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I used to watch Detective Conan when I was younger and remember I got through the first 100 or so episodes. The most prominent "rivals" of Conan from what I remember was Kaitou Kid and Heiji Hattori. Who are some other characters that come later in the series and which episodes do they first appear?

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Kaitou Kid isn't really a rival character, he's somewhat of an antagonist.

Other than Heiji, there's only Sera Masumi who is a recurring character and a detective.
She first appears in episode 646.

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