WO1992012183A1 - Electron beam curable epoxy compositions - Google Patents
Electron beam curable epoxy compositions Download PDFInfo
- Publication number
- WO1992012183A1 WO1992012183A1 PCT/US1991/008800 US9108800W WO9212183A1 WO 1992012183 A1 WO1992012183 A1 WO 1992012183A1 US 9108800 W US9108800 W US 9108800W WO 9212183 A1 WO9212183 A1 WO 9212183A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- metal halide
- silicone
- epoxy
- monomers
- onium salt
- Prior art date
Links
- 0 C*(CCC1CC2OC2CC1)(O)O[S@@](C)(CCC1CC2OC2CC1)O[Si](CCC1CC2OC2CC1)(O*(CCC1CC2OC2CC1)I)I Chemical compound C*(CCC1CC2OC2CC1)(O)O[S@@](C)(CCC1CC2OC2CC1)O[Si](CCC1CC2OC2CC1)(O*(CCC1CC2OC2CC1)I)I 0.000 description 2
- FEEAKBKYWJLHRI-UHFFFAOYSA-N CC1OCCC(CCS(C)(C)O[Si](C)(C)CCC2CC3OC3CC2)C1 Chemical compound CC1OCCC(CCS(C)(C)O[Si](C)(C)CCC2CC3OC3CC2)C1 FEEAKBKYWJLHRI-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/30—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen
- C08G59/306—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen containing silicon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/3254—Epoxy compounds containing three or more epoxy groups containing atoms other than carbon, hydrogen, oxygen or nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
- C08L83/06—Polysiloxanes containing silicon bound to oxygen-containing groups
Definitions
- the invention relates, generally, to electron-beam (e- beam) cure of epoxy compositions and specifically to deepsection, e-beam cure of herein disclosed epoxy monomers.
- E-beam curing is most widely applied to the cure of coating materials which are either heavily pigmented or are comparatively thick in crossection, such as cable insulation. In such applications, ultraviolet radiation-induced polymerization is impractical whereas the great depth of penetration of the electron radiation permits the polymerization of these substrates with relative ease.
- E-beam curing is most widely applied to multifunctional acrylate and methacrylate monomers and polymerization results by a free radical mechanism initiated by solvated electrons and free radicals produced by bond scission in the monomers, the use of multifunctional acrylate and methacrylate monomers for e-beam curing suffers from the fact that these materials are costly, toxic and require an inert atmosphere foi their proper cure.
- Epoxy compositions are characterized by multifunctional cycloaliphatic epoxy monomers or polymers together with an onium salt initiator possessing metal halide anions.
- the epoxy compositions are cured by e-beam, x-ray and ⁇ -ray irradiation methods. These compositions represent a
- Composites applications as coatings, inks, adhesives, composites, fiber optics, electronic packagings and photoresists for integrated circuits.
- Composites applications in particular, represent a new and enormously important area for application of this technology.
- triphenylsulfonium, (4-octyloxyphenyl)phenyliodonium and diphenyl(4-thiophenoxyphenyl)sulfonium salts were carried out as described in: Crivello, J.V. and Lee, J.L.; J. Polym.Sci., Poly. Chem. 1989, 27,3951-3965; Crivello, J.V. and Lam,
- Samples to be irradiated were coated onto 2 mil poly(ethylene terephthalate) film using 1 and 3 mil
- the wet film samples were attached to a continuous web and passed through the beam. Experiments were run under nitrogen and air at a constant web speed. The dose was varied by changing the amperage applied to the filament.
- Tg measurements were made at 20°C/minute using a Perkin-Elmer DSC-7 Differential Scanning Calorimeter.
- Electrocurtin Electron Beam apparatus supplied by Energy Sciences, Corp. Wilmington, MA was used operating at a voltage of 165 KeV. Samples were placed on a poly(ethylene terephthalate) web operated at a fixed rate. The dosage received by the sample was varied by adjustment of the electrode amperage.
- Silicone-epoxy monomers are more reactive than simple epoxy monomers such as I in photoinitiated cationic
- a 2 Mrad dose is sufficient to completely crosslink monomer II in the presence of as little as 0.25 mole % diphenyliodonium SbF 6 -. Again, polymerization was not observed when this monomer is irradiated in the absence of an onium salt initiator.
- the glass transition temperature (Tg) for this polymer was 181° C. The excellent high Tg is characteristic of cured epoxy silicone resins and is
- multifunctional epoxy monomers undergo facile e-beam induced cationic polymerization in the presence of oxygen. What is even more surprising and unexpected is that the dose requirements in the presence of oxygen are not substantially higher than under nitrogen. Approximately 0.5 Mrad is the limiting dose necessary for the cure of a 3 mil film of monomer II in the presence of 0.5 mole % of
- the limiting dose is 1 Mrad at an initiator concentration of 0.25%.
- diaryliodosonium triarylsulfoxonium, diarylbromonium, diarylchloronium and phenacyldialkylsulfonium
- benzyldialkylsulfonium and hydroxyphenyldialkylsulfonium salts those bearing the SbF 6 - anions are preferred.
- electrons from a heated linear cathode are accelerated under high electric potential onto the surface of the substrate.
- Other, similarly designed accelerators employ hot cathodes with accelerating and focusing magnets to deliver a highly penetrating beam of electrons.
- Van de Graff accelerator which generates high energy electrons by classical electrostatic methods can be used.
- ⁇ -irradiation from a 60 Co source can be used for curing.
- fast electrons are generated by interaction of the ⁇ -irradiation with the monomer.
- Still another technique involves focusing a high energy electron beam onto a heavy metal conversion target which converts the electrons to highly penetrating x-rays which can be used to achieve the desired cure.
- the e-beam curing compositions may also include a wide assortment of fibrous and particulate fillers, adhesion promoting agents, pigments, dyes and flating or leveling agents.
- novel e-beam curable epoxy monomers and oligomers can be applied to a wide diversity of applications. Among those which may be mentioned are decorative, protective and insulating coatings for wood, glass, metals and plastics, printing inks and adhesives. One recent application which is being considered is the use of e-beam curable inks for the rapid non-polluting printing of currency and stamps.
- Silicone epoxy monomers in addition to being rapidly curing are non-toxic .
- Other monomers whose structures are also described in this disclosure should also be similarly non- toxic.
- Tg's temperature properties
- solvent resistance and mechanical properties As well as excellent solvent resistance and mechanical properties.
- e-beam curing avoids the high temperatures and long times used in conventional composites fabrication and has the potential of greatly improving the mechanical properties of the final composite. This is achieved as a result of curing at room temperature which reduces the mechanical strain in the composites which results from a mismatch of the
- R is an alkylene, arylene, siloxane group or mixture of these.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Epoxy Resins (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US63810591A | 1991-01-04 | 1991-01-04 | |
US638,105 | 1991-01-04 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1992012183A1 true WO1992012183A1 (en) | 1992-07-23 |
Family
ID=24558664
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1991/008800 WO1992012183A1 (en) | 1991-01-04 | 1991-11-22 | Electron beam curable epoxy compositions |
Country Status (2)
Country | Link |
---|---|
EP (1) | EP0544842A4 (de) |
WO (1) | WO1992012183A1 (de) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2004034104A1 (en) * | 2002-10-11 | 2004-04-22 | Polyset Company Inc. | Siloxane optical waveguides |
DE10001228B4 (de) * | 2000-01-13 | 2007-01-04 | 3M Espe Ag | Polymerisierbare Zubereitungen auf der Basis von siliziumhaltigen Epoxiden |
WO2006083284A3 (en) * | 2004-06-01 | 2007-08-16 | Dow Corning | A material composition for nano- and micro-lithography |
EP3505551A1 (de) * | 2017-12-27 | 2019-07-03 | Shin-Etsu Chemical Co., Ltd. | Lichtempfindliche harzzusammensetzung, musterherstellungsverfahren und fertigung eines opto-halbleiterbauelements |
US11752696B2 (en) | 2018-10-04 | 2023-09-12 | Continuous Composites Inc. | System for additively manufacturing composite structures |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4529490A (en) * | 1983-05-23 | 1985-07-16 | General Electric Company | Photopolymerizable organic compositions and diaryliodonium ketone salts used therein |
US4977199A (en) * | 1986-08-29 | 1990-12-11 | Union Carbide Chemicals And Plastics Company Inc. | Photo curable blends of 2-methyoxytetrahydropyran and a cycloaliphatic diepoxide |
US4990546A (en) * | 1990-03-23 | 1991-02-05 | General Electric Company | UV-curable silphenylene-containing epoxy functional silicones |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4101513A (en) * | 1977-02-02 | 1978-07-18 | Minnesota Mining And Manufacturing Company | Catalyst for condensation of hydrolyzable silanes and storage stable compositions thereof |
US4310469A (en) * | 1978-12-29 | 1982-01-12 | General Electric Company | Diaryliodonium salts |
DE3629701A1 (de) * | 1985-09-04 | 1987-03-05 | Ciba Geigy Ag | Strahlenhaertung von kationisch polymerisierbaren verbindungen |
CA2008848A1 (en) * | 1989-03-30 | 1990-09-30 | Karen D. Riding | Epoxysiloxane cure promoters and accelerators for cationic uv cure systems |
US4994299A (en) * | 1989-06-22 | 1991-02-19 | General Electric Company | Substantially odor free, UV curable organopolysiloxane release coating compositions and coating method |
-
1991
- 1991-11-22 WO PCT/US1991/008800 patent/WO1992012183A1/en not_active Application Discontinuation
- 1991-11-22 EP EP19920902738 patent/EP0544842A4/en not_active Withdrawn
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4529490A (en) * | 1983-05-23 | 1985-07-16 | General Electric Company | Photopolymerizable organic compositions and diaryliodonium ketone salts used therein |
US4977199A (en) * | 1986-08-29 | 1990-12-11 | Union Carbide Chemicals And Plastics Company Inc. | Photo curable blends of 2-methyoxytetrahydropyran and a cycloaliphatic diepoxide |
US4990546A (en) * | 1990-03-23 | 1991-02-05 | General Electric Company | UV-curable silphenylene-containing epoxy functional silicones |
Non-Patent Citations (1)
Title |
---|
See also references of EP0544842A4 * |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10001228B4 (de) * | 2000-01-13 | 2007-01-04 | 3M Espe Ag | Polymerisierbare Zubereitungen auf der Basis von siliziumhaltigen Epoxiden |
WO2004034104A1 (en) * | 2002-10-11 | 2004-04-22 | Polyset Company Inc. | Siloxane optical waveguides |
US6832036B2 (en) | 2002-10-11 | 2004-12-14 | Polyset Company, Inc. | Siloxane optical waveguides |
WO2006083284A3 (en) * | 2004-06-01 | 2007-08-16 | Dow Corning | A material composition for nano- and micro-lithography |
US7648767B2 (en) | 2004-06-01 | 2010-01-19 | Dow Corning Corporation | Material composition for nano- and micro-lithography |
EP3505551A1 (de) * | 2017-12-27 | 2019-07-03 | Shin-Etsu Chemical Co., Ltd. | Lichtempfindliche harzzusammensetzung, musterherstellungsverfahren und fertigung eines opto-halbleiterbauelements |
CN109976091A (zh) * | 2017-12-27 | 2019-07-05 | 信越化学工业株式会社 | 光敏树脂组合物、图案形成方法和光电半导体器件的制造 |
US11156919B2 (en) | 2017-12-27 | 2021-10-26 | Shin-Etsu Chemical Co., Ltd. | Photosensitive resin composition, pattern forming process, and fabrication of opto-semiconductor device |
US11752696B2 (en) | 2018-10-04 | 2023-09-12 | Continuous Composites Inc. | System for additively manufacturing composite structures |
US11760013B2 (en) | 2018-10-04 | 2023-09-19 | Continuous Composites Inc. | System for additively manufacturing composite structures |
US11787112B2 (en) | 2018-10-04 | 2023-10-17 | Continuous Composites Inc. | System for additively manufacturing composite structures |
Also Published As
Publication number | Publication date |
---|---|
EP0544842A1 (de) | 1993-06-09 |
EP0544842A4 (en) | 1993-07-21 |
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