First, recall that Rf is the retention value for a pigment, it is "how high" does a pigment go in a TLC column.
The more polar the pigment is, the lower Rf value it will have, since it will attach mostly to the stationary phase which is polar. For the mobile phase, which is a mix of nonpolar-polar solvents, expect the least solvent material to go to the highest Rf values.
The separation will perform better with nonpolar solvents, in order to split polar + nonpolar solvents in the mobile phase
If you decrease polarity of mobile phase, then the nonpolar speices will favour a higher Rf value and polar pigments will favour a much lower Rf value.
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