Curable compositions having improved adhesion performance

1. A curable composition comprising:

(A) at least one cyclic ether of general formula (I),

wherein R 1 and R 2 are the same or different within (I) and independently denote hydrogen, an aliphatic or heteroaliphatic group, an araliphatic or heteroaraliphatic group, a cycloaliphatic or heterocycloaliphatic group, or an aromatic or heteroaromatic group, and n is 2 or 3;

(B) at least one cyclic thiocarbonate of general formula (II),

wherein R 3 and R 4 are the same or different within (II) and independently denote hydrogen, an aliphatic or heteroaliphatic group, an araliphatic or heteroaraliphatic group, a cycloaliphatic or heterocycloaliphatic group or an aromatic or heteroaromatic group, X and Y denote oxygen or sulfur, and m is 2 to 5;

(C) at least one amine of general formula (III)

NR 5 R 6 R 7   (III)

wherein R 5 , R 6 and R 7 are the same or different within (III) and independently denote hydrogen, an aliphatic or heteroaliphatic group, an araliphatic or heteroaraliphatic group, a cycloaliphatic or heterocycloaliphatic group, an aromatic or heteroaromatic group, or two of R 5 , R 6 or R 7 form together a heterocycloaliphatic group, with the proviso that one or two of R 5 , R 6 and R 7 denote hydrogen;

(D) at least one carboxylic acid of general formula (IV),

R 8 —COOH  (IV)

wherein R 8 denotes an aliphatic or heteroaliphatic group, an araliphatic or heteroaraliphatic group, a cycloaliphatic or heterocycloaliphatic group, or an aromatic or heteroaromatic group; and

whereby instead of or in addition to (A) and (B) a hybrid compound (AB) of general formula (V)

can optionally comprise part of the curable composition,

wherein R 1 , R 2 , R 3 , R 4 , m and n are defined as above and A denotes a bridging group selected from the group consisting of aliphatic and heteroaliphatic groups; araliphatic and heteroaraliphatic groups; cycloaliphatic and heterocycloaliphatic groups; and aromatic and heteroaromatic groups; and

whereby instead of or in addition to (C) and (D) a hybrid compound (CD) of general formula (VI)

HOOC—B—NR 5 R 6   (VI)

can optionally comprise part of the curable composition,

wherein R 5 and R 6 are as defined above and B denotes a bridging group selected from the group consisting of aliphatic or heteroaliphatic groups; araliphatic or heteroaraliphatic groups; cycloaliphatic or heterocycloaliphatic groups and aromatic or heteroaromatic groups.

2. A curable composition according to claim 1 wherein (A) has the general formula (Ia)

wherein D denotes an oxygen or

and

R a is selected from the group consisting of straight-chain and branched alkyl groups with 1 to 18 carbon atoms; aromatic and heteroaromatic groups with 4 to 12 carbon atoms; groups with the structure

wherein all R b within the group are same or different and independently denote hydrogen or an alkyl group with 1 to 4 carbon atoms, and o is 0 or 1, and E is selected from the group consisting of carbon-carbon single bonds and CR c 2 wherein R c is same or different and independently denotes hydrogen or an alkyl group with 1 to 4 carbon atoms; and D is defined as above; and groups with the structure R d —SiR e R f R g wherein R e and R f are the same or different, each of which denotes a straight-chain or branched alkoxy residue with 1 to 6 carbon atoms or an aryloxy or aralkyloxy residue, R g is different or the same as R e or R f or an aliphatic residue, an amino residue, a halogen residue, an aromatic or heteroaromatic residue, or an araliphatic or heteroaraliphatic residue, and R d is a bridging group selected from the groups consisting of aliphatic, heteroaliphatic, araliphatic, heteroaraliphatic, aromatic and heteroaromatic groups.

3. A curable composition according to claim 1 , wherein (B) has the general formula (IIa)

wherein R a is selected from the group consisting of straight-chain and branched alkyl groups with 1 to 18 carbon atoms; aromatic and heteroaromatic groups with 4 to 12 carbon atoms; groups with the structure

wherein all R b within the group are same or different and independently denote hydrogen or an alkyl group with 1 to 4 carbon atoms,

and E is selected from the group consisting of a carbon-carbon single bond and CR c 2 wherein R c is same or different and independently denotes hydrogen or an alkyl group with 1 to 4 carbon atoms and p=0 or 1; and groups with the structure R d —SiR e R f R g wherein R e and R f are the same or different, each of which denotes a straight-chain or branched alkoxy residue with 1 to 6 carbon atoms or an aryloxy or aralkyloxy residue, R g is different or the same as R e or R f or an aliphatic residue, an amino residue, a halogen residue, an aromatic or heteroaromatic residue, or an araliphatic or heteroaraliphatic residue, and

R d is a bridging group selected from the group consisting of aliphatic, heteroaliphatic, araliphatic, heteroaraliphatic, aromatic and heteroaromatic groups.

4. A curable composition according to claim 1 , wherein (C) has the general formula (IIIa)

NHR 6 R 7   (IIIa)

wherein R 6 and R 7 are the same or different within the molecule and independently denote hydrogen; a branched or straight-chain alkyl group, optionally containing oxygen and/or NH; or an aralkyl group, optionally containing oxygen and/or NH; and any of R 6 and R 7 optionally comprise one or more OH and/or NH 2 groups.

5. A curable composition according to claim 1 , wherein R 8 in (D) is selected from the group consisting of branched or straight-chain alkyl groups; aryl groups; aralkyl groups; and alkaryl groups; and R 8 optionally comprises one or more halogen atoms and/or COOH groups.

6. A curable composition according to claim 1 , wherein (AB) comprises a bridging group A having the structure

wherein R b within the bridging group A are same or different and independently denote hydrogen or an alkyl group with 1 to 4 carbon atoms,

E is selected from the group consisting of a carbon-carbon single bond and CR c 2 wherein R c is same or different and independently denotes hydrogen or an alkyl group with 1 to 4 carbon atoms and p is 0 to 10.

7. A curable composition according to claim 1 , wherein (CD) is selected from the group consisting of naturally occurring amino acids and artificial amino acids.

8. A curable composition according to claim 1 , wherein the molar ratios between the following groups:

cyclic ether groups, present in (A) and/or (AB),

cyclic thiocarbonate groups, present in (B) and/or (AB),

amino groups, present in (C) and/or (CD), and

carboxy groups, present in (D) and/or (CD)

are as follows:

[cyclic ether (mol)]:[cyclic thiocarbonate (mol)]=99:1 to 30:70;

[amino group (mol)]:[carboxylic acid (mol)]=95:5 to 5:95;

[cyclic ether (mol)]:[carboxylic acid (mol)]=95:5 to 20:80; and

[amino group]:[cyclic thiocarbonate]=95:5 to 50:50.

9. A curable composition according to claim 1 , wherein the molar ratios between the following groups:

cyclic ether groups, present in (A) and/or (AB),

cyclic thiocarbonate groups, present in (B) and/or (AB),

amino groups, present in (C) and/or (CD), and

carboxy groups, present in (D) and/or (CD)

are as follows:

[cyclic ether (mol)]:[cyclic thiocarbonate (mol)]=95:5 to 80:20;

[amino group (mol)]:[carboxylic acid (mol)]=90:10 to 50:50;

[cyclic ether (mol)]:[carboxylic acid (mol)]=90:10 to 30:70; and

[amino group]:[cyclic thiocarbonate]=90:10 to 60:40.

10. A method for preparing a curable composition in accordance with claim 1 , comprising pre-mixing components (C) and (D) to form a mixture and adding said mixture to a mixture of (A) and (B) and/or (AB).

11. A method of sealing, coating or adhering a substrate, said method comprising applying a curable composition in accordance with claim 1 to said substrate and curing said curable composition.

12. A curable composition according to claim 1 wherein component (C) is at least in part substituted by a complex of component (C) and a cyclodextrin selected from α-cyclodextrin, β-cyclodextrin or γ-cyclodextrin.

13. A curable composition according to claim 12 , wherein the cyclodextrin is β-cyclodextrin and the amine is an amine represented by the general formula (IIIa)

NHR 6 R 7   (IIIa)

wherein R 6 and R 7 are the same or different within (IIIa) and independently denote hydrogen; a branched or straight-chain alkyl group, optionally containing oxygen and/or NH; or an aralkyl group, optionally containing oxygen and/or NH; any of R 6 and R 7 optionally comprising one or more OH and/or NH 2 groups.

14. A curable composition according to claim 1 , comprising at least one poly(propylene glycol) bis(2-aminopropyl ether.

15. A curable composition according to claim 1 , comprising at least one aromatic carboxylic acid.

16. A curable composition according to claim 1 , comprising at least one bisphenol A-diglycidyl ether.

17. A curable composition according to claim 1 , comprising at least one compound selected from the group consisting of bisphenol A-dithiocarbonates, phenol-dithiocarbonates, and bisphenol A-glycidyl ether-dithiocarbonates.