I was unsatisfied by the rigour and completeness of other answers regarding the case of conical (nonnegative coefficient) combinations so have provided an alternative proof at the expense of wordiness. For conical combinations, the problem is known as the Frobenius Coin Problem for $n=2$ or the Chicken McNugget Theorem.
Let $a,b,p,q\in\mathbb{N}_1$. If $p,q$ are not coprime, there exist arbitrarily large integers that are coprime to both and cannot be given in the form $ap+bq$, e.g., if $p=6,q=8$, then $ap+bq=2\left(3p+4q\right)$ is even and cannot express odd numbers. Therefore, let $p,q$ be coprime. We can use the ansatz that the largest number inexpressible in the form $ap+bq$ is $pq-p-q$. This can be proven by first proving that it is indeed inexpressible and then proving that every integer greater than it is expressible.
If $pq-p-q=ap+bq$ for some $a,b$, then $p\left(q-1-a\right)=q\left(1+b\right)$. Since $p,q$ are coprime but $p$ divides the RHS, it must divide $\left(1+b\right)=pk$ for some integer, $k$. Therefore, $pq-p-q=ap+\left(pk-1\right)q$, so $a=q\left(1-k\right)-1$ and $pq-p-q=p\underbrace{\left[q\left(1-k\right)-1\right]}_{a}+q\underbrace{\left[pk-1\right]}_{b}$. For $a,b$ to be positive, we would have $0<\frac{1}{p}<k<1-\frac{1}{q}<1$ and $k$ is not an integer, which is absurd. We have reached a contradiction, therefore $pq-p-q$ cannot be expressed as $ap+bq$.
We would then aim to prove that all integers $n>pq-p-q$ are expressible in the form $ap+bq$. Assume $n=ap+bq$. Since $p,q$ are coprime, by Bezout's identity, there are (not necessarily nonnegative) integers, $a', b'$, such that $a'p+b'q=1$. Therefore all integers can be expressed as $(na'+iq)p+(nb'-ip)q=n$ for all integers $i$. The set of integer pairs $a=(na'+iq),b=(nb'-ip)$ describes all possible values of $a,b$. This can be proven by letting $A,B$ be another pair of integers that satisfies $Ap+Bq=n$. Then, $[ap+bq]-[Ap+Bq]=n-n$, so $(a-A)p=(b-B)q$. But then, since $p,q$ are coprime, $(a-A)$ must be an integer multiple of $q$ and likewise $(b-B)$ an integer multiple of $p$. Therefore, any solution $A,B$ must be be offset from $k,m$ by an integer multiple of $q$ and $p$ respectively, so all solutions are of the form $a=(na'+iq),b=(nb'-ip)$.
Given an integer, $n$, since $b$ is $p$-periodic, there are thus one unique $b$ and $i$ such that $0\le b<p$. So, then $n$ can demonstrably be expressed in the form $ap+bq$ with positive $b$. If the corresponding $a$ is also nonnegative then there is nothing left to prove. However, if $a<0$ then $na'+iq<0$, which remains true when $i$ is decreased. But also, $(nb'-ip)$ would become negative if $i$ were increased, so at least one of $a,b$ would remain negative. Therefore, $n$ is expressible as $ap+bq$ if and only if $a\ge 0$. The largest integer that cannot be expressed with positive $a,b$ is therefore the maximal integer such that $a<0$ and $0\le b <p$, which is $-1\cdot p + (p-1) q=pq-p-q$. Therefore, all integers greater than $pq-p-q$ can be expressed.
Further reading and more proofs
Frobenius coin problem for $n=2$
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