High modulus urethane adhesive compositions, manufacture and use thereof

1. A urethane adhesive composition comprising:

a) more than about 25 wt % of a urethane prepolymer resin consisting essentially of a reaction product of polyoxypropylene diol, polyoxypropylene triol, and methylene diphenyl diisocyanate, reacted in the presence of a catalyst;

b) more than about 0.75 wt % to no more than about 7.5 wt % of aromatic polyisocyanate having a nominal functionality of more than 2.5, combined with the urethane prepolymer after the reaction product is prepared;

c) more than about 0.1 wt % of an organic amine and more than about 60 ppm of a dialkyltin dicarboxylate catalyst compound, for moisture cure;

d) a filler;

e) a dialkyl phthalate; and

f) an aliphatic polyisocyanate;

wherein the composition is free of crystalline polyester so that the composition can be produced at room temperature and is pump transferrable without the need for heating;

wherein the composition exhibits direct adhesion capability toward painted metal substrates; and

wherein the composition has a sag distance of less than 1 mm.

2. The composition according to claim 1 comprising more than about 1 wt % to no more than about 7.5 wt % of aromatic polyisocyanate.

3. The composition according to claim 1 , comprising no more than about 5 wt % of aromatic polyisocyanate.

4. The composition according to claim 3 comprising no more than about 3 wt % of aromatic polyisocyanate.

5. The composition of claim 1 , wherein the composition exhibits the following properties: 100 percent cohesive failure to a painted metal substrate after 7 days of cure at 23° C. and 50% relative humidity; and 100 percent cohesive failure after 7 days of cure at 23° C. and 50% relative humidity and 14 days at 100° C. and 100% relative humidity.

6. The composition of claim 1 which contains:

a) more than about 25 wt % to about 75 wt % of the urethane prepolymer resin;

b) more than about 0.75 wt % to about 7.5 wt % of the aromatic polyisocyanate;

c) more than about 0.1 wt % to about 2.0 wt % of the organic amine and more than about 60 ppm to about 1.0 wt % of the dialkyltin dicarboxylate catalyst compound; and

d) less than about 35 wt % of the filler.

7. The composition of claim 1 which further comprises one or more of the following ingredients: one or more stabilizers; and a moisture scavenger.