Because the white should be transparent. That's what I meant by clearing it.
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The way I make it is resize the png, then create a layer underneath it and fill it with white.
When you open the PNG, it should all be on one layer, named "Layer 0" by default.
When you create a new layer, it should create Layer 1. Put Layer 1 below Layer 0 and fill Layer 1 with white. Now there should be no transparency on the stage.
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Then go to Select > Color Range, leave Select at Sampled Colors, set Fuzziness to 0, leave everything else default. Click on any white space (completely white). The semi-transparent areas that result from resizing will turn some of the white gray, and so that won't get selected by this method.
This is how it should look:
You'll also end up selecting some parts of the cards, like the numbers. This won't matter.
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Now that you have everything that's white (and thus 100% transparent on the original image), make sure you're working with the layer filled in White and clear it.
All this meant that you should be working with Layer 1. By "clear it" I just meant hit delete to delete the selection.
Now you'll see this:
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Then invert the selection (Ctrl+I) and fill it with black. This will fill everything that's not 100% transparent with black.
Now you don't want to end up with a gray border, you want a black border. So you want to fill the remaining area in Layer 1 with black.
Once you deselect, there is now only 100% transparency and 100% opacity, and no partial transparency in between.
The reason you're getting white corners is because that white should be transparent.