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have you tried green people?- i think their website is www.greenpeople.co.uk, they have a childrens and baby range (baby range are the mildest. i think they were developed by a pharamsist after her children developed eczema. i use it myself. the bottle has lasted over a year as you only need tiny amount or sometimes i don't wash my ds's hair for 2-3 weeks only using water. the other thing i would say is try and steer clear of sulphate and parabens in the list of ingredients.
Have you tried not shampooing at all? Just rinse with fresh water (ie not the bathwater). When we do that, accompanied by plenty of brushing when the hair is dry, our 4yo barely ever needs to have his hair shampooed. It doesn't work so well with the 2yo because a lot of her food ends up in her hair, but even so we rarely shampoo her hair more than once or twice a month.
Simple bath wash is really good and has helped ds' excema. I use it to wash his hair too. I use Asda George brand baby moisturiser after his bath too which is gorgeous and makes his skin lovely and soft.