UREA GROUP CONTAINING RHEOLOGY CONTROL ADDITIVE

Abstract

The invention relates to a composition comprising: a) 10 to 60% by weight of one or more urea components having a number average molecular weight Mn above 350 g/mol, and b) 40 to 90% by weight of one or more carboxylic acid components according to formula (I): HO—R.sup.1—COOH, wherein R.sup.1 represents an organic group having 3 to 75 carbon atoms, and wherein the % by weight are calculated on the sum of components a) and b).

Claims

1. A composition comprising: 10 to 60% by weight of one or more urea components having a number average molecular weight Mn above 350 g/mol, determined by gel permeation chromatography (eluent: solution of lithium bromide (content 5g/1) in dimethylacetamide, standard: polymethylmethacrylate, column temperature: 80° C.) according to DIN 55672 part 2 (year: 2008), and 40 to 90% by weight of one or more carboxylic acid components according to formula (I) HO—R.sup.1—COOH, wherein R.sup.1 represents an organic group having 3 to 75 carbon atoms, wherein % by weight is based on the total weight of the one or more urea components and the one or more carboxylic acid components.

2. The composition according to claim 1, wherein the one or more urea components comprises aromatic groups.

3. The composition according to claim 1, wherein the one or more urea components comprises molecules containing at least one urea group and at least one urethane group.

4. The composition according to claim 1, wherein the one or more urea components comprises one or more carboxylic acid groups.

5. The composition according to claim 1, wherein R.sup.1 represents a hydrocarbyl group having 9 to 23 carbon atoms.

6. The composition according to any one of the preceding claims claim 1, wherein the composition further comprises one or more organic diluents.

7. The composition according to claim 6, wherein the composition further comprises one or more salts.

8. The composition according to claim 7, wherein the mixture of the one or more urea components, the one or more carboxylic acid components, the one or more organic diluents, and the one or more has an acid number in the range of 20 to 60 mg KOH/g.

9. The composition according to claim 6, wherein the sum of the weights of the one or more urea components and the one or more carboxylic acid components is 15 to 90% by weight, the one or more organic diluents are included in an amount of 10.0 to 85.0% by weight, and the composition optionally further comprises one or more salts in an amount of 0.0 to 8.0% by weight, wherein % by weight is based on total weight of the one or more urea components, the one or more carboxylic acid components, the one or more organic diluents, and the one or more salts.

10. The composition according to claim 6, wherein the one or more urea components are included in amount of 3.0 to 40.0% by weight, the one or more carboxylic acid components are included in amount of 12.0 to 60.0% by weight the one or more organic diluents are included in amount of 10.0 to 85.0% by weight, and the composition optionally further comprises one or more salts in an amount of 0.0 to 8.0% by weight, wherein % by weight is based on the total weight of the one or more urea components, the one or more carboxylic acid components, the one or more organic diluents, and the one or more salts, with the proviso that the one or more urea components are present in an amount of 10 to 60% by weight, based on the total weight of the one or more urea components and the one or more carboxylic acid components, and the one or more carboxylic acid components are present in an amount of 40 to 90% by weight, based on the total weight of the one or more urea components and the one or more carboxylic acid components.

11. (canceled)

12. A liquid composition comprising 0.1 to 7.5% by weight of a mixture of one or more urea components having a number average molecular weight Mn above 350 g/mol, determined by gel permeation chromatography (eluent: solution of lithium bromide (content 5 g/l) in dimethylacetamide, standard: polymethylmethacrylate, column temperature: 80° C.) according to DIN 55672 part 2 (year: 2008), and one or more carboxylic acid components according to formula (I) HO—R.sup.1—COOH, wherein R.sup.1 represents an organic group having 3 to 75 carbon atoms, wherein the weight ratio of the one or more urea components to the one or more carboxylic acid components is in the range of 10:90 to 60:40, wherein the liquid composition is liquid at a temperature of 23° C., and wherein % by weight is based on the total weight of the liquid composition.

13. The liquid composition according to claim 12, wherein the liquid composition comprises between 0.0 and 7.0% of water, based on the total weight of the liquid composition.

14. The liquid composition according to claim 12, wherein the liquid composition comprises between 0.0 and 10.0% by weight of a volatile organic solvent, based on the total weight of the liquid composition.

15. The liquid composition according to claim 14, wherein the composition comprises a film-forming resin.

16. A process of controlling the rheology of a liquid composition, the process comprising: adding to the liquid composition one or more urea components having a number average molecular weight Mn above 350 g/mol, determined by gel permeation chromatography (eluent: solution of lithium bromide (content 5 g/l) in dimethylacetamide, standard: polymethylmethacrylate, column temperature: 80° C.) according to DIN 55672 part 2 (year: 2008), and one or more carboxylic acid components according to formula (I) HO—R.sup.1—COOH, wherein R.sup.1 represents an organic group having 3 to 75 carbon atoms, wherein the weight ratio of the one or more urea components to the one or more carboxylic acid components is in the range of 60:40 to 10:90.

17. A process of controlling the rheology of a liquid composition comprising adding the composition of claim 1 to the liquid composition.

Description

EXAMPLES

Synthesis Examples

Examples (According to the Invention)

Synthesis Example 1 (SE1)

[0105] A four-necked round-bottom flask equipped with stirrer, thermometer and reflux condenser was charged with 95.0 g N-butylpyrrolidone and 2.6 g (0.06 mol) lithium chloride and heated up to 80° C. under nitrogen atmosphere. After 30 minutes 12.2 g (0.070 mol) tolylene diisocyanate with 80% content of 2,4-diisocyanatotoluene (in the following abbreviated by TDI T 80) were added to the mixture.

[0106] A mixture of 4.8 g (0.035 mol) m-xylylenediamine and 21.7 g N-butylpyrrolidone was added using a dosing pump with a rate of 3.0 mL per minute.

[0107] After three hours reaction time 7.6 g (0.07 mol) benzyl alcohol were added and the mixture was stirred for 30 minutes. 42.0 g (0.140 mol) 12-hydroxystearic acid were added and stirring was continued for another 30 minutes.

[0108] The product was a viscous, orange liquid (GPC: M.sub.n=3757 g/mol; M.sub.w=10093 g/mol).

Synthesis Example 2 (SE2)

[0109] A four-necked round-bottom flask equipped with stirrer, thermometer and reflux condenser was charged with 100.0 g N-butylpyrrolidone and 2.6 g (0.06 mol) lithium chloride and heated up to 80° C. under nitrogen atmosphere. After 30 minutes 12.2 g (0.07 mol) TDI T 80 was added to the mixture.

[0110] A mixture of 2.1 g (0.03 mol) ethylenediamine and 21.7 g N-butylpyrrolidone was added using a dosing pump with a rate of 3.0 mL per minute.

[0111] After three hours reaction time 7.6 g (0.07 mol) benzyl alcohol were added and the mixture was stirred for 30 minutes. 42.0 g (0.14 mol) 12-hydroxystearic acid were added and stirring was continued for another 30 minutes.

[0112] The product was a viscous, orange liquid (GPC: M.sub.n=2559 g/mol; M.sub.w=10660 g/mol).

Synthesis Example 3 (SE3)

[0113] A four-necked round-bottom flask equipped with stirrer, thermometer and reflux condenser was charged with 107.0 g N-butylpyrrolidone and 2.6 g (0.06 mol) lithium chloride and heated up to 80° C. under nitrogen atmosphere. After 30 minutes 12.2 g (0.07 mol) TDI T 80 were added to the mixture.

[0114] A mixture of 5.95 g (0.035 mol) isophorone diamine and 21.7 g N-butylpyrrolidone was added using a dosing pump with a rate of 3.0 mL per minute.

[0115] After three hours reaction time 7.6 g (0.07 mol) benzyl alcohol were added and the mixture was stirred for 30 minutes. 42.0 g (0.14 mol) 12-hydroxystearic acid were added and stirring was continued for another 30 minutes.

[0116] The product was a viscous, orange liquid (GPC: M.sub.n=2812 g/mol; M.sub.w=8651 g/mol).

Synthesis Example 4 (SE4)

[0117] A four-necked round-bottom flask equipped with stirrer, thermometer and reflux condenser was charged with 300.0 g N-butylpyrrolidone and 7.8 g (0.0185 mol) lithium chloride and heated up to 80° C. under nitrogen atmosphere. After 30 minutes 36.5 g (0.21 mol) TDI T 80 were added to the mixture.

[0118] A mixture of 14.4 g (0.105 mol) m-xylylenediamine and 65.1 g N-butylpyrrolidone was added using a dosing pump with a rate of 5.0 mL per minute.

[0119] After three hours reaction time 157.5 g (0.525 mol) 12-hydroxystearic acid were added and stirring was continued for another 30 minutes.

[0120] The product was a viscous, orange liquid (GPC: M.sub.n=2301 g/mol; M.sub.w=11999 g/mol).

Synthesis Example 5 (SE5)

[0121] A four-necked round-bottom flask equipped with stirrer, thermometer and reflux condenser was charged with 113.1 g N-butylpyrrolidone and 2.6 g (0.06 mol) lithium chloride and heated up to 80° C. under nitrogen atmosphere. After 30 minutes 15.56 g (0.07 mol) isophorone diisocyanate were added to the mixture.

[0122] A mixture of 4.8 g (0.035 mol) m-xylylenediamine and 21.7 g N-butylpyrrolidone was added using a dosing pump with a rate of 3.0 mL per minute.

[0123] After three hours reaction time 7.6 g (0.07 mol) benzyl alcohol were added and the mixture was stirred for 30 minutes. 42.0 g (0.14 mol) 12-hydroxystearic acid were added and stirring was continued for another 30 minutes.

[0124] The product was a viscous, yellow liquid (GPC: M.sub.n=1710 g/mol; M.sub.w=3266 g/mol).

Synthesis Example 6 (SE6)

[0125] A four-necked round-bottom flask equipped with stirrer, thermometer and reflux condenser was charged with 95.0 g N-butylpyrrolidone and 2.34 g (0.050 mol) lithium chloride and heated up to 80° C. under nitrogen atmosphere. After 30 minutes 12.2 g (0.07 mol) TDI T 80 were added to the mixture.

[0126] A mixture of 4.8 g (0.035 mol) m-xylylenediamine and 21.7 g N-butylpyrrolidone was added using a dosing pump with a rate of 3.0 mL per minute.

[0127] After three hours reaction time 14.44 g (0.07 mol) butyltriglycol were added and the mixture was stirred for 30 minutes. 42.0 g (0.14 mol) 12-hydroxystearic acid were added and stirring was continued for another 30 minutes.

[0128] The product was a viscous, orange liquid (GPC: M.sub.n=2685 g/mol; M.sub.w=10225 g/mol).

Synthesis Example 7 (SE7)

[0129] A four-necked round-bottom flask equipped with stirrer, thermometer and reflux condenser was charged with 52.4 g N-butylpyrrolidone and 2.1 g (0.06 mol) lithium chloride and heated up to 80° C. under nitrogen atmosphere. After 30 minutes 5.5 g (0.032 mol) TDI T 80 and 2.83 g (0.007 mol) monoadduct made from TDI T65 and butyltriglycol (synthesized as described in EP 1048681 B1, Example 2) were added to the mixture.

[0130] A mixture of 4.8 g (0.035 mol) m-xylylenediamine and 21.7 g N-butylpyrrolidone was added using a dosing pump with a rate of 3.0 mL per minute. After three hours reaction time 42.0 g (0.14 mol) 12-hydroxystearic acid were added and stirring was continued for another 30 minutes.

[0131] The product was a milky, yellow solid (M.sub.n=3684 g/mol).

Synthesis Example 8 (SE8)

[0132] A four-necked round-bottom flask equipped with stirrer, thermometer and reflux condenser was charged with 95 g N-butylpyrrolidone and 2.6 g (0.065 mol) lithium chloride and heated up to 80° C. under nitrogen atmosphere. After 30 minutes 12.2 g (0.070 mol) TDI T 80 were added to the mixture.

[0133] A mixture of 4.8 g (0.035 mol) m-xylylenediamine and 21.7 g N-butylpyrrolidone was added using a dosing pump with a rate of 3.0 mL per minute.

[0134] After three hours reaction time 14.4 g (mol) triethylene glycol monobutyl ether were added and the mixture was stirred for 30 minutes. 42.0 g (0.14 mol) 12-hydroxystearic acid were added and stirring was continued for another 30 minutes.

[0135] The product was a viscous, orange liquid (GPC: M.sub.n=4711; M.sub.w=13194).

Synthesis Example 9 (SE9)

[0136] A four-necked round-bottom flask equipped with stirrer, thermometer and reflux condenser was charged with 95 g N-butylpyrrolidone and 2.6 g (0.065 mol) lithium chloride and heated up to 80° C. under nitrogen atmosphere. After 30 minutes 12.2 g (0.070 mol) TDI T 80 were added to the mixture.

[0137] A mixture of 4.8 g (0.035 mol) m-xylylenediamine and 21.7 g N-butylpyrrolidone was added using a dosing pump with a rate of 3.0 mL per minute.

[0138] After three hours reaction time 8.26 g (mol) ethylene glycol monobutyl ether were added and the mixture was stirred for 30 minutes. 42.0 g (0.14 mol) 12-hydroxystearic acid were added and stirred for another 30 minutes.

[0139] The product was a viscous, yellow liquid (GPC: M.sub.n=4725; M.sub.w=18860).

Comparative Examples (Non-Inventive)

Comparative Example 1 (SC1)

[0140] A four-necked round-bottom flask equipped with stirrer, thermometer and reflux condenser was charged with 102.7 g N-butylpyrrolidone and 2.6 g (0.060 mol) lithium chloride and heated up to 80° C. under nitrogen atmosphere. After 30 minutes 12.2 g (0.07 mol) TDI T 80 were added to the mixture.

[0141] A mixture of 4.8 g (0.035 mol) m-xylylenediamine and 21.7 g N-butylpyrrolidone was added using a dosing pump with a rate of 3.0 mL per minute.

[0142] After three hours reaction time 7.6 g (0.07 mol) benzyl alcohol were added and the mixture was stirred for 30 minutes. 39.8 g (0.140 mol) stearic acid were added and stirring was continued for another 30 minutes.

[0143] The product was a viscous, orange liquid (GPC: M.sub.n=3716 g/mol; M.sub.w=10291 g/mol).

Comparative Example 2 (SC2)

[0144] A four-necked round-bottom flask equipped with stirrer, thermometer and reflux condenser was charged with 95.0 g N-butylpyrrolidone and 2.6 g (0.060 mol) lithium chloride and heated up to 80° C. under nitrogen atmosphere. After 30 minutes 12.2 g (0.07 mol) TDI T 80 were added to the mixture.

[0145] A mixture of 4.8 g (0.035 mol) m-xylylenediamine and 21.7 g N-butylpyrrolidone was added using a dosing pump with a rate of 3.0 mL per minute.

[0146] After three hours reaction time 7.6 g (0.07 mol) benzyl alcohol were added and the mixture was stirred for 30 minutes.

[0147] The product was a viscous, orange liquid (GPC: M.sub.n=2607 g/mol; M.sub.w=8665 g/mol).

Comparative Example 3 (SC3)

[0148] A four-necked round-bottom flask equipped with stirrer, thermometer and reflux condenser was charged with 103.0 g N-butylpyrrolidone and 2.6 g (0.06 mol) lithium chloride and heated up to 80° C. under nitrogen atmosphere. After 30 minutes 12.2 g (0.070 mol) TDI T 80 were added to the mixture.

[0149] A mixture of 4.8 g (0.035 mol) m-xylylenediamine and 21.7 g N-butylpyrrolidone was added using a dosing pump with a rate of 3.0 mL per minute.

[0150] After three hours reaction time 7.6 g (0.07 mol) benzyl alcohol were added and the mixture was stirred for 30 minutes. 40.1 g (0.140 mol) 12-hydroxystearic alcohol were added and stirring was continued for another 30 minutes.

[0151] The product was a viscous, orange liquid (GPC: M.sub.n=1962; M.sub.w=6872).

Comparative Example 4 (SC4)

[0152] A mixture of 26.7 g (0.089 mol) 12-hydroxystearic acid and 80.0 g N-butylpyrrolidone was stirred under heat until the acid was dissolved.

[0153] The product was a clear, colorless product.

Comparative Example 5 (SC5)

[0154] A four-necked round-bottom flask equipped with stirrer, thermometer and reflux condenser was charged with 300.0 g N-butylpyrrolidone and 7.8 g (0.185 mol) lithium chloride and heated up to 80° C. under nitrogen atmosphere. After 30 minutes 36.5g (0.210 mol) TDI T 80 were added to the mixture.

[0155] A mixture of 14.4 g (0.105 mol) m-xylylendiamine and 65.1 g N-butylpyrrolidone was added using a dosing pump with a rate of 5.0 mL per minute.

[0156] After three hours reaction time 63.4 g (0.210 mol) 12-hydroxystearic acid were added and stirring was continued for another 30 minutes.

[0157] The product was a viscous, orange liquid (GPC: M.sub.n=4159 g/mol; M.sub.w=15319 g/mol).

Application Examples and Testing

[0158]

TABLE-US-00001 TABLE 1 Raw materials Product name Description Manufacturer Epikote 828 Liquid epoxy resin produced from Hexion Inc. bisphenol A resin and epichlorohydrin Grilonit RV 1812 1,6-hexane diglycidyl ether EMS-CHEMIE AG DISPERBYK-2152 Hyperbranched polyester W&D BYK Chemie GmbH additive BYK-1790 Mixture of foam-destroying polymers BYK Chemie GmbH Bayferrox 130M Iron oxide red pigment LANXESS EWO Barium sulfate Sachtleben Minerals GmbH & Co. KG Luzenac 20M2 Multipurpose fine talc/chlorite Blagden Specialty Chemicals Ltd. Cardolite LITE 2001 Phenalkamines Cardolite Specialty LV Chemicals Europe NV

[0159] Application test system: 2 Pack-Epoxy Protective Coating

[0160] Component A of the protective coating was produced using the formulation in table 2. Subsequently, 100 g of component A of the formulation was filled in 150 mL glass bottles. After the formulation was cooled down to room temperature (23° C.), 1.0% by weight, based on component A of the active substance of the respective rheology additive SE1 to SE9 and SC1 to SC4 was incorporated into the formulation under stirring with a Dispermat CV (Fa. Getzmann) for 2 min. at 1000 rpm, using a 4 cm diameter toothed plate. Active substance refers to all components of the mixture obtained in the synthesis examples, with exception of the organic diluent (c) contained. For the production of Application Example ACS, no rheology additive was incorporated. Afterwards the samples were stored at room temperature for 24 hours before they were applied. Before application, 33.1 g hardener (component B) was added to component A and incorporated with a spatula by hand stirring until the sample looked homogeneous. After homogenizing the samples were applied with a stepped doctor blade Model 421/S (Erichsen GmbH & Co KG) with 50-500 and 550-1000 μm wet film thickness. The application was done on contrast cards 2801 (BYK-Gardner GmbH) using the automatic applicator byko-drive XL (BYK-Gardner GmbH) with an application speed of 50 mm/s. Directly after application the draw down was hanged up vertical at room temperature until it was dried. After drying the sag resistance was evaluated visually. Therefore, the wet film thickness was chosen that shows after drying a clear separation of the draw down, no runner and also no bulge building between the applied film thickness. Wet film thicknesses obtained are listed in table 3; film thicknesses of more than 1000 μm were not applied, therefore the value “≥1000 μm” refers to a minimum thickness of 1000 μm that could be observed.

TABLE-US-00002 TABLE 2 Formulation of application test: 2pack-EP protective coating Product name Component A Epikote 828 20.0 g Grilonit RV 1812 8.0 g DIS-2152 0.5 g BYK-1790 0.5 g Bayferrox 130 M 4.0 g EWO 36.0 g Luzenac 20 M2 11.0 g Dispermat, 40° C., 30 min., 8500 rpm., 4 cm-toothed plate Epikote 828 20.0 g Sum of Component 100.0 g A Component B Cardolite LITE 2001 LV 33.1 g Sum of Components 133.1 g A and B Mixing ratio component A: component B = 100: 33.1

TABLE-US-00003 TABLE 3 Application test results Synthesis Example No. Application Example No. Sag resistance/μm SE1 AE1 800 SE2 AE2 700 SE3 AE3 500 SE4 AE4 900 SE5 AE5 500 SE6 AE6 600 SE7 AE7 >1000 SE8 AE8 >1000 SE9 AE9 700 SE1 + co-thickener* AE10 >1000 SC1 AC1 250 SC2 AC2 50 SC3 AC3 100 SC4 AC4 150 SC5 AC5 100 — AC6 50 *In this example, the additive prepared in SE1 has been combined with the polyethyleneimine derivative described in “Component b1.2” of EP 3161036 B1 as co-thickener. SE1 was incorporated into the epoxy component A in the same amount and using the same method as described for the other examples. The additional rheology control additive (reaction mixture obtained in “Component b1.2” of EP 3161036 B1) was incorporated into the hardener component B at a dosage of 0.9% by weight, referring to the amount of component B used.

[0161] It was surprisingly found that inventive composition Example AE1 provided a highly improved sag resistance compared to non-inventive Comparison Examples SC1, SC2, SC3, SC4 and SC5. Whereas Example AE1/SE1 contains a urea component as well as 12-hydroxystearic acid, the non-inventive comparison samples SC1 to SC3 and SC5 lack acid or 12-hydroxystearic acid, respectively. Therefore, the non-inventive comparison samples show a lower rheological effectiveness measured by sag resistance than the examples according to the present invention. These samples are obviously better suitable to improve the sag resistance than the non-inventive comparison samples.