Possessive form of children, indicating something belonging to or associated with children. Note: the correct spelling is "children's" with an apostrophe.
From Old English 'cildra' (genitive plural of 'cild'). The possessive 's' was added following standard English possessive formation rules, though the spelling requires an apostrophe before the 's'.
The word 'children' is one of English's few surviving Germanic plural forms - most words form plurals by adding 's', but 'children' preserves an ancient pattern also seen in 'men', 'women', and 'teeth'.
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