First off - if you are recasting for your own use, that is one thing, but remember that Volks holds the copyright on their products. That includes using one of their heads as a base for one of your own if you intend to market a head.
I will now remove my moderator hat.
Now, as to what you wanted to know: Obitsu and Volks are a combination of Vinyl and ABS plastic. The heads are Vinyl, the harder parts are ABS Plastic. Making hollow vinyl requires very expensive and specialized molds that are made of metal. ABS plastic also uses very hot metal molds. If you would like to see how this is done I recommend this site:
http://www.dannychoo.com/en/post/27195/Smart+Doll.html Danny Choo goes into great detail with pictures about the process. The time I did doll prototyping I believe that the creator paid over $10,000 per doll to get them made. So, bad new - expensive. Good news, it can actually be done.
What I suggest you do: Have you considered learning to do 3-D modeling on a computer? There are many 3-D printers available now that are more and more affordable. And they print in ABS plastic! It is safer than resin also.
If the head will be a "one off" you could use the paper clay method.
If you make a resin head, you can manually drill the holes before rooting, or you can just wig the head.
To make a hollow mold you basically make a mold of both the outside and the inside of the head. There are lots of tutorials online that show how to do this. There have even been some here on DS.
You could petition Kiki-chan78 to print her Allison bjd as a 1/6 doll. She did do that with the Alice, and it's available as a 3-D print. It's not cheap but the doll is lovely. She makes a fairy line. [url]sweetdolls-bjd.com[/url]
There are other makers that also do 3-D printed dolls. Again, not necessarily cheaply.
Volks and Obitsu are not the only 1/6th scale vinyl jointed doll. Look for anime boy dolls. Also look for Taeyang bodies. He's the boy version of Pullip and is equivalent to Obitsu - frequently the body is replaced by Obitsu.