Curable composition for use in a high temperature lithography-based photopolymerization process and method of producing crosslinked polymers therefrom
US-2024325117-A1 · Oct 3, 2024 · US
US9944743B2 · US · B2
| Field | Value |
|---|---|
| Publication number | US-9944743-B2 |
| Application number | US-201615009851-A |
| Country | US |
| Kind code | B2 |
| Filing date | Jan 29, 2016 |
| Priority date | Mar 31, 2010 |
| Publication date | Apr 17, 2018 |
| Grant date | Apr 17, 2018 |
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The process for the manufacture of an auto-oxidatively cross-linking hybrid polymer, in particular an aqueous hybrid polymer dispersion, comprises the step of reacting in a mini-emulsion process one or more ethylenically unsaturated monomers to form an addition polymer in the presence of a modified auto-oxidatively crosslinkable (AOC) polymer which has been modified with terminal unsaturated groups of the formula —C(R1)═CH2 wherein R1 is hydrogen, alkyl or aryl and wherein the AOC polymer is a hydrophobic polymer having an acid number between 5 to 30. The resulting aqueous hybrid polymer dispersion can be used for the manufacture of coating compositions, ink compositions or adhesives and coating compositions comprising the hybrid polymer dispersion as a binder.
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The invention claimed is: 1. A process for the manufacture of an auto-oxidatively cross-linking hybrid polymer comprising the step of reacting in a mini-emulsion process, in the presence of a radical initiator and a surfactant, one or more ethylenically unsaturated monomers to form an addition polymer, wherein the addition polymer is a vinyl polymer in the presence of a modified auto-oxidatively crosslinkable (AOC) polymer which is an alkyd resin comprising unsaturated fatty acids, wherein the AOC alkyd polymer is a hydrophobic alkyd polymer having an acid number from 5 to 20 mg KOH/g and an oil length of the resin between 40 and 95% , and wherein the modified AOC alkyd polymer is prepared by reaction of hydroxyl reactive groups on the AOC alkyd polymer with a compound comprising a terminal unsaturated group and isocyanate reactive groups. 2. The process according to claim 1 , wherein the average amount of the terminal unsaturated groups per molecule of the modified AOC polymer is more than 1. 3. The process according to claim 1 , comprising the steps of: I. mixing: a) one or more modified AOC polymers, b) one or more ethylenically unsaturated monomers, c) one or more surfactants II. forming a mini-emulsion in water of the mixture obtained in step I), III. adding a free radical initiator before, during and/or after step I), II) and/or IV), IV. addition polymerizing the unsaturated monomers in the mini-emulsion to form a dispersion of hybrid particles of the auto-oxidatively crosslinkable polymer and the addition polymer. 4. The process according to claim 1 , comprising the steps of: I. mixing: a) one or more modified AOC polymer in an amount of 10 to 90wt %, wherein the wt % is defined as the weight relative to the total weight of the mixture of the components in step (I) to (III), b) one or more ethylenically unsaturated monomers in an amount of 10 to 90 wt %, c) one or more surfactants in an amount of 1 to 15 wt %, II. forming a mini-emulsion in water of the mixture obtained in step I), III. adding a free radical initiator before, during and/or after step I), II) and/or IV), in an amount of 0.05 to 6 wt % (based on the weight of the unsaturated monomers), IV. addition polymerizing the unsaturated monomers in the mini-emulsion forming a dispersion comprising 30 to 70% by weight of solids. 5. The process according to claim 1 , wherein in addition to the hydrophobic modified AOC polymer, the ethylenically unsaturated monomers comprise hydrophobic monomers. 6. The process according to claim 5 , wherein the hydrophobic monomers are lauryl or stearyl acrylate or methacrylate. 7. The process according to claim 5 , wherein the hydrophobic monomers are present in an amount of between 2 and 10 mol %, relative to the total unsaturated monomer content. 8. The process according to claim 1 , wherein the amount of modified AOC polymer relative to the total of the modified AOC polymer and the vinyl polymer is between 25 and 75 wt %. 9. The process according to claim 1 , wherein the number average molecular weight of the modified AOC polymer is between 1000 and 50,000 and the oil length of the resin is between 40 and 85%. 10. An aqueous hybrid polymer dispersion obtained according to the process of claim 1 comprising 30 to 70% by weight of solids of hybrid polymer comprising: a. 10 to 90 wt % of the one or more modified AOC polymers, b. 10 to 90 wt % of an addition polymer. 11. The aqueous hybrid polymer dispersion according to claim 10 , wherein the volatile organic compound (VOC) amount is less than 25 g/l. 12. The aqueous hybrid polymer dispersion according to claim 10 , wherein the aqueous hybrid polymer dispersion is used in the manufacture of coating compositions, ink compositions or adhesives. 13. The hybrid polymer dispersion according to claim 10 , wherein the hybrid polymer dispersion is a binder in a coating composition. 14. A substrate coated with the coating composition according to claim 13 . 15. A substrate coated with the aqueous hybrid polymer dispersion of claim 10 . 16. A substrate coated with the aqueous hybrid polymer dispersion of claim 11 .
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