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//直接循环遍历datagridview即可
int count = datagridview.AllowUserToAddRows ? datagridview.Rows.Count - 1 : datagridview.Rows.Count;
string[] s = new string[count];
for(int r = 0; r < count; r++)
{
string value1 = datagridview.Rows[r].Cell[0].Value == null ? "" : datagridview.Rows[r].Cell[0].Value.ToString();
string value2 = datagridview.Rows[r].Cell[1].Value == null ? "" : datagridview.Rows[r].Cell[1].Value.ToString();
s[r] = value1 + "=" + value2;
}