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United States Patent (19) 11 Patent Number: 4,950,696 Palazotto Et Al

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United States Patent (19) 11 Patent Number: 4,950,696 Palazotto Et Al United States Patent (19) 11 Patent Number: 4,950,696 Palazotto et al. (45) Date of Patent: Aug. 21, 1990 54) ENERGY-INDUCED DUAL CURABLE 4,707,432 11/1987 Gatechair .............................. 522/25 4,734,444 3/1988 Henne ....... ... 522/25 COMPOSTIONS 4,740,577 4/1988 Devoe ................................... 528/51 (75) Inventors: Michael C. Palazotto, St. Paul; 4,849,320 7/1989 Irving et al. ........................ 430/280 Katherine A. Brown-Wensley, Lake Elmo; Robert J. DeVoe, St. Paul, all FOREIGN PATENT DOCUMENTS of Minn. 094914 11/1983 European Pat. Off. 094915 11/1983 European Pat. Off. (73) Assignee: Minnesota Mining and 109851 5/1984 European Pat. Off. Manufacturing Company, St. Paul, 155704 9/1985 European Pat. Off. .............. 522/25 Minn. 207893 1/1987 European Pat. Off. 837966 10/1983 South Africa . (21) Appl. No.: 90,694 2042550 9/1980 United Kingdom . Filed: Aug. 28, 1987 (22) OTHER PUBLICATIONS (51) Int. Cl........................ C08G 18/22; C08G 18/04 (52) U.S. C. ...................................... 522/25; 430/280; McManus et al., "Photoassisted Reaction Between Al 430/281; 430/283; 430/914; 430/921; 430/923; cohols and Isocyanates'; J.C.S. Chem. Comm., 1974, p. 522/170; 522/174; 528/51; 528/52; 528/56; 253. 528/75 T. A. Speckhard, K. K. S. Hwang, S. B. Lin, S. Y. Tsay, 58) Field of Search .......................................... 522/25 M. Koshiba, Y. S. Ding, S. L. Cooper; J. Appl. Polymer Science, 1985, 30, 647-666. 56) References Cited C. Bluestein; Polym.-Plast. Technol. Eng. 1981, 17, U.S. PATENT DOCUMENTS 83-93. 3,705,129 12/1972 Murio et al. .......................... 260/47 Roesler, Modern Paint and Coatings, Apr. 1986, pp. 3,709,861 1/1973 Anderson .............................. 260/47 46-55. 3,714,006 1/1973 Anderson ..... 204/159.14 G. Smets, Pure G. Appl. Chem, 53, 611,615 (1981). 3,729,313 4/1973 Smith ... ... 96/27 H. M. Wagner, M. D. Purbrick, J. Photograph Science, 3,741,769 6/1973 Smith ... ... 96/35.1 29, 230-235 (1981). 3,794,576 2/1974 Watt ..... 204/159.11 3,808,006 4/1974 Smith ...................................... 96/88 J. Kosar, Light Sensitive Systems: Chemistry and Ap 3,867,354 2/1975 Betts et al. ... ... 260/78.4 plication of Nonsilver Halide Photographic Processes, 4,001,015 1/1977 Barzynski ..... ... 430/302 Wiley, New York, 1965, pp. 158-193. 4,010,289 3/1977 Kobayashi ... ... 522/100 H. J. Timpe and H. Baumann, Wiss Z. Tech. Hochsch. 4,026,705 5/1977 Crivello et al... ... 96/27 Leuna-Merseburg, 26, 439 (1984). 4,053,316 10/1977 Lu ........ 522/27 H. Baumann, B. Strehmel, H. J. Timpe and U. Lammel, 4,058,400 1 1/1977 Crivello .................................. 96/86 J. Prakt. Chem., 326 (3) 415, (1984). 4,080,274 3/1978 Schlesinger .. 204/159.8 H. Baumann, U. Oertel and H. J. Timpe, Euro. Polym. 4,086,091 4/1978 Cella ............ ... 96/36.2 4,113,497 9/1978 Schlesinger .. ... 522/25 J., 22, 313 (Apr. 3, 1986). 4,156,035 5/1979 Tsao et al. ............................ 427/44 S. P. McManus, "Stabilization of Cure Rates of Diiso 4,216,288 8/1980 Crivello ....... ... 430/280 cyanates with Hydroxy-Terminated Polybutadiene 4,227,978 iO/1980 Barton ...... 204/159.12 Binders', UAH Research Report No. 140, Apr. 1973. 4,228,232 10/1980. Rousseau .............................. 522/25 4,237,242 12/1980 Frankel .... ... 525/119 Primary Examiner-John C. Bleutge 4,250,053 2/1981 Smith ............... ... 252/426 Assistant Examiner-Arthur H. Koeckert 4,342,793 - 8/1982 Skinner et al. ........................ 427/44 Attorney, Agent, or Firm-Donald M. Sell; Walter N. 4,412,048 1/1983 Dixon .................................... 522/25 Kirn; Lorraine R. Sherman 4,428,807 1/1984 Lee et al. .............................. 522/25 4,521,545 6/1985 Kerimis et al. .. ... 521/107 57 ABSTRACT 4,525,232 6/1985 Rooney ................................. 522/25 An energy polymerizable composition comprises at 4,533,446 8/1985 Conway ... ... 522/25 least one ethylenically-unsaturated monomer, one of 4,544,466 10/1985 Lindstrom 204/159.11 4,549,945 10/1985 Lindstrom ... ... 204/159.11 polyurethane precursors, and at least one epoxy mono 4,582,861 4/1986 Galla et al. ... ... 521/118 mer, and a curing agent comprising an organometallic 4,593,052 6/1986 Irving .................................... 522/25 compound, and an onium salt. 4,623,676 11/1986 Kistner ..... ... 522/15 4,657,779 4/1987 Gaske .................................... 522/25 18 Claims, No Drawings 4,950,696 1. 2 disclosed in U.S. Pat. No. 4,026,705; and the onium salts ENERGY-NDUCED DUAL CURABLE of Group VIA elements, particularly the sulfonium COMPOSITIONS salts, as are disclosed in U.S. Pat. No. 4,058,400), or a dicarbonyl chelate compound of a Group IIIA-VA FIELD OF THE INVENTION element as is disclosed in U.S. Pat. No 4,086,091. These This invention relates to an energy-polymerizable compositions are limited to ultraviolet radiation for composition comprising an ethylenically-unsaturated polymerization. Furthermore, the dicarbonyl chelates monomer and either polyurethane precursors or an are moisture sensitive. epoxy monomer, and as curing agent a combination of U.S. Pat. No. 4,216,288 teaches the thermal curing of an organometallic compound and an oxidizing agent, O cationically polymerizable compositions using onium and a method therefor. In a further aspect, cured arti salts and reducing agents. cles comprising the composition of the invention are disclosed. The compositions are useful, for example, as Radiation dual curable compositions containing eth protective coatings, binders for magnetic media or abra ylenically unsaturated monomers and epoxy monomers 15 have been described in U.S. Pat. Nos. 4,156,035, sives, adhesives, and in graphic arts applications. 4,227,978, and 4,623,676. These compositions include BACKGROUND OF THE INVENTION onium salts combined with organic compounds as the Various polymeric coatings and articles are produced curing agent, but do not contain any organometallic in processes involving the use of organic solvents. compounds. There is an intense effort by law makers, researchers, 20 Energy polymerizable compositions comprising ionic and industry to promote high and 100% solids formula salts of organometallic complex cations and cationically tions to reduce or eliminate the use of such solvents and sensitive materials and the curing thereof has been the attendant costs and environmental contamination. taught (see European Patent Nos. 109,851, 1984; These processes require a latent catalyst or latent reac 094,915, 1983, Derwent abstract; and 094,415, 1983, tion promoter which can be activated in a controlled 25 Derwent abstract). fashion. Neutral organometallic compounds have been used in Thermal curing of polyurethane precursors using combination with neutral halogenated compounds for reaction promoters such as tin salts and tertiaryamines is the photocuring of ethylenically-unsaturated mono known in the art. Curing of polymerizable mixtures of mers. (G. Smets, Pure G. Appl. Chem, 53, 611,615 polyisocyanates with polyols (referred to as polyure 30 thane precursors) using thermally latent catalysts is (1981); H. M. Wagner, M. D. Purbrick, J. Photograph known in the art (see for example U.S. Pat. Nos. Science, 29, 230-235. 4,521,545, and 4,582,861). The use of certain photosensitizers with onium salts Photocuring of urethane (meth)acrylates is well for initiation of polymerization of ethylenically unsatu known (see T. A Speckhard, K. K. S. Hwang, S. B. Lin, 35 rated monomers is also well known in the art. This S. Y. Tsay, M. Koshiba, Y. S. Ding, S. L. Cooper J. technique has found applications in printing, duplica Appl. Polymer Science, 1985, 30, 647-666; C. Bluestein tion, copying, and other imaging systems (see J. Kosar Polym.-Plast Technol. Eng. 1981, 1783-93), and photo in Light Sensitive Systems: Chemistry and Application curing of polyurethane precursors using diazonium of Nonsilver Halide Photographic Processes, Wiley, salts, tertiaryamine precursors, and organotin com 40 New York, 1965, pp 158-193). Aryliodonium salts have pounds is also known (see U.S. Pat. Nos. 4,544,466, been previously described for use as photoinitiators in 4,549,945, and EP No. 28,696, Derwent abstract). All of addition-polymerizable compositions. (See U.S. Pat. these methods suffer from one or more of the following Nos. 3,729,313, 3,741,769, 3,808,006, 4,228,232, disadvantages: sensitivity to oxygen, requirement of 4,250,053 and 4,428,807; H. J. Timpe and H. Baumann, ultraviolet and/or high intensity light, the need for 45 Wiss Z. Tech. Hochsch. Leuna-Merseburg, 26, 439 (1984); modified resins, loss or dilution of urethane properties, H. Baumann, B. Strehmel, H. J. Timpe and U. Lammel, low activity, poor solubility, and poor potlife. J. Prakt, Chem, 326(3), 415 (1984); and H. Baumann, U. The dual curing of acrylate/urethane precursor mix Oertel and H. J. Timpe, Euro, Polym. J., 22 (4), 313 tures is known but these curing methods are not entirely (April 3, 1986). photoactivated nor are any methods known that pro 50 vide for the simultaneous curing of the urethane precur SUMMARY OF THE INVENTION sors and acrylates (see U.S. Pat. 4,342,793 and Roesler, Briefly, the present invention provides an energy Modern Paint and Coatings, April, 1986, pages 46-55). polymerizable composition comprising an ethylenical The prior art discloses processes for the polymeriza ly-unsaturated monomer and either polyurethane pre tion of epoxy materials. It is further known that a metal 55 locene, such as ferrocene, can be used as a curing accel cursors or an epoxy monomer, and as curing agent a erator for epoxy materials (U.S. Pat. No. 3,705,129). combination of a organometallic compound and an U.S.
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