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Try a product called Tite Chairs by Wonder Lock 'em.
Titebond Ultimate wood glue get it almost anywhere Lowes,Home Depot etc. https://www.acmetools.com/blog/choose-best-wood-glue/
You may want to check with an antique dealer to make sure you don't compromise the value of the set. I'm sure it can be fixed, may as well fix it the proper way.
If they are very old, they may have hide glue in the joint.
hardware stores have teeny weeny tiny little strips of metal that look like the side of a cheese grater. I have used them to tighten up chair joints.