Radiation curable composition with high temperature oil resistance

• US 5,183,831 A
• Filed: 08/22/1991
• Issued: 02/02/1993
• Est. Priority Date: 08/22/1991
• Status: Expired due to Fees

• Current Assignee: Ciba-Geigy Corporation (Novartis Ag)
• Original Assignee: Ciba-Geigy Corporation (Novartis Ag)
• Inventors: Drain, Kieran F., Bielat, Richard A.
• Primary Examiner(s): Welsh, Maurice J.
• Assistant Examiner(s): GORR, RACHEL F
• Application Number:
  US07/748,590
• Time in Patent Office: 530 Days
• Field of Search: 522/33, 522/92, 525/452, 525/523, 526/208, 526/301
• US Class Current: 522/33
• CPC Class Codes: C08F 220/00 Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
• CPC Class Codes: C08F 290/144 Polymers containing more than one epoxy group per molecule
• CPC Class Codes: C08F 290/147 Polyurethanes; Polyureas
• CPC Class Codes: C09D 4/00 Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16

Abstract

The present invention relates to a radiation curable composition with high temperature oil resistance comprising

(1) a(meth)acrylated urethane component comprising

(a) the reaction product of hydroxyethyl(meth)acrylate and a monomeric or polymeric aromatic isocyanate,

(b) hydroxyethyl(meth)acrylate, and optionally

(c) a(meth)acylated prepolymer of a monomeric of polymeric aromatic isocyanate and at least one polycaprolactone polyol with a functionality≧2 and a molecular weight in the range of about 500 to about 3,000 or (d) a(meth)acrylated prepolymer of a monomeric or polymeric aromatic isocyanate and at least one polyether polyol with a functionality≧2 and a molecular weight in the range of about 90 to about 7,000, or a mixture of (c) and (d);

(2) an aromatic multifunctional epoxy (meth)acrylate having a molecular weight of less than about 1000;

(3) at least one free radical polymerizable monomer; and

(4) a free radical photoinitiator,

which composition exhibits at 25° C. (i) a Tg greater than about 45° C., (ii) an elongation of greater than about 3%, (iii) a tensile strength of greater than about 1300 psi and (iv) a shear storage modulus of greater than about 4300 psi.

Claims

1. A radiation curable composition with high temperature oil resistance comprising

(1) a (meth)acrylated urethane component comprising

(a) the reaction product of hydroxyethyl(meth)acrylate and a monomeric or polymeric aromatic isocyanate,

(b) hydroxyethyl(meth)acrylate;

and

(c) a (meth)acrylated prepolymer of a monomeric or polymeric aromatic isocyanate and at least one polycaprolactone polyol with a functionality>

2 and a molecular weight in the range of about 500 to about 3,000;

(2) an aromatic multifunctional epoxy (meth)acrylate having a molecular weight of less than about 1000;

(3) at least one free radical polymerizable monomer; and

(4) a free radical photoinitiator,

which composition exhibits at 25°

C.;

;

(i) a Tg greater than about 45°

C., (ii) an elongation of greater than about 3%, (iii) a tensile strength of greater than about 1300 psi and (iv) a shear storage modulus of greater than about 4300 psi.

2. A radition curable composition according to claim 1 wherein said aromatic isocyanate is selected from the group consisting of methylene bis(4-isocyanato benzene), toluene diisocyanate, 3,3'"'"'-toluidine-4,4'"'"'-diisocyanate, 3,3'"'"'-dimethyl-diphenylmethane-4,4'"'"'-diisocyanate, 1,5-diisocyanato-naphthalene, 1,4-diisocyanato-benzene and 1,4- and 1,3-di(isocyanato-dimethyl)-benzene.

3. A radiation curable composition according to claim 1 wherein said aromatic isocyanate is monomeric methylene bis(4-isocyanato benzene).

4. A radiation curable composition according to claim 1 wherein component (a) is present in an amount ranging from about 5 to about 35 wt wt %, based upon the total weight of component (1), component (b) is present in an amount ranging from about 1 to about 20 wt %, based upon the total weight of component (1) and component (c) is present in an amount ranging from about 50 to about 90 wt %, based upon the total weight of component (1).

5. A radiation curable composition according to claim 1 wherein component (a) is present in an amount ranging from about 10 to about 30 wt %, based upon the total weight of component (1), component (b) is present in an amount ranging from about 1 to about 10 wt %, based upon the total weight of component (1), and component (c) is present in an amount ranging from about 70 to about 80 wt %, based upon the total weight of component (1).

6. A radiation curable composition according to claim 1 wherein component (a) is present in an amount of about 23 wt %, based upon the total weight of component (1), component (b) is present in an amount of about 6 wt %, based upon the total weight of component (1), and component (c) is present in an amount of about 71 wt %, based upon the total weight of component (1).

7. A radiation curable composition according to claim 1 wherein component (a) is the reaction product of hydroxyethylmethacrylate and methylene bis(4-isocyanato benzene) and is present in an amount of 23 wt %, based upon the total weight of component (1), component (b) is hydroxyethylmethacrylate and is present in an amount of 6 wt %, based upon the total weight of component (1) and component (c) is the (meth)acrylated prepolymer of methylene bis(4-isocyanatobenzene) and a polycaprolactone triol and is present in an amount of about 71 wt %, based upon the total weight of component (1).

8. A radiation curable composition according to claim 1 wherein component (1) further comprises (d) a (meth)acrylated prepolymer of a monomeric or polymeric aromatic isocyanate and at least one polyether polyol with a functionality ≧

2 and a molecular weight in the range of about 90 to about 7,000.

9. A radiation curable composition according to claim 8 wherein component (a) is present in an amount ranging from about 10 to about 50 wt %, based upon the total weight of component (1), component (b) is present in an amount ranging from about 1 to about 20 wt %, based upon the total weight of component (1), component (c) is present in an amount ranging from about 1 to about 10 wt %, based upon the total weight of component (1) and component (d) is present in an amount ranging from about 25 to about 75 wt %, based upon the total weight of component (1).

10. A radiation curable composition according to claim 8 wherein component (a) is present in an amount ranging from about 20 to about 30 wt %, based upon the total weight of component (1), component (b) is present in an amount ranging from about 5 to about 15 wt %, based upon the total weight of component (1), component (c) is present in an amount ranging from about 1 to about 5 wt %, based upon the total weight of component (1) and component (d) is present in an amount ranging from about 50 to about 75 wt %, based upon the total weight of component (1).

11. A radiation curable composition according to claim 8 wherein component (a) is present in an amount of about 23 wt %, based upon the total weight of component (1), component (b) is present in an amount of about 6 wt %, based upon the total weight of component (1), component (c) is present in an amount of about 3 wt %, based upon the total weight of component (1) and component (d) is present in an amount of about 68 wt %, based upon the total weight of component (1).

12. A radiation curable composition according to claim 8 wherein component (a) is the reaction product of hydroxyethylmethacrylate and methylene bis(4-isocyanato benzene) and is present in an amount of about 23 wt %, based upon the total weight of component (1), component (b) is hydroxyethylmethacrylate and is present in an amount of about 6 wt %, based upon the total weight of component (1), component (c) is the (meth)acrylated prepolymer of methylene bis(4-isocyanatobenzene) and a polycaprolactone triol and is present in an amount of about 3 wt %, based upon the total weight of component (1) and component (d) is the (meth)acrylated prepolymer of methylene bis(4-isocyanatobenzene) and a poly(oxypropylene)-poly(oxyethylene) block copolymer and is present in an amount of about 68 wt %, based upon the total weight of component (1).

13. A radiation curable composition according to claim 1 wherein said aromatic multifunctional epoxy (meth)acrylate is selected from the group consisting of acrylated diglycidyl ether bisphenol A, acrylated epoxy novolacs, amino modified bisphenol A epoxy acrylates, rubber modified acrylated epoxies and fatty acid modified epoxy acrylates.

14. A radiation curable composition according to claim 1 wherein said aromatic multifunctional epoxy (meth)acrylate is present in an amount of from about 10 to about 60 wt %.

15. A radiation curable composition according to claim 1 wherein said aromatic multifunctional epoxy (meth)acrylate is present in an amount of from about 10 to about 40 wt %.

16. A radiation curable composition according to claim 1 wherein said aromatic multifunctional epoxy (meth)acrylate is present in an amount of from about 20 to about 30 wt %.

17. A radiation curable composition according to claim 1 wherein said free radical polymerization monomer is selected from the group consisting of N-vinyl pyrrolidone, N-vinyl caprolactam, acrylic ester with 3-(2-hydroxyethyl)-2-oxazolidone, 2-propenoic acid-2-[[1-methyl ethoxy carbonyl]amino] ethyl ester N,N-dimethylacrylamide and phenoxyethyl acrylate.

18. A radiation curable composition according to claim 1 wherein said free radical polymerization monomer is present in an amount of from about 5 to about 40 wt %.

19. A radiation curable composition according to claim 1 wherein said free radical polymerization monomer is present in an amount of from about 10 to about 30 wt %.

20. A radiation curable composition according to claim 1 wherein said free radical polymerization monomer is present in an amount of from about 20 to about 30 wt %.

21. A radiation curable composition with high temperature oil resistance comprising

(1) a (meth)acrylated urethane component comprising

(a) the reaction product of hydroxyethyl(meth)acrylate and a monomeric or polymeric aromatic isocyanate, and

(b) hydroxyethyl(meth)acrylate;

(2) an aromatic multifunctional epoxy (meth)acrylate having a molecular weight of less than about 1000;

(3) at least one free radical polymerizable monomer selected from the group consisting of N-vinyl pyrrolidone, N-vinyl caprolactam, acrylic ester with 3-(2-hydroxyethyl)-2-oxazolidone, 2-propenoic acid-2-[[1-methyl ethoxy carbonyl]amino] ethyl ester N,N-dimethylacrylamide and phenoxyethyl acrylate; and

(4) a free radical photoinitiator,

which composition exhibits at 25°

C.;

(i) a Tg greater than about 45°

C., (ii) an elongation of greater than about 3%, (iii) a tensile strength of greater than about 1300 psi and (iv) a shear storage modulus of greater than about 4300 psi.

22. A radiation curable composition according to claim 21 wherein component (a) is present in an amount ranging from about 50 to about 99 wt %, based upon the total weight of component (1) and component (b) is present in an amount ranging from about 1 to about 50 wt %, based upon the total weight of component (1).

23. A radiation curable composition according to claim 21 wherein component (a) is present in an amount ranging from about 80 to about 99 wt %, based upon the total weight of component (1) and component (b) is present in an amount ranging from about 1 to about 20 wt %, based upon the total weight of component (1).

24. A radiation curable composition according to claim 21 wherein component (a) is present in an amount of about 94 wt %, based upon the total weight of component (1) and component (b) is present in an amount of 6 wt %, based upon the total weight of component (1).

25. A radiation curable composition according to claim 21 wherein said aromatic isocyanate is selected from the group consisting of methylene bis(4-isocyanato benzene), toluene diisocyanate, 3,3'"'"'-diisocyanate, 4,4'"'"'-diisocyanate, 3,3'"'"'-dimethyl-diphenylmethane-4,4'"'"'-diisocyanate, 1,5-diisocyanato-naphthalene, 1,4-diisocyanato-benzene and 1,4- and 1,3-di(isocyanato-dimethyl)-benzene.

26. A radiation curable composition according to claim 21 wherein said aromatic isocyanate is monomeric methylene bis(4-isocyanato benzene).

27. A radiation curable composition according to claim 21 wherein component (a) is the reaction product of hydroxyethylmethacrylate and methylene bis(4-isocyanato benzene) and is present in an amount of 94 wt %, based upon the total weight of component (1) and component (b) is hydroxyethylmethacrylate and is present in an amount of 6 wt %, based upon the total weight of component (1).

28. A radiation curable composition according to claim 21 wherein said aromatic multifunctinal epoxy (meth)acrylate is selected from the group consisting of acrylated diglycidyl ether bisphenol A, acrylated epoxy novolacs, amino modified bisphenol A epoxy acrylates, rubber modified acrylated epoxies and fatty acid modified epoxy acrylates.

29. A radiation curable composition according to claim 21 wherein said aromatic multifunctional epoxy (meth)acrylate is present in an amount of from about 10 to about 60 wt %.

30. A radiation curable composition according to claim 21 wherein said aromatic multifunctional epoxy (meth)acrylate is present in an amount of from about 10 to about 40 wt %.