The results of the ballot, including a vote on strike action, will be known in a fortnight.
More than 100 children's social workers have been on strike for three months in protest at attempts to modernise working practices (Children Now, 1-7 September).
Stephanie Thomas, Unison's senior regional officer, said: "A number of children have not seen a social worker since the end of August and we do not know what is happening to them."
But Tony Hunter, Liverpool's executive director of social care and president of the Association of Directors of Social Services, said: "I am not looking for polarisation but for a sensible working resolution to get people back to work."
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