SYNERGISTIC COMPOSITION

Abstract

The invention deals with a composition comprising an organically modified silicate, and an organic compound having at least one non-primary amine group and at least three hydroxyl groups, wherein at least two of said hydroxyl groups have an amino group in beta position of the hydroxyl group, and wherein said at least two hydroxyl groups having an amino group in beta position of the hydroxyl group are separated by at least 6 carbon atoms, and wherein at least a part of the hydroxyl groups of the organic compound are secondary hydroxyl groups.

Claims

1. A composition comprising i) an organically modified silicate, and ii) an organic compound having at least one non-primary amine group and at least three hydroxyl groups, wherein at least two of said hydroxyl groups have an amino group in beta position of the hydroxyl group, and wherein said at least two hydroxyl groups having an amino group in beta position of the hydroxyl group are separated by at least 6 carbon atoms, and wherein at least some of the hydroxyl groups of the organic compound are secondary hydroxyl groups.

2. The composition according to claim 1, wherein in the organic compound ii) the proportion of primary amine groups is in the range of 0.0 and 8.0 mol-% of the total amount of amine groups.

3. The composition according to claim 1, wherein the organic compound ii) is the reaction product of at least a compound having at least two epoxide groups and a primary or secondary amine having at least one hydroxyl group.

4. The composition according to claim 1, wherein the organically modified silicate is an organically modified clay.

5. The composition according to claim 4, wherein the composition comprises a mixture of at least two different types of clay.

6. The composition according to claim 1, wherein component i) is a silicate which has been modified with an organic ammonium salt having one or more hydrocarbon chains linked to the ammonium group having at least 10 carbon atoms per hydrocarbon chain.

7. The composition according to claim 6, wherein the organic ammonium salt is a quaternary ammonium salt.

8. The composition according to claim 1, wherein the organic compound ii) is present in an amount of 5 to 100% by weight, calculated on the weight of the organically modified silicate.

9. The composition according to claim 1, wherein the organic compound ii) has an amine value in the range of 10 to 120 mg KOH/g.

10. The composition according to claim 1, wherein the organic compound ii) has a number average molecular weight in the range of 350 to 25000 g/mol.

11. A non-aqueous liquid composition comprising the composition according to claim 1 and a non-aqueous liquid.

12. The non-aqueous liquid composition according to claim 11, wherein the composition further comprises an organic resin.

13. The non-aqueous liquid composition according to claim 12, wherein the organic resin is selected from the group of epoxy resins, isocyanate systems, silyl modified polymers and unsaturated polyester resins.

14. The non-aqueous liquid composition according to claim 11, wherein the non-aqueous liquid comprises a liquid hydrocarbon or a liquid mixture of hydrocarbons.

15. (canceled)

16. A process of preparing a composition, comprising the steps of a) providing an organically modified silicate i), b) providing an organic compound having at least one non-primary amine group and at least three hydroxyl groups, wherein at least two of said hydroxyl groups have an amino group in beta position of the hydroxyl group, and wherein said at least two hydroxyl groups having an amino group in beta position of the hydroxyl group are separated by at least 6 carbon atoms, and wherein at least some of the hydroxyl groups of the organic compound are secondary hydroxyl groups ii), and c) mixing components i) and ii), the resulting composition comprising an organically modified silicate, and ii) an organic compound having at least one non-primary amine group and at least three hydroxyl groups, wherein at least two of said hydroxyl groups have an amino group in beta position of the hydroxyl group, and wherein said at least two hydroxyl groups having an amino group in beta position of the hydroxyl group are separated by at least 6 carbon atoms, and wherein at least some of the hydroxyl groups of the organic compound are secondary hydroxyl groups.

17. An article coated with the non-aqueous liquid composition according to claim 11.

18. A process for thickening a non-aqueous liquid composition, comprising the steps of a) providing an organically modified silicate i), b) providing an organic compound having at least one non-primary amine group and at least three hydroxyl groups, wherein at least two of said hydroxyl groups have an amino group in beta position of the hydroxyl group, and wherein said at least two hydroxyl groups having an amino group in beta position of the hydroxyl group are separated by at least 6 carbon atoms, and wherein at least some of the hydroxyl groups of the organic compound are secondary hydroxyl groups ii), c) providing a non-aqueous liquid, and d) mixing components i) and ii) and the non-aqueous liquid, the resulting composition comprising an organically modified silicate, ii) an organic compound having at least one non-primary amine group and at least three hydroxyl groups, wherein at least two of said hydroxyl groups have an amino group in beta position of the hydroxyl group, and wherein said at least two hydroxyl groups having an amino group in beta position of the hydroxyl group are separated by at least 6 carbon atoms, and wherein at least some of the hydroxyl groups of the organic compound are secondary hydroxyl groups, and the non-aqueous liquid.

Description

EXAMPLE S1

[0074] 94,00 g Butylglycol and 29,10 g (0,2402 mol) TRIS were placed in a glassware reactor and heated up to 140° C. under stirring and a stream of N.sub.2. 76,90 g (0,2003 mol) Epikote 828 were added dropwise within 120 min. Stirring continued for 6 h at 140° C. The product was light yellow, transparent and viscous. GPC: Mn=7292 g/mol; D=2.12; amine value=68.1 mg KOH/g

EXAMPLE S2

[0075] 100.00 g Dowanol DPM und 74.11 g (0.1930 mol) Epikote 828 were placed in a glassware reactor and heated up to 100° C. under stirring and a stream of N.sub.2. 16.54 g (0.1544 mol) Benzylamine were added dropwise and heated up to 125° C. After 2 h 9.35 g (0.0772 mol) TRIS were added and stirred for 6 h. The product was light yellow, transparent and liquid. GPC: Mn=6018 g/mol; D=2.04; amine value=64.2 mg KOH/g.

EXAMPLE S3

[0076] 94.00 g Dowanol DPM und 69.08 g (0.1799 mol) Epikote 828 were placed in a glassware reactor and heated up to 100° C. under stirring and a stream of N.sub.2. 19.50 g (0.0720 mol) Oleylamine were added dropwise within 20 min and heated up to 125° C. After 2 h 17.44 g (0.1440 mol) TRIS were added and stirred for 6 h. The product was light yellow, transparent and viscous. GPC: Mn=7374 g/mol; D=2.11; amine value=60.9 mg KOH/g.

EXAMPLE S4

[0077] 94.00 g Dowanol DPM were placed in a glassware reactor and 93.38 g (0.0869 mol) Epikote 1001 were added while heating up to 100° C. under stirring and a stream of N.sub.2. 12.62 g (0.1042 mol) TRIS were added and stirring continued for 6 h at 125° C. The product was light yellow, transparent and viscous. GPC: Mn=8606 g/mol; D=2.23; amine value=29.4 mg KOH/g.

EXAMPLE S5

[0078] 94.00 g Dowanol DPM were placed in a glassware reactor and 91.14 g (0.0848 mol) Epikote 1001 were added while heating up to 125° C. under stirring and a stream of N.sub.2. 4.60 g (0.0170 mol) Oleylamine were added and the mixture was stirred for 2 h. 10.26 g (0.0847 mol) TRIS were added and stirring continued for 6 h. The product was light yellow, transparent and viscous. GPC: Mn=8761 g/mol; D=2.30; amine value=28.8 mg KOH/g.

EXAMPLE S6

[0079] 94.00 g Dowanol DPM and 76.90 g (0.2003 mol) Epikote 828 were placed in a glassware reactor and heated up to 100° C. under stirring and N.sub.2 atmosphere. 29.10 g (0.2402 mol) TRIS were added and stirring continued for 6 h at 125° C. The product was light yellow, transparent and viscous. GPC: Mn=7868 g/mol; D=2.02; amine value=67.9 mg KOH/g

EXAMPLE S7

[0080] 94.00 g Dowanol DPM and 78.48 g (0.2044 mol) Epikote 828 were placed in a glassware reactor and heated up to 100° C. under stirring and a stream of N.sub.2. 27.52 g (0.2272 mol) TRIS were added and stirring continued for 6 h at 125° C. The product was light yellow, transparent and viscous. GPC: Mn=11056 g/mol; D=2.30; amine value=64.5 mg KOH/g

EXAMPLE S8

[0081] 78.94 g Dowanol DPM and 89.02 g (0.2318 mol) Epikote 828 were placed in a glassware reactor and heated up to 125° C. under stirring and a stream of N.sub.2. 16.98 g (0.2780 mol) Ethanolamine solved in 15.06 g Dowanol DPM were added dropwise within 45 min. Stirring continued for 6 h at 125° C. The product was brown-yellow, transparent and viscous. GPC: Mn=7941 g/mol; D=2.39; amine value=77.1 mg KOH/g.

EXAMPLE S9

[0082] 88.47 g Dowanol DPM and 78.32 g (0.2040 mol) Epikote 828 were placed in a glassware reactor and heated up to 125° C. under stirring and a stream of N.sub.2. 6.24 g (0.1022 mol) Ethanolamine solved in 5.53 g Dowanol DPM were added dropwise and stirred for 2 h. 21.44 g (0.2039 mol) Diethanolamine were added and stirred for 6 h. The product was light yellow, transparent and viscous. GPC: Mn=1786 g/mol; D=1.76; amine value=87.0 mg KOH/g.

EXAMPLE S10

[0083] 84.33 g Dowanol DPM and 85.70 g (0.2232 mol) Epikote 828 were placed in a glassware reactor and heated up to 125° C. under stirring and a stream of N.sub.2. 10.90 g (0.1785 mol) Ethanolamine solved in 9.67 g Dowanol DPM were added dropwise and stirred for 2 h. 9.40 g (0.0894 mol) Diethanolamine were added and the mixture was stirred for 6 h. The product was light yellow, transparent and viscous. GPC: Mn=3966 g/mol; D=2.40; amine value=75.8 mg KOH/g.

EXAMPLE S11

[0084] 3523.6 g (3.278 mol) Epikote 1001 and 476.4 g (3.933 mol) TRIS were grinded to an identical particle size and fed to an extruder (Kinheim Expert 16pc, Prism) at 220° C., 100 rpm with 13.5 g/min. Afterwards the product was grinded (Thermomix TM5) for 20 sec at level 10. The product was a light yellow powder (GPC: Mn=7508 g/mol; D=2.45). GPC: Mn=8963 g/mol; D=2.50; amine value=56.3 mg KOH/g

EXAMPLE S12

[0085] 94.00 g Dowanol DPM and 78.85 g (0.1875 mol) Eponex Resin 1510 were placed in a glassware reactor at 23° C. under stirring and a stream of N.sub.2. 27.25 g (0.2249 mol) TRIS were added and the mixture was heated up to 125° C. Stirring continued for 6 h at 140° C. The product was light yellow, transparent and liquid (GPC: Mn=3786 g/mol; D=1.90). GPC: Mn=3786 g/mol; D=1.90; amine value=62.1 mg KOH/g.

EXAMPLE S13

[0086] 28.20 g Dowanol DPM were placed in a glassware reactor and heated up to 100° C. under stirring and a stream of N.sub.2. 31.80 g of the reaction product S11 were added in portions during heating until the temperature reached 40° C. At 100° C., stirring continued for 1 h and subsequently, the mixture was heated up to 150° C. for 30 min. The product was light yellow, turbid and viscous.

[0087] Evaluation of the Organic Compounds in Application Systems

TABLE-US-00002 TABLE 2 Raw materials Name Description Supplier Epikote 1001- solid epoxy resin Hexion Inc. X-75 from Bisphenol A and epichlorohydrin, 75% in xylene Xylene isomeric mixture Overlack AG Dowanol PM propyleneglycolmethylether Dow Chemical Disperbyk-142 solution of a phosphoric BYK-Chemie GmbH ester salt of a high molecular weight copolymer Byk-A 530 solution of foam-destroying BYK-Chemie GmbH polymers and polysiloxanes Bayferrox ironoxide red pigment LANXESS 130M Deutschland GmbH Talc 20M2 multipurpose fine Imerys Talc Luzenac talc/chlorite France Heucophos zinc aluminium Heubach GmbH ZPA orthophosphate hydrate EWO bariumsulfate Venator Materials PLC Epikure 3155 solution of a polyacrylate Hexion Inc. Garamite 1958 Mixture of two different BYK-Chemie GmbH (OMS) types of clay, modified with alkyl quaternary ammonium salt having a hydrocarbon chain with at least 10 carbon atoms linked to the ammonium group Test system: Solvent based epoxy resin

[0088] Production of the solvent based epoxy resin was carried out using the formulation in table 3. After production of component A as described in table 3, 100 g of this component was filled in 150 ml glass bottles. After it was cooled down to room temperature (23° C.), 20% of the active substance of the respective liquid organic compound (S1 to S10, S12 to S13) calculated on the amount of OMS became 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. In case of the solid organic compound of Example S11, 20% of the active substance of the compound was incorporated simultaneously with OMS into the formulation for 30 min. under the grinding conditions (50° C., 8500 rpm, 4 cm diameter toothed plate) of the production of component A, determined as follows in table 3. Afterwards, the samples were stored at room temperature for 24 hours. Directly before application, component B was added and stirred in with a 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 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.

TABLE-US-00003 TABLE 3 Solvent based epoxy resin Component A Epikote 1001-X-75 23.00 g Xylene 6.00 g Dowanol PM 5.00 g Disperbyk 142 0.90 g Byk-A 530 0.50 g Bayferrox 130M 4.70 g Talc 20M2 12.00 g Heucophos ZPA 20.00 g EWO 14.00 g OMS 2.00 g 30 min., 50° C., 8500 RPM., 4 cm-diameter toothed plate Xylene 8.60 g Dowanol PM 5.30 g 102.00 g 2 min., 3000 RPM, 4 cm-diameter toothed plate Organic compound 20% of the active substance of the organic compound (S1-S10, S12-S13), calculated on amount of OMS 2 min., 1000 rpm, 4 cm diameter toothed plate Component B Epikure 3155 4.60 g mixing rate comp.A:comp.B = 102:4.6 Total formulation 106.60 g

TABLE-US-00004 TABLE 4 Results Sag Application resistance Example [μm] Control 50 [without OMS and without organic compound ii)] OMS 350 S11 200 S12 200 OMS + S1 650 OMS + S2 600 OMS + S3 800 OMS + S4 1000 OMS + S5 1000 OMS + S6 650 OMS + S7 600 OMS + S8 750 OMS + S9 500  OMS + S10 500  OMS + S11 650  OMS + S12 650  OMS + S13 800

[0089] It was surprisingly found that the inventive application examples provided a highly improved sag resistance compared to the non-inventive application example containing OMS only (OMS without organic compound) as well as the non-inventive application examples containing S11 and S12 only (organic compound S11, S12 without OMS respectively). Moreover, comparing the non-inventive examples with their inventive counterparts (OMS in combination with S11 and S12 respectively), a synergistic effect is showing, caused by the combined application of the organically modified silica and the respective organic compound.

[0090] Therefore, the non-inventive comparison examples showed a lower rheological effectiveness measured by sag resistance than the examples according to the present invention. These examples are obviously better suitable to improve the sag resistance than the non-inventive comparison examples.