Materials and processes for coating substrates having heterogeneous surface properties

• US 20080213598A1
• Filed: 01/18/2008
• Published: 09/04/2008
• Est. Priority Date: 01/19/2007
• Status: Active Grant

• Current Assignee: Airbus Operations GmbH (Airbus SE)
• Original Assignee: Airbus Deutschland GmbH (Airbus SE), EADS Deutschland GmbH (Airbus SE)
• Inventors: RAPS, Dominik M., SCHRAMM, Ottmar, PAPENDICK, Wolfgang
• Granted Patent: US 8,747,952 B2
• Time in Patent Office: Days
• US Class Current: 428/418
• CPC Class Codes: B05D 2202/25 based on Al
• CPC Class Codes: B05D 2701/00 Coatings being able to withstand changes in the shape of the substrate or to withstand welding
• CPC Class Codes: B05D 3/0254 After-treatment
• CPC Class Codes: C08G 77/58 Metal-containing linkages C08G77/485 takes precedence
• CPC Class Codes: C09D 183/10 Block or graft copolymers containing polysiloxane sequences obtained by polymerising a compound having a carbon-to-carbon double bond on to a polysiloxane C09D151/08, C09D153/00
• CPC Class Codes: Y10T 428/31529 Next to metal
• CPC Class Codes: Y10T 428/31663 As siloxane, silicone or silane

Abstract

A coating material includes:

• (A) a compound of formula (I)

R^a_4-nSiX^a_n,   (I)

• • wherein:
  • X^a is a hydrolysable radical;
  • R^a is a non-hydrolysable radical;
  • n is 2, 3 or 4;
• (B) a compound of formula (II)

• • wherein:
  • X^b is a hydrolysable radical;
  • R^b is a non-hydrolysable radical without an epoxide function, an acryloxy function, a methacryloxy function and an isocyanate function;
  • Y^b is a non-hydrolysable radical with a crosslinkable function; p is 2 or 3; q is 1 or 2; the sum of p and q is less than or equal to 4;
• (C) a crosslinking agent;
• (D) an organozirconium, organotitanium or organoaluminum compound containing hydrolysable organic radicals;
• (E) a hydrolysis catalyst;
• (F) crosslinkable prepolymers of epoxy and epoxysiloxane resins,
• (G) optional corrosion inhibitors;
• (H) optional compounds for reducing the reactivity of component (D);
• wherein n and the sum of p+q are not at the same time each 4.

Claims

1. A coating material which can be produced using the following components or multicomponent system for producing a coating, comprising or consisting of the following components:

(A) from 15-50 mol % of one or more silicon-organic compounds of formula (I)

R^a_4-nSiX^a_n 

 

(I),

wherein;

each X^a is independently of each other X^a a hydrolysable radical;

each R^a is independently of each other R^a a non-hydrolysable radical;

n is 2, 3 or 4;

(B) from 30-70 mol % of one or more silicon-organic compounds of formula (II)

2. The coating material or multicomponent system as claimed in claim 1, wherein:

X^a and/or X^b is selected from the group consisting of F, Cl, Br, I, OH, alkoxy, aryloxy, acyloxy, alkylcarbonyl and alkoxycarbonyl; and

/or

R^a and/or R^b is selected from the group consisting of alkyl, alkenyl, alkinyl, aryl, arylalkyl, alkylaryl, arylalkenyl, alkenylaryl, arylalkinyl, alkinylaryl and alkylalkenyl;

wherein for R^a and R^b respectively, an H is optionally replaced by a substituent.

3. The coating material or multicomponent system as claimed in claim 1, wherein:

X^a and/or X^b is selected from the group consisting of Cl, Br, OH, alkoxy containing 1 to 22 carbon atoms, aryloxy containing 6 to 10 carbon atoms, acyloxy containing 1 to 22 carbon atoms and alkylcarbonyl containing 2 carbon atoms; and

/or

R^a and/or R^b is selected from the group consisting of alkyl containing 1 to 20 carbon atoms, alkenyl containing 2 to 20 carbon atoms, alkinyl containing 2 to 4 carbon atoms;

aryl containing 6 to 10 carbon atoms;

alkylaryl containing 7 to 28 carbon atoms, alkylalkenyl containing 3 to 22 carbon atoms and alkenylaryl containing 8 to 28 carbon atoms;

wherein for R^a and R^b respectively, an H is optionally replaced by a substituent.

4. The coating material or multicomponent system as claimed in claim 1, wherein:

n is 2 or 3, and

R^a is a non-crosslinkable radical.

5. The coating material or multicomponent system as claimed in claim 1, wherein:

X^a is methoxy or ethoxy, preferably methoxy;

R^a is selected from the group consisting of methyl, ethyl, propyl, hexadecyl, (cyclohexyl)methyl, (octadecyl)methyl, isooctyl, dicyclopentyl and phenyl;

and

n is 2 or 3.

6. The coating material or multicomponent system as claimed in claim 1, wherein:

X^a is methoxy;

R^a is phenyl;

and

n is 3.

7. The coating material or multicomponent system as claimed in claim 1, wherein:

Y^b contains a glycidyl or glycidyloxy group.

8. The coating material or multicomponent system as claimed in claim 1, wherein:

X^b is methoxy or ethoxy, preferably methoxy;

Y^b is 3-glycidyloxypropyl;

p is 3; and

q is 1.

9. The coating material or multicomponent system as claimed in claim 2,

wherein R^a and/or R^b comprises a substituent selected from the group consisting of halogen and alkoxy.

10. The coating material or multicomponent system as claimed in claim 1, wherein for component (C):

the crosslinking agent or agents are Lewis bases.

11. The coating material or multicomponent system as claimed in claim 1, wherein for component (C):

the crosslinking agent or agents are selected from the group consisting of

aromatic polyols, aromatic diols, nitrogen-containing heterocycles, phenols containing one or more non-substituted amino groups, phenols containing one or more substituted amino groups, polycyclic amines, ammonia, silanes containing one or more non-substituted amino groups, silanes containing one or more substituted amino groups and mixtures thereof.

12. The coating material or multicomponent system as claimed in claim 1, wherein for component (C):

the crosslinking agent or agents are selected from the group consisting of

bisphenol A, bisphenol S, dihydroxynaphthalene, 1-methylimidazole, 2-(N,N-dimethylaminomethyl)phenol, aminopropyltrimethoxysilane, aminopropyltriethoxysilane, polyether polyols.

13. The coating material or multicomponent system as claimed in claim 1, wherein component (D) is selected from the group consisting of:

zirconium (IV) propoxide, titanium n-butoxide and aluminum sec-butoxide

wherein preferably zirconium (IV) propoxide is used.

14. The coating material or multicomponent system as claimed in claim 1, wherein component (D) is dispensed with.

15. The coating material or multicomponent system as claimed in claim 1, wherein component (E) is an acid catalyst or a mixture of various acid catalysts.

16. The coating material or multicomponent system as claimed in claim 1, wherein component (E) is selected from the group consisting of

HCl, HNO₃, H₂SO₄, H₃PO₄ and CH₃COOH and mixtures thereof.

17. The coating material or multicomponent system as claimed in claim 1, wherein component (F) is present in a content of at most 10% by weight, preferably at most 5% by weight, based on the total weight of components (A), (B), (C) and (D).

18. The coating material or multicomponent system as claimed in claim 1, wherein component (G) is an inorganic corrosion inhibitor and

is selected from the group consisting of vanadates, borates, phosphates, molybdates, tungstates, oxides and mixtures thereof;

and/or

contains at least one element selected from the group consisting of cerium, yttrium, lanthanum, titanium and zirconium.

19. The coating material or multicomponent system as claimed in claim 1, wherein component (G) is an inorganic corrosion inhibitor and comprises oxidic nanoparticles selected from the group consisting of

titanium oxide, zirconium oxide and cerium oxide, vanadium oxide, zinc oxide and mixtures thereof.

20. The coating material or multicomponent system as claimed in claim 1, wherein component (G) comprises one or more organic corrosion inhibitors selected from the group consisting of

triazoles, 2-benzothiazolylhiosuccinic acid, zinc-5-nitroisophthalate and mixtures thereof.

21. The coating material or multicomponent system as claimed in claim 1, wherein component (G) comprises one or more organic corrosion inhibitors selected from the group consisting of

benzotriazole, 5-methylbenzotriazole, 2-mercaptobenzotriazole and mixtures thereof.

22. The coating material or multicomponent system as claimed in claim 1, wherein component (H) is a chelating agent or a mixture of various chelating agents.

23. The coating material or multicomponent system as claimed in claim 1, wherein component (H) is selected from the group consisting of

acetylacetone, acetoacetic ester, propionic acid and mixtures thereof.

24. The coating material or multicomponent system as claimed in claim 1, comprising

from 20 to 40 mol % of component (A),

from 40 to 50 mol % of component (B), and/or

from 2 to 20 mol % of component (C), and/or

from 0 to 30 mol % of component (D),

based on the total quantity of components (A), (B), (C) and (D).

25. The coating material or multicomponent system as claimed in claim 24,

wherein for component (A):

X^a is selected from the group consisting of F, Cl, Br, I, OH, alkoxy, aryloxy, acyloxy, alkylcarbonyl and alkoxycarbonyl;

R^a is selected from the group consisting of alkyl, alkenyl, alkinyl, aryl, arylalkyl, alkylaryl, arylalkenyl, alkenylaryl, arylalkinyl, alkinylaryl and alkylalkenyl;

wherein for component (B);

X^b is selected from the group consisting of F, Cl, Br, I, OH, alkoxy, aryloxy, acyloxy, alkylcarbonyl and alkoxycarbonyl;

R^b is selected from the group consisting of alkyl, alkenyl, alkinyl, aryl, arylalkyl, alkylaryl, arylalkenyl, alkenylaryl, arylalkinyl, alkinylaryl and alkylalkenyl;

wherein for component (C);

the crosslinking agent or agents are Lewis bases;

wherein component (D) is selected from the group consisting of

tetra-n-propoxyzirconium, tetra-1-propoxyzirconium, titanium n-butoxide and aluminum sec-butylate;

wherein component (E) is an acid catalyst or a mixture of various acid catalysts; and

wherein component (H) is a chelating agent or a mixture of various chelating agents.

26. A process for producing a coating on a substrate, including the following steps:

providing a substrate,

providing or producing a not completely hardened coating material as claimed in claim 24,

hardening the coating material or allowing it to continue hardening and

applying the coating material to the substrate, at least in certain regions, before or during the hardening.

27. The process as claimed in claim 26,

wherein before the coating is applied, the substrate is chemically precleaned, physically precleaned, leached, treated with a primer, exposed to an electric discharge, exposed to an atmospheric pressure plasma process, CO₂-radiated, treated with an abrasive medium and/or baked.

28. The process as claimed in claim 26,

wherein the coating material is applied by spraying or dipping.

29. The process for producing a coating material as claimed in claim 1, including the following steps:

mixing components (A), (B) and (C),

hydrolyzing the hydrolysable groups of components (A) and (B),

adding component (F) before, during and/or after the hydrolysis,

crosslinking the crosslinkable groups of components (B) and (F).

30. The process as claimed in claim 29, wherein component (F) is added after the hydrolysis.

31. The process as claimed in claim 29, wherein component (F) is added during the hydrolysis.

32. The process as claimed in claim 29, wherein the crosslinking is initiated or accelerated after the hydrolysis.

33. A coating material obtainable by a process as claimed in claim 29.

34. A coated substrate obtainable by a process as claimed in claim 26.

35. The coated substrate as claimed in claim 34,

wherein the substrate is an aircraft structure.

36. The coated substrate as claimed in claim 35,

wherein the substrate consists of at least one connecting element or comprises at least one connecting element.

37. The coated substrate as claimed in claim 36,

wherein the connecting element is a rivet.

38. The coated substrate as claimed in claim 36, wherein:

the connecting element comprises or consists of one or more materials selected from the group consisting of aluminum, titanium and steel and the products of oxidation of these materials close to the surface.

39. The coated substrate as claimed in claim 36,

wherein the substrate comprises at least one connecting element in contact with at least one further substrate body,

wherein the further substrate body is painted,

wherein the coating covers a joint between the connecting element and the further substrate body, and

wherein the coating is applied both to the connecting element and to the paint of the further substrate body.

40. The coated substrate as claimed in claim 34,

wherein no further protective layer is provided.

41. The coated substrate as claimed in claim 40,

wherein the substrate is an aircraft structure

comprising a structural part having at least one rivet consisting of one or more materials selected from the group consisting of aluminum, titanium and steel and the products of oxidation of these materials close to the surface.