Urea group containing anti-sagging rheology control agents

Abstract

The present invention relates to a urea group containing product comprising one or more species of formula (I) R.sup.1—X—(C═O)—[NH—R.sup.2—NH—(C═O)—NH—R.sup.3—NH—(C═O)].sub.n—NH—R.sup.2—NH—(C═O)—X—R.sup.1 (I), 5 wherein R.sup.1 is independently selected from organic groups having (4) to (200) carbon atoms, X is O or NR.sup.4, wherein R.sup.4 is a hydrogen atom or an aliphatic or aromatic group having (1) to (30) carbon atoms, R.sup.2 is independently selected from hydrocarbyl groups having (4) to (40) carbon atoms, R.sup.3 is independently selected from hydrocarbyl groups having (2) to (40) carbon atoms, and wherein on average (76) to (100) mol % of all R.sup.3 groups contained in the one or more species of formula (I) are hydrocarbyl groups having (2) or (3) carbon atoms, and n is an integer of (2) to (150). The invention further relates to a method of manufacturing such urea group containing products, liquid compositions containing the same and the use of such liquid compositions as rheology control additives. Furthermore, the invention relates to a process for rheology adjustment adding such liquid composition to semi-finished or final products. The invention also relates to an article coated with the liquid composition.

Claims

1. A urea group containing product comprising one or more species of formula (I)
R.sup.1—X—(C═O)—[NH—R.sup.2—NH—(C═O)—NH—R.sup.3—NH—(C═O)].sub.n—NH—R.sup.2—NH—(C═O)—X—R.sup.1  (I), wherein R.sup.1 independently represent an aliphatic group having 8 to 70 carbon atoms or a group of the formula R.sup.a—[O—(C═O).sub.s—R.sup.b].sub.t, wherein R.sup.a are independently from each other an aromatic hydrocarbyl group having 6 to 40 carbon atoms or an aliphatic hydrocarbyl group having 1 to 40 carbon atoms, R.sup.b are independently from each other a linear or branched alkylene group having 2 to 6 carbon atoms, t is 0 to 60, independently of each other, s is 0 or 1, with the proviso that the number of carbon atoms in R.sup.a plus the number of carbon atoms in the residues [O—(C═O).sub.s—R.sup.b] are from 4 to 200 if R.sup.a is aliphatic and from 6 to 200 if R.sup.a is aromatic, X is O, R.sup.2 independently represent hydrocarbyl groups having 6 to 15 carbon atoms, R.sup.3 independently represent hydrocarbyl groups having 2 to 12 carbon atoms, and wherein on average 76 to 100 mol % of all R.sup.3 groups contained in the one or more species of formula (I) are hydrocarbyl groups having 2 or 3 carbon atoms, and n is an integer of 2 to 40.

2. The urea group containing product according to claim 1, wherein at least 80 mol % of all R.sup.3 groups are ethylene groups.

3. The urea group containing product according to claim 1, wherein R.sup.2 independently represent any of ##STR00002## and the asterisk symbols (*) denote positions where R.sup.2 is bound to adjacent NH groups in the species of formula (I).

4. A liquid composition comprising the urea group containing product according to claim 1 and a carrier medium.

5. The liquid composition according to claim 4, wherein the carrier medium comprises one or more of an amide, a sulfoxide, and an ionic liquid.

6. The liquid composition according to claim 4, wherein the liquid composition comprises: 5 to 70% by weight of the urea group containing product, 30 to 95% by weight of one or more of a polar aprotic solvent and an ionic liquid, and 0 to 8% by weight of one or more ionogenic compounds, the amounts of (a), (b) and (c) being based on the total weight of the liquid composition.

7. A 2-component clear coat composition comprising: a carrier medium; a base component (A), containing the urea group containing product according to claim 1 and a polymeric binder having reactive groups; and a cross-linking component (B), containing a cross-linker having reactive groups, which are reactive towards the reactive groups of the polymeric binder in the base component (A).

8. A process for rheology adjustment, the process comprising adding the liquid composition according to claim 7 to one or more of a coating composition, a clear coat composition, a lacquer, a color resist, a plastic formulation, a pigment paste, an effect pigment paste, a sealant formulation, a wire enamel, a cosmetic formulation, a ceramic formulation, an adhesive formulation, a liquid formulation for use in gas and oil production, a liquid formulation for the manufacture of electrical components and circuits, a liquid formulation for use in energy storage media, a cleaning agent, a potting compound, a building material formulation, a lubricant, a filling compound, a wax emulsion, a metal-processing product, a metal-working fluid, a liquid formulation in the form of a spraying agent, a deposition aid, an ink, a printing ink and an ink jet ink.

9. The urea compound according to claim 1, wherein R.sup.a independently represent a linear alkyl group having 1 to 40 carbon atoms, a branched alkyl group having 3 to 40 carbon atoms, or a linear or branched alkenyl group having 4 to 40 carbon atoms.

10. A coating composition comprising: a carrier medium; a film forming resin; and the urea group containing product according to claim 1.

11. The coating composition according to claim 10, further comprising a pigment.

12. A 1-component clear coat composition comprising: a film forming resin; a carrier medium; and the urea group containing product according to claim 1.

13. A product comprising an article coated with the 2-component clear coat composition according to claim 7.

14. A product comprising an article coated with the coating composition according to claim 10.

15. A product comprising an article coated with the 1-component clear coat composition according to claim 12.

Description

EXAMPLES

Synthesis Examples

(1) TABLE-US-00001 TABLE 1 Aromatic diisocyanates Product name Chemical Composition Manufacturer TDI T100 2,4-toluylene diisocyanate Covestro AG TDI T80 80/20 mixture of 2,4-toluylene Covestro AG diisocyanate and 2,6-toluylene diisocyanate TDI T65 65/35 mixture of 2,4-toluylene Covestro AG diisocyanate and 2,6-toluylene diisocyanate
Manufacture of Intermediates A1 to A4:

(2) Diisocyanates were reacted with mono alcohols according to the procedure described in EP 1188779 to form monoadducts (intermediates), containing one urethane group and one NCO group.

(3) TABLE-US-00002 TABLE 2 Intermediates Intermediate Mono alcohol Diisocyanate A1 (Z)-Octadec-9-enol (oleic alcohol) TDI T65 A2 Poly(ethylene oxide-co-propylene TDI T100 oxide (ratio EO:PO 1:1), starter:n-butanol, M.sub.n = 1300 g/mol A3 Poly(ε-caprolactone), starter:isobutanol, TDI T100 M.sub.n = 750 g/mol A4 Poly(ethylene oxide-co-propylene TDI T80 oxide (ratio EO:PO 1:1), starter:n-butanol, M.sub.n = 1300 g/mol
Step 1:

(4) 2 mol of the diisocyanate and 200 ppm benzoyl chloride were weighed into a glass flask equipped with stirrer, reflux condenser and nitrogen inlet and heated to 40° C. Subsequently 1 mol of the mono alcohol (according to the above table) was added dropwise to the reaction mixture over a period of 30 min. The reaction mixture was stirred for additional 5 hours at 60° C. A clear, light yellow, liquid crude intermediate containing excessive diisocyanate is obtained.

(5) Step 2:

(6) The excess of diisocyanate contained in the crude intermediates obtained in step 1 was removed by distillation, whereby intermediates A1 to A3 were obtained.

Comparative Examples C1 to C10 (Non-Inventive)

(7) Completeness of the following reactions was evaluated with wet chemical methods by determination of NCO content and the amine value.

(8) Comparative Rheology Additive C1:

(9) In a glass flask with stirrer, reflux condenser and nitrogen inlet, 1.600 g (0.037 mol) lithium chloride were dissolved in 105 g N-butyl butyrolactam while stirring over a period of 30 min, whereby a clear solution was obtained. Subsequently 1.100 g (0.018 mol) ethylene diamine and 2.500 g (0.018 mol) m-xylylene diamine (m-XDA) were added and briefly homogenized. A uniform mixture of 35.600 g (0.024 mol) of adduct A2 and 4.300 g (0.024 mol) TDI T80 was added dropwise to the reaction mixture over a period of 25 min. The reaction mixture was stirred for additional 3 hours at 80° C. A slightly turbid, yellow, liquid product was obtained.

(10) Comparative Rheology Additive C2:

(11) In a glass flask with stirrer, reflux condenser and nitrogen inlet, 1.400 g (0.033 mol) lithium chloride were dissolved in 105 g N-butyl butyrolactam while stirring over a period of 30 min, whereby a clear solution was obtained. Subsequently 2.900 g (0.033 mol) 1,4-diaminobutane were added and briefly homogenized. A uniform mixture of 37.000 g (0.022 mol) of adduct A2 and 3.800 g (0.022 mol) TDI T80 was added dropwise to the reaction mixture over a period of 20 min. The reaction mixture was stirred for additional 3 hours at 80° C. A slightly turbid, yellow, liquid product was obtained.

(12) Comparative Rheology Additive C3:

(13) In a glass flask with stirrer, reflux condenser and nitrogen inlet, 1.400 g (0.033 mol) lithium chloride were dissolved in 105 g N-butyl butyrolactam while stirring over a period of 30 min, whereby a clear solution was obtained. Subsequently 3.800 g (0.033 mol) 1,6-diaminohexane were added and briefly homogenized. A uniform mixture of 37.500 g (0.022 mol) of adduct A2 and 3.800 g (0.022 mol) TDI T80 was added dropwise to the reaction mixture over a period of 20 min. The reaction mixture was stirred for additional 3 hours at 80° C. A clear, light brown, liquid product was obtained.

(14) Comparative Rheology Additive C4:

(15) In a glass flask with stirrer, reflux condenser and nitrogen inlet, 1.300 g (0.031 mol) lithium chloride were dissolved in 104.3 g N-butyl butyrolactam while stirring over a period of 30 min, whereby a clear solution was obtained. Subsequently 4.500 g (0.031 mol) 1,8-diaminooctane were added and briefly homogenized. A uniform mixture of 35.300 g (0.021 mol) of adduct A2 and 3.600 g (0.021 mol) TDI T80 was added dropwise to the reaction mixture over a period of 20 min. The reaction mixture was stirred for additional 3 hours at 80° C. A clear, light brown, liquid product was obtained.

(16) Comparative Rheology Additive C5:

(17) In a glass flask with stirrer, reflux condenser and nitrogen inlet, 1.500 g (0.036 mol) lithium chloride were dissolved in 105 g N-butyl butyrolactam while stirring over a period of 30 min, whereby a clear solution was obtained. Subsequently, 4.900 g (0.036 mol) m-xylene diamine were added and briefly homogenized. A uniform mixture of 34.400 g (0.024 mol) of adduct A2 and 4.200 g (0.024 mol) TDI T80 was added dropwise to the reaction mixture over a period of 30 min. The reaction mixture was stirred for additional 3 hours at 80° C. A clear, light brown, liquid product was obtained.

(18) Comparative Rheology Additive C6:

(19) In a glass flask with stirrer, reflux condenser and nitrogen inlet, 1.400 g (0.033 mol) lithium chloride were dissolved in 105 g N-butyl butyrolactam while stirring over a period of 30 min, whereby a clear solution was obtained. Subsequently 4.800 g (0.033 mol) 1,3-bis-aminomethyl cyclohexane were added and briefly homogenized. A uniform mixture of 34.900 g (0.022 mol) of adduct A2 and 3.900 g (0.022 mol) TDI T80 was added dropwise to the reaction mixture over a period of 35 min. The reaction mixture was stirred for additional 3 hours at 80° C. A turbid, yellow, liquid product was obtained.

(20) Comparative Rheology Additive C7:

(21) In a glass flask with stirrer, reflux condenser and nitrogen inlet, 1.400 g (0.033 mol) lithium chloride were dissolved in 105 g N-butyl butyrolactam while stirring over a period of 30 min, whereby a clear solution was obtained. Subsequently 6.300 g (0.033 mol) octahydro-4,7-methano-1H-indenedimethylamine were added and briefly homogenized. A uniform mixture of 33.600 g (0.022 mol) of adduct A2 and 3.700 g (0.022 mol) TDI T80 was added dropwise to the reaction mixture over a period of 20 min. The reaction mixture was stirred for additional 3 hours at 80° C. A clear, yellow, liquid product was obtained.

(22) Comparative Rheology Additive C8:

(23) In a glass flask with stirrer, reflux condenser and nitrogen inlet, 2.200 g (0.053 mol) lithium chloride were dissolved in 140 g N-butyl butyrolactam while stirring over a period of 30 min, whereby a clear solution was obtained. Subsequently 2.400 g (0.040 mol) ethylenediamine and 1.800 g (0.013 mol) m-xylylene diamine were added and briefly homogenized. The mixture became turbid. A uniform mixture of 47.500 g (0.035 mol) of adduct A2 and 6.100 g (0.035 mol) TDI T65 was added dropwise to the reaction mixture over a period of 20 min. During the addition, the reaction mixture cleared up completely. The reaction mixture was stirred for additional 3 hours at 80° C. A slightly turbid, yellow, liquid product was obtained.

(24) Comparative Rheology Additive C9:

(25) In a glass flask with stirrer, reflux condenser and nitrogen inlet, 2.300 g (0.053 mol) lithium chloride were dissolved in 140 g N-butyl butyrolactam while stirring over a period of 30 min, whereby a clear solution was obtained. Subsequently 2.400 g (0.040 mol) ethylendiamine and 1.200 g (0.013 mol) 1,4-diaminobutane were added and briefly homogenized. The mixture became turbid. A uniform mixture of 48.000 g (0.036 mol) of adduct A2 and 6.200 g (0.036 mol) TDI T65 was added dropwise to the reaction mixture over a period of 15 min. During the addition, the reaction mixture cleared up completely. The reaction mixture was stirred for additional 3 hours at 80° C. A slightly turbid, yellow, liquid product was obtained.

(26) Comparative Rheology Additive C10:

(27) In a glass flask with stirrer, reflux condenser and nitrogen inlet, 0.540 g (0.0128 mol) lithium chloride were dissolved in 105 g N-butyl butyrolactam while stirring over a period of 30 min, whereby a clear solution was obtained. Subsequently 0.770 g (0.0128 mol) ethylenediamine were added and briefly homogenized. The mixture became turbid. 42.930 g (0.0256 mol) of adduct A2 was added dropwise to the reaction mixture over a period of 25 min. During the addition, the reaction mixture cleared up completely. The reaction mixture was stirred for additional 3 hours at 80° C. A clear, light yellow, liquid product was obtained.

Examples (According to the Invention)

(28) Completeness of the following reactions was evaluated with wet chemical methods by determination of NCO content and the amine value.

(29) Rheology Additive According to the Invention E1:

(30) In a glass flask with stirrer, reflux condenser and nitrogen inlet, 1.400 g (0.0332 mol) lithium chloride were dissolved in 105 g N-butyl butyrolactam while stirring over a period of 30 min, whereby a clear solution was obtained. Subsequently 2.000 g (0.0332 mol) ethylenediamine were added and briefly homogenized. The mixture became turbid. A uniform mixture of 37.800 g (0.0221 mol) of adduct A2 and 3.900 g (0.0221 mol) TDI T80 was added dropwise to the reaction mixture over a period of 25 min. During the addition, the reaction mixture cleared up completely. The reaction mixture was stirred for additional 3 hours at 80° C. A clear, light brown, liquid product was obtained.

(31) Rheology Additive According to the Invention E2:

(32) In a glass flask with stirrer, reflux condenser and nitrogen inlet, 2.100 g (0.049 mol) lithium chloride were dissolved in 140 g N-butyl butyrolactam while stirring over a period of 30 min, whereby a clear solution was obtained. Subsequently 2.900 g (0.049 mol) ethylenediamine were added and briefly homogenized. The mixture became turbid. 55.000 g of the product obtained in step 1 of the production of adduct A4 (containing 0.098 mol of excessive TDI; “crude intermediate”) were added dropwise to the reaction mixture over a period of 30 min. During the addition, the reaction mixture cleared up completely. The reaction mixture was stirred for additional 3 hours at 80° C. A slightly turbid, yellow, liquid product was obtained.

(33) Rheology Additive According to the Invention E3:

(34) In a glass flask with stirrer, reflux condenser and nitrogen inlet, 1.900 g (0.0440 mol) lithium chloride were dissolved in 105 g N-butyl butyrolactam while stirring over a period of 30 min, whereby a clear solution was obtained. Subsequently 2.600 g (0.0440 mol) ethylenediamine were added and briefly homogenized. The mixture became turbid. A uniform mixture of 21.300 g (0.0147 mol) of adduct A2, 14.100 g (0.0147 mol) of adduct A3 and 5.100 g (0.0293 mol) TDI T80 was added dropwise to the reaction mixture over a period of 18 min. During the addition, the reaction mixture cleared up completely. The reaction mixture was stirred for additional 3 hours at 80° C. A clear, orange, liquid product was obtained.

(35) Rheology Additive According to the Invention E4:

(36) In a glass flask with stirrer, reflux condenser and nitrogen inlet, 2.200 g (0.0521 mol) lithium chloride were dissolved in 105 g N-butyl butyrolactam while stirring over a period of 30 min, whereby a clear solution was obtained. Subsequently 3.100 g (0.0521 mol) ethylenediamine were added and briefly homogenized. The mixture became turbid. A uniform mixture of 25.200 g (0.0174 mol) of adduct A2, 8.400 g (0.0174 mol) of adduct A1 and 6.000 g (0.0347 mol) TDI T80 was added dropwise to the reaction mixture over a period of 20 min. During the addition, the reaction mixture cleared up completely. The reaction mixture was stirred for additional 3 hours at 80° C. A clear, orange, liquid product was obtained.

(37) Rheology Additive According to the Invention E5:

(38) In a glass flask with stirrer, reflux condenser and nitrogen inlet, 2.000 g (0.047 mol) lithium chloride were dissolved in 140 g N-butyl butyrolactam while stirring over a period of 30 min, whereby a clear solution was obtained. Subsequently 2.800 g (0.047 mol) ethylenediamine were added and briefly homogenized. The mixture became turbid. A uniform mixture of 49.800 g (0.031 mol) of adduct A2 and 5.400 g (0.031 mol) TDI T65 was added dropwise to the reaction mixture over a period of 10 min. During the addition, the reaction mixture cleared up completely. The reaction mixture was stirred for additional 3 hours at 80° C. A slightly turbid, yellow, liquid product was obtained.

(39) Rheology Additive According to the Invention E6:

(40) In a glass flask with stirrer, reflux condenser and nitrogen inlet, 2.200 g (0.053 mol) lithium chloride were dissolved in 141.7 g N-butyl butyrolactam while stirring over a period of 30 min, whereby a clear solution was obtained. Subsequently 2.860 g (0.048 mol) ethylenediamine and 0.770 g (0.0057 mol) m-xylylenediamine were added and briefly homogenized. The mixture became turbid. A uniform mixture of 48.800 g (0.035 mol) of adduct A2 and 6.100 g (0.035 mol) TDI T65 was added dropwise to the reaction mixture over a period of 20 min. During the addition, the reaction mixture cleared up completely. The reaction mixture was stirred for additional 3 hours at 80° C. A clear, yellow, liquid product was obtained.

(41) Rheology Additive According to the Invention E7:

(42) In a glass flask with stirrer, reflux condenser and nitrogen inlet, 2.200 g (0.053 mol) lithium chloride were dissolved in 142.1 g N-butyl butyrolactam while stirring over a period of 30 min, whereby a clear solution was obtained. Subsequently 2.700 g (0.045 mol) ethylenediamine and 1.09 g (0.008 mol) m-xylylenediamine were added and briefly homogenized. The mixture became turbid. A uniform mixture of 48.800 g (0.035 mol) of adduct A2 and 6.100 g (0.035 mol) TDI T65 was added dropwise to the reaction mixture over a period of 20 min. During the addition, the reaction mixture cleared up completely. The reaction mixture was stirred for additional 3 hours at 80° C. A clear, yellow, liquid product was obtained.

(43) Rheology Additive According to the Invention E8:

(44) In a glass flask with stirrer, reflux condenser and nitrogen inlet, 2.200 g (0.053 mol) lithium chloride were dissolved in 141.05 g N-butyl butyrolactam while stirring over a period of 30 min, whereby a clear solution was obtained. Subsequently 3.020 g (0.050 mol) ethylenediamine and 0.360 g (0.0026 mol) m-xylylenediamine were added and briefly homogenized. The mixture became turbid. A uniform mixture of 48.800 g (0.035 mol) of adduct A2 and 6.100 g (0.035 mol) TDI T65 was added dropwise to the reaction mixture over a period of 20 min. During the addition, the reaction mixture cleared up completely. The reaction mixture was stirred for additional 3 hours at 80° C. A clear, yellow, liquid product was obtained.

(45) Rheology Additive According to the Invention E9:

(46) In a glass flask with stirrer, reflux condenser and nitrogen inlet, 2.200 g (0.053 mol) lithium chloride were dissolved in 141.1 g N-butyl butyrolactam while stirring over a period of 30 min, whereby a clear solution was obtained. Subsequently 2.860 g (0.048 mol) ethylenediamine and 0.490 g (0.0056 mol) 1,4-diaminobutane were added and briefly homogenized. The mixture became turbid. A uniform mixture of 48.800 g (0.035 mol) of adduct A2 and 6.100 g (0.035 mol) TDI T65 was added dropwise to the reaction mixture over a period of 15 min. During the addition, the reaction mixture cleared up completely. The reaction mixture was stirred for additional 3 hours at 80° C. A slightly turbid, yellow, liquid product was obtained.

(47) TABLE-US-00003 TABLE 3A Starting compounds for Producing Comparative Rheology Additives (used amounts in mol and (gram)) H.sub.2N—R.sup.3—NH.sub.2 Intermediate OCN—R.sup.2—NCO Additives D1 D2 D3 D4 D5 D6 D7 A2 TDI T80 TDI T65 C1 0.018 0.018 0.024 0.024 (1.100) (2.500) (35.60) (4.30) C2 0.033 0.022 0.022 (2.900) (37.00) (3.80) C3 0.033 0.022 0.022 (3.800) (37.50) (3.80) C4 0.031 0.021 0.021 (4.500) (35.30) (3.60) C5 0.036 0.024 0.024 (4.900) (34.40) (4.20) C6 0.033 0.022 0.022 (4.800) (34.90) (3.90) C7 0.033 0.022 0.022 (6.300) (33.60) (3.70) C8 0.040 0.013 0.035 0.035 (2.400) (1.800) (47.50) (6.10) C9 0.040 0.013 0.036 0.036 (2.400) (1.200) (48.00) (6.20) C10 0.013 0.026 (0.770) (42.93) D1: ethylenediamine; D2: m-XDA; D3: 1,4-diaminobutane; D4: 1,6-diaminohexane; D5: 1,8-diaminooctane; D6: 1,3-bis aminomethyl cyclohexane; D7: octahydro-4,7-methano-1H-indenedimethylamine

(48) TABLE-US-00004 TABLE 3B Starting Compounds for Producing Rheology Additives According to the Invention (used amounts in mol and (gram)) Intermediate H.sub.2N—R.sup.3—NH.sub.2 crude OCN—R.sup.2—NCO Additives D1 D2 D3 A1 A2 A3 A4 TDI T80 TDI T65 E1 0.0332  0.0221 0.0221 (2.000) (37.80) (3.90) E2 0.0490 (55.00)- 0.098  (2.900) TDI T80 E3 0.0440  0.0147 0.0147 0.0293 (2.600) (21.30) (14.10) (5.10) E4 0.0521 0.0174  0.0174 0.0347 (3.100) (8.40) (25.20) (6.00) E5 0.0470 0.031 0.031 (2.800) (49.80) (5.40) E6 0.0476 0.0057 0.035 0.035 (2.860) (0.770) (48.80) (6.10) E7 0.0450 0.0080 0.035 0.035 (2.700) (1.090) (48.80) (6.10) E8 0.0500 0.0026 0.035 0.035 (3.020) (0.360) (48.80) (6.10) E9 0.0476 0.0056 0.035 0.035 (2.860) (0.490) (48.80) (6.10) D1: ethylenediamine; D2: m-XDA; D3: 1,4-diaminobutane

Application Examples and Testing

(49) TABLE-US-00005 TABLE 4 Raw Materials Product name Chemical Composition Supplier Setal 1603 BA-78 polyester polyol 78 wt.-% Nuplex in butylacetate Resins B.V. Setalux 1903 BA-75 acrylate polyol 75 wt. % Nuplex in butylacetate Resins B.V. Butylacetat n-butylacetate Overlack GmbH Dowanol PMA 1,2-propanediol monoacetate Dow Chemical monomethylether Tinuvin 1130 hydroxyphenylbenzotriazole BASF (UV absorber) Tinuvin 292 bis- and methyl-(1,2,2,6,6- BASF pentamethyl-4-piperidyl)- sebacate (light stabilizer) TinStab BL 277 dibutyltin dilaurate Akcros (catalyst) Chemicals Ltd. BYK-378 leveling agent BYK-Chemie GmbH Tolonate HDT-LV Solvent-free hexamethylene Vencore diisocyanate trimer Chemicals JV
Test System 1: 2-Component-PU Clear Coat for Automotive Repair

(50) The clear coat composition was prepared according to the formulation shown in Table 5. 200 g of component A was weighed into a 870 ml polyethylene beaker and 8 g of a rheology control additive containing a species according to formula (I) was incorporated using a Dispermat CV (Getzmann) with a 4 cm tooth disk for 2 min at 1000 rpm. Subsequently, the samples were stored at room temperature for 48 hours. For the application, the addition of 100 g of component B was carried out by stirring with a spatula until the clear coat composition was optically homogeneous. The run-out time of the clear coat composition was then determined using a DIN 4 mm outlet beaker (BYK-Gardner GmbH). The clear coat composition was diluted with a solvent mixture (butylacetate/Dowanol PMA; 40:60 w/w) to the extent that it had a DIN 4 run-out time of 21 s (+/−1 s) for the application. The application of the clear coat composition was carried out by means of pneumatic spray application (LacTec paint shop, spray gun De VILBISS 797 “air cap”, 1.3 mm nozzle, air flow speed: 0.6 m/s) on vertically suspended, primed and perforated steel plates (N/16300500L cold rolled fine sheet incl 16 holes a 10 mm with protective coating (gray/white, application side gray 300×500×0.60−0.70 mm) The clear coat composition was applied in three spray passes to determine the sag limit of the clear coat composition (the dry coat thickness of the clear lacquer was between 20-70 μm) After the spraying application, the coated sheets were vented vertically at room temperature for 10 minutes and then dried vertically at 60° C. for 60 minutes in a VTL 60/90 reflow oven (from Vötsch Industrietechnik GmbH). After 24 h the determination of the sag limit was made by optically determining that spot on the perforated plate, that had no clear coat accumulation under the hole (no distinct bead or runner formation). The determination of the dry layer thickness above and below the determined hole was carried out by means of a 3-fold measurement and the subsequent averaging with the dry-film measuring device Byko-Test 1500 (BYK-Gardner GmbH). The test results are shown in Table 6.

(51) TABLE-US-00006 TABLE 5 2-component-PU clear coat composition Component Product name Amount in parts by weight A Setal 1603 BA-78 45.8 Setalux 1903 BA-75 109.4 Butyl acetate 23.4 Dowanol PMA 8.8 Tinuvin 1130 2.9 Tinuvin 292 0.8 TinStab BL 277 8.8 (1 wt.-% in butyl acetate) BYK-378 0.1 B Tolonate HDT-LV 59.7 Butyl acetate 20.5 Dowanol PMA 19.8

(52) TABLE-US-00007 TABLE 6 Results Clear Coat Composition Rheology Additive Sag limit [μm] 0 Reference (no additive) 28 1 C1 30 2 C2 37 3 C3 29 4 C4 31 5 C5 39 6 C6 28 7 C7 28 8 E1 >67 9 E2 >69 10 E3 >60 11 E4 >57 12 E5 64

(53) In Table 6 it is clearly shown that surprisingly the non-inventive clear coat composition 0 (reference, no additive) as well as non-inventive clear coat compositions 1 to 7 (making use of non-inventive rheology additives C1 to C7) have a sag limit which is much lower than the sag limit of the inventive clear coat compositions 8 to 12 (making use of inventive rheology additives E1 to E5). Therefore the sag resistance of the inventive clear coat compositions is much higher compared to the non-inventive clear coat compositions.

(54) Test System 2: 2-Component-PU Clear Coat for Automotive Repair

(55) The clear coat composition used is the one according table 5. The clear coat compositions were prepared according to the same procedure as described for Test System 1. The rheology additives used are shown in table 7. Testing was carried out the same way as for Test System 1. The only difference to Test System 1 was that the spraying device for pneumatic spray application was changed to a spraying unit of Eisenmann LaTec GmbH (spray gun AGMD Pro (De Vilbiss), 1.2 mm nozzle De Vilbiss GTI PRO High Efficiency TE 40 C; air flow speed: 0.6 m/s). Results of the sag limit tests are shown in table 7.

(56) TABLE-US-00008 TABLE 7 Results Clear Coat Composition Rheology Additive Sag limit [μm] 14 Reference (no additive) 25 15 C8 33 16 C9 34 17 E7 52 18 E6 55 19 E8 >64 20 E9 >64 21 C10 28

(57) Table 7 shows that Comparative Rheology Additives C8 (making use of a mixture of 75 mol-% ethylenediamine and 25 mol-% of m-xylylenediamine in its manufacture) and C9 (making use of a mixture of 75 mol-% ethylenediamine and 25 mol-% of 1,4-diaminobutane in its manufacture) cause low sag limits in the respective, non-inventive clear coat compositions 15 and 16. If the molar ratio of ethylenediamine to m-xylylenediamine is increased to e.g. 85:15 (E7), 90:10 (E6) and 95:5 (E8) a much higher sag resistance is obtained for the clear coat composition. The same applies, if the molar ratio of ethylenediamine to 1,4-diaminobutane is increased to 90:10 (E9). Clear coat 21 demonstrates the Comparative Rheology Additive C10 causes a low sag limit. Comparative Rheology Additive C10 represents a urea group containing compound of formula (I), wherein n is 1.