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The employer may not violate the written union contract or employee policy regarding vested PTO. So, if you were eligible, followed the procedure and the employer refuses to honor the obligation, then you have a grievance which you should file with the union.
In other words, you are entitled to demand the benefits of your employment, including PTO, sick days, etc.
By the way, if you are being treated differently than other employees with regard to paid sick time, and you believe it is due to race, religion, ethnicity, or your membership in some other protected class, you can file a discrimination complaint with the EEOC, as well.