Thixotropy-increasing additive and composition containing said additive

Abstract

The invention relates to a use of at least one condensation product (A) in the form of the free compound or in the form of a salt of at least one acid as a thixotropy-increasing additive, which condensation product can be obtained by reacting at least one polymerized fatty acid or at least one reaction product (U) of at least two polymerized fatty acids and at least one polyamine having at least two primary amino groups as component (a1) with at least one polyalkylene polyamine, which is capable of forming at least one imidazoline and/or tetrahydropyrimidine unit and which has at least two primary amino groups or at least one primary and at least one secondary amino group, a composition containing at least one such condensation product (A) and at least one thixotropic agent (B), and a use of said composition, which additionally comprises at least one binder (C), as an adhesive, sealant, paint, coating agent, adhesive resin, casting resin, artificial marble, floor covering, polymer concrete, or fiber composite material.

Claims

1. A process comprising incorporating a thixotropy-increasing additive in a composition, wherein the thixotropy-increasing additive is at least one condensation product (A) in the form of a free compound or in the form of a salt of at least one acid, the at least one condensation product (A) obtained by reaction of (a1) with (a2); wherein (a2) is at least one polyalkylenepolyamine which is capable of forming at least one imidazoline and/or tetrahydropyrimidine unit and which has at least two primary amino groups or at least one primary and at least one secondary amino group; and wherein (a1) is selected from the group consisting of: a mixture of polymerized fatty acids comprising, based on 100 wt % of the mixture, at least 70 wt % and less than 100 wt % of at least one trimerized fatty acid and greater than 0 wt % and not more than 30 wt % of at least one dimerized fatty acid; a mixture of polymerized fatty acids comprising, based on 100 wt % of the mixture, at least 70 wt % and less than 100 wt % of at least one dimerized fatty acid and greater than 0 wt % and not more than 30 wt % of at least one trimerized fatty acid; and a reaction product (U) of at least two polymerized fatty acids selected from the group consisting of dimerized fatty acids, trimerized fatty acids and mixtures thereof, and at least one polyamine having at least two primary amino groups.

2. The process as claimed in claim 1, characterized in that the at least one condensation product (A) has a tertiary nitrogen content of from 0.5 to 20 wt %, based on the total weight of the at least one condensation product (A).

3. The process as claimed in claim 1, characterized in that the at least one condensation product (A) has an amine number in the range from 200 to 1000.

4. The process as claimed in claim 1, characterized in that the at least one condensation product (A) is prepared using at least 0.9 mol of (a2) per carboxylic acid group of (a1).

5. The process as claimed in claim 1, characterized in that (a1) is prepared using at least one at least monounsaturated aliphatic C.sub.16-C.sub.20 monocarboxylic acid.

6. The process as claimed in claim 1, characterized in that (a2) is a polyalkylenepolyamine of the general formula (I) ##STR00006## in which m is 2 or 3, n is 0, 1, 2, 3, or 4, p is 1, 2, 3, 4, or 5, and X is H if n is 0 or X is NH.sub.2 or OH if n is 1, 2, 3, or 4.

7. The process as claimed in claim 6, characterized in that the at least one condensation product (A) contains at least one imidazoline and/or tetrahydropyrimidine unit.

8. A composition comprising (A) a thixotropy-increasing additive, which is at least one condensation product in the form of a free compound or in the form of a salt of at least one acid, the at least one condensation product obtained by reaction of (a1) with (a2); (B) at least one thixotropic agent; (C) at least one binder; and (D) optionally at least one curing agent; wherein (a1) is at least one polymerized fatty acid or at least one reaction product (U) of at least two polymerized fatty acids and at least one polyamine having at least two primary amino groups; wherein (a2) is at least one polyalkylenepolyamine which is capable of forming at least one imidazoline and/or tetrahydropyrimidine unit and which has at least two primary amino groups or at least one primary and at least one secondary amino group; wherein (B) is present in an amount of from 0.5 to 25 wt %, based on the total weight of (C); and wherein (A) is present in an amount of from 10 to 100 wt %, based on the total weight of (B).

9. The composition as claimed in claim 8, characterized in that the thixotropic agent (B) is selected from the group consisting of non-organically modified fumed silica, hydrophobically modified fumed silica, and mixtures thereof.

10. The composition as claimed in claim 8, characterized in that the binder (C) is selected from the group consisting of epoxide-based resins, polyester-based resins, vinyl ester-based resins, poly(meth)acrylate-based resins, resins based on at least one (meth)acrylate copolymer, and polyurethane-based resins.

11. An adhesive, sealant, paint, coating material, adhesive resin, casting resin, synthetic marble, floor covering, polymer concrete, or fiber composite material, comprising the composition of claim 8.

Description

INVENTIVE AND COMPARATIVE EXAMPLES

(1) Unless otherwise stated, the amounts in parts are parts by weight, and amounts in percent are percentages by weight.

(2) 1. Preparation of Condensation Products (A)

(3) 1.1 General Protocol for Preparing Condensation Products (A) Used in Accordance with the Invention as Thixotropy-Increasing Additives:

(4) At least one polymerized fatty acid or at least one reaction product of at least two polymerized fatty acids and at least one polyamine having at least two primary amino groups as component (a1), or a derivative thereof which can be used in each case for preparing the condensation product (A), such as a corresponding ester, for example, is charged to a reaction vessel with stirrer, reflux condenser, and water separator, and is mixed with at least one polyalkylenepolyamine as component (a2) and optionally with at least one solvent, and the mixture is heated with stirring to a temperature in the range from 150° C. to 300° C., until the desired amount of water has separated off, this preferably indicating the complete reaction of component (a1)) with component (a2).

(5) The condensation products (A) below, indicated in table 1, are obtained in this way as examples K1-K31. In each case, 1 mol of component (a2) is used per carboxylic acid group contained in component (a1). Where, for example, 1 mol of a trimerized fatty acid is used as component (a1), 3 mol of component (a2) are used.

(6) TABLE-US-00002 TABLE 1 Amount of Ex- Compo- Amount Compo- Amount Sol- water sep- am- nent of nent of vent arated off ple (a1) (a1) [g] (a2) (a2) [g] L [g] K1 A1 303 B1 150 400 g L1 36 K2 A2 572 B1 292 400 g L1 72 K3 A3 575 B1 292 400 g L1 72 K4 A4 581 B1 292 400 g L1 72 K5 A5 881 B1 438 400 g L1 108 K6 A8 1188 B1 292 200 g L1 72 K7 A9 1250 B1 292 200 g L1 72 K8  A10 1230 B1 292 200 g L1 72 K9  A11 1284 B1 292 — 72 K10  A12 1862 B1 584 — 144 K11  A13 1896 B1 584 — 144 K12  A14 1536 B1 438 — 108 K13 A3 + A5 291 + 291 B1 292 400 g L1 72 K14 A6 + A5 592 + 592 B1 584 400 g L1 144 K15 A3 + A8 882 + 882 B1 292 400 g L1 72 K16 A3 575 B2 206 400 g L1 72 K17 A5 881 B2 309 400 g L1 108 K18 A3 + A5 291 + 291 B2 206 400 g L1 72 K19  A12 1862 B2 412 — 144 K20 A3 575 B3 378 400 g L1 72 K21 A5 881 B3 568 400 g L1 108 K22 A2 572 B3 378 400 g L1 72 K23 A3 575 B4 464 400 g L1 72 K24 A5 881 B4 698 400 g L1 108 K25 A3 575 B5 148 400 g L1 72 K26 A5 881 B5 222 400 g L1 108 K27 A3 575 B6 262 400 g L1 72 K28 A5 881 B6 393 400 g L1 108 K29 A3 575 B7 294 400 g L1 72 K30 A5 881 B7 441 400 g L1 108 K31 A7 603 B7 294 400 g L1 ** ** In the case of K-31, with A-7, a dimethyl ester of a dimerized fatty acid was used as component (a1). In the reaction, therefore, methanol as well as water is separated off. In total 64 g of methanol and 32 g of water are separated off.

(7) The abbreviations used in table 1 have the following meanings:

(8) Component (a1):

(9) A1: mixture of polymerized unsaturated aliphatic C.sub.18 fatty acids with a fraction of 80 wt % of trimerized fatty acid and a fraction of 20 wt % of dimerized fatty acid, based in each case on the total weight of the mixture, having an acid number of 185 mg KOH/g, A2: mixture of polymerized saturated fatty acids with a fraction of 92-98 wt % of dimerized fatty acid, based on the total weight of the mixture, having an acid number of 196 mg KOH/g, available commercially under the name Pripol 1006 from Croda, A3: mixture of polymerized fatty acids with a fraction of >97 wt % of dimerized fatty acid, based on the total weight of the mixture, having an acid number of 195 mg KOH/g, available commercially under the name Pripol 1012 from Croda, A4: mixture of polymerized fatty acids having a fraction of 72-79 wt % of dimerized fatty acid and a fraction of 20-23 wt % of trimerized fatty acid, based in each case on the total weight of the mixture, having an acid number of 193 mg KOH/g, available commercially under the name Pripol 1022 from Croda, A5: mixture of polymerized fatty acids with a fraction of >75 wt % of trimerized fatty acid, based in each case on the total weight of the mixture, having an acid number of 191 mg KOH/g, available commercially under the name Pripol 1040 from Croda, A6: Tall oil fatty acid having an acid number of 186 mg KOH/g, A7: dimethyl ester of a dimerized fatty acid, present in a mixture of polymerized fatty acids with a fraction of >97 wt %, based on the total weight of the mixture.

(10) The compounds A8 to A14 used as component (a1)) are reaction products of at least two polymerized fatty acids and at least one polyamine having at least two primary amino groups. The reaction products A8 to A14 used as component (a1)) can be obtained in accordance with the following general protocol:

(11) At least one polymerized fatty acid or a derivative thereof which can be used to prepare the reaction product (U), such as a corresponding ester, for example, is charged to a reaction vessel with stirrer, reflux condenser, and water separator, and is mixed with at least one polyamine having at least two primary amino groups, such as a diamine, for example, and optionally with at least one solvent, and the mixture is heated with stirring to a temperature in the range from 130° C. to 160° C. until the desired amount of water has separated off.

(12) The stated reaction products A8 to A14 below, which can be used in table 2 as component (a1), are obtained in this way.

(13) TABLE-US-00003 Com- Amount of Amount Amount po- Polymer- polymer- of poly- Sol- of water nent ized fatty ized fatty Poly- amine vent separated (a1) acid used acid [g] amine [g] L off [g] A8 A3 1150 B5 74 200 g L1 36 A9 A3 1150 B8 136 200 g L1 36 A10 A3 1150 B9 116 200 g L1 36 A11 A3 1150  B10 170 400 g L1 36 A12 A5 1762 B8 136 400 g L1 36 A13 A5 1762  B10 170 400 g L1 36 A14 A3 + A5 728 + 728 B9 116 400 g L1 36

(14) The abbreviations A3, A5, L1, and B5 used in table 2 have the meanings as in table 1.

(15) The abbreviations additionally used in table 2 have the following meanings:

(16) B8: m-xylylenediamine (CAS No.: 153326-45-5)

(17) B9: 1,6-diaminohexane (CAS No.: 124-09-4)

(18) B10: isophoronediamine (isomer mixture, CAS No.: 2855-13-2)

(19) Component (a2):

(20) B1: triethylenetetramine (CAS No.: 112-24-3)

(21) B2: diethylenetriamine (CAS No.: 111-40-0)

(22) B3: tetraethylenepentamine (CAS No.: 112-57-2)

(23) B4: pentaethylenehexamine (isomer mixture, CAS No.: 4067-16-7)

(24) B5: 1,3-diaminopropane (CAS No.: 109-76-2)

(25) B6: dipropylenetriamine (CAS No.: 56-18-8)

(26) B7: 2-(2-(2-aminoethylamino)ethylamino)ethanol (CAS: 1965-29-3)

(27) Solvent:

(28) L1: solvent naphtha, aromatic hydrocarbon fraction, boiling range: 150° C. to 210° C.

(29) 2. Production of Inventive Compositions and Comparative Compositions

(30) General protocol for producing inventive compositions comprising at least one condensation product (A), at least one thixotropic agent (B), and at least one binder (C), and optionally at least one curing agent (D), and also corresponding comparative compositions.

(31) 2.1 Compositions Comprising at Least One Poly(Meth)Acrylate-Based Resin as Binder (C)

(32) To prepare the binder (C), 20% of Degalan LP 51/3 (acrylic polymer from Evonik) is dissolved in methyl methacrylate (from Evonik). 50 fractions of this liquid base syrup are admixed with 0.25 fraction of the accelerator Pergaquick A150 (N,N-di-(2-hydroxyethyl)-p-toluidine from Pergan), and the accelerator is incorporated into the syrup using a Dispermat CV (toothed disk 2 cm, 1500 rpm for 2 minutes).

(33) This is followed by the addition of one fraction of Aerosil 200 (hydrophilic fumed silica, specific surface area of 200 m.sup.2/g, from Evonik) as thixotropic agent (B). This mixture is dispersed in the system for 5 minutes in the Dispermat CV (toothed disk 4 cm, 8000 rpm).

(34) Added to this mixture subsequently is a condensation product (A), for producing an inventive composition Z1 to Z7, or a compound C1 known from DE 37 06 860 A1 (disclosed therein as example 8), for producing a comparative composition CZ1 (see table 3), with incorporation in each case for 1 minute using the Dispermat CV, toothed disk 2 cm, 1500 rpm. In addition, a corresponding composition is produced without addition of a further component (comparative composition CZ2).

(35) After they have cooled to room temperature, 50 g of each of the compositions Z1 to Z7 and CZ1 to CZ2 are admixed with 0.75 g of Peroxan BP powder 50W (dibenzoyl peroxide from Pergan) as curing agent (D), and the compositions are homogenized over a period of 60 seconds.

(36) For the compositions Z1 to Z7 and CZ1 to CZ2, their sagging behavior and the sagging limit are determined by the method described above, with the curing taking place at room temperature. The highest stable film thickness at which no sagging is observed is reported as the sagging limit in μm. The results are set out in table 3:

(37) TABLE-US-00004 TABLE 3 Amount of (A), Amount of based in each (B), based in case on the each case on total weight of the total Inventive/ Conden- the thixotropic weight of the Sagging comparative sation agent (B) binder (C) limit example product (A) [wt %] [wt %] [μm] CZ2 — — 2.0 <500 CZ1 C1* 20 2.0 800 Z1 K1 20 2.0 >1000 Z2 K3 20 2.0 900 Z3 K4 20 2.0 >1000 Z4 K13 20 2.0 >1000 Z5 K16 20 2.0 950 Z6 K17 20 2.0 >1000 Z7 K24 20 2.0 950 *C1: as comparative example C1, example compound 8 from DE 3706860 A1 was used.
2.2 Compositions Comprising at Least One Polyester-Based Resin (Unsaturated Polyester) as Binder (C)

(38) To prepare the binder (C), 100 fractions of Palatal P 4-01 (unsaturated polyester resin based on orthophthalic acid and glycols in solution in styrene, from DSM) are introduced together with 1.0 fraction of NL 49 P (cobalt octoate, from AKZO Nobel) as accelerator and with 0.5 fraction of BYK-A 555 (deaerating agent, BYK-Chemie) and incorporated by means of a Dispermat CV (toothed disk 2 cm, 1500 rpm) for 2 minutes.

(39) This is followed by the addition of 2.0 fractions of Aerosil 200 (hydrophilic fumed silica, specific surface area of 200 m.sup.2/g, from Evonik) as thixotropic agent (B). The mixture is dispersed for 15 minutes in the Dispermat CV (toothed disk 4 cm, 8000 rpm).

(40) Added to this mixture subsequently is a condensation product (A), for producing an inventive composition Z8 to Z14, or a compound C1 known from DE 37 06 860 A1 (disclosed therein as example 8), for producing a comparative composition CZ3 (see table 4), with incorporation in each case for 1 minute using the Dispermat CV, toothed disk 2 cm, 1500 rpm. In addition, a corresponding composition is produced without addition of a further component (comparative composition CZ4). Moreover, a corresponding composition is produced without addition of a further component and also without addition of the thixotropic agent (B) (comparative composition CZ5).

(41) Added to 50 g of each of the compositions is 0.5 g of Trigonox 44 B (acetylacetone peroxide, AKZO Nobel) as curing agent (D), and the compositions are homogenized over a time of 60 seconds.

(42) For the compositions Z8 to Z14 and CZ3 to CZ5, their sagging behavior and the sagging limit are determined by the method described above, with the curing taking place at 60° C. The highest stable film thickness at which no sagging is observed is reported as the sagging limit in μm. The results are set out in table 4:

(43) TABLE-US-00005 TABLE 4 Amount of (A), Amount of based in each (B), based in case on the each case on total weight of the total Inventive/ Conden- the thixotropic weight of the Sagging comparative sation agent (B) binder (C) limit example product (A) [wt %] [wt %] [μm] CZ5 — — — 50 CZ4 — — 2.0 <500 CZ3 C1* 20 2.0 650 Z8 K1 20 2.0 850 Z9 K3 20 2.0 700 Z10 K4 20 2.0 >1000 Z11 K13 20 2.0 900 Z12 K16 20 2.0 750 Z13 K17 20 2.0 950 Z14 K24 20 2.0 900 *C1: as comparative example C1, example compound 8 from DE 3706860 A1 was used.
2.3 Compositions Comprising at Least One Polyester-Based Resin (Unsaturated Polyester) as Binder (C)

(44) To prepare the binder (C), 100 fractions of KRF-1100 (unsaturated polyester resin based on orthophthalic acid and standard glycols from CCP) are introduced together with 1.0 fraction of accelerator NL 49 P and with 0.5 fraction of BYK-A 555 and incorporated by means of a Dispermat CV (toothed disk 2 cm, 1500 rpm) for two minutes.

(45) This is followed by the addition of 3.0 fractions of Aerosil 200 as thixotropic agent (B). The whole system is dispersed for 15 minutes in the Dispermat CV, toothed disk 4 cm, 8000 rpm.

(46) Added to this mixture subsequently is a condensation product (A), for producing an inventive composition Z15 to Z21, or a compound C1 known from DE 37 06 860 A1 (disclosed therein as example 8), for producing a comparative composition CZ6 (see table 5), with incorporation in each case for 1 minute using the Dispermat CV, toothed disk 2 cm, 1500 rpm. In addition, a corresponding composition is produced without addition of a further component (comparative composition CZ7). Moreover, a corresponding composition is produced without addition of a further component and also without addition of the thixotropic agent (B) (comparative composition CZ8).

(47) Added to 50 g of each of the compositions is 0.5 g of Trigonox 44 B (acetylacetone peroxide, AKZO Nobel) as curing agent (D), and the compositions are homogenized over a time of 60 seconds.

(48) For the compositions Z15 to Z21 and CZ6 to CZ8, their sagging behavior and the sagging limit are determined by the method described above, with the curing taking place at 60° C. The highest stable film thickness at which no sagging is observed is reported as the sagging limit in μm. The results are set out in table 5.

(49) TABLE-US-00006 TABLE 5 Amount of (A), Amount of based in each (B), based in case on the each case on total weight of the total Inventive/ Conden- the thixotropic weight of the Sagging comparative sation agent (B) binder (C) limit example product (A) [wt %] [wt %] [μm] CZ8 — — — 50 CZ7 — — 3.0 <500 CZ6 C1* 20 3.0 650 Z15 K1 20 3.0 >1000 Z16 K3 20 3.0 850 Z17 K4 20 3.0 >1000 Z18 K13 20 3.0 750 Z19 K16 20 3.0 800 Z20 K17 20 3.0 >1000 Z21 K24 20 3.0 850 *C1: as comparative example C1, example compound 8 from DE 3706860 A1 was used.
2.4 Compositions Comprising at Least One Epoxide-Based Resin as Binder (C)

(50) To prepare the binder (C), 99.5 fractions of liquid epoxy resin blend (RIM R 1335: modified bisphenol A resin, molecular weight >700 g/mol, epoxide value: 5.6 mol/kg, from Momentive) are admixed with 0.5 fraction of BYK A-530 (deaerating agent, from BYK-Chemie) and incorporated using a Dispermat CV (toothed disk 2 cm, 1500 rpm) for 2 minutes.

(51) This is followed by the addition of 2.6 parts of Aerosil 200 or Aerosil 380 (hydrophilic fumed silica, specific surface area of 380 m.sup.2/g, from Evonik) as thixotropic agent (B). This mixture is dispersed for 15 minutes in the Dispermat CV (toothed disk 4 cm, 8000 rpm) (component M1).

(52) 100 fractions of an amine curing agent blend as curing agent (D) (CeTePox 1393-02H (mixture of isophoronediamine, m-xylylenediamine, benzyl alcohol, salicylic acid, and nonylphenol, H equivalent 93, from CTP GmbH)) are introduced in a mixing vessel. Added to this mixture subsequently is a condensation product (A), for producing an inventive composition Z22 to Z29, or a compound C1 known from DE 37 06 860 A1 (disclosed therein as example 8), for producing a comparative composition CZ9 (see table 6), with incorporation in each case for 2 minutes using the Dispermat CV, toothed disk 2 cm, 1500 rpm (component M2). In addition, a corresponding composition is produced without addition of a further component (comparative composition CZ10).

(53) 100 parts of component M1 are mixed thoroughly with 50 parts of component M2 in a beaker for 1 minute.

(54) For the compositions Z22 to Z29 and CZ9 to CZ10, their sagging behavior and the sagging limit are determined by the method described above, with the curing taking place at room temperature. The highest stable film thickness at which no sagging is observed is reported as the sagging limit in μm. The results are set out in table 6.

(55) The compositions CZ9, CZ10, Z22 and Z24-Z29 contain Aerosil 200 as thixotropic agent (B), and composition Z23 contains Aerosil 380 as thixotropic agent (B).

(56) TABLE-US-00007 TABLE 6 Amount of (A), Amount of based in each (B), based in case on the each case on total weight of the total Inventive/ Conden- the thixotropic weight of the Sagging comparative sation agent (B) binder (C) limit example product (A) [wt %] [wt %] [μm] CZ10 — — 2.6 <550 CZ9 C1* 20 2.6 <550 Z22 K1 20 2.6 >1000 Z23 K1 20 2.6 >1000 Z24 K3 20 2.6 900 Z25 K4 20 2.6 >1000 Z26 K13 20 2.6 900 Z27 K16 20 2.6 750 Z28 K17 20 2.6 >1000 Z29 K24 20 2.6 >1000 *C1: as comparative example C1, example compound 8 from DE 3706860 A1 was used.
2.5 Compositions Comprising at Least One Epoxide-Based Resin as Binder (C)

(57) For the preparation of the binder (C), 64 parts of liquid epoxy resin (Epikote 1001: modified bisphenol-A resin from Momentive) are admixed with 0.5 fraction of BYK-052 (silicone-free, polymer-based defoamer, BYK-Chemie), 7.5 fractions of Bayferrox 130 M (red iron oxide pigment from Lanxess), 57 fractions of Blanc Fixe N (barium sulfate from Sachtleben), and 21 parts of isobutanol, and incorporated using a Dispermat CV (toothed disk 4 cm, 8500 rpm) for 30 minutes.

(58) This is followed by the addition of 1 part of thixotropic agent (B). This mixture is dispersed for 15 minutes with the Dispermat CV, toothed disk 4 cm, 8500 rpm (component M1). Used as thixotropic agent (B) is Aerosil 200 or Aerosil R972 (fumed silica hydrophobized with dimethyldichlorosilane, from Evonik) (component M1).

(59) 100 parts of Epikure 550 (amine curing agent blend, Momentive) as curing agent (D) are introduced in a mixing vessel. Added to this mixture subsequently is a condensation product (A) for producing an inventive composition Z30 to Z37, or a compound C1 known from DE 37 06 860 A1 (disclosed therein as example 8), for producing a comparative composition CZ11 (see table 7), with incorporation in each case for 2 minutes with the Dispermat CV, toothed disk 2 cm, 1500 rpm (component M2). Moreover, a corresponding composition is produced without addition of a further component (comparative composition CZ12).

(60) 100 parts of component M1 are mixed thoroughly with 33 parts of component M2 in a beaker for 1 minute.

(61) For the compositions Z30 to Z37 and CZ11 to CZ12, their sagging behavior and the sagging limit are determined by the method described above, with the curing taking place at room temperature. The highest stable film thickness at which no sagging is observed is reported as the sagging limit in μm. The results are set out in table 7.

(62) The compositions CZ11, CZ12, Z30, and Z32-Z37 contain Aerosil 200 as thixotropic agent (B), and the composition Z31 contains Aerosil R972 as thixotropic agent (B).

(63) TABLE-US-00008 TABLE 7 Amount of (A), Amount of based in each (B), based in case on the each case on total weight of the total Inventive/ Conden- the thixotropic weight of the Sagging comparative sation agent (B) binder (C) limit example product (A) [wt %] [wt %] [μm] CZ12 — — 1 100 CZ11 C1* 66 1 <550 Z30 K1 66 1 700 Z31 K1 66 1 >1000 Z32 K3 66 1 750 Z33 K4 66 1 950 Z34 K13 66 1 650 Z35 K16 66 1 800 Z36 K17 66 1 750 Z37 K24 66 1 600 *C1: as comparative example C1, example compound 8 from DE 3706860 A1 was used.
2.6 Compositions Comprising at Least One Polyurethane-Based Resin as Binder (C)

(64) For the preparation of the binder (C), 50 fractions of Setathone 1150 (branched polyester/polyether polyol, OH number 4.7, from Nuplex) are introduced. This is followed by the addition of 2.25 parts of Aerosil 200 as thixotropic agent (B). The mixture is dispersed in the system for 15 minutes in a Dispermat CV (toothed disk 4 cm, 8000 rpm).

(65) Added to this mixture subsequently is a condensation product (A), for producing an inventive composition Z38 to Z44, or a compound C1 known from DE 37 06 860 A1 (disclosed therein in example 8), for producing a comparative composition CZ13 (see table 8), with incorporation in each case for 1 minute with the Dispermat CV, toothed disk 2 cm, 1500 rpm. Moreover, a corresponding composition is produced without addition of a further component (comparative composition CZ14).

(66) After the compositions produced have cooled to room temperature, 50 g of the composition thus produced are admixed with 21.1 g of the curing agent Desmodur VL (aromatic polyisocyanate based on diphenylmethanediisocyanate, 31.5% NCO content, from Bayer) and the composition is homogenized for 60 seconds.

(67) For the compositions Z38 to Z44 and CZ13 to CZ14, their sagging behavior and the sagging limit are determined by the method described above, with the curing taking place at room temperature. The highest stable film thickness at which no sagging is observed is reported as the sagging limit in μm. The results are set out in table 8.

(68) TABLE-US-00009 TABLE 8 Amount of (A), Amount of based in each (B), based in case on the each case on total weight of the total Inventive/ Conden- the thixotropic weight of the Sagging comparative sation agent (B) binder (C) limit example product (A) [wt %] [wt %] [μm] CZ14 — — 4.5 <550 CZ13 C1* 40 4.5 650 Z38 K1 40 4.5 850 Z39 K3 40 4.5 900 Z40 K4 40 4.5 750 Z41 K13 40 4.5 850 Z42 K16 40 4.5 800 Z43 K17 40 4.5 >1000 Z44 K24 40 4.5 950 *C1: as comparative example C1, example compound 8 from DE 3706860 A1 was used.
2.7 Comparative Example: Composition Comprising at Least One Epoxide-Based Resin as Binder (C)

(69) This comparative example (CZ15) comprises an inventively employed condensation product (A), but no thixotropic agent (B) (not inventive).

(70) To prepare the binder (C), 99.5 fractions of liquid epoxy resin blend (RIM R 1335: modified bisphenol A resin, molecular weight >700 g/mol, epoxide value: 5.6 mol/kg, from Momentive) are admixed with 0.5 fraction of BYK A-530 (deaerating agent, from BYK-Chemie) and incorporated using a Dispermat CV (toothed disk 2 cm, 1500 rpm) for 2 minutes (component M1).

(71) 100 fractions of an amine curing agent blend as curing agent (D) (CeTePox 1393-02H (mixture of isophoronediamine, m-xylylenediamine, benzyl alcohol, salicylic acid, and nonylphenol, H equivalent 93, from CTP GmbH)) are introduced in a mixing vessel. Added to this mixture subsequently as condensation product (A) is the compound K5 (0.2 fraction), which is incorporated for 2 minutes with the Dispermat CV, toothed disk 2 cm, 1500 rpm (component M2).

(72) Moreover, a further corresponding comparative composition (CZ16) is produced without addition of K5, i.e., a comparative composition containing neither (A) nor (B).

(73) 100 parts of component M1 are in each case mixed thoroughly with 50 parts of component M2 in a beaker for 1 minute. The materials are applied and the sagging behavior is determined.

(74) The sagging limit ascertained for both compositions CZ15 and CZ16 is <550 μm in each case. No differences are observed in the thixotropic properties of these comparative compositions. The results are set out in table 9.

(75) TABLE-US-00010 TABLE 9 Conden- Sagging Comparative sation Thixotropic limit example product (A) agent (B) [μm] CZ15 K5 — <550 CZ16 — — <550