Asked by reporters on Friday whether he would succumb to the protesters' request and resign, Prime Minister Prayuth replied "No, I won't.What wrong did I do?"
The government claimed that it was because of the incident with the royal motorcade that they imposed the emergency decree early Thursday morning, CNN reported.
Hundreds of Thais chanted at protests that popped up across Bangkok on Saturday in defiance of a crackdown on three months of demonstrations aimed at the government and the powerful monarchy, reports Reuters.
Police largely kept their distance on Saturday, in contrast to the tactics used to break up Friday's protest.
There were some injuries to both protesters and police officers in connection with the operation, according to medical authorities.
Prime Minister Prayut Chan-O-Cha extended an emergency decree banning gatherings of more than four people by another month on Friday.
Many protesters said they had been stirred into action by the police's use of water cannons on Friday to disperse thousands of youth-led protesters who included many children.
The underground metro system in the Thai capital of Bangkok has been completely shut down amid ongoing protests and the related state of emergency, operating firm MRT said on Saturday.
Under the new measures, which will last 30 days, political gatherings of five or more people are banned, as well as the publication of news and online information that could threaten national security.
Two other activists were arrested Friday under a rarely used law banning "violence against the queen" after they joined a group Wednesday that surrounded a royal motorcade carrying Queen Suthida, flashing a pro-democracy salute as the vehicle drove by.
Those found guilty of Section 110 face 16 years to a maximum life imprisonment for violence or attempted violence against the Queen, the heir-apparent or regent.
The state of emergency for Bangkok was announced after tens of thousands of protesters broke through police lines and surrounded Prayuth's office on Wednesday night.
The protesters charge that Prayuth, who as army commander led a 2014 coup that toppled an elected government, was returned to power unfairly in last year's general election because laws had been changed to favour a pro-military party.
The order followed elections in March previous year - the first since the military seized power in 2014 and the first chance to vote for many young people and first-time voters.
"The (use of force) will increase the numbers of protesters", said 21-year-old Nine, an engineering student.
The Metropolitan Rapid Transit announced the suspension of service from 12.30 am on Saturday, while police have ordered the closure of 14 major train stations that are close to possible protest venues in central of Bangkok. The call by the protesters for reform of the monarchy has significantly raised the political temperature in Thailand.
The protesters reportedly defied orders to disperse from the police, who estimated the protesters to number 10,000. The king was alongside Queen Suthida Bajrasudhabimalalakshana, whose motorcade passed through the demonstration area earlier this week when protesters shouted "my taxes" and gave her the three-finger salute - a symbol of the demonstrations.
"There is no defeat or victory for any particular side in this protest", the premier said, according to a government spokesman. "Only governments should be afraid of their people".