Depending on which shell you are using, you may be able to use parameter expansion to double \ in your substitution string and prevent the \u interpretation:
path="first\usr"
sed -e "s/\\usr/${path//\\/\\\\}/g" <<< "D:\usr"
The syntax for replacing a pattern with the shell parameter expansion is ${parameter/pattern/string} (one replacement) or ${parameter//pattern/string} (replace all matches).
This substitution is not specified by POSIX, but is available in Bash.
Where it is not available, you may need to filter $path through a process:
path=$(echo "$path" | sed 's/[][\\*.%$]/\\&/g')
(N.B. I have also quoted other sed metacharacters in this filter).