Aqueous radiation curable polyurethane compositions
The invention relates to radiation-curable aqueous composition comprising an (meth)acrylated polyurethane prepolymer 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),
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 at least one (meth)acrylated compound (iv) is present in an amount of 5 to 30% by weight relative to total weight of the at least one (meth)acrylated polyurethane pre-polymer (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, and
optionally, at least one ethylenically unsaturated compound (B),
wherein said (meth)acrylated polyurethane pre-polymer (A) comprises a total amount of (meth)acrylated groups of at least 3.0 meq of (meth)acrylated groups per g of total weight of compounds (i), (ii), (iii), (iv) and (v).
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 dispersion in an aqueous medium of said end-capped (meth)acrylated polyurethane pre polymer obtained after the second step,
an optional step comprising the reaction with a neutralizing agent in order to convert the hydrophilic groups provided by compound (iii) into anionic salts,
an optional step wherein the (meth)acrylated polyurethane pre-polymer obtained after the second step is reacted with a chain extender (vii),
optionally 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 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.
6. 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.
7. The radiation curable composition according to claim 6 , wherein the (meth)acrylated compound (iv) is the diacrylate ester of bisphenol A diglycidylether.
8. 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.
9. 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.
10. A process for the preparation of a radiation-curable composition according to claim 1 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 dispersion in an aqueous medium of said end-capped (meth)acrylated polyurethane pre-polymer obtained after the second step,
an optional step comprising the reaction with a neutralizing agent in order to convert the hydrophilic groups provided by compound (iii) into anionic salts,
an optional step wherein the (meth)acrylated polyurethane pre-polymer obtained after the second step is reacted with a chain extender (vii),
an optional step comprising the addition of an ethylenically unsaturated compound (B).
11. A process for preparing a coated article comprising a step wherein the article is coated with a radiation curable composition according to claim 1 .
12. 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 3.0 meq per total weight in g of total weight of compounds (i),(ii),(iii),(iv),(v) and (B).