Dimethicone is a chain of silicon and oxygen atoms with methyl groups attached. The chain is large and flexible, so it spreads into a thin, even film that sits on the surface and is not absorbed. That film does two useful things. It slows water evaporating out, though less strongly than petrolatum — enough to help dry skin, not enough to rescue deep fissures. And it puts a physical layer between your skin and whatever is irritating it: water, detergents, urine, or friction from a waistband or a bra strap.
It also explains the feel of a great deal of modern skincare. Dimethicone fills the microscopic gaps between surface cells, which makes rough skin feel instantly smooth and gives creams, primers and foundations their silky slip. That is a cosmetic effect sitting on top of a real functional one, and the two often get confused. The film is permeable to water vapour and gases, so despite its reputation it is nothing like cling film.
Dimethicone is among the best-tolerated ingredients in skincare, and allergic reactions to it are close to nonexistent.
There is no group that needs to avoid dimethicone. It is safe in pregnancy, while breastfeeding, on babies, and on every skin tone, and it is not absorbed into the body.
The genuine gates are situational rather than personal. Do not put it on an open, weeping or infected wound — use a plain ointment or whatever has been prescribed. And do not choose it when you need a stronger seal, because deeply fissured hands, heels and lips need petrolatum.
If you avoid silicones on environmental grounds, that is a fair position and a separate question from safety on skin. The one worth knowing about is not dimethicone but D4 (cyclotetrasiloxane), a volatile silicone restricted in the EU for environmental reasons. Dimethicone itself is not restricted.
Immediately. Rough skin feels smooth as soon as the film is on. That is genuine, but it is the film and not the skin.
Within a day. Chafing and stinging from friction settle once there is a barrier between skin and whatever is rubbing it.
One to two weeks. Irritant hand dermatitis improves noticeably with a barrier cream used after every wash — provided the irritant exposure has also been reduced. The cream alone rarely does it.
Two to four weeks. Dryness and roughness stay controlled with regular use.
When you stop. It washes off at the next wash, and the protection goes with it. This is a shield, not a repair, so it needs reapplying and it builds up no lasting benefit.