General definition:
5R is a 5-groove rifling pattern with sloped or angled sides to the lands. All rifling has a certain amount of angle to the sides of the lands as a natural effect of the rifling process. The sides of the grooves are parallel, but the sides of the lands are not and the 5R carries this to an extreme.
So why should this be good? It is felt the 5R may seal off the bullet better. Also, the angle of the lands may be less stressful to the bullet jacket, so thin-jacketed match bullets would be less likely to come apart at the high spin rates longer bullets require. It is also felt to be easier to clean as there are no tight corners next to the lands to hold powder fouling.
The 5-groove type of rifling comes from the belief an odd number of grooves is also less stressful to the bullet because it doesn't have two lands directly across from one another.