Reactive polyurethane compositions with a low residual monomer content
The present invention describes reaction products from 2,4′-diphenylmethane diisocyanate with a content of at least 95 wt. % of 2,4′ isomer with at least one polyether-polyol and/or polyalkylene glycol with a molecular weight of less than 1,000 and/or one crystalline or partly crystalline or vitreously amorphous polyester-polyol and optionally polyester-polyols and/or polyether-polyols which are liquid at room temperature and have molecular weights of greater than 1,000 can be converted into adhesive compositions which have a very low content of monomeric diisocyanate of less than 0.5, preferably less than 0.25 wt. %. Such hot melt adhesive compositions have a high melt stability and a low viscosity, in addition to the low content of monomeric diisocyanate.
1. A reactive adhesive, which is solid at room temperature, and which comprises:
(i) at least one reaction product having free isocyanate groups obtained by reacting reactants consisting essentially of:
(a) diphenylmethane diisocyanate, of which at least 95 wt. % is 2,4′-diphenylmethane diisocyanate; and
(b) one or more compounds, each selected from the group consisting of polyalkylene diols having number average molecular weights less than 1,000 and polyester-polyols which are solid at room temperature and are crystalline, partly crystalline or vitreously amorphous, wherein said one or more compounds includes at least one of said polyester polyols;
(c) optionally, one or more of tackifying resins containing active hydrogen atoms, low molecular weight polymers of olefinically unsaturated monomers containing hydroxyl groups, and polyether-polyols having a number average molecular weight greater than 1,000; and
wherein said polyether-polyols are selected from the group consisting of polytetramethylene glycols, polypropylene glycols, copolymers of ethylene oxide and propylene oxide, and alkylene diols and
(ii) at least one adhesion-intensifying additive which is capable of migration; said adhesion-intensifying additive comprising polyisocyanate having a vapour pressure of less than 10 −6 hPa at 20° C.;
wherein said adhesive has a monomeric diisocyanate content of less than 0.5 wt. %.
2. The adhesive of claim 1 , wherein said adhesive has a concentration of monomeric diisocyanate of less than 0.25 wt. %.
3. The adhesive of claim 1 , wherein at least 97.5 wt. % of said diphenylmethane diisocyanate is 2,4′-diphenylmethane diisocyanate.
4. The adhesive of claim 1 , wherein the NCO to OH ratio of the 2,4′-diphenylmethane diisocyanate to the sum of the polyols is 1.1 to 1.9.
5. The adhesive of claim 1 , wherein the NCO to OH ratio of the 2,4′-diphenylmethane diisocyanate to the sum of the polyols is 1.2 to 1.75.
6. The adhesive of claim 1 , wherein less than 0.3 wt. % of 2,2′-diphenylmethane diisocyanate is present.
7. The adhesive of claim 1 , wherein less than 0.1 wt. % of 2,2′-diphenylmethane diisocyanate is present.
8. The adhesive of claim 1 , wherein less than 0.06 wt. % of 2,2′-diphenylmethane diisocyanate is present.
9. The adhesive of claim 1 , further comprising at least one reaction product of 2,4′-diphenylmethane diisocyanate and at least one compound selected from the group consisting of polyester-polyol and polyether-polyol.
10. The adhesive of claim 4 , further comprising at least one reaction product of 2,4′-diphenylmethane diisocyanate and at least one compound selected from the group consisting of polyester-polyols and polyether-polyols, wherein said at least one compound is liquid at room temperature and has a molecular weight of greater than 1,000.
11. The adhesive of claim 1 , wherein the reaction product is crystalline, partly crystalline, or vitreously amorphous.
12. The adhesive of claim 1 , wherein the adhesive is a hot melt adhesive.
13. The adhesive of claim 1 , wherein the adhesion-intensifying additive is present in less than 30 wt. %.
14. The adhesive of claim 1 , wherein the adhesion-intensifying additive is present in less than 10 wt. %.
15. The adhesive of claim 1 , wherein the adhesion-intensifying additive is at least one compound selected from the group consisting of thiophosphoric acid tris-(p-isocyanato-phenyl ester), triphenylmethane 4,4′,4″-triisocyanate, isomeric trifunctional homologues of diphenylmethane diisocyanate (MDI), isocyanato-bis-((4-isocyanatophenyl)methyl)-benzene, 2-isocyanato-4-((3-isocyanatophenyl)methyl)-1-((4-isocyanatophenyl)methyl)-benzene, 4-isocyanato-1,2-bis((4-isocyanatophenyl)methyl)-benzene, 1-isocyanato-4-((2-isocyanatophenyl)methyl)-2-((3-isocyanatophenyl)methyl)-benzene, 4-isocyanato-α-1-(o-isocyanatophenyl)-α-3-(p-isocyanatophenyl)-m-xylene, 2-isocyanato-(o-isocyanatophenyl)-α′-(p-isocyanatophenyl)-m-xylene, 2-isocyanato-1,3-bis((2-isocyanatophenyl)methyl)-benzene, 2-isocyanato-1,4-bis((4-isocyanatophenyl)methyl)-benzene, isocyanato-bis((isocyanatophenyl)methyl)-benzene, 1-isocyanato-2,4-bis((4-isocyanatophenyl)methyl)-benzene, adducts of diisocyanates and low molecular weight triols, adducts of aromatic diisocyanates and triols, an adduct of trimethylolpropane and glycerol, a biuretization product of hexamethylene diisocyanate (HDI), an isocyanuration product of HDI, and a trimerization product of isophorone diisocyanate (IPDI), or mixtures thereof.
16. The adhesive of claim 1 , wherein the adhesion-intensifying additive is an adduct of 2,4′-diphenylmethane diisocyanate and a diol with a molecular weight of less than 2,000.
17. The adhesive of claim 16 , wherein, the content of monomeric diisocyanate in the adduct is less than 2 wt. %.
18. The adhesive of claim 16 , wherein, the content of monomeric diisocyanate in the adduct is less than 1 wt. %.
19. The adhesive of claim 1 , wherein the adhesion-intensifying additive is an adduct of 2,4′-diphenylmethane diisocyanate and a polyol with a functionality of less than 3.3.
20. The adhesive of claim 19 , wherein the polyol with a functionality of less than 3.3 is trimethylolpropane or glycerol.
21. The adhesive of claim 19 , wherein, the content of monomeric diisocyanate in the adduct is less than 2 wt. %.
22. The adhesive of claim 19 , wherein, the content of monomeric diisocyanate in the adduct is less than 1 wt. %.
23. The adhesive of claim 1 , wherein the adhesion-intensifying additive is an organofunctional alkoxysilane.
24. A process for the preparation of an adhesive according to claim 1 , comprising:
contacting the reactants and preventing the reaction temperature from exceeding 160° C.
25. A process for the preparation of an adhesive according to claim 1 , comprising:
contacting the reactants and preventing the reaction temperature from exceeding 130° C.
26. A process for the preparation of an adhesive according to claim 1 , comprising:
contacting the reactants and preventing the reaction temperature from exceeding 110° C.
27. A process for the preparation of an adhesive according to claim 1 , comprising:
forming the reaction product; and thereafter
adding the adhesion-intensifying additive.
28. The adhesive of claim 1 , wherein said adhesive has a concentration of monomeric diisocyanate of less than 0.5 wt. %.
29. The adhesive of claim 1 , wherein said optional component (c) is a tackifying resin containing active hydrogen atoms.
30. The adhesive of claim 1 , wherein said optional component (c) is a low molecular weight polymer of olefinically unsaturated monomer containing hydroxyl groups.
31. The adhesive of claim 1 , wherein said optional component (c) is a polyether-polyol having a number average molecular weight greater than 1,000.
32. The adhesive of claim 1 , wherein said one or more compounds of (i)(b) is a polyester-polyol which is solid at room temperature.