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Patent US4640967 - Ultraviolet radiation-curable silicone release compositions with epoxy and ... - Google PatentsSearch Images Maps Play YouTube News Gmail Drive More »Sign inPatentsEpoxy- and/or acrylic-functional polysiloxanes are disclosed which, when combined with onium salt photoinitiating catalysts or free-radical photoinitiating catalysts or both, form ultraviolet radiation-curable release coating compositions which render surfaces non-adherent to other surfaces which would...http://www.google.com/patents/US4640967?utm_source=gb-gplus-sharePatent US4640967 - Ultraviolet radiation-curable silicone release compositions with epoxy and/or acrylic functionalityAdvanced Patent SearchTry the new Google Patents, with machine-classified Google Scholar results, and Japanese and South Korean patents.Publication numberUS4640967 APublication typeGrantApplication numberUS 06/810,484Publication dateFeb 3, 1987Filing dateDec 18, 1985Priority dateMay 6, 1982Fee statusPaidPublication number06810484, 810484, US 4640967 A, US 4640967A, US-A-4640967, US4640967 A, US4640967AInventorsRichard P. EckbergOriginal AssigneeGeneral Electric CompanyExport CitationBiBTeX, EndNote, RefManPatent Citations (3), Referenced by (48), Classifications (25), Legal Events (3) External Links: USPTO, USPTO Assignment, EspacenetUltraviolet radiation-curable silicone release compositions with epoxy and/or acrylic functionality
US 4640967 AAbstract
8. A process for preparing an organopolysiloxane having epoxy and acrylic functionality comprising the steps:(1) reacting an epoxy olefin compound with a hydrogen-functional polysiloxane in the presence of a small amount of a precious metal catalyst for a period sufficient to react some but not all of the hydrogen-silicon groups; (2) recovering an epoxy-functional, hydrogen-functional polysiloxane product and reacting it with an ω-halogen-containing olefin in the presence of a precious metal catalyst; (3) recovering an epoxy-functional, halogenated polysiloxane and reacting it with a hydroxy-functional acrylate in the presence of pyridine; and (4) recovering a polysiloxane having epoxy and acrylic functionality. 9. A process as defined in claim 8 wherein the epoxy olefin compound is limoneneoxide, ω-halogen-containing olefin is methallylchloride and the hydroxy-functional acrylate is acrylic acid.
Silicone compositions have long been used as release coatings, which render a surface or material relatively non-adherent to other materials which would normally adhere thereto. For example, silicone release compositions have found application as coatings which release pressure-sensitive adhesives for labels, decorative laminates, transfer tapes, etc. Silicone release coatings on paper, polyethylene, Mylar� and other such substrates are also useful to provide non-stick surfaces for food handling and industrial packaging.
The ultraviolet-curable epoxy-functional silicone intermediate fluid comprises a pre-crosslinked epoxy functional dialkylepoxy-chainstopped polydialkyl-alkylepoxy siloxane copolymer fluid which is the reaction product of a vinyl- or allylic-functional epoxide and a vinyl functional siloxane cross-linking fluid having a viscosity of approximately 1 to 100,000 centipoise at 25� C. with a hydrogen-functional siloxane precursor fluid having a viscosity of approximately 1 to 10,000 centipoise at 25� C. in the presence of an effective amount of precious metal catalyst for facilitating an addition cure hydrosilation reaction between the vinyl-functional cross-linking fluid, vinyl-functional epoxide, and hydrogen-functional siloxane precursor fluid.
The epoxy monomers, which are simply mixed with the silicone polymer compositions before application to a substrate, include olefinic epoxy monomers such as limoneneoxide, 4-vinylcyclohexeneoxide, allylglycidyl ether, 7-epoxy-1-octene, vinylcyclohexenedioxide, bis(2,3-epoxycyclopentyl) ether, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, cresylglycidyl ether, butanedioldiglycidyl ether and the like. Mixtures of such epoxides are also suitable. The reactive diluents should be soluble in the epoxysilicone fluid/photoinitiator release composition, and judicious pairing of the polymeric epoxy functionality and epoxy monomer allows tailoring of performance to particular situations. For the purposes herein, where the epoxysilicone functionality is derived from limoneneoxide, preferred epoxy monomer reactive diluents are ω-epoxy C.sub.(8-11) aliphatic hydrocarbons. A mixture of such monomers is available commercially as Vikolox� 11-14 (Viking Chemical).
Synthesis of β-(3,4 epoxy cyclohexyl)ethyl silicone fluids from 4-vinylcyclohexene
33 parts by weight of vinylcyclohexene, 33 parts by weight of a 150 cps. dimethylvinyl-chainstopped polydimethylsiloxane fluid and 0.05 parts by weight of a platinum catalyst (chloroplatinic acid-octyl alcohol complex) were dissolved in 300 parts by weight hexane. 300 parts by weight of a polydimethyl-methylhydrogen siloxane copolymer (135 cps. viscosity) containing 7.3% methylhydrogen siloxy units, was slowly added to the stirring hexane solution. This reaction mixture was then refluxed at 73� C. for 4 hours. 10 parts hexene were added, and the reflux continued 16 hours more. A clear, 500 cps. β-(3,4-cyclohexenyl)ethyl-functional fluid product was obtained after stripping the solvent and unreacted vinylcyclohexene and hexene at 110� C. under a vacuum.
(epoxidized)
200 parts by weight of the Sample 1 product were dissolved in 800 parts by weight dichloromethane and cooled to 3� C. 40 parts by weight of 40% peracetic acid in acetic acid solution with potassium acetate buffer (FMC Corp.) was added slowly to the stirring cooled solution. An exothermic reaction ensued which raised the reaction mixture's temperature approximately 20� C. The mixture was stirred, after addition of the peracid was completed, for an additional 18 hours at room temperature. The resulting solution was then shaken with sodium bicarbonate and anhydrous magnesium sulfate, filtered, and the filtrate shaken with an equal volume of a 4% aqueous KOH solution. The organic phase was collected, treated with anhydrous magnesium sulfate and filtered. Solvent was stripped off under vacuum at 75� C. to yield approximately 130 parts by weight of a clear, 600 cps. viscosity fluid (about a 60% yield).
75 parts by weight of 4-vinylcyclohexene, 15 parts by weight of a dimethylvinyl-chainstopped polydimethyl siloxane fluid (150 cps.) and 0.05 parts by weight platinum catalyst were dissolved in 300 parts by weight toluene. 300 parts by weight of a 95 cps. polydimethyl-methylhydrogen siloxane fluid containing 9.9% methylhydrogen siloxy units were slowly added to the toluene solution, the complete reaction mixture being then refluxed at 115� C. for 4 hours. 10 parts by weight hexene were added, and the reflux continued 16 hours more until no unreacted SiH groups were detected by infrared analysis. This β-(3,4 cyclohexenyl)ethyl-functional fluid in toluene product was stored over anhydrous magnesium sulfate.
220 parts by weight of the Sample 2 product were combined with approximately 610 parts by weight of toluene. 0.27 parts by weight hexacarbonyl molybdenum (Alfa Inorganic Chemicals) and 0.4 parts by weight dibasic anhydrous sodium phosphate (NaHPO4) were added and the reaction mixture heated to reflux temperature at 110� C., at which point 100 parts by weight of an anhydrous 40% solution of tetrabutylhydroperoxide (TBHP)* was slowly added over one hour to the refluxing, stirring reaction mixture. The mixture was refluxed for another hour, then cooled to 30� C. 40 parts by weight anhydrous sodium sulfite were added and the reaction mixture stirred overnight. The product solution was filtered and the toluene removed under a vacuum at 60� C. to yield about 120 parts by weight of a clear, amber-colored, 700 cps. β-(3,4-epoxy cyclohexyl)ethyl siloxane fluid (approximately 90% yield).
(preparation of Eckberg et al. 717 Patent)
Rub-off occurs when a silicone coating fails to adhere to the substrate and can be rubbed off in little balls of cured silicone by gentle finger pressure. Smear is detected in an incompletely cured coating when a finger firmly pressed across the silicone film leaves an obvious permanent streak. Migration is detected by the Scotch� cellophane tape test. The coating is considered well cured and migration-free if a piece of No. 610 Scotch� tape will stick to itself after having been first firmly pressed into the silicone coating, then removed and doubled back on itself. If a silicone coating is shown to be migration-free by means of the Scotch� tape test, it is considered to be a release coating because it adheres to the substrate with an adhesive force much greater than the adhesive force between the cured composition and the released aggressive Scotch� tape. These qualitative tests are universally employed to ascertain the completeness of cure in silicone paper release coatings.
Synthesis of novel epoxy-functional polysiloxanes from epoxy monomers
130 parts by weight of a 250 cps dimethylvinyl-chainstopped polydimethylsiloxane fluid, 700 parts by weight of limoneneoxide (SCM Corp.), and 1 part by weight of a platinum-octyl alcohol complex were added to 4000 parts by weight of toluene. 2600 parts by weight of a 150 cps dimethylhydrogen-chainstopped polydimethyl-methylhydrogen-siloxane copolymer fluid containing 8.7 weight percent .tbd.SiH groups were added slowly to the stirring mixture at 26� C. over 1 hour. The reaction mixture was then refluxed at 120� C. for 6 hours, at which point 580 parts by weight of n-hexene were added and refluxing continued for 10 hours more. The solvents were removed by heating under a vacuum to yield an 800 cps fluid product containing about 17 weight percent limoneneoxide and 0.8 weight percent unreacted .tbd.SiH groups.
20 parts by weight of the vinyl-containing siloxane fluid of Sample 4, 40 parts by weight of 2,6-dimethyl-2,3-epoxy-7-octene (DMEO; SCM Organics) and 0.05 parts by weight of the platinum catalyst used in Sample 4 were added to 200 parts by weight toluene. 150 parts by weight of a 95 cps dimethylhydrogen-chainstopped polydimethyl-methylhydrogen siloxane copolymer fluid containing 9.5 weight percent .tbd.SiH groups were added slowly to the stirring toluene solution. The complete reaction mixture was refluxed at 115� C. for 15 hours, at which point 10 parts by weight hexene were added and the refluxing continued for 5 more hours. Less than 0.6 weight percent unreacted .tbd.SiH was detected. The solvents were stripped to yield a clear 300 cps epoxysilicone fluid product containing about 19 weight percent functionalized DMEO.
Samples 4, 5 and 6 are each "precrosslinked" polydimethyl-methylalkyl (epoxy) siloxane linear polymers, chainstopped by dimethyl-alkyl (epoxy) siloxy groups. These fluids are clearly different in structure from the β-(3,4-epoxycyclohexyl)ethyl-substituted polysiloxanes described above. The three samples were combined with 1.5 weight percent of bis(dodecylphenyl)iodonium hexafluoroantimonate cationic photoiniator and coated onto polyethylene Kraft (PEK) paper, supercalendered Kraft (SCK) paper and Mylar�, then exposed to UV radiation in a PPG model 1202 AN UV Processor housing two Hanovia medium pressure mercury UV lamps, each generating 200 watts/in2 focused power to evaluate cure performance. The exposed films were evaluated for rub-off, smear, migration and release properties using techniques well known to persons familiar with release coating technology.
Laminates were prepared on silicone-coated SCK substrates by 0.3 seconds UV exposure followed by 6 mil coatings of an SBR rubber adhesive (No. 4950; Coated Products, Inc.) cured on top of the silicone layer. A second sheet of uncoated SCK paper was firmly pressed onto the adhesive layer. Release performance was tested by pulling the SCK-SBR lamina from the SCK-silicone lamina at a 180� angle at 400 feet/min. The force required to separate two inch wide strips of the two lamina was recorded, and the following results observed:
Aging of these laminates for 4 weeks at 140� F. did not significantly effect release performance.
Synthesis of epoxy-functional silicone from vinylnorbornene
Release performance of the coatings was determined by preparing laminates of epoxysilicone-coated SCK sheets with 10 mil films of Gelva� 263 (Monsanto) aggressive acrylic adhesive. Release testing was carried out using a Scott tester as described above, with the following results:
500 parts by weight of a 70 cps dimethylhydrogen-chainstopped linear polydimethyl-methylhydrogen siloxane copolymer fluid were dissolved in 500 parts by weight toluene. 126 parts by weight limoneneoxide and 25 parts by weight of a 3000 cps dimethylvinyl-chainstopped linear polydimethyl siloxane fluid were then added. The reaction mixture was catalyzed with 0.2 parts by weight of a platinum catalyst, then refluxed for 18 hours. Unreacted .tbd.SiH groups were removed by reaction with hexene. Excess hexene and toluene were stripped under a vacuum at 150� C. to yield 581 parts by weight of a 660 cps epoxy-functional silicone fluid.
Synthesis of prior art acrylic-functional silicones
(Nordstrom et al., U.S. Pat. No. 3,650,811)
81 parts by weight of a 8-(tris(ethoxy)silyl) ethyl-chainstopped linear polydimethyl siloxane fluid prepared by hydrosilation addition of vinyltriethoxysilane to a dimethylhydrogen-chainstopped dimethyl fluid were mixed with 6 parts by weight hydroxyethyl acrylate, 0.1 parts by weight tetraisopropyltitanate and 0.5 parts by weight hydroquinone. This reaction mixture was heated, with stirring, to 140� C. After 3 hours, generation of 1.58 parts by weight ethanol was observed. The reaction mixture was stirred at 100� C. under a vacuum to provide a hazy yellow 280 cps fluid product. The generation of ethanol indicates that at least partial acrylation of the siloxane fluid had occurred.
This composition was tested for release performance by mixing 5 parts by weight of the fluid product with 0.2 parts by weight of a benzoin ether photoinitiator (Trigonal 14 �; Noury Chemical Corp.). This material was coated on SCK paper and exposed to a single H3T7 mercury vapor UV source in a nitrogen atmosphere at 6 inches until a smear free cured surface was obtained (about 1 min. exposure time) The cured film was smear-free and migration-free, but was easily rubbed off of the substrate.
35 parts by weight of allylacrylate and 0.05 parts by weight of a platinum catalyst [grade 88257] were dissolved in 150 parts by weight hexane. 100 parts by weight of methylhydrogen fluid containing 17.6 weight percent .tbd.SiH units was added slowly to the stirring hexane solution. The complete reaction mixture was heated to reflux (80� C.). An intractable solid gel formed within 1 hour, and the reactants were discarded.
37 parts by weight allylacrylate and 0.05 parts by weight of a platinum catalyst [grade 88034] were dissolved in 200 parts by weight toluene. 100 parts by weight of a methylhydrogen copolymer containing 9.9 weight percent .tbd.SiH groups were added slowly to the stirring solution. The complete reaction mixture was heated to 65� C. for 10 hours, then to 85� C. for 6 hours, at which point no unreacted .tbd.SiH groups could be detected by infrared spectroscopy. The solvent and excess allylacrylate were stripped off under a vacuum to yield 120 parts by weight of a 443 cps fluid product.
100 parts by weight of a 450 cps epoxy silicone copolymer incorporating 16 weight percent 2,6-diemthyl-2,3-epoxy-7-octene (Sample 5, above) were dissolved in 200 parts by weight toluene with 15 parts by weight acrylic acid. The reaction mixture was heated to 115� C. under nitrogen for 90 minutes. Toluene and excess acrylic acid were stripped off under a vacuum to yield 98 parts by weight of a hazy amber 633 cps fluid. The higher viscosity of the product is an indication that the opening of the oxirane ring occurred.
2-step synthesis of acrylic-functional silicones
35 parts by weight of allylchloride were dissolved in 300 parts by weight hexane with 0.05 parts by weight of a platinum catalyst [grade 88257]. 300 parts by weight of an 80 cps linear methylhydrogen silicone fluid containing 8.5 weight percent .tbd.SiH groups were added to the hexane solution. This mixture was refluxed at 70� C. for 20 hours, at which point no .tbd.SiH-functionality was detected. Hexane and excess allylchloride were removed under a vacuum to yield a 100 cps fluid containing γ-chloropropyl substitution. 150 parts by weight of this material were stirred with 15 parts by weight acrylic acid and 21 parts by weight triethylamine at 100� C. for 30 minutes under nitrogen. Stripping unreacted materials and filtering off the aminehydrochloride provided a hazy fluid product of 620 cps viscosity.
60 parts by weight methallylchloride and 0.05 parts by weight of a platinum catalyst were dissolved in 200 parts by weight toluene. 200 parts by weight of a 95 cps methylhydrogen silicone fluid containing 9.9 weight percent .tbd.SiH groups were added slowly to the toluene solution. The reaction mixture was refluxed for 15 hours, at which point no reactive .tbd.SiH groups were detected. Excess methallylchloride was removed under vacuum, then 24 parts by weight acrylic acid and 33 parts by weight triethylamine were consecutively added to the reaction vessel. Following addition of the amine, the reaction mixture was heated to 113� C. for 1 hour, then stripped and filtered. A clear yellow 217 cps fluid product was obtained.
__________________________________________________________________________                             Cure TimeSample    Acrylic Function      Photoinitiator                             (sec)__________________________________________________________________________10  --CH2 CH2 CH2 OOCCH&#9552;CH2                     5% Trigonal 14                             3.011  --CH2 CH2 CH2 OCH2 CH2 OOCCH&#9552;CH2                     "       1.512  --CH2 CH2 CH2 OCH2 CH2 OOCC(CH3)&#9552;CH.    sub.2                 "       5.013  --CH2 CH2 CH2 OCH2 CH2 OOCCH&#9552;CH2                     4% DEAP 1.514  --CH2 CH(CH3)CH2 OOCCH&#9552;CH2                     "       1.5__________________________________________________________________________
Preparation of epoxy-acrylic-functional polysiloxanes
200 parts by weight of a 300 cps dimethylhydrogen-chainstopped linear polydimethyl-methylhydrogen siloxane copolymer fluid containing 8 weight percent methylhydrogen siloxane units were added to a reaction vessel. 40 parts by weight limoneneoxide and 0.1 parts by weight of a platinum catalyst (U.S. Pat. No. 3,814,730 (Karstedt), incorporated herein by reference) were added, along with 240 parts by weight toluene. This reaction mixture was refluxed for 16 hours. Infrared analysis showed 2.5 weight percent methylhydrogen siloxy units remained unreacted. Approximately 11.16 parts by weight methallylchloride were added, and refluxing resumed for 30 minutes, at which time no unreacted .tbd.SiH groups were detected. Excess methallylchloride was removed by distillation. 6 parts by weight acrylic acid were then added to the reaction vessel, followed by slow dropwise addition of 8 parts by weight pyridine to the stirring solution. A hazy precipitate formed as the pyridine was added. Solvent and excess amine were removed under a vacuum at 150� C. 206 parts by weight of a 2970 cps fluid were obtained. Analysis revealed that 11.7 weight percent limoneneoxide and 3.35 weight percent acrylic acid functionality were included in the polymer composition. The foregoing synthesis can be illustrated as follows: ##STR15##
______________________________________                            Parts by Weight  Parts by Weight              Parts by Weight                            Diethoxy-Coating  Terpolymer  (C12 H25 Ph)2 ISbF6                            acetophenone______________________________________16A    10          0.2           --16B    10          0.2           0.516C    10          --            0.5______________________________________
200 parts by weight of a 70 cps dimethylhydrogen-chainstopped polydimethyl-methylhydrogen siloxane copolymer fluid containing 10 weight percent .tbd.SiH groups were added to a reaction vessel. 150 parts by weight toluene, 51 parts by weight limoneneoxide and approximately 0.1 part by weight platinum catalyst were added and the mixture refluxed at 120� C. for 17 hours, at which point 2.08 weight percent .tbd.SiH functionality remained. 10 parts by weight methallylchloride were added and refluxing resumed for an additional 11/2 hours. No unreacted .tbd.SiH groups were detected. Excess methallylchloride was removed by distilling 50 ml of solvent at atmospheric pressure. The solution was cooled to 30� C. and 5.0 parts by weight of acrylic acid were added, followed by dropwise addition of 14.0 parts by weight of triethylamine. The complete reaction mixture was then stirred for 12 hours at room temperature. The dispersion was filtered and stripped of solvent, amine and low-boiling side products under a vacuum at 150� C. to yield 197 parts by weight of a hazy yellow 440 cps fluid containing an oxirane/acrylate group ratio of 3.4/1.
______________________________________dual-Sam- functional Photoinitiatorple  silicone fluid           PhC:OC(CH3)2 OH*                          (C12 H25 Ph)2 ISbF6______________________________________17A  10 parts by           0.3 parts by weight                          --weight17B  10 parts by           --             0.15 parts by weightweight17C  10 parts by           0.3 parts by weight                          0.15 parts by weightweight______________________________________ *free-radical-type catalyst, available as Darocure � 1173 (E.M. Chemicals)
______________________________________     PhotoinitiatorBath Silicone Fluid           PhC:OC(CH3)2 OH                          (C12 H25 Ph)2 ISbF6______________________________________17D  20 parts by weight           0.6 parts by weight                          --17E  20 parts by weight           --             0.3 parts by weight17F  20 parts by weight           0.6 parts by weight                          0.3 parts by weight______________________________________ (the above ingredients dispersed in 80 parts by weight of hexane)
8"�10" SCK sheets were coated from the D, E and F baths with a No. 2 wire-wound rod to provide depositions of approximately 0.5 lbs/ream. The sheets were exposed to UV light for 0.3 seconds in a PPG Processor as described above. The cured coatings were then laminated with 5 mil layers of SBR adhesive and a second SCK sheet pressed on to the adhesive layer. 2"�8" strips of the silicon-coated lamina were pulled away from the adhesive lamina at 180� at 400 feet/min. using a Scott tester, which recorded the force (in grams) required to separate the lamina:
Dual Catalyst System For Rapid Curing of Epoxy-Functional Silicones
An epoxy-functional silicone fluid composition containing 80% epoxy-functional fluid having 20 weight percent limoneneoxide reactivity and 20% Vikolox� 11-14 epoxy monomer was used to form the following two release coating compositions:
______________________________________         PhotoinitiatorSam-  Epoxysilicone +               Diethoxy-ple   Vikolox 11-14 acetophenone                          (C12 H25 Ph)2 ISbF6______________________________________18    10 parts by weight               --         0.15 parts by weight19    10 parts by weight               0.15 parts by                          0.15 parts by weight               weight______________________________________
______________________________________Sample     Atmosphere Cure Time (sec.)______________________________________18         air        0.318         N2    0.319         air        0.319         N2     0.075______________________________________
Release performance of hand-coated (solventless) specimens was tested using nitrogen-cured samples in laminates prepared with 10 mil layers of Gelva� (Monsanto) acrylic adhesive. Release at different UV exposure times were recorded on a Scott tester:
Further trails similar to the Examples 18 and 19 were set up in order to test another free-radical photoinitiator, Trigonal� 14 (Noury Chemical Co.), a benzoin ether compound. An epoxysilicone-Vikolox? 11-14 blend similar to that used in Examples 18 and 19 was used.
______________________________________Sam- Epoxysilicone            Photoinitiatorple  Vikolox 11-14            Trigonal � 14                          (C12 H25 Ph)2 ISbF6______________________________________20   10 parts by --            0.15 parts by weightweight21   10 parts by 0.15 parts by weight                          0.15 parts by weightweight22   10 parts by 0.15 parts by weight                          --weight______________________________________
______________________________________Sample     Atmosphere Cure Time (sec.)______________________________________20         air        0.620         N2    0.621         air        0.621         N2     0.07522         air        &gt;3.0 (no cure)22         N2    &gt;3.0 (no cure)______________________________________
A toluene solution of an epoxy-functional silicone fluid was prepared to test benzophenone, a crystalline solid at room temperature, as a free-radical photoinitiator in the dual catalyst system of this invention. 300 parts by weight of an 85 cps dimethyl-methylhydrogen silicone fluid, 99 parts by weight limoneneoxide and 300 parts by weight toluene were mixed and refluxed 20 hours. Unreacted .tbd.SiH groups were eliminated by reaction with hexene to yield 725 parts by weight of a limonenoxide-functional polysiloxane in toluene. Half this product was stripped of solvent and designated Sample 23. The remainder was treated with 0.32 parts by weight benzophenone, which readily dissolved in the hexane solution. The solvent was then stripped and designated Sample 24. Both samples were diluted with 17 weight percent Vikolox� 11-14 epoxy monomer as a reactive diluent, bringing the viscosity of the fluid samples to about 225 cps. No evidence of the benzophenone coming out of solution was observed over four months' storage at room temperature.
______________________________________Sam-            UV Exposureple  Atmosphere Time (sec.)                      Remarks______________________________________23   air        0.6        cured-no smear, no migration23   air        0.3        smears, migrates24   air        0.6        cured-no smear, no migration24   air        0.3        smears, migrates23   N2    0.3        smears, migrates24   N2     0.07      cured-no smear, no migration______________________________________
______________________________________(1) ##STR16##     "Darocure � 1173" (E.M. Chemicals)(2) ##STR17##     "Irgacure � 651" (Ciba Geigy)(3) ##STR18##     "Irgacure � 184" (Ciba Geigy)______________________________________
Four portions of a limoneneoxide-functional silicone fluid (the same limoneneoxide-silicone fluid described in Examples 23-24) in toluene were prepared. To each of three portions were added 0.15 weight percent of Darocure 1173, Irgacure 651 and Irgacure 184, respectively, to form Samples 25, 26 and 27. Sample 28, containing no free-radical photocatalyst was maintained as a control. All four samples were stripped under a vacuum at 150� C. to yield four fluids of approximately 600 cps. No reactive diluents were added in these examples.
______________________________________            ExposureSample Atmosphere Time (sec.)                      Remarks______________________________________25    air        1.5       cured-no smear, no migration25    air        0.3       smear, migration25    N2     0.075    cured-no smear, no migration26    air        0.6       cured-no smear, no migration26    air        0.3       smear, migration26    N2     0.15     cured-no smear, no migration26    N2     0.075    smear, migration27    air        0.6       cured-no smear, no migration27    air        0.3       smear, migration27    N2     0.06     cured-no smear, no migration28    air        0.6       cured-no smear, no migration28    air        0.3       smear, migration28    N2    0.3       smear, migration______________________________________
Epoxysilicones enhanced by addition of aliphatic epoxy monomers
40 parts by weight limoneneoxide were dispersed in 160 parts by weight toluene. To this were added 200 parts by weight of a 170 cps dimethylhydrogen-chainstopped linear polydimethyl-methylhydrogen siloxane copolymer fluid having 8 weight percent .tbd.SiH groups and 10 parts by weight of a 250 cps dimethylvinyl-chainstopped polydimethyl siloxane fluid. This mixture was catalyzed with 0.05 parts by weight of a platinum catalyst, then refluxed at 120� C. for six hours. Hexene was added to react with the remaining .tbd.SiH functions, followed by resumption of reflux for 16 hours. Hexene and solvents were stripped under a vacuum to yield 217 parts by weight of a 1730 cps epoxy-functional dimethyl silicone copolymer fluid containing about 14 weight percent limoneneoxide functionality.
This reaction product was combined with varying amounts of an epoxidized α-olefin, Vikolox� 11-14 (Viking Chemical Co.) having the formula: ##STR19## where n is an integer from 8 to 11. Vikalox 11-14 is a mixture of epoxides of from 11 through 14 carbons. The following coating samples were prepared to examine cure performance:
__________________________________________________________________________         Epoxy Monomer      ViscositySample    Epoxysilicone         (Vikolox)                  C12 H25 Ph)2 ISbF6                            (cps)__________________________________________________________________________29  100 parts by weight         --       1.5 parts by weight                            173030  90 parts by weight         10 parts by weight                  1.5 parts by weight                            82031  80 parts by weight         20 parts by weight                  1.5 parts by weight                            46532  70 parts by weight         30 parts by weight                  1.5 parts by weight                            275__________________________________________________________________________
Laminates prepared as in previous examples using Gelva� 263 acrylic adhesive (Monsanto) and SCK paper, were cut into 2"�9" tapes, then pulled apart at 400 feet/min. using a Scott tester. The following release data were generated (Adhesive Transfer measures any adhesive sticking to silicon/SCK lamina pulled away):
An epoxysilicone fluid of approximately 9000 cps was prepared as described in Examples 29-32. This material was blended with Vikolox� 12 monomer (epoxidized 1-dodecene) to furnish the following coating composition:
__________________________________________________________________________                            ViscositySample    Epoxysilicone         Epoxy Monomer                  (C12 H25 Ph)2 ISbF6                            (cps)__________________________________________________________________________33  100 parts by weight         --       1.5 parts by weight                            900034  90 parts by weight         10 parts by weight                  1.5 parts by weight                            480035  80 parts by weight         20 parts by weight                  1.5 parts by weight                            226036  70 parts by weight         30 parts by weight                  1.5 parts by weight                            114037  60 parts by weight         40 parts by weight                  1.5 parts by weight                             610__________________________________________________________________________
The samples were coated and cured � � in Examples 29-32, with the following results:
A 960 cps epoxy-functional silicone fluid was synthesized as described in Examples 29-37. This product was blended with Vikolox� 11-14 epoxy monomer, the blends cured and evaluated on 40-pound SCK paper as in previous examples. The results are shown below:
__________________________________________________________________________                            ViscositySample    Epoxysilicone         Epoxy Monomer                  (C12 H25 Ph)2 ISbF6                            cps__________________________________________________________________________37  100 parts by weight         --       1.5 parts by weight                            96038  90 parts by weight         10 parts by weight                  1.5 parts by weight                            50039  80 parts by weight         20 parts by weight                  1.5 parts by weight                            290__________________________________________________________________________
______________________________________Sample Epoxysilicone            Epoxy Monomers*                          (C12 H25 Ph)2 ISbF6______________________________________40     10 parts  (none)        0.15 parts by weight by weight41    8.5 parts  1.5 parts by weight                          0.15 parts by weight by weight  Vikolox 11-1442    8.5 parts  1.5 parts by weight                          0.15 parts by weight by weight  CY-18343    8.5 parts  1.5 parts by weight                          0.15 parts by weight by weight  DY-02344    8.5 parts  1.5 parts by weight                          0.15 parts by weight by weight  Epoxide 745    8.5 parts  1.5 parts by weight                          0.15 parts by weight by weight  Epoxide 846    8.5 parts  1.5 parts by weight                          0.15 parts by weight by weight  BDGE______________________________________ ##STR20## ##STR21## ##STR22## ##STR23## ##STR24## BDGE = butanedioldiglycidyl ether
______________________________________Sam-ple  Blend Appearance              Cure Performance______________________________________40   hazy          slight smear &amp; migration, easily              rubbed off substrate41   clear         cured-no smear, migration or rub-off42   opaque        no cure43   opaque        poor cure-smearing, migration44   clear         cured-no smear migration or rub-off45   clear         cured-no smear migration or rub-off46   opaque        no cure______________________________________
__________________________________________________________________________Sample    Epoxysilicone        Diluent               (C12 H25 Ph)2 ISbF6                         Hexane__________________________________________________________________________40A 20 parts by weight        none   0.3 parts by weight                         80 parts by weight41A 17 parts by weight        3 parts               0.3 parts by weight                         80 parts by weight        by weight        Vikalox 11-1444A 17 parts by weight        3 parts               0.3 parts by weight                         80 parts by weight        by weight        Epoxide 745A 17 parts by weight        3 parts               0.3 parts by weight                         80 parts by weight        by weight        Epoxide 8__________________________________________________________________________
These samples were applied to 40-pound SCK stock with a No. 2 wire-wound rod to give thin, even coating depositions of 0.5-0.6 lb/ream. UV exposure for 0.3 seconds cured all coatings, with 40A showing some rub-off. Laminates were prepared using an aggressive SBR adhesive. 2"�8" strips of the epoxysilicone/SCK lamina were pulled way from: the adhesive/SCK lamina at 180� at 400 feet/min., generating the data below:
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