First, turn off all the profiling and DEBUG switches. These can slow down STL immensely.
If that's not it, part of the problem may be that your strings are identical for the first 80-90% of the string. This isn't bad for map, necessarily, but it is for string comparisons. If this is the case, your search can take much longer.
For example, in this code find() will likely result in a couple of string compares, but each will return after comparing the first character until "david", and then the first three characters will be checked. So at most, 5 characters will be checked per call.
map<string,int> names;
names["larry"] = 1;
names["david"] = 2;
names["juanita"] = 3;
map<string,int>::iterator iter = names.find("daniel");
On the other hand, in the following code, find() will likely check 135+ characters:
map<string,int> names;
names["/usr/local/lib/fancy-pants/share/etc/doc/foobar/longpath/yadda/yadda/wilma"] = 1;
names["/usr/local/lib/fancy-pants/share/etc/doc/foobar/longpath/yadda/yadda/fred"] = 2;
names["/usr/local/lib/fancy-pants/share/etc/doc/foobar/longpath/yadda/yadda/barney"] = 3;
map<string,int>::iterator iter = names.find("/usr/local/lib/fancy-pants/share/etc/doc/foobar/longpath/yadda/yadda/betty");
That's because the string comparisons have to search deeper to find a match since the beginning of each string is the same.
Using size() in your comparison for equality won't help you much here since your data set is so small. A std::map is kept sorted so its elements can be searched with a binary search. Each call to find should result in less than 5 string comparisons for a miss, and an average of 2 comparisons for a hit. But it does depend on your data. If most of your path strings are of different lengths, then a size check like Motti describes could help a lot.
Something to consider when thinking of alternative algorithms is how many many "hits" you get. Are most of your find() calls returning end() or a hit? If most of your find()s return end() (misses) then you are searching the entire map every time (2logn string compares).
Hash_map is a good idea; it should cut your search time in about half for hits; more for misses.
A custom algorithm may be called for because of the nature of path strings, especially if your data set has common ancestry like in the above code.
Another thing to consider is how you get your search strings. If you are reusing them, it may help to encode them into something that is easier to compare. If you use them once and discard them, then this encoding step is probably too expensive.
I used something like a Huffman coding tree once (a long time ago) to optimize string searches. A binary string search tree like that may be more efficient in some cases, but its pretty expensive for small sets like yours.
Finally, look into alternative std::map implementations. I've heard bad things about some of VC's stl code performance. The DEBUG library in particular is bad about checking you on every call. StlPort used to be a good alternative, but I haven't tried it in a few years. I've always loved Boost too.