Step 1: Permanent hardness of water is caused by soluble salts of calcium and magnesium.
Step 2: Chlorides and sulphates of calcium and magnesium cause permanent hardness.
Step 3: The important chloride salts responsible for permanent hardness are:
\[
MgCl_2
\]
and
\[
CaCl_2
\]
Step 4: Sodium chloride and potassium chloride do not cause hardness because \(Na^+\) and \(K^+\) are not hardness-producing ions.
\[
\boxed{MgCl_2,\ CaCl_2}
\]