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The hospital is not bound by your separation agreement, as they were not a party to the agreement. The hospital will look only at the insurance contract terms, and since you are the responsible party on the insurance contract, they will seek collection from you.
Generally, a spouse is not liable for the debts of the other as long as it is an individual account, the spouse running up the debt is not an authorized user, surety, guarantor, or cosignor, and the couple does not live in a community property state. However, even in a community property state the assets of the spouse not running up the debt could be at risk. For example, in cases involving, among others, bankruptcy, divorce, or other litigation, creditors may go after assets held jointly by the debtor and non-debtor spouse, such as a bank account in both their names. If your spouse agrees to pay off a joint credit card debt but does not, the bank may successfully sue you for that debt. However, state laws vary about which marriage partner is responsible for certain debts, depending upon when the debt was incurred, the identity of the debtor, or the purpose of the debt.