Aqueous radiation curable polyurethane compositions
The invention relates to radiation-curable aqueous composition comprising an (meth)acrylated polyurethane pre-polymer obtained from the reaction of a polyisocyanate, optionally a polyol, at least one hydrophilic compound containing at least one reactive group capable to react with isocyanate groups and which is capable to render the polyurethane pre-polymer dispersible in aqueous medium either directly or after the reaction with a neutralizing agent to provide a salt, an (meth)acrylated compound containing at least two reactive groups capable to react with isocyanate groups and an (meth)acrylated compound containing essentially one reactive group capable to react with isocyanate groups, said composition comprising an amount of (meth)acrylated and polymerizable ethylenically unsaturated groups of at least 3 meq per g.
1. An aqueous radiation-curable composition comprising
at least one (meth)acrylated polyurethane pre-polymer (A) obtained from the reaction of:
at least one polyisocyanate compound (i), wherein the amount of the at least one polyisocyanate compound (i) is in the range of from 10 to 60 wt % of the polyurethane prepolymer (A),
optionally, at least one polyol (ii),
at least one hydrophilic compound (iii) containing at least one reactive group capable to react with isocyanate groups and which is capable to render the polyurethane pre-polymer dispersible in aqueous medium either directly or after the reaction with a neutralizing agent to provide a salt,
at least one (meth)acrylated compound (iv) containing at least two reactive groups capable to react with isocyanate groups, wherein the amount of the at least one (meth)acrylated compound (iv) is in the range of from 5 to 30 wt % of the polyurethane prepolymer (A),
at least one (meth)acrylated compound (v) containing essentially at least two (meth)acrylates and only one reactive group capable to react with isocyanate groups selected from poly(meth)acryloyl mono-hydroxy compounds, wherein the amount of the (meth)acrylated compound (v) is in the range of from 10 to 60% by weight of the polyurethane prepolymer (A), and
at least one ethylenically unsaturated compound (B),
wherein said composition comprises a total amount of (meth)acrylated and, optionally, polymerizable ethylenically unsaturated groups of at least 3 meq per total weight in g of (i), (ii), (iii), (iv), (v) and (B).
2. The radiation curable composition according to claim 1 obtained by a process comprising
a first step comprising the reaction of compounds (i), (iii) and (iv), and optionally compound (ii),
a second step comprising the reaction of the product of the first step with a compound (v) so that an end-capped (meth)acrylated polyurethane pre-polymer is obtained;
the dispersing of said end-capped (meth)acrylated polyurethane pre-polymer obtained after the second step in an aqueous medium,
an optional step comprising the reaction with a neutralizing agent in order to convert the hydrophilic groups provided by compound (iii) into anionic salts, and
a step comprising the addition of an ethylenically unsaturated compound (B).
3. The radiation curable composition according to claim 1 , wherein the polyisocyanate (i) is selected from aliphatic and cycloaliphatic polyisocyanates.
4. The radiation curable composition according to claim 1 , wherein the polyol (ii) is a polyester polyol having a number average molecular weight of at least 400.
5. The radiation curable composition according to claim 1 , wherein the amount of the polyol (ii) is in the range of from 2 to 50 wt % of the polyurethane prepolymer (A).
6. The radiation curable composition according to claim 1 , wherein the hydrophilic compound (iii) is selected from hydroxycarboxylic acids represented by the general formula (HO)xR(COOH)y, wherein R represents a straight or branched hydrocarbon residue having 1 to 12 carbon atoms, and x and y independently are integers from 1 to 3.
7. The radiation curable composition according to claim 1 , wherein the amount of the hydrophilic compound (iii) is in the range of from 1 to 25 wt % of the polyurethane prepolymer (A).
8. The radiation curable composition according to claim 1 , wherein the (meth)acrylated compound (iv) is selected from the reaction products of diglycidyl compounds with (meth)acrylic acid.
9. The radiation curable composition according to claim 8 , wherein the (meth)acrylated compound (iv) is the diacrylate ester of bisphenol A diglycidylether.
10. The radiation curable composition according to claim 1 , wherein the (meth)acrylated compound (v) is selected from the esterification products of aliphatic and/or aromatic polyols with (meth)acrylic acid having a residual average hydroxyl functionality of about 1.
11. The radiation curable composition according to claim 1 , comprising an ethylenically unsaturated compound (B) selected from the esterification products of (meth)acrylic acid with tri-, tetra-, penta and/or hexahydric polyols and their mixtures.
12. The radiation curable composition according to claim 1 , comprising the ethylenically unsaturated compound (B) in an amount in the range of between 5 and 50% by weight relative to the total amount of pre-polymer (A).
13. The radiation curable composition according to claim 1 , further comprising non-ethylenically unsaturated compounds (C).
14. The radiation curable composition according to claim 13 , wherein the amount of the non-ethylenically unsaturated compounds (C) in the range of between 0 and 30% by weight relative to the total amount of pre-polymer (A) and optionally compound (B).
15. The radiation curable composition according to claim 1 wherein said composition comprises a total amount of (meth)acrylated and, optionally, polymerizable ethylenically unsaturated groups of at least 3.5 meq per total weight in g of (i), (ii), (iii), (iv), (v) and (B).
16. The radiation curable composition according to claim 1 wherein said composition comprises a total amount of (meth)acrylated and, optionally, polymerizable ethylenically unsaturated groups of at least 4 meq per total weight in g of (i), (ii), (iii), (iv), (v) and (B).
17. The radiation curable composition according to claim 1 wherein the total amount of (meth)acrylated groups in the pre-polymer (A) is at least 3.0 meq, at least 3.5 meq of (meth)acrylated groups per total weight in g of compounds (i), (ii), (iii), (iv) and (v).
18. The radiation curable composition according to claim 2 which is obtained by a process further comprising a step wherein the (meth)acrylated polyurethane pre-polymer obtained after the second step is reacted with a chain extender (vii), which is an amine.
19. The radiation curable composition according to claim 1 wherein the (meth)acrylated polyurethane pre-polymer (A) is further reacted with at least one chain extender (vii) comprising active amino groups capable of making a chain extension of the remaining isocyanate end-groups of the pre-polymer.
20. The radiation curable composition according to claim 2 obtained by a process further comprising a step of reacting the (meth)acrylated polyurethane pre-polymer obtained after the second step with a chain extender (vii).
21. The radiation curable composition according to claim 1 wherein the (meth)acrylated polyurethane pre-polymer (A) is not further reacted with a chain extender (vii).