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Hello @Brendonly
Welcome to the Bunnings Workshop community. It's sensational to have you join us, and thanks for sharing your question about how to paint over your door frame.
If you're planning on painting your door frames, it's necessary to sand off all the old stain that's currently on it. I suggest using Flexovit 115mm x 1m 180 Grit Painted Surface Sandpaper Roll to remove all the old stain and varnish. Once you've sanded it down to timber, I recommend doing a fine sanding of the surface using Flexovit 115mm x 1m 240 Grit Painted Surface Sandpaper Roll.
If you're not keen on doing it by hand, I propose looking into the possibility of using an electric sander to shorten the sanding time. Make sure to wipe off all the sanding dust on the door frame with a clean rag. Once the frame is ready for painting, I recommend masking the surrounding area with painter's tape and drop sheets. This will protect the area from errant paint splashes and accidental over painting.
I recommend priming the surface with Zinsser 1L Bulls Eye 1-2-3 Undercoat Primer Sealer Stain Blocker - 1L White. Once the primer has fully cured you can use a water-based topcoat of your choice. I propose looking at the Dulux 1L White Aquanamel High Gloss Enamel Paint for your door frames.
I also suggest having a look at this discussion - How to sand back paint on trims. by@amy2
Here is a link to a handy guide: How to paint like a professional by @Peggers
Please remember to wear personal protection such as gloves, goggles and a paint mask.
If you have any other questions we can help with, please let us know.
Eric
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