Thiol-ene-based polymerizable composition

1 . A use of compounds comprising, per molecule, at least one polymerizable C—C double bond, at least one adhesion-providing moiety, and one at least bivalent hydrocarbon moiety in between as a spacer as primers in a thiol-ene-based polymerizable composition for improving the adhesion of the composition on a substrate to be coated therewith, wherein the composition further comprises a radical initiator, monomers with at least two polymerizable C—C double bonds per molecule, and polythiols with at least two SH groups per molecule, wherein the primers comprise 5-norbornen-2-yl groups as polymerizable C—C double bonds,

characterized in that

compounds are used as primers in the polymerizable composition that

a) comprise phosphonic acid groups as adhesion-providing moieties; or

b) comprise groups selected from phosphonic acid groups and 3,4-dihydroxyphenyl groups as adhesion-providing moieties, and that the polymerizable composition is used as a bone adhesive.

2 . The use according to claim 1 , characterized in that the primers each comprise at least two 5-norbornen-2-yl groups and/or at least two adhesion-providing moieties.

3 . The use according to claim 1 or 2 , characterized in that the spacer moiety of the primers has a chain length of at least 3 or at least 6 carbon atoms.

4 . The use according to claim 1 , characterized in that the spacer moiety of the primer has a chain length of not more than 12 or not more than 10 carbon atoms.

5 . The use according to claim 1 , characterized in that the monomers are selected from compounds with at least two allyl or vinyl ester groups.

6 . The use according to claim 5 , characterized in that the monomers comprise 1,3,3-triallyl-1,3,5-triazin-2,4,6-trione (TATATO).

7 . The use according to claim 1 , characterized in that the polythiols are selected from compounds with at least three SH groups per molecule.

8 . The use according to claim 7 , characterized in that the polythiols comprise tris[2-(3-mercaptopropionyloxy)ethyl]isocyanurate (TEMPIC).

9 . The use according to claim 1 , characterized in that the composition is a one-component composition.

10 . The use according to claim 1 , characterized in that the composition is a two-component composition, of which only the first component comprises the primers.

11 . The use according to claim 1 , characterized in that the composition comprises approximately 0.1 wt % to approximately 5 wt % of a radical initiator, approximately 10 wt % to approximately 50 wt % of monomers, approximately 40 wt % to approximately 80 wt % of polythiols, and approximately 5 wt % to approximately 25 wt % of primers, in such amounts that the sum is 100 wt %.

12 . The use according to claim 9 , characterized in that the composition contains approximately 0.5 wt % to approximately 2 wt % of a radical initiator, approximately 40 wt % to approximately 60 wt % of monomers, approximately 60 wt % to approximately 80 wt % of polythiols, and approximately 10 wt % to approximately 20 wt % of primers, in such amounts that the sum is 100 wt %.

13 . The use according to claim 1 , characterized in that the radical initiator is a radical photoinitiator and the composition is photopolymerizable.

14 . The use according to claim 9 , characterized in that the radical initiator is a radical photoinitiator and the composition is photopolymerizable and the composition is appliable to the substrate to be coated in one step and then curable by irradiation.

15 . A norbornene derivative of the following formula

wherein

Norb represents a 5-norbornen-2-yl radical;

each AM independently represents a phosphonic acid group (HO) 2 P(═O)— or a 3,4-dihydroxyphenyl groups;

n and m each independently represent an integer ≥1; and

Sp represents a spacer group selected from (n+m)-valent hydrocarbon residues with 1 to 40 carbon atoms;

provided that at least one of n and m represents an integer >1 when AM represents a 3,4-dihydroxyphenyl group.

16 . The norbornene derivative according to claim 15 , characterized in that

a) one or both of n and m represent(s) 2; and/or

b) S represents an (n+m)-valent hydrocarbon residue with 3 to 20 or 6 to 16 carbon atoms, one or more of which are optionally replaced by a heteroatom selected form O, S and N; and/or

c) AM represents a phosphonic acid group (HO)2P(═O)—.

17 . The norbornene derivative according to claim 15 ,

characterized in that it is selected from the following compounds:

N-(4-hydroxy-4,4-diphosphonobutyl)-5-norbornene-2-carboxylic acid amide sodium salt (N-(4-hydroxy-4,4-diphosphonobutyl)alendronic acid amide sodium salt) (Alendronate-Norb) (E1):

5-norbornen-2-ylcarbonyloxymethylphosphonic acid (Phn-1C-Norb) (E3):

6-(5-norbornen-2-ylcarbonyloxy)hexylphosphonic acid (Phn-6C-Norb) (E4):

6-(2,3-bis(5-norbornen-2-ylcarbonyloxy)propylthio)hexylphosphonic acid (Phn-6C-bisNorb) (E5):

6-(2,3-bis(5-norbornen-2-ylcarbonyloxy)propylthio)hexane-1,1-diyl-bis(phosphonic acid) (bisPhn-6C-bisNorb) (E6):

3-(3-(3,4-dihydroxyphenyl)propylthio)propane-1,2-diyl-bis(norbornen-2-carboxylate) (Catechol-3C-bisNorb) (E7):

ethylenediaminetetraacetic acid-bis(2-(3,4-dihydroxyphenyl)ethyl)amide-bis(2-(5-norbornen-2-yl)ethyl)amide (bisCatechol-EDTA-bisNorb) (E8):

and

diethylenetriaminepentaacetic acid-bis(2-(5-norbornen-2-yl)ethyl)amide-tris(2-(3,4-dihydroxyphenyl)ethyl)amide (triCatechol-DTPA-bisNorb) (E9):

18 . The use according to claim 1 , characterized in that the primer used is a norbornene derivative of the following formula

wherein

Norb represents a 5-norbornen-2-yl radical;

each AM independently represents a phosphonic acid group (HO) 2 P(═O)— or a 3,4-dihydroxyphenyl groups;

n and m each independently represent an integer ≥1; and

Sp represents a spacer group selected from (n+m)-valent hydrocarbon residues with 1 to 40 carbon atoms;

provided that at least one of n and m represents an integer >1 when AM represents a 3,4-dihydroxyphenyl group.