Flexible working can be good for employers, the TUC says.
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Firms are being urged to bring in new ways of working after research showed almost 10% of people would like to work fewer hours, even if it meant less pay.
The TUC study found half a million workers had had a request for shorter working hours turned down by managers.
And of 100,000 employees questioned, 75% had no element of flexibility in their contracts.
TUC chief Brendan Barber said a more flexible working culture for all could benefit employers as well as staff.
Learning new skills
The research found public sector workers were likely to have a better work-life balance than those in the private sector.
It also found an extra 150,000 people were working on flexi-time than were 18 months ago - before the right to request to work flexibly was introduced for parents of young children.
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The right to request to work flexibly has unfortunately had little impact on the UK's long hours culture
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Mr Barber said there were many other reasons why an employee might want to work flexibly, including having elderly relatives to care for or wanting to learn new skills.
He said employers should see flexible working not as a burden but as a positive move which made sound business sense.
He said: "The right to request to work flexibly has unfortunately had little impact on the UK's long hours culture. "Though a few forward-thinking employers can see the benefit of a more intelligent organisation of workload and working hours, many bosses are not imaginative enough to meet flexible requests from employees with anything other than a firm 'No'.
"Extending the right to request to work flexibly to all workers might actually help more employers embrace a new working culture that benefits them as well."
The report is being published to mark the first day of a TUC conference in London to discuss work.