Transdermal drug delivery devices with amine-resistant silicone adhesives

Claim 2

In a transdermal drug delivery device for the controlled transdermal delivery of a drug comprising a container having a controlled drug delivery means associated therewith, said container being adapted to hold said drug delivery means in close proximity to the skin of a wearer, said device having a biocompatible silicone pressure-sensitive adhesive layer thereon for maintaining contact between said container and the skin of a wearer, the improvement which comprises the combination of an amino-functional drug to be delivered from said drug delivery means and a biocompatible silicone pressure-sensitive adhesive layer which has been deposited from a silicone pressure-sensitive adhesive composition containing silicon-bonded hydroxyl radicals which comprises a combination of (A) from 40 to 70 inclusive parts by weight of at least one benzene-soluble resinous copolymer containing silicon-bonded hydroxyl radicals and consisting essentially of triorganosiloxy units of the formula R 3 SiO 1/2 and tetrafunctional siloxy units of the formula SiO 4/2 in a ratio of about 0.6 to 0.9 triorganosiloxy units for each tetrafunctional siloxy unit present in the copolymer and (B) from 30 to 60 parts by weight of at least one polydiorganosiloxane consisting essentially of ARSiO units terminated with endblocking TRASiO 1/2 units, each said polydiorganosiloxane having a viscosity of from 100 centipoise to 30,000,000 centipoise at 25° C. where each T is R-- or X--, which composition has been chemically treated with at least one chemical treating agent that is reactive to silicon-bonded hydroxyl groups to reduce the silicon-bonded hydroxyl content of the composition to a sufficient degree to thereby render said adhesive layer more resistant to the loss of tack and instant adherence to the skin caused by said amino-functional drug, wherein each R is a monovalent organic radical selected from the group consisting of hydrocarbon radicals of from 1 to 6 inclusive carbon atoms, each X radical is selected from the group consisting of HO--, H-- and R'O-- radicals, each R' is an alkyl radical of from 1 to 4 inclusive carbon atoms, and each A radical is selected from the group consisting of R-- and halohydrocarbon radicals of from 1 to 6 inclusive carbon atoms.

Claim 3

The device as claimed in claim 1 wherein prior to said chemical treatment, the silicone components of said adhesive composition are composed of (A) from 40 to 70 inclusive parts by weight of at least one benzene soluble resin copolymer containing silicon-bonded hydroxyl radicals and consisting essentially of triorganosiloxy units of the formula R 3 SiO 1/2 and tetrafunctional siloxy units of the formula SiO 4/2 in a mole ratio of 0.6 to 0.9 R 3 SiO 1/2 units for each SiO 4/2 unit present and (B) from 30 to 60 parts by weight of at least one polydiorganosiloxane consisting essentially of ARSiO units terminated with endblocking TRASiO 1/2 units, each said polydiorganosiloxane having a viscosity of from 100 centipoise to 30,000,000 centipoise at 25° C. where each T is R-- or X--, said chemical treatment is accomplished by a method which comprises condensing at least said (A), optionally in the presence of (B), with (C) a sufficient amount of at least one organosilicon endblocking agent capable of generating an endblocking triorganosilyl unit selected from the group consisting of ZR 2 Si-- units, CH 3 Z'-- units, RZ"-- units, and Z'"R 2 Si-- units to provide a 1:0.8 to 1:3 mole ratio of total silicon-bonded hydroxyl radicals present in said (A) and, when present, any silicon-bonded hydroxyl and X radicals present in said (B) to total endblocking triorganosilyl units provided by all endblocking agent present, said agent being selected from the group consisting of ZR 2 SiY, (ZR 2 Si) q D, CH 3 Z'Y, (CH 3 Z') 2 O, RZ"Y' and (RZ") 2 O and Z"'R 2 SiY' at least until a substantial amount of the endblocking triorganosilyl units have reacted with the silicon-bonded hydroxyl radicals of said (A), and when present, with the silicon-bonded hydroxyl radicals and X radicals of said (B), wherein each R is a monovalent organic radical selected from the group consisting of hydrocarbon radicals of from 1 to 6 inclusive carbon atoms, each X radical is selected from the group consisting of HO--, H' and R'O-- radicals, each R' is an alkyl radical of from 1 to 4 inclusive carbon atoms, each Y radical is a monovalent hydrolyzable organic radical or HO--, each Y' is HO-- or a monovalent hydrolyzable organic radical free of nitrogen, each A radical is selected from the group consisting of R-- and halohydrocarbon radicals of from 1 to 6 inclusive carbon atoms, each Z radical is A-- or QR"--, each R" is a divalent alkylene radical of from 1 to 6 inclusive carbon atoms, each Q is an organofunctional monovalent radical selected from the group consisting of RCOE'--, RE'OC--, NC--, R'E'--, HO--, G 2 N--, HO(R"O) n -- and G 2 NCH 2 CH 2 NG--, where E' is -- 0--, --NG-- or --S--, n has a value of from 1 to 6, Z' is ##STR7## Z" is ##STR8## Z'" is selected from the group consisting of HSR"--, HSCH 2 CH 2 NGR"-- and HOCH 2 CH 2 SR"-- radicals, each G is R-- or H--, D is a divalent or trivalent radical capable of being hydrolyzed to release said endblocking silyl units, q has a value of 2 when D is a divalent radical and q has a value of 3 when D is a trivalent radical, any (B) not having been present when the chemical treatment was made being combined with the endblocked material to complete formation of the silicone portion of said pressure-sensitive adhesive composition.

Claim 4

The device of claim 2 wherein said silicone pressure-sensitive adhesive composition is made by a method comprising the steps of (I) mixing said (A), (B), (C), (D) optionally, an additional catalytic amount of a mild silanol condensation catalyst in the event that none is provided by said (C) and (E) when necessary, an effective amount of an organic solvent which is inert with respect to (A), (B), (C) and (D) to reduce the viscosity of a mixture of (A), (B), (C), and (D), and (II) condensing the mixture of (A), (B), (C), and (D) at least until a substantial amount of the endblocking triorganosilyl units have reacted with the silicon-bonded hydroxyl radicals and X radicals of said (A) and (B).

Claim 5

The device as claimed in claim 3 wherein R is a methyl radical, each said polydiorganosiloxane (B) is composed of ARSiO units selected from the group consisting of (C 6 H 5 ) 2 SiO, R'"RSiO units and combinations of both where each R'" is selected from the group consisting of methyl, vinyl and 3,3,3-trifluoropropyl radicals and no more than 50 mole percent of the ARSiO units present in said (B) are (C 6 H 5 ) 2 SiO units, the endblocking agent of (C) is selected from the group consisting of ZRR""SiY, (ZRR""Si) 2 NH, and mixtures thereof where each Z is R'" and Y is NH 2 -- or R'O--, and each R"" is a methyl or a phenyl radical, there being present 50 to 65 parts by weight of said (A) and 35 to 50 parts by weight of said (B) and the pKa of the most basic amino-functional radical of said amino-functional drug is at least equal to 8.5.

Claim 6

The device as claimed in claim 4 wherein R"" is a methyl radical, all of said ARSiO units in said (B) are R 2 SiO units and said (C) is (R 3 Si) 2 NH.

Claim 7

The device as claimed in claim 3 wherein said method by which the adhesive composition is made is one wherein Step (I) comprises the steps of (Ia) mixing (A), (B) and any (E) together in the presence of a silanol condensation catalyst, (Ib) condensing said (A) and (B) to form a condensed product and (Ic) mixing the product of Step (Ib) with (C), and (D) and any further amount of (E) which is necessary prior to proceeding with Step (II), said polydiorganosiloxane of (B) having a viscosity of from 100 to 100,000 centipoise at 25° C.

Claim 8

The device as claimed in claim 4 wherein said method by which the adhesive composition is made is one wherein Step (I) comprised the Steps of (Ia) mixing (A), (B) and any (E) together in the presence of a silanol condensation catalyst, (Ib) condensing said (A) and (B) to form a condensed product and (Ic) mixing the product of Step (Ib) with (C), any (D) and any further amount of (E) which is necessary prior to proceeding with Step (II), said polydiorganosiloxane of (B) having a viscosity of from 100 to 100,000 centipoise at 25° C.

Claim 9

The device as claimed in claim 5 wherein said method by which the adhesive composition is made is one wherein Step (I) comprises the Steps of (1a) mixing (A), (B) and any (E) together in the presence of a silanol condensation catalyst, (Ib) condensing said (A) and (B) to form a condensed product and (Ic) mixing the product of Step (Ib) with (C), any (D) and any further amount of (E) which is necessary prior to proceeding with Step (II), said polydiorganosiloxane of (B) having a viscosity of from 100 to 100,000 centipoise at 25° C.

Claim 10

The device as claimed in claim 2 wherein the pressure sensitive adhesive composition comprises a blend of the chemically treated silicone pressure-sensitive adhesive composition with less than about 30 weight percent based on nonvolatile solids content of a chemically-treated modifier comprising from 1 to 100 parts by weight of a silicone resin copolymer consisting essentially of R 3 SiO 1/2 units and SiO 4/2 units in a mole ratio of from 0.6 to 0.9 R 3 SiO 1/2 units for each SiO 4/2 unit present and from 0 to 99 parts by weight of at least one polydiorganosiloxane consisting essentially of ARSiO units terminated with endblocking TRASiO 1/2 units, each said polydiorganosiloxane having a viscosity of from 100 centipoise to 30,000,000 centipoise at 25° C. wherein the chemical treatment has been made with said endblocking agent (C).

Claim 11

The device as claimed in claim 3 wherein said (C) is selected from the group consisting of ZR 2 SiNH 2 , (ZR 2 Si) 2 NH and mixtures thereof and Q is an organofunctional monovalent radical selected from the group consisting of RCOE'--, RE'OC--, NC--, GE', HO(R"O) n --, where E' is --0--, --NH-- or --S--, and said silicone pressure-sensitive adhesive composition is made by a method comprising the steps of (I) mixing (A), (B), (C), (E), (D) and (F) from 0.1 to 10 moles of water per mole of =NH provided by said (C), (G) optionally, from 0.001 to 10 parts by weight per 100 parts by weight of (A) and (B) of at least one ammonia scavenger compound selected from the group consisting of HOC m H 2m+1 , HOC x H 2x (OC x H 2x ) y (O) v H, C w H 2w+1 (OC x H 2x ) y OC w H 2w+1 , C w H 2w+1 C(O)OC n H 2n+1 , H 2 C(O)OC n H 2n+1 , and (II) condensing (A), (B) and (C) at a temperature of from 80° C. to 160° C. and at the same time at least periodically removing any condensation by-products from the mixture at least until a substantial amount of the endblocking triorganosilyl units have reacted with the silicon-bonded hydroxyl radicals and X radicals of said (A) and (B), and (III) stripping substantially any remaining condensation by-products, (F) and any (G) from the mixture after the condensation reaction of step II is substantially complete, wherein m has a value of from 2 to 4, n has a value of from 1 to 6, v is 0 or 1, w has a value of from 1 to 3, x has a value of from 2 to 6 and y has a value of from 0 to 3, there being at least 0.5 moles of water present when (G) is not present.

Claim 12

The device as claimed in claim 10 wherein R is a methyl radical, each said polydiorganosiloxane (B) is composed of ARSiO units selected from the group consisting of (C 6 H 5 ) 2 SiO, R'"RSiO units and combinations of both where each R'" is selected from the group consisting of methyl, vinyl and 3,3,3-trifluoropropyl radicals and no more than 50 mole percent of the ARSiO units present in said (B) are (C 6 H 5 ) 2 SiO units, the endblocking agent of (C) is selected from the group consisting of ZRR""SiNH 2 , (ZRR""Si) 2 NH, and mixtures thereof where each Z is R'" and each R"" is a methyl or a phenyl radical, there being present 50 to 65 parts by weight of said (A) and 35 to 50 parts by weight of said (B) and the pKa of the most basic amino-functional radical of said amino-functional drug is at least 8.5.

Claim 13

The device as claimed in claim 11 wherein R"" is a methyl radical, all of said ARSiO units in said (B) are R 2 SiO units and said (C) is (R 3 Si) 2 NH.

Claim 14

The device as claimed in claim 10 wherein said method by which the adhesive composition is made is one wherein Step (I) comprises the steps of (Ia) mixing (A), (B) and any (E) together in the presence of a silanol condensation catalyst, (Ib) condensing said (A) and (B) to form a condensed product and (Ic) mixing the product of Step (Ib) with (C), (F), (G) and any further amount of (E) which is necessary prior to proceeding with Step (II), said polydiorganosiloxane of (B) having a viscosity of from 100 to 100,000 centipoise at 25° C.

Claim 15

The device as claimed in claim 11 wherein said method by which the adhesive composition is made is one wherein Step (I) comprised the Steps of (Ia) mixing (A), (B) and any (E) together in the presence of a silanol condensation catalyst, (Ib) condensing said (A) and (B) to form a condensed product and (Ic) mixing the product of Step (Ib) with (C), (F), (G) and any further amount of (E) which is necessary prior to proceeding with Step (II), said polydiorganosiloxane of (B) having a viscosity of from 100 to 100,000 centipoise at 25° C.

Claim 16

The device as claimed in claim 12 wherein said method by which the adhesive composition is made is one wherein Step (I) comprises the Steps of (1a) mixing (A), (B) and any (E) together in the presence of a silanol condensation catalyst, (Ib) condensing said (A) and (B) to form a condensed product and (Ic) mixing the product of Step (Ib) with (C), (F), (G) and any further amount of (E) which is necessary prior to proceeding with Step (II), said polydiorganosiloxane of (B) having a viscosity of from 100 to 100,000 centipoise at 25° C.

Claim 17

The device as claimed in claim 10 wherein Step (I) comprises the steps of (1a) mixing (A), (B) and any (E) together, (1b) adding said (C) to the mixture formed in step (1a) to form a reaction mixture and (1c) adding said (F) and (G) to the reaction mixture at a preselected point during said Step (II) prior to commencing Step (III).

Claim 18

The device as claimed in claim 10 wherein the pressure sensitive adhesive composition comprises a blend of the chemically-treated silicone pressure-sensitive adhesive composition with less than about 30 weight percent based on nonvolatile solids content of a chemically-treated modifier comprising from 1 to 100 parts by weight of a silicone resin copolymer consisting essentially of R 3 SiO 1/2 units and SiO 4/2 units in a mole ratio of from 0.6 to 0.9 R 3 SiO 1/2 units for each SiO 4/2 unit present and from 0 to 99 parts by weight of at least one polydiorganosiloxane consisting essentially of ARSiO units terminated with endblocking TRASiO 1/2 units, each said polydiorganosiloxane having a viscosity of from 100 centipoise to 30,000,000 centipoise at 25° C. wherein the chemical treatment has been made with said endblocking agent (C).

Claim 19

The device as claimed in claim 4 wherein there is present from 58 to 65 parts by weight of said (A) and from 35 to 42 parts by weight of said (B).

Claim 20

The device as claimed in claim 7 wherein there is present from 58 to 65 parts by weight of said (A) and from 35 to 42 parts by weight of said (B).

Claim 21

The device as claimed in claim 3 wherein a catalytic amount of said (D) is present.

Claim 22

The device as claimed in claim 5 wherein a catalytic amount of said (D) is present.

Claim 23

The device as claimed in claim 10 wherein a catalytic amount of said (D) is present.

Claim 24

The device as claimed in claim 12 wherein a catalytic amount of said (D) is present.

Claim 25

The device as claimed in claim 2 wherein said (C) is selected from the group consisting of ZRR""SiNH 2 , (ZRR""Si) 2 NH, and mixtures thereof where each R"" is a methyl or a phenyl radical and Q is an organofunctional monovalent radical selected from the group consisting of RCOE'--, RE'OC--, NC--, GE', HO(R"O) n --, where E' is --O--, --NH-- or --S--, and said silicone pressure-sensitive adhesive composition is made by a method comprising the steps of (I) mixing (A), (B), (C), (E), (D) and (F) from 0.1 to 10 moles of water per mole of =NH provided by said (C), (II) condensing (A), (B) and (C) at a temperature of from 80° C. to 160° C. and at the same time at least periodically removing any condensation by-products from the mixture at least until a substantial amount of the endblocking triorganosilyl units have reacted with the silicon-bonded hydroxyl radicals and X radicals of said (A) and (B), (III) mixing, from 0.001 to 10 parts by weight per 100 parts by weight of (A) and (B) of at least one ammonia scavenger compound selected from the group consisting of HOC m H 2m+1 , HOC x H 2x (OC x H 2x ) y (O) v H, C w H 2w+1 (OC x H 2x ) y OC w H 2w+1 , C w H 2w+1 C(O)OC n H 2n+1 , H 2 C(O)OC n H 2n+1 , with the product of Step (II), (IV) maintaining the mixture of Step III at reflux temperature for a period of time sufficient to improve the removal of residual ammonia present in the mixture of Step III by a stripping step, and (V) stripping substantially any remaining condensation by-products, (F) and (G) from the mixture of Step IV, wherein m has a value of from 2 to 4, n has a value of from 1 to 6, v is 0 or 1, w has a value of from 1 to 3.

Claim 26

The device as claimed in claim 24 wherein R"" is a methyl radical, all of said ARSiO units in said (B) are R 2 SiO units and said (C) is (R 3 Si) 2 NH.

Claim 27

The device as claimed in claim 24 wherein said method by which the adhesive composition is made is one wherein Step (I) comprises the steps of (Ia) mixing (A), (B) and any (E) together in the presence of a silanol condensation catalyst, (Ib) condensing said (A) and (B) to form a condensed product and (Ic) mixing the product of Step (Ib) with (C), (F), and any further amount of (E) which is necessary prior to proceeding with Step (II), said polydiorganosiloxane of (B) having a viscosity of from 100 to 100,000 centipoise at 25° C.

Claim 30

The method as claimed in claim 27 wherein prior to said chemical treatment, the silicone components of said adhesive composition are composed of (A) from 40 to 70 inclusive parts by weight of at least one benzene soluble resin copolymer containing silicon-bonded hydroxyl radicals and consisting essentially of triorganosiloxy units of the formula R 3 SiO 1/2 and tetrafunctional siloxy units of the formula SiO 4/2 in a mole ratio of 0.6 to 0.9 R 3 SiO 1/2 units for each SiO 4/2 unit present and (B) from 30 to 60 parts by weight of at least one polydiorganosiloxane consisting essentially of ARSiO units terminated with endblocking TRASiO 1/2 units, each said polydiorganosiloxane having a viscosity of from 100 centipoise to 30,000,000 centipoise at 25° C. where each T is R-- or X--, said chemical treatment is accomplished by a method which comprises condensing at least said (A), optionally in the presence of (B), with (C) a sufficient amount of at least one organosilicon endblocking agent capable of generating an endblocking triorganosilyl unit selected from the group consisting of ZR 2 Si-- units, CH 3 Z'-- units, RZ"-- units, and Z'"R 2 Si-- units to provide a 1:0.8 to 1:3 mole ratio of total silicon-bonded hydroxyl radicals present in said (A) and, when present, any silicon-bonded hydroxyl and X radicals present in said (B) to total endblocking triorganosilyl units provided by all endblocking agent present, said agent being selected from the group consisting of ZR 2 SiY, (ZR 2 Si) q D, CH 3 Z'Y, (CH 3 Z') 2 O, RZ"Y' and (RZ") 2 O and Z'"R 2 SiY' at least until a substantial amount of the endblocking triorganosilyl units have reacted with the silicon-bonded hydroxyl radicals of said (A), and when present, with the silicon-bonded hydroxyl radicals and X radicals of said (B), wherein each R is a monovalent organic radical selected from the group consisting of hydrocarbon radicals of from 1 to 6 inclusive carbon atoms, each X radical is selected from the group consisting of HO--, H-- and R'O-- radicals, each R' is an alkyl radical of from 1 to 4 inclusive carbon atoms, each Y radical is a monovalent hydrolyzable organic radical or HO--, each Y' is HO--or a monovalent hydrolyzable organic radical free of nitrogen, each A radical is selected from the group consisting of R-- and halohydrocarbon radicals of from 1 to 6 inclusive carbon atoms, each Z radical is A-- or QR"--, each R" is a divalent alkylene radical of from 1 to 6 inclusive carbon atoms, each Q is an organofunctional monovalent radical selected from the group consisting of RCOE'--, RE'OC--, NC--, R'E'--, HO--, G 2 N--, HO(R"O) n -- and G 2 NCH 2 CH 2 NG--, where E' is --0--, --NG-- or --S--, n has a value of from 1 to 6, Z' is ##STR9## Z" is ##STR10## Z'" is selected from the group consisting of HSR"--, HSCH 2 CH 2 NGR"-- and HOCH 2 CH 2 SR"-- radicals, each G is R-- or H--, D is a divalent or trivalent radical capable of being hydrolyzed to release said endblocking silyl units, q has a value of 2 when D is a divalent radical and q has a value of 3 when D is a trivalent radical, any (B) not having been present when the chemical treatment was made being combined with the endblocked material to complete formation of the silicone portion of said pressure-sensitive adhesive composition.

Claim 31

The method as claimed in claim 28 wherein said silicone pressure-sensitive adhesive composition is made by a method comprising the steps of (I) mixing said (A), (B), (C), (D) optionally, an additional catalytic amount of a mild silanol condensation catalyst in the event that none is provided by said (C) and (E) when necessary, an effective amount of an organic solvent which is inert with respect to (A), (B), (C) and (D) to reduce the viscosity of a mixture of (A), (B), (C), and (D), and (II) condensing the mixture of (A), (B), (C), and (D) at least until a substantial amount of the endblocking triorganosilyl units have reacted with the silicon-bonded hydroxyl radicals and X radicals of said (A) and (B).

Claim 32

The method as claimed in claim 29 wherein R is a methyl radical, each said polydiorganosiloxane (B) is composed of ARSiO units selected from the group consisting of (C 6 H 5 ) 2 SiO, R'"RSiO units and combinations of both where each R'" is selected from the group consisting of methyl, vinyl and 3,3,3-trifluoropropyl radicals and no more than 50 mole percent of the ARSiO units present in said (B) are (C 6 H 5 ) 2 SiO units, the endblocking agent of (C) is selected from the group consisting of ZRR""SiY, (ZRR""Si) 2 NH, and mixtures thereof where each Z is R'" and Y is NH 2 -- or R'O--, and each R"" is a methyl or a phenyl radical, there being present 50 to 65 parts by weight of said (A) and 35 to 50 parts by weight of said (B) and the pKa of the most basic amino-functional radical of said amino-functional drug is at least equal to 8.5.

Claim 33

The method as claimed in claim 30 wherein R"" is a methyl radical, all of said ARSiO units in said (B) are R 2 SiO units and said (C) is (R 3 Si) 2 NH.

Claim 34

The method as claimed in claim 29 wherein said method by which the adhesive composition is made is one wherein Step (I) comprises the steps of (Ia) mixing (A), (B) and any (E) together in the presence of a silanol condensation catalyst, (Ib) condensing said (A) and (B) to form a condensed product and (Ic) mixing the product of Step (Ib) with (C), and (D) and any further amount of (E) which is necessary prior to proceeding with Step (II), said polydiorganosiloxane of (B) having a viscosity of from 100 to 100,000 centipoise at 25° C.

Claim 35

The method as claimed in claim 30 wherein said method by which the adhesive composition is made is one wherein Step (I) comprises the Steps of (Ia) mixing (A), (B) and any (E) together in the presence of a silanol condensation catalyst, (Ib) condensing said (A) and (B) to form a condensed product and (Ic) mixing the product of Step (Ib) with (C), any (D) and any further amount of (E) which is necessary prior to proceeding with Step (II), said polydiorganosiloxane of (B) having a viscosity of from 100 to 100,000 centipoise at 25° C.

Claim 36

The method as claimed in claim 31 wherein said method by which the adhesive composition is made is one wherein Step (I) comprises the Steps of (1a) mixing (A), (B) and any (E) together in the presence of a silanol condensation catalyst, (Ib) condensing said (A) and (B) to form a condensed product and (Ic) mixing the product of Step (Ib) with (C), any (D) and any further amount of (E) which is necessary prior to proceeding with Step (II), said polydiorganosiloxane of (B) having a viscosity of from 100 to 100,000 centipoise at 25° C.

Claim 37

The method as claimed in claim 28 wherein the pressure sensitive adhesive composition comprises a blend of the chemically treated silicone pressure-sensitive adhesive composition with less than about 30 weight percent based on nonvolatile solids content of a chemically-treated modifier comprising from 1 to 100 parts by weight of a silicone resin copolymer consisting essentially of R 3 SiO 1/2 units and SiO 4/2 units in a mole ratio of from 0.6 to 0.9 R 3 SiO 1/2 units for each SiO 4/2 unit present and from 0 to 99 parts by weight of at least one polydiorganosiloxane consisting essentially of ARSiO units terminated with endblocking TRASiO 1/2 units, each said polydiorganosiloxane having a viscosity of from 100 centipoise to 30,000,000 centipoise at 25° C. wherein the chemical treatment has been made with said endblocking agent (C).

Claim 38

The method as claimed in claim 29 wherein said (C) is selected from the group consisting of ZR 2 SiNH 2 , (ZR 2 Si) 2 NH and mixtures thereof and Q is an organofunctional monovalent radical selected from the group consisting of RCOE'--, RE'OC--, NC--, GE', HO(R"O) n --, where E' is --0--, --NH-- or --S--, and said silicone pressure-sensitive adhesive composition is made by a method comprising the steps of (I) mixing (A), (B), (C), (E), (D) and (F) from 0.1 to 10 moles of water per mole of =NH provided by said (C), (G) optionally, from 0.001 to 10 parts by weight per 100 parts by weight of (A) and (B) of at least one ammonia scavenger compound selected from the group consisting of HOC m H 2m+1 , HOC x H 2x (OC x H 2x ) y (O) v H, C w H 2w+1 (OC x H 2x ) y OC w H 2w+1 , C w H 2w+1 C(O)OC n H 2n+1 , H 2 C(O)OC n H 2n+1 , and (II) condensing (A), (B) and (C) at a temperature of from 80° C. to 160° C. and at the same time at least periodically removing any condensation by-products from the mixture at least until a substantial amount of the endblocking triorganosilyl units have reacted with the silicon-bonded hydroxyl radicals and X radicals of said (A) and (B), and (III) stripping substantially any remaining condensation by-products, (F) and any (G) from the mixture after the condensation reaction of step II is substantially complete, wherein m has a value of from 2 to 4, n has a value of from 1 to 6, v is 0 or 1, w has a value of from 1 to 3, x has a value of from 2 to 6 and y has a value of from 0 to 3, there being at least 0.5 moles of water present when (G) is not present.

Claim 39

The method as claimed in claim 36 wherein R is a methyl radical, each said polydiorganosiloxane (B) is composed of ARSiO units selected from the group consisting of (C 6 H 5 ) 2 SiO, R'"RSiO units and combinations of both where each R'" is selected from the group consisting of methyl, vinyl and 3,3,3-trifluoropropyl radicals and no more than 50 mole percent of the ARSiO units present in said (B) are (C 6 H 5 ) 2 SiO units, the endblocking agent of (C) is selected from the group consisting of ZRR""SiNH 2 , (ZRR""Si) 2 NH, and mixtures thereof where each Z is R'" and each R"" is a methyl or a phenyl radical, there being present 50 to 65 parts by weight of said (A) and 35 to 50 parts by weight of said (B) and the pKa of the most basic amino-functional radical of said amino-functional drug is at least 8.5.

Claim 40

The method as claimed in claim 37 wherein R"" is a methyl radical, all of said ARSiO units in said (B) are R 2 SiO units and said (C) is (R 3 Si) 2 NH.

Claim 41

The method as claimed in claim 36 wherein said method by which the adhesive composition is made is one wherein Step (I) comprises the steps of (Ia) mixing (A), (B) and any (E) together in the presence of a silanol condensation catalyst, (Ib) condensing said (A) and (B) to form a condensed product and (Ic) mixing the product of Step (Ib) with (C), (F), (G) and any further amount of (E) which is necessary prior to proceeding with Step (II), said polydiorganosiloxane of (B) having a viscosity of from 100 to 100,000 centipoise at 25° C.

Claim 42

The method as claimed in claim 37 wherein said method by which the adhesive composition is made is one wherein Step (I) comprised the Steps of (Ia) mixing (A), (B) and any (E) together in the presence of a silanol condensation catalyst, (Ib) condensing said (A) and (B) to form a condensed product and (Ic) mixing the product of Step (Ib) with (C), (F), (G) and any further amount of (E) which is necessary prior to proceeding with Step (II), said polydiorganosiloxane of (B) having a viscosity of from 100 to 100,000 centipoise at 25° C.

Claim 43

The method as claimed in claim 38 wherein said method by which the adhesive composition is made is one wherein Step (I) comprises the Steps of (1a) mixing (A), (B) and any (E) together in the presence of a silanol condensation catalyst, (Ib) condensing said (A) and (B) to form a condensed product and (Ic) mixing the product of Step (Ib) with (C), (F), (G) and any further amount of (E) which is necessary prior to proceeding with Step (II), said polydiorganosiloxane of (B) having a viscosity of from 100 to 100,000 centipoise at 25° C.

Claim 44

The method as claimed in claim 36 wherein Step (I) comprises the steps of (1a) mixing (A), (B) and any (E) together, (1b) adding said (C) to the mixture formed in step (1a) to form a reaction mixture and (1c) adding said (F) and (G) to the reaction mixture at a preselected point during said Step (II) prior to commencing Step (III).

Claim 45

The method as claimed in claim 36 wherein the pressure sensitive adhesive composition comprises a blend of the chemically-treated silicone pressure-sensitive adhesive composition with less than about 30 weight percent based on nonvolatile solids content of a chemically-treated modifier comprising from 1 to 100 parts by weight of a silicone resin copolymer consisting essentially of R 3 SiO 1/2 units and SiO 4/2 units in a mole ratio of from 0.6 to 0.9 R 3 SiO 1/2 units for each SiO 4/2 unit present and from 0 to 99 parts by weight of at least one polydiorganosiloxane consisting essentially of ARSiO units terminated with endblocking TRASiO 1/2 units, each said polydiorganosiloxane having a viscosity of from 100 centipoise to 30,000,000 centipoise at 25° C. wherein the chemical treatment has been made with said endblocking agent (C).

Claim 46

The method as claimed in claim 30 wherein there is present from 58 to 65 parts by weight of said (A) and from 35 to 42 parts by weight of said (B).

Claim 47

The method as claimed in claim 33 wherein there is present from 58 to 65 parts by weight of said (A) and from 35 to 42 parts by weight of said (B).

Claim 48

The method as claimed in claim 29 wherein a catalytic amount of said (D) is present.

Claim 49

The method as claimed in claim 31 wherein a catalytic amount of said (D) is present.

Claim 50

The method as claimed in claim 36 wherein a catalytic amount of said (D) is present.

Claim 51

The method as claimed in claim 38 wherein a catalytic amount of said (D) is present.

Claim 52

The method as claimed in claim 36 wherein said (C) is selected from the group consisting of ZRR""SiNH 2 , (ZRR""Si) 2 NH, and mixtures thereof where each R"" is a methyl or a phenyl radical and Q is an organofunctional monovalent radical selected from the group consisting of RCOE'--, RE'OC--, NC--, GE', HO(R"O) n --, where E' is --0--, --NH-- or --S--, and said silicone pressure-sensitive adhesive composition is made by a method comprising the steps of (I) mixing (A), (B), (C), (E), (D) and (F) from 0.1 to 10 moles of water per mole of =NH provided by said (C), (II) condensing (A), (B) and (C) at a temperature of from 80° C. to 160° C. and at the same time at least periodically removing any condensation by-products from the mixture at least until a substantial amount of the endblocking triorganosilyl units have reacted with the silicon-bonded hydroxyl radicals and X radicals of said (A) and (B), (III) mixing, from 0.001 to 10 parts by weight per 100 parts by weight of (A) and (B) of at least one ammonia scavenger compound selected from the group consisting of HOC m H 2m+1 , HOC x H 2x (OC x H 2x ) y (O) v H, C w H 2w+1 (OC x H 2x ) y OC w H 2w+1 , C w H 2w+1 C(O)OC n H 2n+1 , H 2 C(O)OC n H 2n+1 , with the product of step (II), (IV) maintaining the mixture of Step III at reflux temperature for a period of time sufficient to improve the removal of residual ammonia present in the mixture of Step III by a stripping step, and stripping substantially any remaining condensation by-products, (F) and (G) from the mixture of Step IV, wherein m has a value of from 2 to 4, n has a value of from 1 to 6, v is 0 or 1, w has a value of from 1 to 3.

Claim 53

The method as claimed in claim 50 wherein R"" is a methyl radical, all of said ARSiO units in said (B) are R 2 SiO units and said (C) is (R 3 Si) 2 NH.

Claim 54

The method as claimed in claim 50 wherein said method by which the adhesive composition is made is one wherein Step (I) comprises the steps of (Ia) mixing (A), (B) and any (E) together in the presence of a silanol condensation catalyst, (Ib) condensing said (A) and (B) to form a condensed product and (Ic) mixing the product of Step (Ib) with (C), (F), and any further amount of (E) which is necessary prior to proceeding with Step (II), said polydiorganosiloxane of (B) having a viscosity of from 100 to 100,000 centipoise at 25° C.