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Hello and thank you for your question.
No, there is no legal requirement that police have you sign the sample.
The following regulations set out the sampling process.
In any event, if they have not followed the law correctly in taking the samples it may invalidate the use of the samples as evidence, and since presumably they were taken to assess whether you were under the influence of alcohol or some other prescribed substance, if they are invalidated because of improper procedure, then they won't be able to use this evidence against you.
I trust the above assists your understanding.
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