The sensitivity of ALMA makes it possible to detect thermal mm/submm emission from small/distant Solar System bodies at the sub-mJy level. Measured fluxes are primarily sensitive to the objects diameters, but deriving precise sizes is somewhat hampered by the uncertain effective emissivity at these wavelengths. Following Brown and Butler (2017) who presented ALMA data for four binary TNOs, we report ALMA 1.29 mm measurements of four Centaurs (2002 GZ$_{32}$, Bienor, Chiron, Chariklo) and two TNOs (Huya and Makemake), sampling a range of size, albedo and composition. These thermal fluxes are combined with mid/far-infrared fluxes to derive the relative emissivity at radio (mm/submm) wavelengths, using NEATM and thermophysical models. We reassess earlier thermal measurements of these and other objects -- including Pluto/Charon and Varuna -- exploring effects due to non-spherical shape and varying apparent pole orientation, and show that those can be key for reconciling previous diameter determinations and correctly estimating the spectral emissivities. We also evaluate the possible contribution to thermal fluxes of established (Chariklo) or claimed (Chiron) ring systems. As a general conclusion, all the objects, except Makemake, have radio emissivities significantly lower than unity. Although the emissivity values show diversity, we do not find any significant trend with physical parameters such as diameter, composition, beaming factor, albedo, or color, but we suggest that the emissivity could be correlated with grain size. The mean relative radio emissivity is found to be 0.70$pm$0.13, a value that we recommend for the analysis of further mm/submm data.
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