural buildup of the silica no longer takes place, which means that the viscosity of the mixture of base components SK.A and SK.B remains low.

[0242] In the inventive examples U1 to U44, different two-component systems were prepared from the constituents listed in tables 2 to 11, in the quantities indicated in the tables in each case.

[0243] As a result of the use of the respective wetting and dispersing agents (a2.x), the viscosity of the thixotroped base component SK.UA and SK.E is significantly lower than in the case of the respective base component without the respective wetting and dispersing agent (a2.x). The addition of the wetting and dispersing agent to base components SK.A, SK.C and SK.E leads to a reduction in viscosity (loss of viscosity) of from 4% (example U43) up to 91% (examples U22, U23, U33, U34, and U35). The base components (curing agent components) SK.UB, SK.UD and SK.UF, which are not thixotroped but contain the polymer (b1.x), have low viscosities before being mixed with the respectively complementary base components SK.A, SK.C, and SK.E. In view of the low initial viscosities of the base components supplemented with the modules A or B, respectively, they have good processing qualities and in particular can be mixed readily and homogeneously. The viscosities of the two-component systems, as obtained two minutes after mixing of the mutually corresponding base components, far exceed the viscosities of the base components SK.A, SK.C, and SK.E that have been supplemented with module A. The corresponding increase in viscosity of the base components SK.B, SK.D and SK.F that have been supplemented with module B is from 31% (example U21) up to more than 15000% (example U39).

(a1.x)(a2.x)-(b1.x) Combinations without Polyol-Polyisocyanate Constituents

[0244] Described below is a simple preliminary test for selecting (a1.x) (a2.x)-(b1.x) combinations having potential suitability. For this test (a1.x) and (a2.x) are introduced in a solvent and then (b1.x) is incorporated in pure form or in solution. The thickening effect is ascertained from the increase in viscosity.

Preparation of the Binder-Free Test Systems

[0245] The solvent (PMA=methoxypropyl acetate, benzyl alcohol, styrene or water) and the inorganic thickeners (a1.x) (for amounts see tables) are mixed with the Pendraulik TD 100 dissolver with a toothed disk at 2 m/s and then homogenized by stirring for a further 1 minute at 5 m/s, 1 minute at 10 m/s, and 1 minute at m/s. Subsequently the wetting and dispersing agent (a2.x) (for amounts see tables) is added and homogenization takes place for 1 minute at 10 m/s. After cooling to room temperature (23 C.), a measurement is made of the viscosity of the system SK.MA, SK.MC, SK.ME, SK.MG and SK.MI, respectively. Thereafter the components SK.MB, SK.MD, SK.MF, SK.MH and SK.MJ, respectively, comprising component (b1.x), are added. This is followed by homogenization for 1 minute at 5 m/s and by measurement of the viscosity after 2 minutes (viscosity after incorporation of (b1.x)).

TABLE-US-00015 TABLE 13 (quantity figures in g) Comp. ex. M1 Comp. ex. M2 Constituents SK.MA SK.MB SK.MA SK.MB PMA 90.0 90.0 (a1.1) 10.0 10.0 (a2.x) 0.0 0.0 Benzyl alcohol 0.0 0.0 (b1.1) 0.0 2.0

TABLE-US-00016 TABLE 14 (quantity FIGURES in g) Ex. M1 Ex. M2 Ex. M3 Ex. M4 Ex. M5 SK. SK. SK. SK. SK. SK. SK. SK. SK. SK. Constituents MA MB MA MB MA MB MA MB MA MB PMA 90.0 90.0 90.0 90.0 90.0 (a1.1) 10.0 10.0 10.0 10.0 10.0 (a2.x) 5.0.sup.1 5.0.sup.1 5.0.sup.2 5.0.sup.2 5.0.sup.2 Benzyl 0.0 0.0 0.0 98.0 98.0 alcohol (b1.x) 2.0* 1.0** 1.0*** 2.0* 2.0** .sup.1= (a2.1); .sup.2= (a2.4); *= (b1.1); **= (b1.2); ***= (b1.3)

TABLE-US-00017 TABLE 15 (quantity figures in g) Ex. M6 Ex. M7 Constituents SK.MA SK.MB SK.MA SK.MB PMA 90.0 90.0 (a1.1) 10.0 10.0 (a2.5) 5.0 5.0 Benzyl alcohol 98.0 98.0 (b1.x) 2.0* 2.0** *= (b1.1); **= (b1.2)

TABLE-US-00018 TABLE 16 (quantity FIGURES in g) Ex. M8 Ex. M9 Ex. M10 Constituents SK.MC SK.MD SK.MC SK.MD SK.MC SK.MD PMA 87.0 87.0 87.0 (a1.4) 13.0 13.0 13.0 (a2.1) 5.2 5.2 5.2 (b1.x) 2.6* 1.95** 1.3*** *= (b1.3); **= (b1.1); ***= (b1.2)

TABLE-US-00019 TABLE 17 (quantity FIGURES in g) Ex. M11 Ex. M12 Ex. M13 Constituents SK.MC SK.MD SK.MC SK.MD SK.MC SK.MD PMA 87.0 87.0 87.0 (a1.4) 13.0 13.0 13.0 (a2.4) 5.2 5.2 5.2 (b1.x) 2.6* 1.95** 1.3*** *= (b1.3); **= (b1.1); ***= (b1.2)

TABLE-US-00020 TABLE 18 (quantity FIGURES in g) Ex. M14 Ex. M15 Ex. M16 Constituents SK.MC SK.MD SK.MC SK.MD SK.MC SK.MD PMA 87.0 87.0 87.0 (a1.4) 13.0 13.0 13.0 (a2.9) 5.2 5.2 5.2 (b1.x) 2.6* 1.95** 1.3*** *= (b1.3); **= (b1.1); ***= (b1.2)

TABLE-US-00021 TABLE 19 (quantity FIGURES in g) Ex. M17 Ex. M18 Ex. M19 Constituents SK.ME SK.MF SK.ME SK.MF SK.ME SK.MF PMA 85.0 85.0 85.0 (a1.3) 15.0 15.0 15.0 (a2.1) 6.0 6.0 6.0 (b1.x) 3.0* 2.25** 1.5*** *= (b1.3); **= (b1.1); ***= (b1.2)

TABLE-US-00022 TABLE 20 (quantity FIGURES in g) Ex. M20 Ex. M21 Ex. M22 Constituents SK.ME SK.MF SK.ME SK.MF SK.ME SK.MF PMA 85.0 85.0 85.0 (a1.3) 15.0 15.0 15.0 (a2.3) 6.0 6.0 6.0 Benzyl 0.0 0.0 98.5 alcohol (b1.x) 3.0* 2.25** 1.5*** *= (b1.3); **= (b1.1); ***= (b1.2)

TABLE-US-00023 TABLE 21 (quantity FIGURES in g) Ex. M23 Ex. M24 Ex. M25 Constituents SK.ME SK.MF SK.ME SK.MF SK.ME SK.MF PMA 85.0 85.0 85.0 (a1.3) 15.0 15.0 15.0 (a2.8) 6.0 6.0 6.0 Benzyl 0.0 0.0 98.5 alcohol (b1.x) 3.0* 2.25** 1.5*** *= (b1.3); **= (b1.1); ***= (b1.2)

TABLE-US-00024 TABLE 22 (quantity FIGURES in g) Ex. M26 Ex. M27 Ex. M28 Constituents SK.MG SK.MH SK.MG SK.MH SK.MG SK.MH Styrene 85.0 85.0 85.0 (a1.5) 15.0 15.0 15.0 (a2.12) 6.0 6.0 6.0 (b1.x) 3.0* 3.0** 3.0*** *= (b1.3); **= (b1.7); ***= (b1.10)

TABLE-US-00025 TABLE 23 (quantity FIGURES in g) Ex. M29 Ex. M30 Ex. M31 Constituents SK.MG SK.MH SK.MG SK.MH SK.MG SK.MH Styrene 85.0 85.0 85.0 (a1.5) 15.0 15.0 15.0 (a2.3) 6.0 6.0 6.0 (b1.x) 3.0* 3.0** 3.0*** *= (b1.3); **= (b1.7); ***= (b1.10)

TABLE-US-00026 TABLE 24 (quantity FIGURES in g) Ex. M32 Ex. M33 Ex. M34 Constituents SK.MG SK.MH SK.MG SK.MH SK.MG SK.MH Styrene 85.0 85.0 85.0 (a1.5) 15.0 15.0 15.0 (a2.9) 6.0 6.0 6.0 (b1.x) 3.0* 3.0** 3.0*** *= (b1.3); **= (b1.7); ***= (b1.10)

TABLE-US-00027 TABLE 25 (quantity figures in g) Ex. M35 Ex. M36 Constituents SK.MI SK.MJ SK.MI SK.MJ Water 85.0 85.0 (a1.5) 15.0 15.0 (a2.1) 6.0 6.0 (b1.6) 0.75 3.0

TABLE-US-00028 TABLE 26 Viscosity* SK.MA Viscosity Viscosity Comp. without Viscosity* loss Viscosity* Viscosity* increase.sup.1 ex. (a2.x) SK.MA in % SK.MB SK.MA + SK.MB in % VM1 16.7 ./. ./. ./. ./. ./. VM2 16.7 ./. ./. ./. 54.8 ./. Viscosity* SK.MA Viscosity Viscosity without Viscosity* loss Viscosity* Viscosity* increase.sup.1 Ex. (a2.x) SK.MA in % SK.MB SK.MA + SK.MB in % M1 16.7 0.44 97 0.3 51.0 10 491 M2 16.7 0.44 97 0.3 46.4 10 445 M3 16.7 0.19 99 0.3 1.8 847 M4 16.7 0.19 99 0.01 8.9 4584 M5 16.7 0.19 99 0.01 31.5 16 479 M6 16.7 1.18 93 0.01 30.6 2493 M7 16.7 1.18 93 0.01 29.2 2375 Viscosity* SK.MC Viscosity Viscosity without Viscosity* loss Viscosity* Viscosity* increase.sup.2 Ex. (a2.x) SK.MC in % SK.MD SK.MC + SK.MD in % M8 162 10.8 93 0.3 98.7 814 M9 162 10.8 93 0.3 184.1 1605 M10 162 10.8 93 0.3 48.1 345 M11 162 15.7 90 0.3 100.7 541 M12 162 15.7 90 0.3 130.5 731 M13 162 15.7 90 0.3 58.1 270 M14 162 35.1 78 0.3 475.6 1255 M15 162 35.1 78 0.3 488.2 1291 M16 162 35.1 78 0.3 108.9 210 Viscosity* SK.ME Viscosity Viscosity without Viscosity* loss Viscosity* Viscosity* increase.sup.3 Ex. (a2.x) SK.ME in % SK.MF SK.ME + SK.MF in % M17 15.1 6.7 96 0.3 45.0 572 M18 15.1 6.7 96 0.3 319.2 4664 M19 15.1 6.7 96 0.3 168.0 2407 M20 15.1 35.3 80 0.3 200.3 467 M21 15.1 35.3 80 0.3 754.3 2037 M22 15.1 35.3 80 0.01 419.9 1090 M23 15.1 4.3 98 0.3 5.1 19 M24 15.1 4.3 98 0.3 21.4 398 M25 15.1 4.3 98 0.01 113.5 2540 Viscosity* SK.MG Viscosity Viscosity without Viscosity* loss Viscosity* Viscosity* increase.sup.4 Ex. (a2.x) SK.MG in % SK.MH SK.MG + SK.MH in % M26 30.8 16.7 46 0.3 163.4 878 M27 30.8 16.7 46 0.3 68.4 310 M28 30.8 16.7 46 0.3 516.6 2993 M29 30.8 1.0 97 0.3 179.3 17 830 M30 30.8 1.0 97 0.3 18.5 1750 M31 30.8 1.0 97 0.3 301.8 30 080 M32 30.8 8.1 74 0.3 942.1 11 531 M33 30.8 8.1 74 0.3 603.3 7348 M34 30.8 8.1 74 0.3 1037.0 12 702 Viscosity* SK.MI Viscosity Viscosity without Viscosity* loss Viscosity* Viscosity* increase.sup.5 Ex. (a2.x) SK.MI in % SK.MJ SK.MI + SK.MJ in % M35 442 22.1 95 1.8 34.4 56 M36 442 22.1 95 1.8 217.7 885 *in pascal-seconds; .sup.1relative to SK.MA; .sup.2relative to SK.MC; .sup.3relative to SK.ME; .sup.4relative to SK.MG; .sup.5relative to SK.MI