RHEOLOGY CONTROL AGENT

Abstract

The invention relates to the use of a composition as rheology control agent comprising (A) silicate and (B) a polyethylenimine comprising the structure (I), wherein R.sup.1 is formula (I), or part of the polyethylenimine, and wherein R.sup.2 is H or an organic group, R.sup.3 is H or an organic group, with the proviso that one of R.sup.2 or R.sup.3 is H and wherein the polyethyleneimine has a weight average molecular weight Mw in the range of 40000 to 300000 g/mol before the reaction with the epoxide compound.

##STR00001##

Claims

1. A process of controlling rheology of a liquid preparation, the process comprising: adding a silicate (A) to the preparation, and adding a reaction product (B) to the preparation, the reaction product (B) obtained by reacting a polyethylenimine with at least one compound having at least one epoxide group, the reaction product (B) comprising structure (I) ##STR00016## wherein R.sup.1 is H, ##STR00017## or part of the polyethylenimine, and wherein R.sup.2 is H or an organic group, R.sup.3 is H or an organic group, with the proviso that one of R.sup.2 or R.sup.3 is H.sub.L and wherein the polyethyleneimine has a weight average molecular weight Mw in the range of 40000 to 300000 g/mol before the reaction with the at least one compound having at least one epoxide group.

2. The process according to claim 1, wherein the silicate (A) comprises one or more of clay and silica.

3. The process according to claim 1, wherein R.sup.2 and R.sup.3 are independently selected from hydrocarbyl groups, organic groups comprising an ether group, and organic groups comprising an ester group.

4. The process according to claim 1, wherein the reaction product (B) comprises one or more of a carboxylic acid salt, a phosphoric acid salt, a phosphonic acid salt, or a sulfonic acid salt.

5. The process according to claim 1, wherein adding the reaction product (B) to the preparation comprises adding a solution to the preparation, the solution comprising the reaction product (B) and a high boiling solvent having a boiling point of at least 250° C. at 100 kPa.

6. The process according to claim 5, wherein the solution is a liquid at 23° C. and at 100 kPa.

7. The process according to claim 5, wherein the high boiling solvent comprises a polyether.

8. (canceled)

9. The process according to claim 1, the preparation being non-aqueous preparation.

10. The process according to claim 1, wherein the reaction product (B) is added to the preparation in an amount ranging from 0.1 to 100.0% by weight, calculated on the weight of the silicate (A).

11. The process according to claim 1, wherein the preparation includes a binder comprising at least one of an alkyd resin, an unsaturated polyester resin, a vinylester resin, an acrylate resin, an epoxy resin, a polyurethane resin, a polyaspartic resin, and a silyl modified polymer.

12. (canceled)

13. A kit of parts comprising: at least one binder module and at least one crosslinking module, wherein one or more of the at least one binder module and the at least one crosslinking module comprises a silicate (A) and a reaction product (B), the reaction product (B) obtained by reacting a polyethylenimine with at least one compound having at least one epoxide group, the reaction product (B) comprising structure (I) ##STR00018## wherein R.sup.1 is H, ##STR00019## or part of the polyethylenimine, and wherein R.sup.2 is H or an organic group, R.sup.3 is H or an organic group, with the proviso that one of R.sup.2 or R.sup.3 is H.sub.L and wherein the polyethylenimine has a weight average molecular weight Mw in the range of 40000 to 300000 g/mol before the reaction with the at least one compound having at least one epoxide group.

14. The kit of parts according to claim 13 wherein the at least one binder module comprises an epoxy resin.

15. A process comprising: applying a preparation to at least part of a surface of a three-dimensional article, wherein the preparation comprises at least one binder, a silicate (A), and a reaction product (B), the reaction product (B) obtained by reacting a polyethylenimine with at least one compound having at least one epoxide group, the reaction product (B) comprising structure (I) ##STR00020## wherein R.sup.1 is H, ##STR00021## or part of the polyethylenimine, and wherein R.sup.2 is H or an organic group, R.sup.3 is H or an organic group, with the proviso that one of R.sup.2 or R.sup.3 is H.sub.L and wherein the polyethyleneimine has a weight average molecular weight Mw in the range of 40000 to 300000 g/mol before the reaction with the at least one compound having at least one epoxide group, wherein the preparation optionally further comprises at least one crosslinking agent, and optionally curing the preparation.

16. A three-dimensional article comprising a preparation, wherein the preparation comprises at least one binder, a silicate (A), and a reaction product (B), the reaction product (B) obtained by reacting a polyethylenimine with at least one compound having at least one epoxide group, the reaction product (B) comprising structure (I) ##STR00022## wherein R.sup.1 is H, ##STR00023## or part of the polyethylenimine, and wherein R.sup.2 is H or an organic group, R.sup.3 is H or an organic group, with the proviso that one of R.sup.2 or R.sup.3 is H.sub.L and wherein the polyethyleneimine has a weight average molecular weight Mw in the range of 40000 to 300000 g/mol before the reaction with the epoxide compound, wherein the preparation optionally further comprises at least one crosslinking agent.

17. The process according to claim 1, comprising adding the silicate (A) to the preparation before adding the reaction product (B) to the preparation.

18. The process according to claim 1, comprising adding the reaction product (B) to the preparation before adding the silicate (A) to the preparation.

19. The process according to claim 1, comprising adding a composition to the preparation, the composition comprising the silicate (A) and the reaction product (B).

20. The process according to claim 2, wherein the silicate (A) comprises clay and silica.

Description

SYNTHESIS EXAMPLES

[0117]

TABLE-US-00001 TABLE 1 Raw materials Name Chemical description Polyamine A Polyethyleneimine, M.sub.n = 33212, M.sub.w = 196844 Polyamine B Polyethyleneimine, M.sub.n = 31155, M.sub.w = 65421 Polyamine C Polyethyleneimine, M.sub.n = 33832, M.sub.w = 92607 Polyamine D Polyethyleneimine, M.sub.n = 6326, M.sub.w = 8714 Polyamine E Polyethyleneimine, M.sub.n = 15038, M.sub.w = 19124 MPEG 350 Methoxypolyethyleneglycol, molecular weight 350 g/mol Glycidylether A linear C13/C15-alkyl glycidyl ether Acid A Alkylethercarboxylic acid, C12/C14-based, 2.5 repeating units of ethylene oxide; available via reaction of the ethoxylated alcohol with chloroacetic acid

[0118] Mn and Mw of the polyethyleneimines were measured via GPC according to the method describe above.

[0119] Synthesis of Modifying Agents According to the Invention

[0120] IS 1

[0121] Polyamine A (50 wt. % solution in water, 110.3 g) and MPEG 350 (630 g) were combined. The mixture was heated under stirring to 105° C. Vacuum was applied and all water was distilled off. The resulting material was cooled to 55° C. and Glycidylether A (14.84 g) was added. The mixture was stirred at 100° C. for 2 h.

[0122] IS 2

[0123] Polyamine A (50 wt. % solution in water, 70 g) and MPEG 350 (630 g) were combined. The mixture was heated under stirring to 105° C. Vacuum was applied and all water was distilled off. The resulting material was cooled to 55° C. and Glycidylether A (17.5 g) and Acid A (17.5 g) were added subsequently. The mixture was stirred at 100° C. for 2 h.

[0124] IS3

[0125] Polyamine B (56 wt. % solution in water, 21.11 g) and MPEG 350 (135.0 g) were combined. The mixture was heated under stirring to 105° C. Vacuum was applied and all water was distilled off. The resulting material was cooled to 55° C. and Glycidylether A (3.18 g) was added. The mixture was stirred at 100° C. for 2 h.

[0126] IS4

[0127] Polyamine C (25 wt. % solution in water, 47.28 g) and MPEG 350 (135.0 g) were combined. The mixture was heated under stirring to 105° C. Vacuum was applied and all water was distilled off. The resulting material was cooled to 55° C. and Glycidylether A (3.18 g) was added. The mixture was stirred at 100° C. for 2 h.

[0128] IS5

[0129] Polyamine A (50 wt. % solution in water, 13.3 g) and MPEG 350 (84.0 g) were combined. The mixture was heated under stirring to 105° C. Vacuum was applied and all water was distilled off. The resulting material was cooled to 55° C. and 2-Ethylhexylglycidylether (2.69 g) was added. The mixture was stirred at 100° C. for 2 h.

[0130] Synthesis of Comparative Modifying Agents

[0131] NS 2

[0132] Polyamine A (50 wt. % solution in water, 200 g) and benzyl alcohol (300 g) were combined. The mixture was heated under stirring to 105° C. Vacuum was applied and all water was distilled off. The resulting material was cooled to 55° C. and tall oil fatty acid (100 g) was added. The mixture was homogenized.

[0133] 24.8 g of the material obtained were diluted with benzyl alcohol (74.4 g) and homogenized.

[0134] NS 3

[0135] Polyamine A (50 wt. % solution in water, 30 g) and MPEG 350 (135 g) were combined. The mixture was heated under stirring to 105° C. Vacuum was applied and all water was distilled off.

[0136] NS 4

[0137] Polyamine D (10.95 g) and MPEG 350 (125.14 g) were combined. The mixture was heated under stirring to 105° C. Vacuum was applied and all water was distilled of. The resulting material was cooled to 55° C. and Glycidylether A (14.84 g) was added. The mixture was stirred at 100° C. for 2 h.

[0138] NS 5

[0139] Polyamine E (21.91 g) and MPEG 350 (125.14 g) were combined. The mixture was heated under stirring to 105° C. Vacuum was applied and all water was distilled off. The resulting mixture was cooled to 55° C. and Glycidylether A (2.94 g) was added. The mixture was stirred at 100° C. for 2 h.

[0140] All inventive and comparative modifying agents mentioned above contain 10% by weight of modified or unmodified polyamine after completion of the synthesis.

APPLICATION EXAMPLES AND TESTING

[0141]

TABLE-US-00002 TABLE 2 Raw materials Product name Description Supplier Aerosil 200 Hydrophilic fumed silica Evonik Aerosil R202 Hydrophobic fumed silica Evonik Bayferrox 130BM Iron oxide red pigment Lanxess Bayferrox Rot Iron oxide red pigment Lanxess 130M Bayferrox 130M Iron oxide red pigment Lanxess Bayferrox 303 T Iron oxide black Lanxess Bayferrox 3920 Iron Oxide yellow pigment Lanxess Borchi Nox M2 Butanone Oxime OMG Borchers GmbH Butanox M50 Methyl ethyl keton Akzo Nobel peroxide BYK-054 Solution of foam BYK-Chemie GmbH destroying polymers, silicone-free BYK-306 Solution of polyether- BYK-Chemie GmbH modified polydimethylsiloxane BYK-A 530 Solution of foam- BYK-Chemie GmbH destroying polymers and polysiloxane BYK-A 555 Solution of foam BYK-Chemie GmbH destroying polymers, silicone-free BYK-1790 Mixture of foam- BYK-Chemie GmbH destroying polymers BYKANOL-A Solution of an alkylol BYK-Chemie GmbH ammonium salt of acidic phosphoric acid esters and an oxime Cardiolite LITE Phenalkamine Curing Cardolite Specialty 2001 LV agent Chemicals Europe NV Chromoxide Green synthetic chromium oxide Lanxess GN M green Octa-Soligen Cobalt Cobalt drier OMG Borchers GmbH 10 Desmodur N 3390 Aliphatic polyisocyanate Covestro BA HDI-trimer Desmodur N 3600 aliphatic polyisocyanate Covestro (low viscous HDI trimer) Desmophen NH aminofunctional co- Covestro 1520 reactant for polyisocyanates Desmophen NH aminofunctional co- Covestro 1420 reactant for polyisocyanates Palatinol N Diisononyl phthalate BASF DISPERBYK-108 Hydroxy-functional BYK-Chemie GmbH carboxylic acid ester with pigment-affinic groups DISPERBYK-110 Solution of a copolymer BYK-Chemie GmbH with acidic groups DISBERBYK-142 Solution of a phosphoric BYK-Chemie GmbH ester salt of a high molecular weight copolymer with pigment- affinic groups DISPERBYK-2152 Hyperbranched polyester BYK-Chemie GmbH Dowanol PM Propylene glycol mono Dow methyl ether Epikure 3140 A Curing Agent - reactive Hexion polyamide Epikure 3155 modified polyamide epoxy Hexion curing agent based on dimerized fatty acid and polyamines Epikote 828 Bisphenolic A resin Hexion Epikote 1001X75 75% solids solution in Hexion xylene based on epichlorohydrin and bisphenol-A Epilox P13-20 reactive diluent for epoxy LEUNA-Harze GmbH resins EWO Barium sulfate Sachtleben Finntalc 15 M Calcium carbonate Mondus Finntalc M 65 Magnesium silicate Mondo Minerals Garamite 1958 Organophilic BYK-Chemie GmbH phyllosilicates Grilonit RV 1812 1,6-Hexandiglycidylether EMS-Griltech Hakuenka CCR S10 precipitated calcium Omya carbonate Heucophos CAPP calcium aluminum Heubach polyphosphate silicate hydrate Heucophos ZPA zinc aluminum Heubach orthophosphate hydrate Incozol 2 moisture scavenger in Incorez polyurethane coatings and sealants Kaneka S 303 H silyl-terminated polyether Kaneka Kronos 2190 Titanium dioxide Kronos Kronos 2310 Titanium dioxide Kronos Luzenac 20 M2 talc/chlorite Imerys Minerals Macrynal SM 510/ hydroxy functional acrylic Allnex 60LG resin Dowanol PMA Methoxypropylacetat Dow MPA NL 49P Accelerator NL-49P: Nouryon Cobalt(II) 2- ethylhexanoate. Solution of 1% cobalt in solvent mixture used for curing Nuodex Combi APB combination drier based Huntsman on cobalt, calcium and zirconium Omyacarb 5GU Calcium Carbonate Omya Palatal A 400-01 unsaturated polyester Buefa based on isophthalic acid and standard glycols, dissolved in styrene pBQ solution 5% 5% by weight solution of p-benzoquinone in styrene Setal A F 48 TB/X Medium oil alkyd 55% in Allnex white spirit/xylene Sylosiv A3 Molecular sieve powder Grace moisture scavengers for 1K and 2K-Polyurethane systems Ti-Pure R 960 Titan dioxide pigment DuPont TiO.sub.2 RKB-4 Titan dioxide pigment Tinuvin 292 liquid hindered amine light BASF stabilizer White spirit K30 hydrocarbon solvent Overlack (petroleum-derived clear organic solvent) Worleekyd AC 2943 Acrylated low viscous Worlee alkyd resin for high solid primers

[0142] 1. 1 Pack Silane Terminated Sealing Compound

[0143] Production of the 1 pack silane terminated sealing compound using the formulation in Table 3. All raw materials were weight in a PP speedmixer cup and were mixed three times at 2.500 rpm for 30 seconds with the Speedmixer DAC 400.1 FVZ. Samples were stored for 24 h at 23° C. in the speedmixer cups before testing. To evaluate the rheological behavior the viscosity was measured using the rheometer Anton Paar MCR 102 with a plate-plate system. A small amount of the sealing compound is placed on the rheometer plate using a metal spatula. After trimming excess material is removed by using a paper card. The viscosity measurement starts using the following parameters: Plate: PP25, Gap: 0.5 mm, Waiting time before shearing: 10 sec, Pre-shearing: 10 data points á 2 sec at 0.11/s, Shearrate: 0.1-100 1/s, Datapoints: 16 in a logarithmic ramp (Start: 10 sec, End: 1 sec)

TABLE-US-00003 TABLE 3 Raw material Weight [g] Kaneka S 303 H 36.30 DINP 18.15 Omyacarb 5GU 21.78 Hakuenka CCR S10 21.78 Fumed silica 1.00 Modifying agent 30% by wt. on fumed silica

[0144] Inventive modifying agents IS1, IS2 and comparative NS2 were employed in combination with Aerosil 200, respectively. Furthermore, modifying agents IS1, IS2 and NS2 were tested without addition of silica.

TABLE-US-00004 TABLE 4 Results viscosity at 0.16 Example Rheology pack 1/s [Pa*s] 1.1 Aerosil R202 722 1.2 Aerosil 200 1790 1.3 none 297 1.4 IS1/Aerosil 200 4828 1.5 IS2/Aerosil 200 5107 1.6 NS2/Aerosil 200 1186 1.7 IS1 only (without fumed silica) 1357 1.8 IS2 only (without fumed silica) 895 1.9 NS2 only (without fumed silica) 326

[0145] The results in Table 4 show that samples using the combination of hydrophilic fumed silica and the modifying agents IS1 and IS2 have a higher viscosity compared to samples using hydrophilic or hydrophobic fumed silica without modifying agent and also have a higher viscosity than the sample using the combination of hydrophilic fumed silica and NS2. Samples IS1 only and IS2 only comprising the modifying agent without hydrophilic fumed silica have a higher viscosity compared to the non-inventive sample NS2 only, but not as high as the combination of the inventive modifying agents in combination with hydrophilic fumed silica.

[0146] 2. 1K Short Oil Alkyd-System

[0147] In a first step, the components of List 1 (comprising the alkyd binder, cf. Table 5) were homogenized for 2 minutes at a stirring speed of 2 m/s using a dissolver (Getzmann Dispermat LC 30; toothed plate with 4 cm diameter). Afterwards, the components of List 2 were subsequently added while stirring at 2 m/s.

[0148] The components of List 3 were added subsequently to the mixture while stirring and dispersing for 20 minutes at 12 m/s.

[0149] The components of List 4 were added subsequently to the formulation obtained from List 1, List 2, List 3 and homogenized for 2 minutes at a stirring speed of 2 m/s.

TABLE-US-00005 TABLE 5 Raw Material Weight [g] List 1 Worleekyd AC2943 32.0 DISBERBYK-2152 0.5 Xylene 5.0 List 2 Garamite 1958 1.0 Xylene 4.0 List 3 Kronos 2310 8.0 Bayferrox 303 T 0.5 EWO 24.0 Finntalc 15 M 12.0 Heucophos CAPP 8.0 List 4 Xylene 3.0 BYKANOLA-A 0.5 Cobalt 10 0.5 Xylene 1.0 Modifying agent 15% by weight on Garamite 1958

[0150] Inventive modifying agents IS1 as well as IS2 were employed in combination with Garamite 1958, respectively. Comparative example 2.1 contained Garamite 1958 only, without modifying agent.

[0151] The formulation is stored at room temperature (23° C.) for 24 hours. For the sag resistance test the samples were applied with a stepped doctor blade Model 421/S (Erichsen GmbH & Co KG) with 50-500 μm wet film thickness. The application is 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 is hanged up vertically at room temperature until it is dried. After drying the visual evaluation of the sag resistance is done. Therefore, among the lines of 50 to 500 μm wet film thickness, the wet film thickness is considered that shows after drying a clear separation of the draw down, no runner and also no bulge building between the applied lines of different film thickness.

TABLE-US-00006 TABLE 6 Results Rheology pack Sag resistance [μm] 2.1 Garamite 1958 500 2.2 IS1/Garamite 1958 750 2.3 IS2/Garamite 1958 800

[0152] As can be seen from the results in the above table, the sag resistance of the short oil alkyd system could significantly be improved by using an inventive combination of organically modified clay and modifying agent compared to the use of the organically modified clay only.

[0153] 3. 1p Medium Oil Alkyd-System

[0154] Production of the medium oil alkyd system using the formulation in table 7 on a CV (VMA Getzmann GmbH). Subsequent 70 g of the formulation were filled in 100 ml glass bottles. Then 10% of the respective modifying agent(calculated on the amount of Garamite 1958) became incorporated with the Dispermat CV (VMA Getzmann GmbH) 2 minutes at 1500 rpm using a 3 cm diameter toothed plate. After that the formulation is stored at room temperature (23° C.) over night . For the sag resistance test the samples were applied with a stepped doctor blade Model 421/S (Erichsen GmbH & Co KG) with 50-500 μm wet film thickness. The application is 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 is hanged up vertical at room temperature until it is dried. After drying the visual evaluation of the sag resistance is done. Therefor the wet film thickness is taken that shows after drying a clear separation of the draw down, no runner and also no bulge building between the applied film thickness. Furthermore the viscosity of the samples was measured on rheometer Physica MCR-301 (Anton-Paar GmbH) with the following parameters: cone-plate system, Cone CP-50-1, Controlled shear rate measurement D=0.1-1000 1/s, at 23° C. The viscosity value at 0.4 1/s was taken for the characterization of the low shear viscosity of the sample.

TABLE-US-00007 TABLE 7 Grind Raw Material Weight [g] Setal A F 48 TB/X 18.2 White spirit K 030 8.2 Xylene 16.6 Disperbyk 108 0.3 Kronos 2190 25.0 Garamite 1958 2.0 Modifying Agent 15% by weight on Garamite 1958 Dispermat CV, 40° C., 30 min., 8500 RPM, 4 cm-diameter toothed plate Letdown Setal A F 48 TB/X 29.7 Nuodex Combi APB 1.5 Borchi Nox M2 0.5 Dispermat CV, 40° C., 5 min., 1500 RPM, 4 cm-diameter toothed plate

[0155] Inventive modifying agents IS1 was employed in combination with Garamite 1958, as well as non-inventive example NS2 which was used in combination with Garamite 1958, too. Non-inventive example 3.2 contained Garamite 1958 only, without modifying agent. Sample 3.1 contained neither modifying agent nor Garamite 1958.

TABLE-US-00008 TABLE 8 Results Sag resistance Viscosity Rheology pack [μm] [Pas] at 0.4 1/s 3.1 none <50 0.08 3.2 Garamite 1958 100 1.80 3.3 IS1/Garamite 1958 200 10.20 3.4 NS2/Garamite 150 8.40 1958

[0156] From the table 8 it is visible, that the non-inventive example 3.2 that contains only organically modified clay shows a lower sag resistance and a lower viscosity than the inventive sample 3.3. IS1 improves obviously the anti-sagging behavior and the viscosity of the medium oil alkyd system better than non-inventive example NS2.

[0157] 4. 2p Gel Coat

[0158] Production of the gel coat using the formulation in table 9 on a Dispermat CV (VMA Getzmann GmbH). Subsequent 100 g of the polyester resin formulation (Table 9, component A) were filled in 150 ml glass bottles. Then 30% of the respective modifying agent (calculated on the amount of Aerosil 200) became incorporated with a Dispermat CV (VMA Getzmann GmbH) 2 minutes at 1500 rpm using a 3 cm diameter toothed plate. After that the mixture is stored at room temperature (23° C.) over night. Immediately before the viscosity measurement, the peroxide (Table 9, component B) was incorporated by stirring with spatula. For the viscosity characterization the samples were measured on rheometer Physica MCR-301 (Anton-Paar GmbH) with the following parameters: cone-plate system, Cone CP-50-1, Controlled shear rate measurement D=0.1-1000 1/s, at 23° C. The viscosity value at 0.4 1/s was taken for the characterization of the low shear viscosity of the sample.

TABLE-US-00009 TABLE 9 Component Raw Material Weight [g] A Palatal A 400-01 78.25 Aerosil 200 2.00 Styrene monomer 19.75 pBQ solution 5% 1.00 NL 49P 0.50 BYK A 555 1.00 Dispermat CV, RT, 5 min, 4800 rpm, 4 cm toothed plate Modifying agent 0.60 Dispermat CV, RT, 2 min, 1500 rpm, 3 cm toothed plate B Butanox M50 1.00

[0159] Inventive modifying agents IS1 and non-inventive NS2 were employed in combination with Aerosil 200, respectively.

TABLE-US-00010 TABLE 10 Results Viscosity [Pas] Example Rheology pack at 0.4 1/s 4.1 none 0.16 4.2 Aerosil 200 11.90 4.3 IS1/Aerosil 200 26.30 4.4 NS2/Aerosil 200 19.10

[0160] From the table 10 it is visible, that non-inventive example 4.2 that contains only Aerosil 200 shows a lower viscosity than the sample with the inventive modifying agent IS1. IS1 obviously increases the viscosity of the gel coat better than non-inventive example NS2.

[0161] 5. 2-K Epoxy-Adhesive

[0162] Production of the 2 pack Epoxy Adhesive using the formulation in Table 11. Raw materials of component A were weight in a PP Speedmixer cup and were mixed with the Speedmixer DAC 400.1 FVZ 2 times at 2500 rpm for 30 seconds. Raw materials of component B were weight in a PP Speedmixer cup and were mixed with the Speedmixer 2 times at 2500 rpm for 30 seconds. All samples were stored for 24 h at 23° C. Afterwards, component B was added to component A and mixed by hand directly before testing.

[0163] In addition, samples of component A were stored for 12 months at 23° C. Samples of freshly formulated component B were added to stored component A and mixed by hand directly before testing.

[0164] To evaluate the rheological behavior the viscosity was measured using the rheometer Anton Paar MCR 102 with the plate-plate system. A small amount of the epoxy adhesive is placed on the rheometer plate using a metal spatula. After trimming excess material is removed by using a paper card. The viscosity measurement starts using the following parameter: Plate: PP25, Gap: 0.5 mm, Shear rate: 0.1-1000 1/s, Datapoints: 21 in a linear ramp (Start 10 sec, End 2 sec).

TABLE-US-00011 TABLE 11 Combination sample Reference Control (hydrophilic Modifying Sample Sample No silica + agent only (hydrophobic (hydrophilic rheology modifying sample (no Raw silica), silica), pack), agent), silica), Component material Weight [g] Weight [g] Weight [g] [Weight [g] Weight [g] A Epikote 32.50 32.50 32.50 32.50 32.50 828 Aerosil R 2.00 202 Aerosil 2.00 2.00 200 B Epikure 16.25 16.25 16.25 16.25 16.25 3140 A Modifying 0.60 (30 wt % 0.60 agent on fumed silica)

[0165] Inventive modifying agents IS1, IS2 and non-inventive NS3 were employed in combination with Aerosil 200 respectively. Non-inventive example 5.2 contained Aerosil 200 only, without modifying agent. For non-inventive example 5.1, Aerosil R202 was employed without modifying agent. Furthermore, IS1 and IS2 were employed without addition of silica (IS1 only, IS2 only). Example 5.3 contained neither modifying agent nor silica.

TABLE-US-00012 TABLE 12 Results Initial sample Stored sample (24 h at (12 months at 23° C.), viscosity 23° C.), viscosity at 0.16 1/s at 0.16 1/s Example Rheology pack [Pa*s] [Pa*s] 5.1 Aerosil R202 262 235 5.2 Aerosil 200 424 70 5.3 none 21 20 5.4 IS1/Aerosil 200 675 448 5.5 IS2/Aerosil 200 506 378 5.6 NS3/Aerosil 200 465 334 5.7 IS1 only 18 18 5.8 IS2 only 18 18

[0166] The result in table 12 shows that samples using the combination of inventive modifying agents IS1 and IS2 with hydrophilic fumed have a higher viscosity than all comparative examples. Using the inventive modifying agents IS1 and IS2 without fumed silica has no significant influence on the viscosity.

[0167] After a storage time of 12 months at 23° C. the sample using hydrophilic fumed silica has a low viscosity, whereas samples using the combination of hydrophilic fumed silica and the inventive modifying agents IS1 and IS2 keep a high viscosity level.

[0168] 6. Conventional 2K Epoxy-System

[0169] Preparation of the Epoxy component (component A): The components of List 1 were added in chronological order to the mixing pot and homogenized for 2 min at 2 m/s using a dissolver (Getzmann Dispermat LC 30; toothed plate with 4 cm diameter). After that, components from List 2 were added while stirring and dispersed for 20 min at 12 m/s. Then, components of List 3 were added subsequently while stirring for 2 min at 2 m/s.

[0170] Preparation of the hardener component (component B): Epikure 3155 and the organic modifying agent were mixed using a shaker (Fast&Fluid, Model SK 450, frequency: 50/60 Hz; 5 minutes).

TABLE-US-00013 TABLE 13 Component Raw Material Weight [g] A List 1 Epikote 1001X75 23.0 Xylene 6.0 Dowanol PM 5.0 Garamite 1958 1.0 DISBERBYK-142 0.9 List 2 Bayferrox 130M 4.7 Finntalc M 65 12.0 Heucophos ZPA 20.0 EWO 14.0 BYK-A 530 0.5 List 3 Dowanol PM 5.2 Xylene 7.7 B Epikure 3155 4.6 Modifying agent 15% by weight on Garamite 1958

[0171] Inventive modifying agents IS1 and IS2 as well as non-inventive NS2 were employed in combination with Garamite 1958, respectively. Non-inventive example 6.1 contained Garamite 1958 only, without modifying agent.

[0172] Components A and B were separately stored at room temperature (23° C.) for 24 hours. Directly before application, components A and B were mixed using an electrical stirrer (Getzmann Dispermat CV, toothed plate: 2 cm diameter) for 2 min at 2 m/s.

[0173] For the sag resistance test the samples were applied with a stepped doctor blade Model 421/S (Erichsen GmbH & Co KG) with 50-500 μm wet film thickness. The application is 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 is hanged up vertically at room temperature until it is dried. After drying the visual evaluation of the sag resistance is done. Therefore, among the lines of 50 to 500 μm wet film thickness, the wet film thickness is considered that shows after drying a clear separation of the draw down, no runner and also no bulge building between the applied lines of different film thickness.

TABLE-US-00014 TABLE 14 Results Rheology packs Sag resistance [μm] 6.1 Garamite 1958 150 6.2 IS1/Garamite 1958 300 6.3 IS2/Garamite 1958 300 6.4 NS2/Garamite 1958 150

[0174] As can be seen from the above table, the sag resistance of the formulation using the organically modified clay only could be significantly increased by using the combinations with the inventive modifying agents IS1 and IS2, whereas no improvement could be achieved when using non-inventive NS2.

[0175] 7. High Solid 2K Epoxy-System

[0176] Preparation of the Epoxy component (component A): The components of List 1 were added in chronological order to the mixing pot and homogenized for 2 min at 2 m/s using a dissolver (Getzmann Dispermat LC 30; toothed plate with 4 cm diameter). After that, components from List 2 were added while stirring and dispersed for 20 min at 12 m/s. Then, the component of List 3 was added subsequently while stirring for 2 min at 2 m/s.

[0177] Preparation of the hardener component (component B): Epikure 3155 and the organic modifying agent were mixed using a shaker (Fast&Fluid, Model SK 450, frequency: 50/60 Hz; 5 minutes).

TABLE-US-00015 TABLE 15 Component Raw Material Weight [g] A List 1: Epikote 828 23.7 Xylene 4.8 Garamite 1958 1.0 DISBERBYK-2152 0.6 BYK-A 530 0.5 List 2: Ti-Pure R 960 17.5 Finntalc M65 13.2 EWO 28.7 List 3: Xylene 10.0 B Epikure 3155 16.9 Modifying agent 15% by weight on Garamite 1958

[0178] Inventive modifying agents IS1 as well as non-inventive NS2 were employed in combination with Garamite 1958, respectively. Non-inventive example 7.1 contained Garamite 1958 only, without modifying agent.

[0179] Components A and B are separately stored at room temperature (23° C.) for 24 hours. Directly before application, components A and B were mixed using an electrical stirrer (Getzmann Dispermat CV, toothed plate: 2 cm diameter) for 2 min at 2 m/s.

[0180] For the sag resistance test the samples were applied with a stepped doctor blade Model 421/S (Erichsen GmbH & Co KG) with 50-500 μm wet film thickness. The application is 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 is hanged up vertically at room temperature until it is dried. After drying the visual evaluation of the sag resistance is done. Therefore, among the lines of 50 to 500 μm wet film thickness, the wet film thickness is considered that shows after drying a clear separation of the draw down, no runner and also no bulge building between the applied lines of different film thickness.

TABLE-US-00016 TABLE 16 Results Example Rheology pack Sag resistance [μm] 7.1 Garamite 1958 200 7.2 IS1/Garamite 1958 1000 7.3 NS2/Garamite 1958 500

[0181] As can be seen from table 16, the sag resistance of the formulation using the organically modified clay only could be significantly increased by using the inventive modifying agent IS1, while only a minor improvement could be achieved when using non-inventive NS2.

[0182] 8. Total Solid 2K Epoxy-System

[0183] Preparation of the Epoxy component (component A): The components of List 1 were added in chronological order to the mixing pot and homogenized for 2 min at 2 m/s using a dissolver (Getzmann Dispermat LC 30; toothed plate with 4 cm diameter). After that, components from List 2 were added while stirring and dispersed for 20 min at 12 m/s. Then, the component of List 3 was added subsequently while stirring for 2 min at 2 m/s.

[0184] Preparation of the hardener component (component B): Epikure 3155 and the organic modifying agent were mixed by using a shaker (Fast&Fluid, Model SK 450, frequency: 50/60 Hz; 5 minutes).

TABLE-US-00017 TABLE 17 Component Raw Material Weight [g] A List 1: Epikote 828 20.0 Epilox P13-20 8.0 Garamite 1958 1.0 DISBERBYK-2152 0.5 BYK-1790 0.5 List 2: Bayferrox 130BM 4.0 Finntalc M65 11.0 EWO 35.0 List 3: Epikote 828 20.0 B Epikure 3155 34.1 Modifying agent 15% by weight on Garamite 1958

[0185] Inventive modifying agents IS1 and IS2 were employed in combination with Garamite 1958, respectively. Non-inventive example 8.1 contained Garamite 1958 only, without modifying agent.

[0186] Components A and B are separately stored at room temperature (23° C.) for 24 hours. Directly before application, components A and B were mixed using an electrical stirrer (Getzmann Dispermat CV, toothed plate: 2 cm diameter) for 2 min at 2 m/s.

[0187] For the sag resistance test the samples were applied with a stepped doctor blade Model 421/S (Erichsen GmbH & Co KG) with 50-500 μm wet film thickness. The application is 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 is hanged up vertically at room temperature until it is dried. After drying the visual evaluation of the sag resistance is done. Therefore, among the lines of 50 to 500 μm wet film thickness, the wet film thickness is considered that shows after drying a clear separation of the draw down, no runner and also no bulge building between the applied lines of different film thickness.

TABLE-US-00018 TABLE 18 Results Example Rheology pack Sag resistance [μm] 8.1 Garamite 1958 250 8.2 IS1/Garamite 1958 500 8.3 IS2/Garamite 1958 500

[0188] As can be seen from the table 18, the sag resistance of the formulation using the organically modified clay only could be significantly increased by using the inventive modifying agents IS1 and IS2, respectively.

[0189] 9. Total Solid 2K Epoxy-System

[0190] Production of the Solvent free epoxy primer using the formulation in table 19 on Dispermat CV (VMA Getzmann GmbH). Subsequent 70 g of the formulation were filled in 100 ml glass bottles. After the formulation is stored at room temperature (23° C.) over night 10% of the respective modifying agent (calculated on the amount of GARAMITE-1958) became incorporated together with the required amount of the hardener into the formulation by stirring with spatula. For the sag resistance test 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 is 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 is hanged up vertical at room temperature until it is dried. After drying the visual evaluation of the sag resistance is done. Therefor the wet film thickness is taken that shows after drying a clear separation of the draw down, no runner and also no bulge building between the applied film thickness.

TABLE-US-00019 TABLE 19 Component Raw Material Weight [g] A Epikote 828 40.0 Grilonit RV 1812 8.0 DISBERBYK-2152 0.5 BYK-1790 0.5 Bayferrox Red 130M 4.0 Luzenac 20 M2 11.0 EWO 36.0 Garamite 1958 1.0 Dispermat CV, 50° C., 30 min, 8500 RPM, 4 cm diameter toothed plate B Cardiolite LITE 2001 LV 33.1 Modifying agent (10% 0.1 delivery form on Garamite 1958)

[0191] Inventive modifying agents IS1, IS2, IS3, IS4 and IS5 as well as non-inventive NS2 were employed in combination with Garamite 1958, respectively. Non-inventive example 9.1 contained Garamite 1958 only, without modifying agent. Non-inventive sample 9.2 contained neither Garamite 1958 nor modifying agent.

TABLE-US-00020 TABLE 20 Results Example Rheology pack Sag resistance [μm] 9.1 Garamite 1958 250 9.2 none 50 9.3 IS1/Garamite 1958 >1000 9.4 IS2/Garamite 1958 950 9.5 IS3/Garamite 1958 950 9.6 IS4/Garamite 1958 1000 9.7 IS5/Garamite 1958 >1000 9.8 NS2/Garamite 1958 500 9.9 NS4/Garamite 1958 450 9.10 NS5/Garamite 1958 500

[0192] From the table 20 it is visible, that non-inventive 9.1 that contains only Garamite 1958 shows a lower sag resistance than the samples containing the inventive modifying agents IS1-IS5. These samples improve obviously the anti-sagging behavior of the solvent-free epoxy primer much better than NS2.

[0193] 10. 2-Pack PU

[0194] Production of the 2-pack PU using the formulation in table 21 with Dispermat CV (VMA Getzmann GmbH). Subsequent 70 g of the formulation were filled in 100 ml glass bottles. After the formulation is stored at room temperature (23° C.) over night 10% by weight of the respective modifying agent solution (calculated on the amount of GARAMITE-1958) became incorporated together with the required amount of the hardener into the formulation by stirring with spatula. For the sag resistance test the samples were applied with a stepped doctor blade Model 421/S (Erichsen GmbH & Co KG) with 50-500 μm wet film thickness. The application is 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 is hanged up vertical at room temperature until it is dried. After drying the visual evaluation of the sag resistance is done. Therefor the wet film thickness is taken that shows after drying a clear separation of the draw down, no runner and also no bulge building between the applied film thickness.

TABLE-US-00021 TABLE 21 Control sample without Samples with Garamite paste, Garamite paste, Component Grind Weight [g] Weight [g] A Macrynal 23.5 23.5 SM 510/60LG Butylacetate 9.0 — Dowanol PMA 8.0 — Disperbyk 110 1.2 1.2 TiO.sub.2 RKB-4 34.0 34.0 Garamite 1958 — 20.0 paste 10% solid Dispermat CV, 40° C., 8500 RPM, 4 cm toothed plate, 20 min Let-down Macrynal 24.0 24.0 SM 510/60LG BYK 306 0.3 0.3 Dispermat CV, 23° C., 3000 RPM, 4 cm toothed plate, 5 min. B Hardening Desmodur 16.4 16.4 N 3390 BA Modifying agent — 0.2 (10% wton Garamite 1958)

TABLE-US-00022 TABLE 21a Garamite 1958 paste (10% solid): Buac/Dowanol PMA = 9:8 85.0 g Ethanol/water 95:5  5.0 g GARAMITE 1958 10.0 g Total 100.0 g 

[0195] Grinding: Dispermat CV, room temperature, 20 minutes at 8500 rpm, 4 cm diameter toothed plate

[0196] Inventive modifying agent IS1 as well as non-inventive NS2 were employed in combination with Garamite 1958, respectively. Non-inventive example 10.2 contained Garamite 1958 only, without modifying agent. Non-inventive sample 10.1 contained neither Garamite 1958 nor modifying agent.

TABLE-US-00023 TABLE 22 Results Example Rheology pack Sag resistance [μm] 10.1 none <50 10.2 Garamite 1958 100 10.3 IS1/Garamite 1958 200 10.4 NS2/Garamite 1958 150

[0197] From the table 22 it is visible, that non-inventive example 10.2 that contains only Garamite 1958 shows a lower sag resistance than the sample with the modifying agent IS1. IS1 improves obviously the anti-sagging behavior of the 2p-PU formulation better than non-inventive sample NS2.

[0198] 11. 2K Polyaspartics-System

[0199] Preparation of component A: The components of List 1 were added in chronological order to the mixing pot and homogenized for 2 min at 2 m/s using a dissolver (Getzmann Dispermat LC 30; toothed plate with 4 cm diameter). After that, components from List 2 were added while stirring and dispersed for 20 min at 12 m/s. Then, the component of List 3 was added subsequently while stirring for 2 min at 2 m/s. Finally, the modifying agent (List 4) was added while stirring for 2 min at 2 m/s.

TABLE-US-00024 TABLE 23 Component Raw Material Weight [g] A List 1: Desmophen NH 1520 11.3 Desmophen NH 1420 17.1 Garamite 1958 1.0 DISBERBYK-2152 1.5 List 2: Sylosiv A3 2.9 Chromoxide Green GN M 7.3 Bayferrox 3920 1.3 Ti-Pure R 960 10.6 EWO 29.0 List 3: BYK-054 0.7 Tinuvin 292 0.5 Incozol 2 3.0 Dowanol PMA 5.8 Butylacetate 8.0 List 4: Modifying agent 15% by weight on Garamite 1958 B Desmodur N 3600 16.8

[0200] Component A has been stored for 4 weeks at 23° C. Directly before application, components A and B were mixed using an electrical stirrer (Getzmann Dispermat CV, toothed plate: 2 cm diameter) for 2 min at 2 m/s.

[0201] For the sag resistance test the samples were applied with a stepped doctor blade Model 421/S (Erichsen GmbH & Co KG) with 50-500 μm wet film thickness. The application is 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 is hanged up vertically at room temperature until it is dried. After drying the visual evaluation of the sag resistance is done. Therefore, among the lines of 50 to 500 μm wet film thickness, the wet film thickness is considered that shows after drying a clear separation of the draw down, no runner and also no bulge building between the applied lines of different film thickness.

[0202] Inventive modifying agents IS1 was employed in combination with Garamite 1958. Non-inventive example 11.1 contained Garamite 1958 only, without modifying agent.

TABLE-US-00025 TABLE 24 Results Example Rheology pack Sag resistance [μm] 11.1 Garamite 1958 150 11.2 IS1/Garamite 1958 300

[0203] As can be seen from the above table, the sag resistance obtained with organoclay could significantly be improved by using the inventive combination with the modifying agent IS1.