Novel dual cure silicone compositions

Claim 1

In a curable composition containing polymers having silicon-bonded hydrogen atoms and polymers having silicon-bonded acrylate radicals, the improvement comprising at least one part by weight per 100 parts by weight of said polymers having silicon-bonded hydrogen atoms and polymers having silicon-bonded acrylate radicals of at least one free radical photoinitiator and at least one precious metal-containing hydrosilation catalyst for effecting crosslinking of said silicon-bonded hydrogen atoms and said silicon-bonded acrylate radicals.

Claim 25

A method for making a curable composition comprising mixing: (A) a polysiloxane having the general formula: ##STR27## wherein each R is an independently selected substituted or unsubstituted monovalent hydrocarbon radical having from 1 to 20 carbon atoms; R 1 is hydrogen, a hydroxyl radical or a substituted or unsubstituted hydrocarbon or hydrocarbonoxy radical having from 1 to 20 carbon atoms; A is an acrylate radical having the general formula: ##STR28## where R 2 and R 3 are, independently, hydrogen or a substituted or unsubstituted monovalent hydrocarbon radical; R 4 is a divalent hydrocarbon radical having from 1 to 10 carbon atoms; x is a number such that there is present from about 0.1 to about 50 mole percent acrylate-containing siloxy units; y is a number such that there is present from about 0 to 50 mole percent hydrogen-containing siloxy units with the proviso that if y is 0 there is present an organohydrogenpolysiloxane; and x+y+z is a number such that the viscosity of said polysiloxane is from about 25 centipoise to about 2,500,000 centipoise at 25° C.; (B) at least one part by weight per 100 parts by weight of said polysiloxane of a free radical photoinitiator; and (C) a precious metal-containing hydrosilation catalyst.

Claim 26

A method for making a curable composition comprising mixing: (A) a polysiloxane having the general formula: ##STR27## wherein each R is an independently selected substituted or unsubstituted monovalent hydrocarbon radical having from 1 to 20 carbon atoms; R 1 is hydrogen, a hydroxyl radical or a substituted or unsubstituted hydrocarbon or hydrocarbonoxy radical having from 1 to 20 carbon atoms; A is an acrylate radical having the general formula: ##STR28## where R 2 and R 3 are, independently, hydrogen or a substituted or unsubstituted monovalent hydrocarbon radical; R 4 is a divalent hydrocarbon radical having from 1 to 10 carbon atoms; x is a number such that there is present from about 0.1 to about 50 mole percent acrylate-containing siloxy units; y is a number such that there is present from about 0 to 50 mole percent hydrogen-containing siloxy units with the proviso that if y is 0 there is present an organohydrogenpolysiloxane; and x+y+z is a number such that the viscosity of said polysiloxane is from about 25 centipoise to about 2,500,000 centipoise at 25° C.; (B) at least one part by weight per 100 parts by weight of said polysiloxane of a free radical photoinitiator; and (C) a precious metal-containing hydrosilation catalyst.

Claim 37

The method of claims 20 or 21 wherein the precious metal-containing hydrosilation catalyst is selected from the group consisting of platinum metal, platinum complexes, rhodium metal and rhodium complexes.

Claim 43

A method for making a curable composition comprising mixing: (A) a polysiloxane having the general formula: ##STR31## wherein substantially all of the R radicals are selected from the group consisting of methyl, vinyl and phenyl radicals; R 1 is selected from the group consisting of hydrogen atoms, hydroxyl radicals, methyl radicals and methoxy radicals; A is an acrylate radical having the general formula ##STR32## wherein R 2 and R 3 are, independently, selected from the group consisting of hydrogen and C 1-3 hydrocarbon radicals; R 4 is a C 1-3 divalent hydrocarbon radical; R 5 is an olefinically unsaturated hydrocarbon radical, w is a number such that there is present up to 20 mole percent of siloxy units having olefinically unsaturated hydrocarbon radicals, x is a number such that there is from about 2 to about 20 mole percent acrylate-containing siloxy units; y is a number such that there is from zero to about 20 mole percent hydrogen-containing siloxy units; and w+x+y+z is a number such that the viscosity of said polysiloxane varies from about 100 centipoise to about 5000 centipoise at 25° C.; (B) from 1 to 10 parts by weight per 100 parts by weight polysiloxane (A) of a free radical photoinitiator selected from the group consisting of t-butylperbenzoate, t-butylper-p-nitrobenzoate, t-butylper-p-methoxybenzoate, t-butylper-p-methylbenzoate, and t-butylper-p-chlorobenzoate, benzophenone, t-butylanthraquinone and diethoxyacetophenone; (C) from 10 ppm to 500 ppm based on polysiloxane (A) of a platinum-containing hydrosilation catalyst, as platinum metal; (D) optionally, an organohydrogenpolysiloxane; (E) optionally, a vinyl-containing polydiorganosiloxane; and (F) an inhibitor effective for preventing curing of said composition at temperatures below the heat cure temperature.

Claim 44

A method for making a curable composition comprising mixing: (A) a polysiloxane having the general formula: ##STR31## wherein substantially all of the R radicals are selected from the group consisting of methyl, vinyl and phenyl radicals; R 1 is selected from the group consisting of hydrogen atoms, hydroxyl radicals, methyl radicals and methoxy radicals; A is an acrylate radical having the general formula ##STR32## wherein R 2 and R 3 are, independently, selected from the group consisting of hydrogen and C 1-3 hydrocarbon radicals; R 4 is a C 1-3 divalent hydrocarbon radical; R 5 is an olefinically unsaturated hydrocarbon radical, w is a number such that there is present up to 20 mole percent of siloxy units having olefinically unsaturated hydrocarbon radicals, x is a number such that there is from about 2 to about 20 mole percent acrylate-containing siloxy units; y is a number such that there is from zero to about 20 mole percent hydrogen-containing siloxy units; and w+x+y+z is a number such that the viscosity of said polysiloxane varies from about 100 centipoise to about 5000 centipoise at 25° C.; (B) from 1 to 10 parts by weight per 100 parts by weight polysiloxane (A) of a free radical photoinitiator selected from the group consisting of t-butylperbenzoate, t-butylper-p-nitrobenzoate, t-butylper-p-methoxybenzoate, t-butylper-p-methylbenzoate, and t-butylper-p-chlorobenzoate, benzophenone, t-butylanthraquinone and diethoxyacetophenone; (C) from 10 ppm to 500 ppm based on polysiloxane (A) of a platinum-containing hydrosilation catalyst, as platinum metal; (D) optionally, an organohydrogenpolysiloxane; (E) optionally, a vinyl-containing polydiorganosiloxane; and (F) an inhibitor effective for preventing curing of said composition at temperatures below the heat cure temperature.

Claim 54

A method for making an article of manufacture, comprising: I. mixing, so as to form a curable composition comprising: (A) a polysiloxane having the general formula: ##STR35## wherein each R is an independently selected substituted or unsubstituted monovalent hydrocarbon radical having from 1 to 20 carbon atoms; R 1 is hydrogen, a hydroxyl radical or a substituted or unsubstituted hydrocarbon or hydrocarbonoxy radical having from 1 to 20 carbon atoms; A is an acrylate radical having the general formula: ##STR36## where R 2 and R 3 are, independently, hydrogen or a substituted or unsubstituted monovalent hydrocarbon radical; R 4 is a divalent hydrocarbon radical having from 1 to 10 carbon atoms; x is a number such that there is present from about 0.1 to about 50 mole percent acrylate-containing siloxy units; y is a number such that there is present from about 0 to 50 mole percent hydrogen-containing siloxy units with the proviso that if y is 0 there is present an organohydrogenpolysiloxane; and x+y+z is a number such that the viscosity of said polysiloxane is from about 25 centipoise to about 2,500,000 centipoise at 25° C.; (B) at least one part by weight per 100 parts by weight of polysiloxane of a free radical photoinitiator; and (C) a precious metal-containing hydrosilation catalyst; and II. applying a coating of said curable composition to a substrate; and III. curing said coating to said substrate by exposing the coated substrate to a source of ultraviolet radiation and thereafter thermally curing said coating.

Claim 55

A method for making an article of manufacture, comprising: I. mixing, so as to form a curable composition comprising: (A) a polysiloxane having the general formula: ##STR35## wherein each R is an independently selected substituted or unsubstituted monovalent hydrocarbon radical having from 1 to 20 carbon atoms; R 1 is hydrogen, a hydroxyl radical or a substituted or unsubstituted hydrocarbon or hydrocarbonoxy radical having from 1 to 20 carbon atoms; A is an acrylate radical having the general formula: ##STR36## where R 2 and R 3 are, independently, hydrogen or a substituted or unsubstituted monovalent hydrocarbon radical; R 4 is a divalent hydrocarbon radical having from 1 to 10 carbon atoms; x is a number such that there is present from about 0.1 to about 50 mole percent acrylate-containing siloxy units; y is a number such that there is present from about 0 to 50 mole percent hydrogen-containing siloxy units with the proviso that if y is 0 there is present an organohydrogenpolysiloxane; and x+y+z is a number such that the viscosity of said polysiloxane is from about 25 centipoise to about 2,500,000 centipoise at 25° C.; (B) at least one part by weight per 100 parts by weight of polysiloxane of a free radical photoinitiator; and (C) a precious metal-containing hydrosilation catalyst; and II. applying a coating of said curable composition to a substrate; and III. curing said coating to said substrate by exposing the coated substrate to a source of ultraviolet radiation and thereafter thermally curing said coating.