Sounds more like a client issue than an issue with the server/PHP. However, note that per RFC 2822 (my emphasis):
[indent][FONT="Courier New"]3.6.2. Originator fields
The originator fields of a message consist of the from field, the
sender field (when applicable), and optionally the reply-to field.
The from field consists of the field name "From" and a
comma-separated list of one or more mailbox specifications. If the
from field contains more than one mailbox specification in the
mailbox-list, then the sender field, containing the field name
"Sender" and a single mailbox specification, MUST appear in the
message. In either case, an optional reply-to field MAY also be
included, which contains the field name "Reply-To" and a
comma-separated list of one or more addresses.[/FONT][/indent]
