Curable compositions

Patent metadata

Field	Value
Publication number	US-11518873-B2
Application number	US-201716462573-A
Country	US
Kind code	B2
Filing date	Nov 17, 2017
Priority date	Nov 28, 2016
Publication date	Dec 6, 2022
Grant date	Dec 6, 2022

Abstract

Useful articles, such as coatings, adhesives, printed graphics, 3D printed articles and molded articles are prepared by curing compositions containing one or more salts of ethylenically unsaturated carboxylic acids comprising six or more carbon atoms, one or more multifunctional (meth)acrylate oligomers and one or more mono(meth)acrylate esters of alcohols which, when polymerized as homopolymers, have glass transition temperatures of at least 50° C.

First claim

The invention claimed is:

1. A curable composition comprised of:
a) at least one salt of at least one ethylenically unsaturated carboxylic acid comprising six or more carbon atoms, wherein the at least one salt comprises at least one polyvalent cation and additionally comprises a carboxylate portion that is not ethylenically unsaturated and/or an ethylenically unsaturated carboxylate portion containing fewer than six carbon atoms
b) at least one multifunctional (meth)acrylate oligomer and
c) at least one mono(meth)acrylate ester of an alcohol which, when polymerized as a homopolymer, has a glass transition temperature of at least 50° C. as measured by Dynamic Mechanical Analysis in accordance with ASTM E1640-13.

2. The curable composition of claim 1 , wherein the ethylenically unsaturated carboxylic acid is comprised of seven, eight, nine, ten, eleven, twelve, thirteen or more carbon atoms.

3. The curable composition of claim 1 , wherein the ethylenically unsaturated carboxylic acid contains at least one functional group selected from the group consisting of acryloyl, methacryloyl, allyl, propenyl and vinyl.

4. The curable composition of claim 1 , wherein the ethylenically unsaturated carboxylic acid is a (meth)acrylate-functionalized carboxylic acid.

5. The curable composition of claim 1 , wherein the at least one salt comprises at least one zinc or calcium salt.

6. The curable composition of claim 1 , wherein the ethylenically unsaturated carboxylic acid is a half ester which is a reaction product of a hydroxy-functionalized ethylenically unsaturated compound and a polycarboxylic acid or carboxylic acid anhydride.

7. The curable composition of claim 1 , wherein the salt corresponds to Formula (I):
M(OC(═O)CR 1 ═CH 2 ) x (O—C(═O)—R 2 —C(═O)—O—R 3 —O—C(═O)CR 4 ═CH 2 ) y   (I)

wherein M is the at least one polyvalent cation and has a valence n, n=x+y, y=an integer of at least 1, R 1 and R 4 are the same or different and are H or CH 3 and R 2 and R 3 are the same or different and are divalent organic moieties each containing two or more carbon atoms.

8. The curable composition of claim 7 , wherein M is selected from the group consisting of Ce, Mg, Ca, Sr, Ba, Ti, Zr, V, Cr, Mo, W, Mn, Fe, Co, Ni, Pd, Cu, Zn, Cd, Hg, B, Al, Ga, In, Si, Ge, Sn, Pb, Sb and Bi.

9. The curable composition of claim 1 , wherein the at least one mono(meth)acrylate ester of an alcohol, when polymerized as a homopolymer, has a glass transition temperature of at least 75° C. as measured by Dynamic Mechanical Analysis in accordance with ASTM E1640-13.

10. The curable composition of claim 1 , wherein the at least one multifunctional (meth)acrylate oligomer is selected from the group consisting of urethane (meth)acrylates, epoxy (meth)acrylates, polyester (meth)acrylates, polyether (meth)acrylates, polycarbonate (meth)acrylates and combinations thereof.

11. The curable composition of claim 1 , wherein the at least one multifunctional (meth)acrylate oligomer comprises at least one di(meth)acrylate-functionalized oligomer.

12. The curable composition of claim 1 , wherein the at least one multifunctional (meth)acrylate oligomer has a number average molecular weight of from about 1000 to about 10,000 daltons.

13. The curable composition of claim 1 , wherein the alcohol contains at least one of a cyclic structural moiety or a hydroxyalkyl structural moiety.

14. The curable composition of claim 1 , wherein the alcohol contains at least one of a cyclic structural moiety selected from the group consisting of aromatic groups and alicyclic groups.

15. The curable composition of claim 1 , wherein the alcohol contains at least one of a cyclic structural moiety selected from the group consisting of monocyclic, bicyclic, tricyclic, tetracyclic, pentacyclic and hexacyclic hydrocarbon radicals.

16. The curable composition of claim 1 , wherein the alcohol contains at least one of a cyclic structural moiety selected from the group consisting of isobornyl, cyclohexyl, tricyclodecanyl and phenyl.

17. The curable composition of claim 1 , wherein the salt is obtained by reacting a M-containing compound, wherein M is the at least one polyvalent cation of an element selected from the group consisting of Ce, Mg, Ca, Sr, Ba, Ti, Zr, V, Cr, Mo, W, Mn, Fe, Co, Ni, Pd, Cu, Zn, Cd, Hg, B, Al, Ga, In, Si, Ge, Sn, Pb, Sb and Bi, with the at least one ethylenically unsaturated carboxylic acid comprising six or more carbon atoms corresponding to Formula (II):
HO—C(═O)—R 2 —C(═O)—O—R 3 —O—C(═O)CR 4 ═CH 2   (II)

wherein R 4 is H or CH 3 , and R 2 and R 3 are the same or different and are divalent organic moieties each containing two or more carbon atoms.

18. The curable composition of claim 17 , wherein the M-containing compound is selected from the group consisting of M-containing oxides, M-containing halides, M-containing alkoxides, M-containing hydroxides, M-containing nitrates, M-containing sulfates, M-containing carboxylates, M-containing carbonates and combinations thereof.

19. The curable composition of claim 17 , wherein the M-containing compound is zinc oxide or calcium oxide.

20. The curable composition of claim 17 , wherein the salt is obtained by reacting the M-containing compound with both the carboxylic acid corresponding to Formula (II) and (meth)acrylic acid.

21. The curable composition of claim 1 , comprising 1 to 25% by weight a), 20 to 55% by weight b) and 25 to 60% by weight c), based on the total weight of a)+b)+c).

22. A method of making a cured article, comprising curing a curable composition in accordance with claim 1 .

23. A method of making a three-dimensional article, comprising the steps of:
a) coating a first layer of a curable composition in accordance with claim 1 onto a surface;
b) at least partially curing the first layer to provide a cured first layer;
c) coating a second layer of the curable composition onto the cured first layer;
d) at least partially curing the second layer to provide a cured second layer adhered to the cured first layer and
e) repeating steps c) and d) a desired number of times to build up the three-dimensional article.

24. The method of claim 23 , wherein the curing steps are performed by exposing the layers of the curable composition to radiation.

25. A cured finished product obtained by curing a curable composition in accordance with claim 1 .

26. The cured finished product of claim 25 , wherein the cured finished product is selected from the group consisting of coated articles, adhered articles, sealed articles, 2D printed articles, 3D printed articles, composites and molded articles.

Assignees

• Arkema France

Inventors

• Hazell Thomas W
• Wolf William
• David Florian J

Classifications

• C09J4/00

  Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond {; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16} · CPC title

• B29K2105/0085

  Copolymers · CPC title

• C09J2301/416

  use of irradiation · CPC title

• C09D11/101

  Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing · CPC title

• C09K2200/0627

  Nitrogen-containing polymers, e.g. polyacrylamide · CPC title