Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Compositions to be polymerized by wave energy wherein said...
Reexamination Certificate
1999-01-29
2003-04-29
Seidleck, James J. (Department: 1711)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Compositions to be polymerized by wave energy wherein said...
C522S167000, C522S166000, C522S178000, C522S181000, C522S182000, C522S033000, C522S046000
Reexamination Certificate
active
06555593
ABSTRACT:
FIELD OF THE INVENTION
This invention relates generally to photopolymerizable compositions and more particularly to photopolymerizable compositions which include maleimide compounds as a component and methods of using the same.
BACKGROUND OF THE INVENTION
Ethylenically unsaturated compounds, such as acrylate derivatives, can be polymerized by exposure to radiation, typically ultraviolet light, in the presence of a photoinitiating system. Typically, the photoinitiating system includes (1) a compound capable of initiating polymerization of the ethylenically unsaturated compound upon exposure to radiation (a “photoinitiator”) and optionally (2) a coinitiator or synergist, that is, a molecule which serves as a hydrogen atom donor. The coinitiators or synergists are typically alcohols, tertiary amines, amides, or ethers which have labile hydrogens attached to a carbon adjacent to a heteroatom. Currently commercially available photoinitiators include benzophenones and derivatives thereof, such as thioxanthone derivatives.
Maleimides, and in particular N-aliphatic and ortho-substituted (i.e. “twisted”) N-aromatic maleimides have been investigated as comonomer-photoinitiators of UV-curable acrylic systems. These maleimides have been observed to require the presence of a hydrogen atom-donor synergist (such as an amine, ether, thiol, or the like) to obtain reasonable rates of initiation and polymerization.
J. Put and F. C. De Schryver, “Photochemistry of Nonconjugated Bichromophoric Systems,” Journal of the American Chemical Society. 95, 1, 137-45 (1973); “Photocyloaddition Polymerization. I. Preparation and Characterization of Poly-N,N′-polymethylenebisdichloromaleimides,” Journal of Polymer Science: Part A-1. 8, 1939-48 (1970); and N. Boens et al., “Solid-State Ultraviolet Irradiation of Some Maleimides and Bismaleimides,” Journal of Polymer Science: Polymer Chemistry Edition 13, 210-13 (1975) report studies of the sensitization of maleimides with benzophenone and thioxanthones for the formation of maleimide 2+2 cycloadducts. F. C. De Schryver, et al, “Photochemistry of Nonconjugated Bichromophoric Systems. Photopolymerization of N,N-Alkylenebis (dimethylmaleimides),” Journal of the American Chemical Society 96, 20, 6463-69 (1974) also report the formation polymer networks by the sensitized step-wise 2+2 cycloaddition of maleimides.
SUMMARY OF THE INVENTION
The present invention is directed to photopolymerizable compositions and methods for radiation curing of the same. The compositions of the invention include at least one radiation curable compound. The compositions preferably include ethylenically unsaturated compounds, and in particular, acrylate derivatives.
The compositions further include at least one maleimide which is capable of initiating the photopolymerization of a radiation curable compound. The maleimide can be an alkyl maleimide, functionalized aliphatic maleimide, aromatic maleimide, maleimide, maleic anhydride, or mixtures thereof. The maleimide component can be substantially completely consumed during initiation and photopolymerization (incorporated into the polymer structure).
The composition further includes additional photoactive compounds as sensitizers. Specifically, the composition includes at least one benzophenone compound which is capable of initiating polymerization of the ethylenically unsaturated compound upon exposure to radiation. As used herein, the term “benzophenone compound” includes benzophenone and derivatives thereof, including thioxanthone and derivatives of thioxanthone. In addition, the composition optionally includes at least one coinitiator or synergist as a hydrogen atom donor or an electron donor. The hydrogen atom donor can be present as a separate compound or can be included as a molecular component of the photopolymerizable compound. The synergistic effect described herein which occurs when a sensitizer is used in conjunction with a maleimide in the presence of a hydrogen atom donor has been observed to dramatically increase rates of polymerization of typical acrylic photo-curable systems, as compared to rates obtained using the same acrylic photo-curable system with either maleimide with a hydrogen-atom donor or the sensitizer with a hydrogen-atom donor as the initiating system.
The present invention also provides methods for radiation curing of photopolymerizable compositions of the invention.
REFERENCES:
patent: 3129225 (1964-04-01), Shapiro et al.
patent: 3729814 (1973-05-01), Wright et al.
patent: 3850955 (1974-11-01), Bublitz
patent: 3855180 (1974-12-01), Schroeter
patent: 3890270 (1975-06-01), Minieri et al.
patent: 4025409 (1977-05-01), McGinniss
patent: 4071425 (1978-01-01), Guarino et al.
patent: 4072524 (1978-02-01), Kleeberg et al.
patent: 4266005 (1981-05-01), Nakamura et al.
patent: 4276352 (1981-06-01), Green
patent: 4287294 (1981-09-01), Rubner et al.
patent: 4329556 (1982-05-01), Rubner et al.
patent: 4383903 (1983-05-01), Ayano et al.
patent: 4416975 (1983-11-01), Green et al.
patent: 4544621 (1985-10-01), Roth
patent: 4626497 (1986-12-01), Roth et al.
patent: 4656292 (1987-04-01), Roth
patent: 4886842 (1989-12-01), Drain et al.
patent: 5087552 (1992-02-01), Horigome et al.
patent: 5171655 (1992-12-01), Aoshima
patent: 5196550 (1993-03-01), Long, II et al.
patent: 5319101 (1994-06-01), Long, II et al.
patent: 5446073 (1995-08-01), Jonsson et al.
patent: 6034150 (2000-03-01), Hoyle et al.
patent: 6153662 (2000-11-01), Miller et al.
patent: 4 024 710 (1991-02-01), None
patent: 0 094 913 (1983-11-01), None
patent: 0 304 174 (1988-07-01), None
patent: 0 318 893 (1989-06-01), None
patent: 0 410 794 (1991-01-01), None
patent: 2 293 467 (1976-07-01), None
patent: 2 438 282 (1980-04-01), None
patent: 62010179 (1987-01-01), None
patent: 3 084 016 (1991-04-01), None
patent: 0 4161 413 (1992-06-01), None
patent: WO 99/03930 (1999-01-01), None
International Search Report for PCT/US 99/01989 mailed May 21, 1999 by J. M. Dupart.
Patent Abstracts of Japan, vol. 018, No. 201 (C-1188), Apr. 8, 1994 & JP 06 001944 A (Hitachi Chem Co. Ltd), Jan. 11, 1994.
Patent Abstracts of Japan, vol. 005, No. 168 (C-077), Oct. 27, 1981 & JP 56 098245 A (Mitsubishi Gas Chem Co. Inc), Aug. 7, 1981.
Woo-Sik Kim et al., “Synthesis and Photocrosslinking of Maleimide-Type Polymers,”Macromol. Rapid Commun., vol. 17, No. 11, pp. 835-841, Nov., 1996.
Chemical Abstracts, vol. 91, No. 6, Aug. 6, 1979, Columbus, Ohio, US; abstract No. 39958x, Shulyndin S.V. et al., “Synthesis and Properties of Polymers Containing Phosphorous and Nitrogen,” p. 39962.
J. Put and F.C. DeSchryver, “Photochemistry of Nonconjugated Bichromophoric Systems, Intramolecular Photocycloaddition of N,N′-Alkylenedimaleimides in Solution,”J. Ameri. Chem. Soc.,95, 140, Jan. 10, 1973.
F.C. DeSchryver, N. Boens and G. Smets; “Photopolymerization V. Unsensitized Solution Photocyclopolymerization of N, N′-Alkylenedimaleimides,”Journal of Polymer Science, vol. 10, 1687-1699 (1972).
F.C. DeSchryver, W.J. Feast and G. Smets, “Photocycloaddition Polymerization, I. Preparation and Characterization of Poly-N, N′-polymethylenebisdichloromaleimides,”Journal of Polymer Science, vol. 8, 1939-1948 (1970).
N. Boens, F.D. DeSchryver, and G. Smets, “Solid-State Ultraviolet Irradiation of Some Maleimides and Bismaleimides,”Journal of Polymer Science, vol. 13, 201-213 (1975).
H. Zorr and H. Heusinger, “Intermediates of Radiation-Induced Polymerisation of Maleimides Studied by ESR,”European Polymer J., 14, 89 (1978).
Miller, et al., Polymer Preprints, 38(2), 454-55 (1997).
Miller et al..,Polymer Preprints, 37(2), 346 (1996).
M. Yamada et al.,J. Polym. Sci., Part B, 6, 883(1968).
F.C. DeSchryver et al.,J. Am. Chem. Soc., 96, 6463:6469 (1974). K. Meier et al.,J. Photochem., 35, 353-366. 1986.
K. Meier et al.,J. Photochem., 35, 353-366 (1986.
Shimose, et al.,Polymer Preprints, vol. 36, 1(1995).
Hoyle et al.Academic Day Proceedings Radtech Europe '97, pp. 115-120.
Jönsson et al.,PMSE Preprints, 74, 319 (1996).
Decker et al.,Polym. Mater. Sci. Eng., 75, 198 (1996).
Clark et al.,P
Clark Shan Christopher
Hoyle Charles E.
Jönsson E. Sonny
Miller Christopher W.
Nagarajan Rajamani
Albemarle Corporation
McClendon Sanza L.
Seidleck James J.
LandOfFree
Photopolymerization compositions including maleimides and... does not yet have a rating. At this time, there are no reviews or comments for this patent.
If you have personal experience with Photopolymerization compositions including maleimides and..., we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Photopolymerization compositions including maleimides and... will most certainly appreciate the feedback.
Profile ID: LFUS-PAI-O-3089570