Radiation curable printing ink composition
| Title: | Radiation curable printing ink composition |
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| Patent Number: | H1,517 |
| Publication Date: | February 06, 1996 |
| Appl. No: | 08/091,481 |
| Application Filed: | July 12, 1993 |
| Abstract: | The invention is a radiation curable printing ink composition comprising a liquid viscous epoxidized diene polymer and a pigment. Preferred diene polymers are block copolymers comprising at least interior and exterior diene blocks wherein the exterior diene blocks contain a greater concentration of di-, tri-, and tetrasubstituted olefinic epoxides than the interior blocks and wherein the copolymer contains from 0.1 to 3.0 Meq of olefinic epoxides per gram of copolymer and the peak molecular weights as determined by gel permeation chromatography of the exterior blocks of from 300 to 2000 and the peak molecular weights as determined by gel permeation chromatography of the interior blocks are from 2,000 to 10,000. In another preferred embodiment, the polymer is a star polymer having a random distribution of from 0.5 to 5 Meq of di-, tri-, and tetrasubstituted olefinic epoxides per gram of polymer and greater than four arms wherein the peak molecular weights as determined by gel permeation chromatography of the arms are from 1500 to 15,000. |
| Inventors: | Erickson, James R. (Katy, TX); Masse, Michael A. (Richmond, TX); Dillman, Steven H. (Houston, TX); Zimmermann, Esther M. (Houston, TX) |
| Assignees: | Shell Oil Company (Houston, TX) |
| Claim: | We claim |
| Claim: | 1. A radiation curable printing ink composition comprising a liquid viscous diene block polymer wherein a portion of the olefinic double bonds in the diene are epoxidized and a pigment. |
| Claim: | 2. The composition of claim 1 wherein the polymer is a block copolymer comprising at least interior and exterior diene blocks wherein the exterior diene blocks contain a greater concentration of di-, tri- and tetrasubstituted olefinic epoxides than the interior blocks and wherein the copolymer contains from 0.1 to 3.0 Meq of olefinic epoxides per gram of copolymer and the peak molecular weights as determined by gel permeation chromatography of the exterior blocks are from 300 to 2000 and the peak molecular weights as determined by gel permeation chromatography of the interior blocks are from 2000 to 10,000. |
| Claim: | 3. The composition of claim 2 wherein the external diene block is 1,4-polyisoprene and the internal diene block is polybutadiene. |
| Claim: | 4. The composition of claim 2 wherein the external diene block is 1,4-polybutadiene and the internal diene block is 1,2-polybutadiene. |
| Claim: | 5. The composition of claim 2 wherein the polymer is hydrogenated such that less than 1 Meq of olefinic double bonds per gram of polymer remain in the block copolymer. |
| Claim: | 6. The composition of claim 5 wherein the ratio of the amount of epoxy in the external blocks to that in the internal blocks is at least 3:1. |
| Claim: | 7. The composition of claim 1 wherein the polymer is crosslinked through at least some of the epoxy functionality by exposure to radiation. |
| Claim: | 8. The composition of claim 2 wherein the copolymer is crosslinked through at least some of the epoxy functionality by exposure to radiation. |
| Claim: | 9. The composition of claim 2 wherein the block copolymer is of the formula [equation included] |
| Claim: | wherein A is an exterior diene block; and |
| Claim: | wherein B is an interior diene block; and |
| Claim: | wherein j is 1 to 6 and k is 2 to 6. |
| Claim: | 10. The composition of claim 9 wherein the copolymer is hydrogenated such that less than 1Meq of olefinic double bonds per gram of polymer remain in the copolymer. |
| Claim: | 11. The composition of claim 9 wherein the copolymer is crosslinked through at least some of the epoxy functionality by exposure to radiation. |
| Claim: | 12. The composition of claim 2 wherein block copolymer is of the formula [equation included] |
| Claim: | wherein D is A-B-M.sub.p or (A-B).sub.j -M.sub.p or A-(B-A).sub.j -M.sub.p ; and |
| Claim: | wherein C is a block or multiblock segment which has a peak molecular weight as determined by gel permeation chromatography of 100 to 18,000 and comprises A, B or methacrylate or mixtures thereof but is not identical to D; and |
| Claim: | wherein the B block may contain a monoalkenyl aromatic hydrocarbon monomer and the A blocks may comprise up to 99% of a monoalkenyl aromatic hydrocarbon monomer; and |
| Claim: | wherein M is a miniblock of a monomer selected form the group consisting of vinyl aromatic hydrocarbons and dienes and which has a peak molecular weight as determined by gel permeation chromatography of 50 to 3000; and |
| Claim: | wherein X is a coupling agent or coupling monomers or initiator, j is 1 to 6, n.gtoreq.2, r.gtoreq.0, n.gtoreq.r, n+r ranges from 3 to 100 and p is 0 or 1. |
| Claim: | 13. The composition of claim 12 wherein the polymer is hydrogenated such that less than 1 Meq of olefinic double bonds per gram of polymer remain in the copolymer. |
| Claim: | 14. The block copolymer of claim 12 wherein the copolymer is crosslinked through at least some of the epoxy functionality by exposure to radiation. |
| Claim: | 15. The composition of claim 1 wherein the polymer is a star polymer having a random distribution of from 0.5 to 5 Meq of di-, tri- and tetrasubstituted olefinic epoxides per gram of polymer and greater than 4 arms wherein the peak molecular weights as determined by gel permeation chromatography of the arms are from 1500 to 15,000. |
| Claim: | 16. The composition of claim 15 wherein the arms are primarily 1,4-polyisoprene. |
| Claim: | 17. The composition of claim 15 wherein the arms are primarily 1,4-polybutadiene. |
| Claim: | 18. The composition of claim 15 wherein the polymer is hydrogenated such that less than 1Meq of olefinic double bonds per gram of polymer remain in the polymer. |
| Claim: | 19. The composition of claim 15 wherein the polymer is crosslinked through at least some of the epoxy functionality by exposure to radiation. |
| Claim: | 20. The composition of claim 15 wherein the star polymer is of the formula |
| Claim: | wherein D is (A-M.sub.p); and |
| Claim: | wherein A is a block comprising at least one diene and the peak molecular weight as determined by gel permeation chromatography of A is from 1,500 to 15,000; and |
| Claim: | wherein C is a block or multiblock segment which has a peak molecular weight as determined by gel permeation chromatography of 50 to 15,000 and comprises at least one diene or vinyl aromatic hydrocarbon or methacrylate or combinations thereof but is not identical to D; and |
| Claim: | wherein the A blocks may comprise up to 99% of a monoalkenyl aromatic hydrocarbon monomer; and |
| Claim: | wherein M is a miniblock of a monomer selected from the group consisting of vinyl aromatic hydrocarbons and dienes and has a peak molecular weight as determined by gel permeation chromatography of 50 to 1000; and |
| Claim: | wherein X is a coupling agent or coupling monomers or initiator, n.gtoreq.2, r.gtoreq.0, n.gtoreq.r, n+r ranges from greater than 4 to 100 and p is 0 or 1. |
| Claim: | 21. The composition of claim 20 wherein the polymer is hydrogenated such that less than 1 Meq of olefinic double bonds per gram of polymer remain in the copolymer. |
| Claim: | 22. The composition of claim 20 wherein the polymer is crosslinked through at least some of the epoxy functionality by exposure to radiation. |
| Current U.S. Class: | 523/400; 525/314; 106/20R; 106/22R; 106/23R |
| Current International Class: | C08L 6102 |
| Patent References Cited: | 3341617 September 1967 Schleimer et al. 3551518 December 1970 Pornin 3555112 January 1971 Winkler 3607977 September 1971 Taylor et al. 3607982 June 1970 Winkler et al. 3652732 March 1972 Makowski et al. 3699184 October 1972 Taylor et al. 3714297 January 1973 Blaise et al. 3899474 August 1975 Goldenberg et al. 3970608 July 1976 Fukukawa et al. 4051199 September 1977 Udipi et al. 4074034 February 1978 Soga et al. 4086298 April 1978 Fahrbach et al. 4091195 May 1978 Vitek 4100046 July 1978 Hodakowski et al. 4131653 December 1978 Hsieh et al. 4131725 December 1978 Udipi 4135037 January 1979 Udipi et al. 4237245 December 1980 Halasa et al. 4341672 July 1982 Hsieh et al. 4391927 July 1983 Farmer, III 4417029 November 1983 Milkovich 4477610 October 1984 Ishimura et al. 4769416 September 1988 Gelling et al. 4879349 November 1989 Hoxmeier 5001199 March 1991 Hoxmeier 5034470 July 1991 Geiser et al. 5039755 August 1991 Chamberlain et al. 5066728 November 1991 Audett 5149895 September 1992 Coolbaugh et al. 5210359 May 1993 Coolbaugh et al. 5229464 July 1993 Erickson et al. 5247026 September 1993 Erickson et al. |
| Other References: | U.S. Ser. No. 692,839, Apr. 29, 1991, Erickson et al. U.S. Ser. No. 901,349, Jul. 19, 1992, Erickson et al. |
| Primary Examiner: | Walsh, Donald P. |
| Assistant Examiner: | Chi, Anthony R. |
| Accession Number: | edspgr.H0001517 |
| Database: | USPTO Patent Grants |
| Language: | English |
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