The notation $$ a\equiv b \pmod n $$
means that $a$ and $b$ are in the same residue class modulo $n$. If you're more used to $\bmod$ as a binary operator, this is the same as saying
$$ a\bmod n = b\bmod n$$
though we have to remember that the $\bmod$ here is one that always produces a result in $[0,n)$ even for a negative argument, such that, as will be relevant here, $(-19)\bmod 96 = 77$.
When you're being asked to find a multiplicative inverse of $5$ modulo $96$, what this means is to find an $x$ such that
$$\tag1 5x\equiv 1 \pmod{96} $$
Through the previous steps of the solution you have reached the knowledge that
$$\tag2 1 \equiv -5 \cdot 19 \pmod{96} $$
which is almost the same as what you're looking for, except that
- The $1$ is on the other side -- but that doesn't matter, because the definition of $\equiv$ is clearly symmetric in $a$ and $b$.
- There is a $-5$ instead of a $5$ in $\text{(2)}$. But we can get a $5$ instead by rembering (basic aritmetic) that $(-5)\cdot 19 = 5\cdot(-19)$.
So, since we know $\text{(2)}$ is true, we also know
$$\tag3 5\cdot(-19) \equiv 1 \pmod{96} $$
which tells us that $-19$ is a solution for $x$ in $\text{(1)}$.
All that is left to do is find the canonical representive of the residue class that contains $-19$, by adding or subtracting some multiple of $96$ to get it into the range $[0,96)$:
$$ -19 \bmod 96 = 77 $$
In other words, since changing one factor by a multiple of $n$ doesn't change the residue modulo $n$, we also know that
$$ 5\cdot 77 \equiv 1 \pmod{96}$$
which says that $5$ and $77$ are multiplicative inverses modulo $96$.