阅读说明：本技术 制备防污涂料组合物的方法和由所述方法制备的涂料 (Method for preparing antifouling coating composition and coating prepared by said method ) 是由 卡洛·维尔穆伦 迈克尔·阿尔芬斯·科尼利斯·约翰尼斯·范迪克 于 2018-04-17 设计创作，主要内容包括：本公开涉及提供具有改善的防污性能的基材的方法。本发明还涉及防污涂料组合物,以及制备防污涂料组合物的方法。所述涂料组合物用于改善基材的防污性能的用途。(The present disclosure relates to methods of providing substrates with improved stain resistance. The invention also relates to an antifouling coating composition, and a method of preparing an antifouling coating composition. Use of the coating composition for improving the antifouling properties of a substrate.)

1. A method of providing a substrate having improved stain resistance, the method comprising the steps of:

a) providing a substrate having a surface;

b) providing a coating composition comprising:

i. organic-inorganic core-shell nanoparticles having a core comprising emulsion stabilizer C and a shell comprising an inorganic oxide; and

at least one water soluble solvent;

at least 5 wt% water, based on the total weight of the coating composition; and

an organic compound a;

c) applying a layer of the composition on the surface to obtain a coated substrate; and

d) drying the applied layer to obtain a coated substrate.

2. The method of claim 1, wherein in step d) the applied layer is exposed to a temperature of at least 5 degrees celsius for a time of at least one hour.

3. The method of claim 1 or 2, wherein the composition comprises a binder, preferably the binder comprises an inorganic oxide binder, preferably the inorganic oxide binder comprises an inorganic oxide precursor selected from the group consisting of metal alkoxides, metal chelates, metal salts, and mixtures thereof, preferably the inorganic oxide binder comprises an alkoxysilane.

4. The method of any one of claims 1 to 3, wherein the composition comprises from 0 to 30 wt.%, preferably from 0.1 to 30 wt.%, preferably from 1 to 15 alumina equivalents of the aluminum-containing compound, preferably the coating formulation comprises from 0.5 to 30 wt.% alumina equivalents of the aluminum-containing compound.

5. The method of any one of claims 1-4, wherein the organic-inorganic core-shell nanoparticles have a particle size in the range of 20-300nm as measured using DLS.

6. The method of any one of claims 1-5, wherein Compound A is a non-polymeric compound.

7. The process according to any one of claims 1-6, wherein the boiling point of Compound A is at least 10 ℃ and at most 300 ℃, preferably the boiling point of Compound A is at least 30 ℃ and at most 200 ℃.

8. The method according to any one of claims 1 to 7, wherein compound A has a solubility in water of at most 3kg/m at room temperature³。

9. The process according to any one of claims 1 to 8, wherein copolymer C is obtained from the following monomers:

1-25 mole% of at least one cationic or basic monomer M1, such as a vinyl monomer having a tertiary amine group;

50-99 mol% of at least one non-ionic, non-polar monomer M2; and

0-25 mol% of at least one polar, anionic or acidic monomer M3; wherein the sum of M1, M2 and M3 totals 100%.

10. The process according to any one of claims 1 to 9, wherein the mass ratio C/a is between 0.15 and 1.0.

11. The method of any one of claims 1 to 10, wherein the metal comprises at least one element selected from the group consisting of Si, Al, Be, Bi, B, Fe, Mg, Na, K, In, Ge, Hf, La and lanthanides, Sb, Sn, Ti, Ta, Nb, Y, Zn and Zr.

12. A coated substrate obtained by the method of any one of claims 1-11.

13. Use of a coating composition as defined in any one of claims 1 to 11 for improving the antifouling properties of a substrate.

14. An antifouling coating composition comprising

i. Organic-inorganic core-shell nanoparticles having a core comprising emulsion stabilizer C and a shell comprising an inorganic oxide;

at least 5 wt% water, based on the total weight of the coating composition;

at least one water soluble solvent; and

an organic compound a.

15. A method of preparing an antifouling coating composition, the method comprising the steps of:

1) preparing an oil-in-water emulsion by mixing the following substances in a mass ratio C/A of 0.1 to 2 to produce 1 to 50 mass% (based on the emulsion) of emulsified droplets having a particle size of 30 to 300 nm;

a non-polar organic compound A;

cationic addition copolymers C as emulsion stabilizers; and

an aqueous medium at pH 2-6;

2) providing the emulsified droplets with an inorganic oxide shell layer by adding at least one inorganic oxide precursor to the emulsion obtained in step 1) to produce organic/inorganic core-shell nanoparticles having a core/shell mass ratio of 0.2 to 25;

3) optionally combining the thus obtained core-shell nanoparticles with water and/or a water-soluble solvent;

4) optionally adjusting the pH; and

5) optionally, an organic or inorganic polymeric binder or a polymerizable binder is added.

Example 1

Using an Ultra-turrax unit T25, 20 grams of cyclohexane (p.a.) containing 1 mass% heptadecane was dispersed in a mixture of: 14 g of Milli-Q water, 1 g of 2-propanol and 15 g of a dispersion containing 21.5% by mass of cationic copolymer C1(Mw about 30 kDa). The resulting crude emulsion was further dispersed using a high pressure homogenizer (DeBee, operating at 30kPsi pressure, using diamond pores and water cooling), subjected to 9 cycles of about 15 strokes (strokes) and the temperature was reduced to 40 ℃ after each cycle. This gives a stable emulsion with emulsion droplets having a particle diameter (DLS Z-average hydrodynamic diameter) of 265nm (polydispersity, PDI 0.28). To this emulsion, 2g of copolymer C1 were added to give a net positive charge to the droplets, as indicated by the zeta potential > +11mV (pH 4). Silicidation is then performed by: 41.5g of Tetramethoxysilane (TMOS) were gradually added (90 minutes) by means of a syringe pump to a mixture of 35g of the emulsion obtained and 80g of Milli-Q water, with firm stirring by means of a magnetic stirring bar. After the addition was complete, stirring was continued for an additional 90 minutes. 100g of the mixture was diluted with 100g of Milli-Q water and concentrated with 6 drops of HNO₃And (4) acidifying. The DLS size of the final product was 255nm (PDI0.20) and TEM analysis showed that the spherical silica particles had a particle size in the range of 60-120 nm. (see FIG. 1).

The cyclohexane can be removed by a rotary evaporation process while gradually increasing the water temperature of the water bath from 30 to 40 ℃ and reducing the pressure from 300 to 100 mbar. The final dispersion contained 6.4 mass% hollow silica particles having a DLS size of 219nm (PDI0.35) and a zeta potential of 12mV (pH 4); it has been shown to be stable over time.