MICROSTRUCTURED MULTIFUNCTIONAL INORGANIC COATING ADDITIVES FOR PREVENTING FOULING (GROWTH OF BIOFILM) IN AQUATIC APPLICATIONS

• US 20110030578A1
• Filed: 08/05/2010
• Published: 02/10/2011
• Est. Priority Date: 08/05/2009
• Status: Active Grant

• Current Assignee: Evonik Degussa GmbH
• Original Assignee: Evonik Degussa GmbH
• Inventors: Meyer, Jürgen, Schulz, Katharina, Tschernjaew, Juri, Michael, Günther, Mertsch, Rüdiger, Rochnia, Matthias, Schultz, Thorsten
• Granted Patent: US 8,597,789 B2
• Time in Patent Office: Days
• US Class Current: 106/15.05
• CPC Class Codes: C01P 2002/02 Amorphous compounds
• CPC Class Codes: C01P 2002/85 by XPS, EDX or EDAX data
• CPC Class Codes: C01P 2004/61 Micrometer sized, i.e. from 1-100 micrometer
• CPC Class Codes: C01P 2006/11 Powder tap density
• CPC Class Codes: C01P 2006/12 Surface area
• CPC Class Codes: C01P 2006/14 Pore volume
• CPC Class Codes: C01P 2006/19 Oil-absorption capacity, e.g. DBP values
• CPC Class Codes: C09C 1/3063 Treatment with low-molecular organic compounds
• CPC Class Codes: C09C 1/3072 Treatment with macro-molecular organic compounds
• CPC Class Codes: C09C 1/309 Combinations of treatments provided for in groups C09C1/3009 - C09C1/3081
• CPC Class Codes: C09D 5/14 Paints containing biocides, e.g. fungicides, insecticides or pesticides C09D5/16 takes precedence
• CPC Class Codes: C09D 5/1606 characterised by the anti-fouling agent
• CPC Class Codes: Y10T 428/249955 Void-containing component partially impregnated with adjacent component
• CPC Class Codes: Y10T 428/249956 Void-containing component is inorganic
• CPC Class Codes: Y10T 428/2989 Microcapsule with solid core [includes liposome]
• CPC Class Codes: Y10T 428/2991 Coated
• CPC Class Codes: Y10T 428/2993 Silicic or refractory material containing [e.g., tungsten oxide, glass, cement, etc.]

Abstract

The present invention relates to innovative antifouling additives, to a process for producing them, to coating systems comprising the antifouling systems of the invention, to a process for producing the coating systems, and to the use of the antifouling additives and coating systems of the invention for preventing the underwater fouling of surfaces of objects which are in contact or come into contact with water.

Claims

1. Antifouling additive comprising

at least one inorganic and/or organic porous carrier,

at least one active antifouling ingredient incorporated into the porous carrier,

characterized in that, as demonstrated by XPS analysis of the outermost atomic layer of the product system, at least part of the outermost surface of the product system is formed by the carrier material.

2. Antifouling additive according to claim 1, characterized in that at least 10%, preferably at least 20%, of the outermost atomic layer of the product system is formed by the carrier material.

3. Antifouling additive according to one of claims 1 or 2, characterized in that the carrier material is an amorphous silicon dioxide, preferably a precipitated silica, a silica gel, a fumed silica, a silica prepared on the basis of fumed silica, a silicate, or hybrid forms thereof.

4. Antifouling additive according to claim 3, characterized in that the amorphous silicon dioxide has an average particle size d₅₀ of 4 to 70 μ

m, preferably 4 to 50 μ

m, more preferably 4 to 20 μ

m, very preferably 4 to 15 μ

m, especially preferably 5 to 13 μ

m and very especially preferably 6 to 12 μ

m or in that it is a granulated silicon dioxide with a d₅₀ of preferably 20 to 180 μ

m, more preferably 50 to 150 μ

m, very preferably 70 to 130 μ

m.

5. Antifouling additive according to claim 3, characterized in that the amorphous silicon dioxide comprises Aeroperls having an average particle size d₅₀ of 4 to 70 μ

m, preferably 5 to 50, more preferably 6 to 40 μ

m.

6. Antifouling additive according to claims 3 to 5, characterized in that the amorphous silicon dioxide has a grindometer value of 18 to 45 μ

m, preferably 20 to 43 μ

m and/or a tapped density of 50 to 350 g/l, preferably 50 to 300 g/l, and/or an oil number of 180 to 360 g/100 g and/or a DBP number of 200 to 450 g/100 g, preferably 320 to 400 g/100 g, and/or a BET of 100 to 600 m²/g, preferably 200 to 550 m²/g, more preferably 300 to 550 m²/g and very preferably 350 to 500 m²/g, and/or a total pore volume of 6 to 14 ml/g (0.0042-414 MPa, 140°

).

7. Antifouling additive according to any of claims 1 to 6, characterized in that besides the active ingredient it comprises at least one further substance, of which at least part of the total amount present in the product system is incorporated in the pores of the carrier material.

8. Antifouling additive according to claim 7, characterized in that the protection substance comprises water-soluble and/or water-swellable and/or biodegradable polymers preferably selected from the group consisting of polysaccharides, block copolymers, caprolactones, lactide and glycolide polymers, polyanhydrides, polyesters, hydroxybutyric acids, polyphosphazenenes and polyphosphoesters.

9. Antifouling additive according to one of claim 7 or 8, characterized in that the weight ratio of protection system to active ingredient is in the range from 10:

1 to 1;

10.

10. Antifouling additive according to any of the preceding claims, characterized in that the active ingredient charge of the porous carrier is at least 10% by weight, based on the DBP absorption of the porous carrier.

11. Antifouling additive according to any of claims 7 to 10, characterized in that the protection system charge of the porous carrier is at least 10% by weight, based on the DBP absorption of the porous carrier.

12. Antifouling additive according to any of the preceding claims, characterized in that the active ingredient is a biodegradable active ingredient preferably selected from the group of secondary active plant ingredients or from the group consisting of natural oils, vitamins, algal extracts, plant extracts, metal salts, terpenes, gramins, pyrroles, pyrazoles, phenols and steroids.

13. Antifouling additive according to any of the preceding claims, characterized in that it has a free-flowability as measured using the flow funnels of DIN 53492 in the range from 1 to 4, preferably 1 to 3, more preferably 1 to 2 and very preferably 1.

14. Process for producing an antifouling additive according to any of claims 1 to 13, characterized in that at least one porous, preferably inorganic solid is contacted with at least one active ingredient in such a way that the active ingredient is drawn into the pores of the solid.

15. Process according to claim 14, characterized in that suitable washing operations and/or inhibiting steps ensure that there is no active ingredient on the outer surface of the particles.

16. Process according to one of claim 14 or 15, characterized in that an active ingredient is incorporated into a porous carrier and, furthermore, a protection system is produced.

17. Process according to claim 16, characterized in that it comprises the following steps:

a) introducing at least one carrier material in a solids mixing unit

d) adding at least one active ingredient to the solids mixing unit

e) impregnating the carrier with active ingredient.

18. Process according to claim 17, characterized in that it further comprises at least one of the following steps:

b) evacuating the solids mixing unit

f) inhibiting the active ingredient adhering to the outer particle surface of the carrier material, and/or washing and/or drying.

19. Process according to claim 17 or 18, characterized in that it comprises one or more of the following further steps:

c) preimpregnating the carrier material with at least one protection substance until a maximum of 50% by weight of the DBP absorption value is reached

g) adding at least one protection substance

h) impregnating the carrier with at least one protection substance

i) washing and/or drying

j) reactively inhibiting the active ingredient adhering to the outer particle surface of the carrier material, and/or washing and/or drying.

20. Process according to claim 18 or 19, characterized in that stages b) to e) and/or g) to h) are carried out repeatedly, it being possible, on repetition of steps d) and e) and/or g) and h), to use identical or different active ingredients and/or protection substances in each case.

21. Process according to any of claims 17 to 20, characterized in that the carrier material and the active ingredient/ingredients are mixed before being introduced into the solids mixing unit.

22. Process according to any of claims 19 to 21, characterized in that the amount of protection substance/substances added in step g) is regulated such that the total amount of active ingredient/ingredients and protection substance/substances added in the production of the product systems is 50% to 100% by weight of the DBP absorption value of the carrier material.

23. Process according to any of claims 19 to 22, characterized in that the amount of protection substance/substances added in step g) is regulated such that the total amount of active ingredient/ingredients and protection substance/substances added in the production of the product systems is greater than the total pore volume of the carrier material and in that the excess of protection substance/substances is absorbed by addition of carrier material and/or of carrier material charged with active ingredient/ingredients.

24. Coating system, preferably a surface-coating-material system, comprising at least one antifouling additive according to any of claims 1 to 13, preferably in a fraction of 5% to 15% by weight.

25. Coating system according to claim 24, characterized in that it is an eroding coating system or a coating system having an insoluble matrix or is an antistick coating or a microstructured surface-coating.

26. Method of protecting the surface of objects which are in contact with water, more particularly sea water, characterized in that a coating system according to one of claim 24 or 25 is applied to the surface of the objects.

27. Use of antifouling additives according to any of claims 1 to 13 or of coating systems according to one of claim 24 or 25 for protecting the surface of objects which are in contact with water, especially sea water, against biofouling.