The rate of heat loss from one object (e.g. a house) to another (e.g. the environment) is proportionate to the difference in temperature, squared. Obviously insulation delays the rate of loss, but if you keep a house at an elevated temperature all day, you are bound to lose more heat - and hence spend money to replace it - than if you switch off the heating and let the house cool down to nearer the outside temperature for most of the day.
The only thing that would invalidate this argument is if your boiler is much more inefficient from a cold start, so inefficient that it outwieghs all the energy lost if you keep it running all day.