Looks like the MIME type in a Content-type header value is case-insensitive, so application/PDF and application/pdf are equivalent. It does say parameter values are case-sensitive, so technically "text/html; charset=UTF-8" is not equivalent to "text/html; charset=utf-8". But that's not a good example because http://www.w3.org/TR/html4/charset.html#h-5.2.1 says "Names for character encodings are case-insensitive".
http://www.w3.org/Protocols/rfc1341/4_Content-Type.html
The type, subtype, and parameter names are not case sensitive. For
example, TEXT, Text, and TeXt are all equivalent. Parameter values are
normally case sensitive, but certain parameters are interpreted to be
case- insensitive, depending on the intended use. (For example,
multipart boundaries are case-sensitive, but the "access- type" for
message/External-body is not case-sensitive.)