The Democrats say they are all in Illinois and won't return.
Senate Majority Leader Scott Fitzgerald says the orders are only binding in Wisconsin.
The Senate passed a resolution calling for the action earlier Thursday but gave Democrats until 4 p.m. to return. None of them did, which led Fitzgerald to sign 14 orders of detainment in dramatic fashion in the center of the Senate chamber.
State patrol officers watched silently from the gallery as Fitzgerald signed the orders executing the order. The Democrats left in protest over an anti-union bill.
Wis. layoff notices to come Friday
Walker also said in an interview with The Associated Press that he is negotiating with Democrats who stymied passage of the bill by leaving the state for changes to the proposal that would get them to return. Walker said he won't compromise on the collective bargaining issue or anything that saves the state money.
"I can't take any of that off the table," he said.
Walker's budget proposal hinges on the state saving $330 million over two years from forcing state workers to pay more for their benefits. He's also cutting aid to schools and local governments by about $1 billion, reductions he says they can't handle without the freedom he gives them through eliminating nearly all collective bargaining with public workers.
Walker said he has to issue the layoff notices starting Friday so the state can start to realize the $30 million savings he had assumed would come from the state worker concessions contained in the bill. The layoffs wouldn't be effective for 31 days, and Walker said he could rescind them if the bill passed in the meantime.
All state workers, except those in prisons, state hospitals and other facilities open around the clock, would be potential layoff targets, he said.
"We'll prepare them, let them out by the end of the day," Walker said. "I pushed it off as long as I could ... I do not want to have layoffs."
As for the Senate Democrats, Walker said he was talking with some of the "more reasonable members" about a deal that could get them to come back.
"I'm still cautiously optimistic we can get this done," Walker said. "I think we're close, but the problem is we thought we were close the past couple days."