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Papyrus is someone who only wants to do the right thing and is someone who wants to help everyone. Though his "help" sometimes only makes things much worse. Papyrus is the hard working one of the two older brothers and there is something about him (biology maybe) that prevents his body from producing melatonin (the chemical that induces sleep). Though he never feels the adverse effects of sleep deprivation. In fact, it would seem that he is always extremely wound up and always excited to do things.
Sans is the older brother of Papyrus. Papyrus is always looking out for his brother, and sometimes provides "encouragement" to do some work.
Papyrus and Frisk are very great friends, Papyrus tries to defend his human friend.
The Shadowy Figure doesn't interact with Papyrus, in fact, he normally tries to avoid Papyrus as he doesn't know how to interact with morons.
Papyrus and Alphys really only know each-other through Undyne and through the Undernet.
Undyne is Papyrus's friend and mentor. He began training under her to in order to join the royal guard.