Aqueous polyurethane compositions
View Patent ↗An aqueous polyurethane composition comprising a polyurethane which is the reaction product of: (A) an isocyanate-terminated prepolymer and (B) at least one active-hydrogen chain-extending compound comprising at least 0.20 stoichiometric equivalents with respect to the isocyanate content of the isocyanate-terminated prepolymer (A), of an active-hydrogen chain-extending compound selected from the group consisting of hydrazine, hydrazine derivatives and mixtures thereof; and wherein at least 0.2 stoichiometric equivalents of the anionic or potentially anionic water-dispersing groups are neutralised with ammonia.
1. An aqueous polyurethane composition comprising a polyurethane having an acid value in the range of from 4 to 150 mgKOH/g and which comprises the reaction product of:
(A) an isocyanate-terminated prepolymer comprising a terminal isocyanate group, the prepolymer (A) being obtained by the reaction of components comprising:
(i) at least one organic polyisocyanate compound comprising isocyanate groups;
(ii) at least one isocyanate-reactive compound comprising an isocyanate reactive group, the compound (ii) bearing anionic or potentially anionic water-dispersing groups;
(iii) at least one isocyanate-reactive compound comprising an isocyanate reactive group, the compound (iii) not comprising compound (ii); wherein the isocyanate terminated prepolymer components are reacted in a ratio of the isocyanate groups of compound (i) to the isocyanate-reactive groups of compounds (ii) and (iii) in the range of from 1.1:1 to 6:1; and
(B) at least one isocyanate reactive active-hydrogen chain-extending compound comprising an isocyanate reactive active-hydrogen group, where the compound (B) comprises at least 0.20 stoichiometric equivalents with respect to the isocyanate content of the isocyanate-terminated prepolymer (A), of an isocyanate reactive active-hydrogen chain-extending compound selected from the group consisting of hydrazine, hydrazine derivatives and mixtures thereof;
Wherein the prepolymer (A) and the compound (B) are reacted in a ratio of the isocyanate groups of the prepolymer (A) to the isocyanate reactive active-hydrogen groups of the compound (B) in the range of from 1:0.5 to 1:1; and
wherein at least 0.2 stoichiometric equivalents of the anionic or potentially anionic water-dispersing groups are neutralised with ammonia.
2. An aqueous polyurethane composition according to claim 1 having a free hydrazine content ≦20 ppm.
3. An aqueous polyurethane composition according to claim 1 wherein the polyurethane has an acid value in the range of from 4 to 100 mgKOH/g.
4. An aqueous polyurethane composition according to claim 1 wherein the active-hydrogen containing chain-extender (B) comprises at least 0.4 stoichiometric equivalents with respect to the isocyanate content of the isocyanate-terminated prepolymer (A) of an active-hydrogen chain-extending compound selected from the group consisting of hydrazine, hydrazine derivatives and mixtures thereof.
5. An aqueous polyurethane composition according to claim 1 wherein the ratio of isocyanate groups in the isocyanate-terminated prepolymer (A) to active-hydrogens in the chain-extender (B) is in the range of from 1:0.6 to 1:1.
6. An aqueous polyurethane composition according to claim 1 wherein at least 0.25 stoichiometric equivalents of the anionic or potentially anionic water-dispersing groups are neutralised with ammonia.
7. An aqueous polyurethane composition according to claim 1 comprising a polyurethane having an acid value in the range of from 10 to 42 mgKOH/g and which comprises the reaction product of:
(A) an isocyanate-terminated prepolymer comprising a terminal isocyanate group, the prepolymer (A) being obtained by the reaction of components comprising:
(i) 10 to 90 wt % at least one organic polyisocyanate compound comprising isocyanate groups;
(ii) 0.1 to 80 wt % of at least one isocyanate-reactive compound comprising an isocyanate-reactive group, the compound (ii) bearing anionic or potentially anionic water-dispersing groups;
(iii) 5 to 90 wt % of at least one isocyanate-reactive compound comprising an isocyanate-reactive group, the compound (iii) not comprising compound (II);
where (i)+(ii)+(iii)=100%;
wherein the isocyanate terminated prepolymer components are reacted in a ratio of the isocyanate groups of compound (i) to the isocyanate-reactive groups of compounds (ii) and (iii) in the range of from 1.1:1 to 6:1; and
(B) at least one isocyanate reactive active-hydrogen chain-extending compound comprising an isocyanate reactive active-hydrogen group, where the compound (B) comprises at least 0.4 stoichiometric equivalents with respect to the isocyanate content of the isocyanate-terminated prepolymer (A), of an isocyanate reactive active-hydrogen chain-extending compound selected from the group consisting of hydrazine, hydrazine derivatives and mixtures thereof;
wherein the prepolymer (A) and the compound (B) are reacted in a ratio of the isocyanate groups of prepolymer (A) to the isocyanate-reactive active-hydrogen groups of compound (B) in the range of from 1:0.8 to 1:0.99; and
wherein in the range of from 0.25 and 3 stoichiometric equivalents of the anionic or potentially anionic water-dispersing groups are neutralised with ammonia.
8. An aqueous polyurethane composition according to claim 7 wherein component (i) is selected from the group consisting of isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, 2,4-toluene diisocyanate and mixtures thereof.
9. An aqueous polyurethane composition according to claim 7 wherein component (ii) is selected from the group consisting of 2,2-dimethylol propionic acid (DMPA), 2,2-dimethylolbutanoic acid (DMBA) and mixtures thereof.
10. An aqueous polyurethane composition according to claim 7 wherein component (iii) is selected from the group consisting of polytetrahydrofuran; polypropylene glycol; polyester; amine group terminated polyalkylene oxides or derivatives; and mixtures thereof.
11. An aqueous polyurethane composition according to claim 10 wherein component (iii) has a Mw in the range of from 300 to 3000 g/mol.
12. An aqueous polyurethane composition according to claim 10 wherein component (iii) comprises <15 wt % of organic compounds having a Mw below 500 g/mol.
13. An aqueous polyurethane composition according to claim 1 , additionally comprising a vinyl polymer wherein the weight ratio of polyurethane to vinyl polymer is in the range of from 10:90 to 99:1.
14. An aqueous polyurethane composition according to claim 13 wherein the vinyl polymer is a (meth)acrylate polymer.
15. An aqueous polyurethane composition according to claim 13 where the vinyl polymer has a Tg in the range of from −80 to 150° C.
16. An aqueous polyurethane composition according to claim 13 wherein the acid value of the vinyl polymer is in the range of from 0 to 100 mgKOH/g.
17. An aqueous polyurethane composition according to claim 13 comprising a separately prepared vinyl polymer with a polyurethane to vinyl solids ratio in the range of from 60:40 to 80:20; wherein the vinyl polymer has a Tg in the range of from 0 to 50° C. and is prepared from vinyl monomers selected from the group comprising of methyl methacrylate, ethyl (meth)acrylate, butyl (meth)acrylate, styrene, (meth)acrylic acid and mixtures thereof.
18. A process for preparing the aqueous composition according to claim 1 comprising the following steps:
a) reaction of components (i) to (iii) to form an isocyanate-terminated prepolymer (A);
b) forming an aqueous dispersion of the isocyanate-terminated prepolymer (A);
c) neutralising the isocyanate-terminated prepolymer (A);
d) chain-extension of the isocyanate-terminated prepolymer (A) by reaction with the active-hydrogen chain-extending compound (B).
19. A process according to claim 18 additionally comprising steps:
e) the addition of a reactive diluent; and f) the subsequent polymerisation of the reactive diluent.
20. A coated substrate comprising a substrate and a coating on the substrate comprised of the aqueous polyurethane composition according to claim 1 .
21. A method for coating a substrate with an aqueous polyurethane composition comprising applying the aqueous polyurethane composition according to claim 1 to a substrate and removing the aqueous medium.
22. A primer comprising an aqueous polyurethane composition according to claim 1 .
23. A label coating composition comprising the aqueous polyurethane composition according to claim 1 .
24. A heat-sealable coating composition comprising the aqueous polyurethane composition according to claim 1 which when heat sealed has a heat seal strength ≧200 g/inch (78.74 g/cm).
25. A coated label comprising a label and a coating on the label which comprises the aqueous polyurethane composition according to claim 1 .
26. A heat-sealed coated substrate comprising a substrate and a heat-sealed coating on the substrate, wherein the heat sealed coating comprises a dried residue of the aqueous polyurethane composition according to claim 1 having a heat seal strength of ≧200 g/inch (78.74 g/cm).