In order to invert an image’s color completely, consider the following steps: Hit the “Ctrl” and “A” keys together. This should select the whole image. You can also go to the Select menu at the top and click on “Select All” and that will do the same. Once you have made the selection, you can right click anywhere within it and from the drop-down select “Invert color”. This should invert the image’s colors and a “negative” version of it would be generated.
If you intend to color selected parts of the image, it shouldn’t be a problem. All you have to do is reduce your selection radius. To select, you can go with the default select tool in paint that is available in the top menu bar but it will only allow rectangular selections. To make a free selection, you can choose the “Free form selection” tool which can be found in the “Select” drop-down list. After you have selected the area, you can just click on “Invert color” in the same way by right clicking as you did before and you would be done. A thing to note here is that Paint would highlight a rectangular area even if you made a free selection. There is nothing to worry about that. Once you hit “Invert color” only the freely selected part of the image will be inverted, as indicated by the screenshot.
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