Process for preparing low-viscosity allophanates containing actinically curable groups
View Patent ↗The present invention relates to a process for preparing low-viscosity reaction products of polyisocyanates containing activated groups which react, with polymerization, with ethylenically unsaturated compounds on exposure to actinic radiation.
1. A process for preparing radiation-curing allophanates having residual monomer contents of less than 0.5% by weight and an NCO content of less than 1% by weight, the process comprising:
1) preparing NCO-group-containing urethanes having radiation-curing groups by reacting:
A) one or more compounds containing isocyanate groups,
B) one or more hydroxy-functional compounds which contain groups which react, with polymerization, with ethylenically unsaturated compounds on exposure to actinic radiation (radiation-curing groups) and
C) optionally further compounds containing NCO-reactive groups;
D) optionally in the presence of a catalyst
2) reacting the NCO-group-containing urethanes having radiation-curing groups subsequently, without further addition of compounds containing isocyanate groups, in the presence of:
E) zinc octoate and,
F) a tertiary amine,
the ratio of NCO groups of the compounds from A) to the OH groups of the compounds from B) and, where used, C) being 1.45: 1.0 to 1.1 : 1.0.
2. Process for preparing radiation-curing allophanates according to claim 1 , wherein the tertiary amine comprises at least nine carbon atoms and contains no further functionality.
3. Process for preparing radiation-curing allophanates according to claim 1 , wherein component A) comprises compounds selected from the group consisting of hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), 4,4′-diisocyanatodicyclohexylmethane and mixtures thereof.
4. Process for preparing radiation-curing allophanates according to claim 1 , wherein component B)) comprises compounds selected from the group consisting of hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate and mixtures thereof.
5. Process for preparing radiation-curing allophanates according to claim 1 , wherein the ratio of NCO groups of the compounds from A) to the OH groups of the compounds from B) and, where used, C) is 1.35:1.0 to 1.3:1.0.
6. Process for preparing radiation-curing allophanates according to claim 1 , wherein the allophanatization reaction is carried out until the reaction product has an NCO content of below 0.2% by weight.
7. Radiation-curing allophanates obtained by a process according to claim 1 .
8. A composition comprising the radiation-curing allophanates according to claim 7 , the composition selected from the group consisting of coatings, coating materials, adhesives, printing inks, casting resins, dental compounds, sizes, photoresists, stereolithography systems, resins for composite materials and sealants.
9. A coating composition comprising
a) one or more of the radiation-curing allophanates according to claim 7 ,
b) optionally one or more polyisocyanates containing free or blocked isocyanate groups, which are free from groups which react, with polymerization, with ethylenically unsaturated compounds on exposure to actinic radiation,
c) optionally other compounds, different from those of a), which contain groups which react, with polymerization, with ethylenically unsaturated compounds on exposure to actinic radiation, and optionally contain free or blocked NCO groups,
d) optionally one or more isocyanate-reactive compounds containing active hydrogen,
e) one or more initiators,
f) optionally solvents and
g) optionally auxiliaries and additives.
10. Substrates coated with coatings obtained from the radiation-curing allophanates according to claim 7 .