Labor Senator Penny Wong hit back: "You should apologise to the Australian people."
But Senator Cash maintained that she had not deserved the attack from Senator Wong.
"Are you now going to apologise to me for the last 15 months of allegations you have putting to me?"
Labor Senator Doug Cameron said "hell would freeze over" before he apologised to the minister.
The October 2017 raids on AWU offices shot to prominence when staff from the offices of two ministers - Senator Cash and former justice minister Michael Keenan - tipped off the media.
The raids were launched in connection with decades-old donations made when Opposition Leader Bill Shorten was the AWU national secretary.
Tensions rose as Labor senators grilled Senator Cash over discrepancies between her comments and evidence given by the AFP on Monday.
Senator Cash maintains she gave a witness statement to the AFP, despite the AFP Deputy Commissioner Leanne Close telling the committee they received a letter from Senator Cash and she "would not classify it as a witness statement".
"In the event that the AFP were not satisfied with the statement I provided they could have come back and ask for further information," Senator Cash told the hearing.
Labor Senator Murray Watt accused Senator Cash of preventing the DPP from launching a prosecution by refusing to cooperate with police - an assertion the minister strongly rejected.
"I did provide a statement to the Australian Federal Police, I also have given evidence under oath," Senator Cash responded. "I gave evidence that I had no knowledge of the raids."
It was also revealed in the hearing that Senator Cash has racked up an almost $300,000 legal bill, funded by taxpayers, dealing with the case.