Curable compositions

• US 3,935,173 A
• Filed: 03/18/1974
• Issued: 01/27/1976
• Est. Priority Date: 03/22/1973
• Status: Expired due to Term

• Current Assignee: Toagosei Chemical Industry Company Limited (Toagosei Company Limited)
• Original Assignee: Toagosei Chemical Industry Company Limited (Toagosei Company Limited)
• Inventors: Ogasawara, Takahisa, Tatemichi, Hidemaro, Nakagawa, Teruo, Mizutani, Kiyokazu, Hisanaga, Noboru, Kobayashi, Yorimasa
• Primary Examiner(s): Kight, III, John
• Application Number:
  US05/452,266
• Time in Patent Office: 680 Days
• Field of Search: 260/76, 260/75 NT, 260/75 EP, 260/75 H, 260/75 R, 260/75 UA, 260/78.5 B, 260/78.5 E, 260/89.5 A, 260/872, 260/861
• US Class Current: 522/104
• CPC Class Codes: C08F 20/20 of polyhydric alcohols or polyhydric phenols , e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate

Abstract

A low viscous and solvent-free curable composition comprising a polyester type oligo(meth)acrylate having a plurality of (meth)acryloyl groups, and a polyol poly(meth)acrylate.

Claims

1. A curable composition comprising (A) an oligo(meth)acrylate having a (meth)acroyl group equivalent of not more than 1000 and being prepared by esterifying (1) a polyhydric alcohol, (2) a polycarboxylic compound selected from the group consisting of a polycarboxylic acid and the anhydride thereof, said polyhydric alcohol and polycarboxylic compound not being a dihydric alcohol and dicarboxylic compound respectively at the same time, and (3) (meth)acrylic acid to produce the oligo(meth)acrylate and (B) a polyol poly(meth)acrylate prepared by esterifying a polyhydric alcohol and (meth)acrylic acid to produce the polyol poly(meth)acrylate.

2. A curable composition according to claim 1, wherein the polycarboxylic compound is a member selected from the group consisting of (a) a 4,5-unsaturated alicyclic polycarboxylic acid, (b) an anhydride thereof, and (c) a mixture of said alicyclic polycarboxylic compound with a member selected from the group consisting of dicarboxylic and higher polycarboxylic acids and anhydrides thereof other than said alicyclic polycarboxylic compound.

3. A curable composition according to claim 2, wherein said oligo(meth)acrylate is reacted with a modifying compound selected from the group consisting of isocyanates, epoxy compounds and acid chlorides.

4. A curable composition according to claim 2, wherein the acryloyl groups are contained in amounts of 50-100 mol% of the total of the acryloyl and methacryloyl groups.

5. A curable composition according to claim 2, wherein the (meth)acryloyl group equivalent of the component A is not more than 600.

6. A curable composition according to claim 2, wherein the polyhydric alcohol used in the production of the oligo(meth)acrylate is a member selected from the group consisting of trihydric and higher polyhydric alcohols, and dihydric and higher polyhydric alcohols containing such trihydric and higher polyhydric alcohols.

7. A curable composition according to claim 6, wherein the trihydric and higher polyhydric alcohols are trihydric, tetrahydric and hexahydric alcohols.

8. A curable composition according to claim 6, wherein the trihydric and higher polyhydric alcohols are trimethylolethane, trimethylolpropane, glycerine, 1,2,6-hexanetriol, pentaerithritol, erithritol and sorbitol.

9. A curable composition according to claim 2, wherein the polycarboxylic compound used in the production of the oligo(meth)acrylate is selected from the group consisting of 4,5-unsaturated alicyclic tricarboxylic and higher polycarboxylic acids, mixtures of these alicyclic polycarboxylic acids with dicarboxylic and higher polycarboxylic acids, and mixtures of 4,5-unsaturated alicyclic dicarboxylic acids with tricarboxylic and higher polycarboxylic acids.

10. A curable composition according to claim 9, wherein the tricarboxylic and higher polycarboxylic acids are tricarboxylic and tetracarboxylic acids.

11. A curable composition according to claim 2, wherein the 4,5-unsaturated alicyclic polycarboxylic acid is selected from the group consisting of tetrahydrophthalic acid, Himic acid and Het acid.

12. A curable composition according to claim 2, wherein the 4,5-unsaturated alicyclic polycarboxylic acid is 6-methyl-cyclohexene-4-1,2,3-tricarboxylic acid.

13. A curable composition according to claim 2, wherein the dicarboxylic and higher polycarboxylic acids other than the 4,5-unsaturated alicyclic polycarboxylic acid are phthalic, tetrachlorophthalic, tetrabromophthalic, hexahydrophthalic, malonic, succinic, maleic, fumaric, itaconic, glutaric, adipic, sebacic, 1,12-dodecanedioic, polybutadienedicarboxylic acid, trimellitic and pyromellitic acids.

14. A curable composition according to claim 2, wherein the polyhydric alcohol used in the production of the oligo(meth)acrylate is selected from the group consisting of ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, 1,3-butanediol, 1,6-hexanediol, neopentyl glycol, hydrogenated bisphenol A, bisphenol dioxyethyl ether, bisphenol dioxypropyl ether and polybutadienediol.

15. A curable composition according to claim 2, wherein the polyol poly(meth)acrylate is a member selected from the group consisting of tri(meth)acrylate and di(meth)acrylate of a trihydric alcohol selected from the group consisting of trimethylolmethane, trimethylolethane, trimethylolpropane and 1,2,6-hexanetriol and glycerine.

16. A curable composition according to claim 2, wherein the polyol poly(meth)acrylate is a di(meth)acrylate of a dihydric alcohol selected from the group consisting of ethanediol, 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, hydrogenated bisphenol A, bisphenol dioxyethyl ether, bisphenol dioxypropyl ether and 1,6-hexanediol.

17. A curable composition according to claim 2, wherein the polyol poly(meth)acrylate is a member selected from the group consisting of tetra(meth)acrylate, tri(meth)acrylate and di(meth)acrylate of a member selected from the group consisting of pentaerithritol and erithritol.

18. A curable composition according to claim 2, wherein the oligo(meth)acrylate is contained in amounts of 10-99% by weight of the composition.

19. A curable composition according to claim 2, wherein the oligo(meth)arcylate is contained in amounts of 30-99% by weight of the composition.

20. A curable composition according to claim 2, containing a photoinitiator in amounts of 0.001-10% by weight thereof.

21. A curable composition according to claim 2, containing a photoinitiator in amounts of 0.01-5% by weight thereof.

22. A curable composition according to claim 2, containing with an organic peroxide in amounts of 0.001-10% by weight thereof.

23. A curable composition according to claim 2, containing with an organic peroxide in amounts of 0.01-5% by weight thereof.

24. A curable composition comprising an oligoacrylate having an acryloyl group equivalent of about 120-600 and being prepared by the esterification of trimethylolpropane, tetrahydrophthalic anhydride and acrylic acid, and trimethylolpropane triacrylate.

25. A curable composition comprising an oligoacrylate having an acryloyl group equivalent of about 120-600 and being prepared by the esterification of pentaerithritol, tetrahydrophthalic anhydride and acrylic acid, and trimethylolpropane triacrylate.

26. A curable composition comprising an oligoacrylate having an acryloyl group equivalent of about 120-600 and being prepared by the esterification of pentaerithritol, diethylene glycol, tetrahydrophthalic anhydride and acrylic acid, and trimethylolpropane triacrylate.