CHOI HOJIN (KR)
KIM DEOKGU (KR)
LIU NANGUO (US)
WENZLICK ZACHARY (US)
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CLAIMS: 1. A silicone hybrid pressure sensitive adhesive composition comprises: 100 parts by weight of (A) a linear, or substantially linear, polydiorganosiloxane having reactive groups comprising a silicon bonded (meth)acryloxyalkyl-functional group in a pendant position and optionally a silicon bonded aliphatically unsaturated hydrocarbon group in a terminal position, wherein starting material (A) comprises unit formula MpM”qDmD’nD”oT’”rQs, where M represents a unit of formula (R13SiO1/2), M” represents a unit of formula (R12R3SiO1/2), D represents a unit of formula (R12SiO2/2), D’ represents a unit of formula (R1R2SiO2/2), D” represents a unit of formula (R1R3SiO2/2), T”’ represents a unit of formula (R5SiO3/2), and Q represents a unit of formula (SiO4/2), where each R1 is a monovalent hydrocarbon group free of aliphatic unsaturation, each R2 is the (meth)acryloxyalkyl functional group, each R3 is the aliphatically unsaturated monovalent hydrocarbon group, each R5 is independently selected from the group consisting of R1, R2, and R3, and subscripts p, q, m, n, o, r, and s have values such that 0 ≤ p, 0 ≤ q, 0 ≤ o, a quantity (p + q) ≥ 2, a quantity (q + o) ≥ 2 0 < m < 10,000, 2 < n ≤ 10,000, o ≥ 0, a quantity (m + n + o) is 100 to 10,000, a ratio (m+o)/n is 1/1 to 500/1, a ratio (q + o)/(m+n) is 0 ≤ to 1/5, 0 ≤ r ≤ 100, and 0 ≤ s ≤ 100, a ratio (m + n + o)/(r+s) is 50/1 to 10,000/1 if 0 < r or if 0 < s; (B) a polyorganosilicate resin in an amount sufficient to provide a weight ratio of the polyorganosilicate resin to (A) the polydiorganosiloxane (Resin/Polymer Ratio) of 0.15/1 to 4/1, where the polyorganosilicate resin comprises unit formula MaM”bM”’cDdD’eT”’fQhXi, where M”, D, D’, T, and Q are as described above, M”’ represents a unit of formula (R12R2SiO1/2), where R1 and R2 are as described above, X represents a hydroxyl group, and subscripts a, b, c, d, e, f, h, and i, have values such that a ≥ 0, b ≥ 0, c ≥ 0 and a quantity (a + b + c) > 10 mole %; d ≥ 0, e ≥ 0, and a quantity (d + e) is 0 to a number sufficient to provide 30 mole % of D units and D’ units combined to the resin; f ≥ 0, with the proviso that subscript f has a maximum value sufficient to provide 40 mole % of T”’ units to the resin; h > 0, with the proviso that subscript h has a value sufficient to provide 30 mole % to 70 mole % of Q units to the resin; a + b + c + d + e + f + h = 100 mole %; i ≥ 0 is not included in the molar ratio, with the proviso that subscript i has a maximum value sufficient to provide 5 mole % of hydroxyl groups to the resin (C) a polyorganohydrogensiloxane comprising unit formula where M, D, T, and Q represent units of the formulas shown above, and MH represents a unit of formula (HR12SiO1/2), DH represents a unit of formula (HR1SiO2/2), T represents a unit of formula (R1SiO3/2), represents a unit of formula (HSiO3/2), and subscripts t, u, v, w, x, y, and z have values such that t ≥ 0, u ≥ 0, v ≥ 0, w ≥ 0, x ≥ 0, y ≥ 0, z ≥ 0, a quantity (u + w + y) ≥ 2, and a quantity (t + u + v + w + x + y + z) is sufficient to give the polyorganohydrogensiloxane a viscosity of 3 mPa·s to 1,000 mPa·s at 25˚C; with the provisos that starting materials (A), (B), and (C), and amounts of each, are sufficient to provide: i) a molar ratio of silicon bonded hydrogen atoms in starting material (C) to aliphatically unsaturated monovalent hydrocarbon groups R3 in starting materials (A) and/or (B) (SiH/Vi ratio) of > 0.2/1, ii) a molar ratio of silicon bonded hydrogen atoms in starting material (C) to reactive groups in starting materials (A) and/or (B) (SiH/reactive group ratio) of < 0.34, where the reactive groups are R2 and R3 combined; (D) a hydrosilylation reaction catalyst in an amount sufficient to provide 2 ppm to 500 ppm of platinum based on combined weights of starting materials (A), (B), and (C); 0.1 weight % to 10 weight %, based on combined weights of starting materials (A), (B), and (C), of (E) a photoradical initiator; 10 ppm to 5,000 ppm, based on combined weights of starting materials (A), (B), and (C), of (F) a hydrosilylation reaction inhibitor; 5 ppm to 2,000 ppm, based on combined weights of starting materials (A) and (B), of (G) a free radical scavenger; 0 to 90 weight %, based on combined amounts of all starting materials in the composition, of (H) a solvent; 0 to 5 weight % based on combined weights of starting materials (A) and (B), of (I) an additive selected from the group consisting of a sensitizer and a synergist; and 0 to 30 weight % based on combined weights of starting materials (A) and (B), of (J) filler selected from the group consisting of a fumed silica or participated silica. 2. The composition of claim 1, where (A) the polydiorganosiloxane comprises unit formula M”2DmD’n, a quantity (m + n) is 100 to 9,900, and a ratio m/n is 10/1 to 500/1. 3. The composition of claim 1 or claim 2, where (B) the polyorganosilicate resin comprises a unit formula selected from the group consisting of MaQh, MaM”bQh, MaM”bM”’cQh, MaM”’cQh, MaDdQh, MaD’eQh, MaM”bD’eQh, MaM”bT”’fQh, MaM”bT’”fQh, where subscript a,b and c is 20 to 70 mole %, subscript d and e is 1 to 20 mole %, subscript f is 1 to 25 mole %, and subscript h is 35 to 65 mole %. 4. The composition of any one of claims 1 to 3, where (C) the polyorganohydrogensiloxane crosslinker comprises unit formula MtMHuDvDHw, where a quantity (t + u) = 2, and a quantity (u + w) ≥ 3. 5. The composition of any one of claims 1 to 4, where Resin/Polymer Ratio is 0.2/1 to 3/1. 6. The composition of any one of claims 1 to 5, where (D) the hydrosilylation reaction catalyst is selected from the group consisting of: i) a platinum group metal, ii) a compound of said metal, iii) a complex of said metal or said compound, v) the complex microencapsulated in a matrix or coreshell type structure. 7. The composition of any one of claims 1 to 6, where (E) the photoradical initiator is selected from the group consisting of benzophenone, a substituted benzophenone compound, acetophenone, a substituted acetophenone compound, benzoin, an alkyl ester of benzoin, xanthone, and a substituted xanthone. 8. The composition of any one of claims 1 to 7, where (F) the hydrosilylation reaction inhibitor is present and is selected from the group consisting of acetylenic alcohols, cycloalkenylsiloxanes, ene-yne compounds, triazoles, phosphines, mercaptans, hydrazines, amines, fumarates, maleates, nitriles, ethers, carbon monoxide, alcohols, and silylated acetylenic alcohols. 9. The composition of any one of claims 1 to 8, where the free radical scavenger is present and is selected from the group consisting of a phenolic compound, phenothiazine and an anaerobic inhibitor. 10. The composition of any one of claims 1 to 9, where (H) the solvent is present and is selected from the group consisting of an aliphatic hydrocarbon and an aromatic hydrocarbon. 11. A method for preparing an adhesive article comprising a pressure sensitive adhesive layer on a surface of a substrate, the method comprising: optionally 1) treating the surface of the substrate; 2) coating the silicone hybrid pressure sensitive adhesive composition of any one of claims 1 to 39 on the surface, optionally 3) removing all or a portion of (H) the solvent, if present, 4) heating the silicone hybrid pressure sensitive adhesive composition to form a silicone hybrid pressure sensitive adhesive layer on the surface of the substrate. 12. The method of claim 11, further comprising; 5) applying the adhesive article to an uneven surface such that the silicone hybrid pressure sensitive adhesive layer contacts the uneven surface opposite the substrate, optionally 6) applying heat and/or pressure to the adhesive article and the uneven surface, and 7) exposing the silicone hybrid pressure sensitive adhesive layer to UV radiation; thereby conforming the silicone hybrid pressure sensitive adhesive layer to the uneven surface 13. The method of claim 11 or claim 12, where the uneven surface is all or a portion of a ball grid array. 14. The composition of any one of claims 1 to 9, where in (B) the polyorganosilicate resin, the maximum value of subscript f is sufficient ot provide 30 mole % of T”’ units to the resin and the value of subscript h is sufficient to provide 30 mole % to 60 mole % of Q units to the resin. 15. The composition of claim 1 or claim 2, where where (B) the polyorganosilicate resin comprises a unit formula selected from the group consisting of MaQh, MaM”bQh, MaM”bM”’cQh, MaM”’cQh, MaDdQh, MaD’eQh, MaM”bD’eQh, MaM”bT”’fQh, MaM”bT’”fQh, where subscript a is 20 to 65 mole %, subscript b and c is 1 to 30 mole %, subscript d and e is 1 to 20 mole %, subscript f is 1 to 25 mole %, and subscript h is 35 to 55 mole %. |
[0067] Starting materials branded DOWSIL™ are commercially available from Dow Silicones Corporation and/or its subsidiaries. [0068] In this Reference Example 1, a bis-vinyl-terminated poly(dimethyl/methyl,methacryloxypropyl)siloxane copolymer shown as Starting Material A-1 in Table 1, above, was synthesized as follows. To a 4-neck 1 liter round bottom flask 3-methacryloxypropyl methyl dimethoxysilane (120.00 g, DOWSIL™ Z-6033) and 0.1N HCl (128.87 g) were added and mixed using a magnetic stir bar at ~23℃. Using a simple distillation glassware setup vacuum was pulled to ~20 mmHg for 1.5 hours. After 1.5 hours the vacuum was released and bis-hydroxy-terminated polydimethylsiloxane (786.50 g, OH Fluid) along with 0.23 g of (G-1) MEHQ were added to the reaction solution. The magnetic stir bar was removed and a Teflon paddle with a glass stir rod was used to mix the solution. Vacuum was pulled to ~5 mmHg and the reaction was heated to 80℃ for 1.5 hours. The simple distillation glassware setup was dissembled, and a Dean Stark distillation setup was used for the last reaction step. To the reaction solution, (H-1) toluene (380 g, Sigma-Aldrich) and bis-dimethylvinylsiloxy-terminated polydimethylsiloxane (2.87 g, End-blocker) were added. The solution was then heated to 111-115℃, with 0.3 mL of phosphazene catalyst being added at 90℃. The overheads were collected in the Dean Stark trap and an additional 0.3 mL of phosphazene catalyst was added. The solution was held at toluene reflux for 1 hour. The heat was removed, and the solution was cooled. At ~60℃, trihexylamine (0.3 g, Sigma Aldrich) was added to the reaction solution and mixed for 2 hours. And, the solution was heated to 120°C with nitrogen/2% oxygen gas bubbling for 1 hours and cooled to RT. The solid content of the solution was adjusted to 75% by adding additional toluene. Then, the product dissolved in toluene was obtained. Based on 13 C- and 29 Si-NMR analysis, the obtained bis-vinyldimethylsiloxy-terminated poly(dimethyl/methyl,methacryloxypropyl)siloxane copolymer comprised the following unit formula: (R 4 3 SiO 1/2 ) 0.00071 (R4 2 SiO 2/2 ) 0.99929 ; where each R4 was independently selected from methyl, methacryloxypropyl, and vinyl; and the subscripts represent mole fractions. The methacryl content was 2.406 mole % of total R 4 , the vinyl content was 0.012 mole % of total R 4 , and the methyl content was 97.582 mole% of total R 4 . The (m+o)/n ratio is 20/1. [Methacryl Content = 0.604 mmol/g, Vi Content = 0.009 mmol/g, Total Reactive group = 0.613 mmol/g]. The obtained bis-vinyldimethylsiloxy-terminated poly(dimethyl/methyl,methacryloxypropyl)siloxane copolymer can also be expressed as unit formula: (ViMe 2 SiO) 2 (MaMeSiO) 136 (Me 2 SiO) 2679 . [0069] In this Reference Example 2, a bis-vinyl-terminated poly(dimethyl/methyl,methacryloxypropyl)siloxane copolymer shown as Starting Material A-2 in Table 1, above, was synthesized as follows. To a 4-neck 1 liter round bottom flask 3-methacryloxypropyl methyl dimethoxysilane (50.78 g, DOWSIL™ Z-6033) and 0.1N HCl (45.45 g) were added and mixed using a magnetic stir bar at ~23℃. Using a simple distillation glassware setup vacuum was pulled to ~20 mmHg for 1.5 hours. After 1.5 hours the vacuum was released and bis-hydroxyl-terminated polydimethylsiloxane (550.00 g, OH FLUID) along with 0.16 g of (G-1) MEHQ were added to the reaction solution. The magnetic stir bar was removed and a Teflon paddle with a glass stir rod was used to mix the solution. Vacuum was pulled to ~5 mmHg and the reaction was heated to 80℃ for 1.5 hours. The simple distillation glassware setup was dissembled, and a Dean Stark distillation setup was used for the last reaction step. To the reaction solution, (H-1) toluene (300 g, Sigma-Aldrich) and bis-dimethylvinylsiloxy-terminated polydimethylsiloxane (2 g, End-blocker) were added. The solution was then heated to 111-115℃, with 0.4 mL of phosphazene catalyst being added at 90℃. The overheads were collected in the Dean Stark trap and an additional 0.4 mL of phosphazene catalyst was added. The solution was held at toluene reflux for 1 hour. The heat was removed, and the solution was cooled. At ~60℃, DVTMDZ (1 g, Sigma Aldrich) was added to the reaction solution and mixed for 2 hours. And, the solution was heated to 120°C with nitrogen/2% oxygen gas bubbling for 1 hours and cooled to RT with gas bubbling. The solid content of the solution (which was measured the weight before and after drying 150°C for 1 hour) was adjusted to 75% by adding additional toluene. Then, the product dissolved in toluene was obtained. Based on 13 C- and 29 Si-NMR analysis, the obtained bis-dimethylvinylsiloxy-terminated poly(dimethyl/methyl,methacryloxypropyl)siloxane copolymer comprised the following average unit formula: (R4 3 SiO 1/2 ) 0.00091 (R4 2 SiO 2/2 ) 0.99909 ; where each R4 was independently selected from methyl, methacryloxypropyl, and vinyl; and the subscripts represented mole fractions. The methacryl content was 1.325 mole % of total R 4 , the vinyl content was 0.015 mole % of total R 4 , and the methyl content was 98.660 mole% of total R 4 . The (m+o)/n ratio is 37/1. [Methacryl Content = 0.343 mmol/g, Vi Content = 0.012, total reactive group = 0.355]. Alternatively, the obtained bis-dimethylvinylsiloxy- terminated poly(dimethyl/methyl,methacryloxypropyl)siloxane copolymer could be shown with the average unit formula (ViMe 2 SiO) 2 (MaMeSiO) 58 (Me 2 SiO) 2130 . [0070] In this Reference Example 3, a bis-vinyldimethylsiloxy-terminated poly(dimethyl/methyl,methacryloxypropyl)siloxane copolymer shown as Starting Material A-3 in Table 1, above, was synthesized as follows. To a 4-neck 1 liter round bottom flask 3-methacryloxypropyl methyl dimethoxysilane (33.3 g, DOWSIL™ Z-6033) and 0.1N HCl (45.45 g) were added and mixed using a magnetic stir bar at room temperature (~23℃). Using a simple distillation glassware setup vacuum was pulled to ~20 mmHg for 1.5 hours. After 1.5 hours the vacuum was released and dimethyl siloxane, silanol terminated (600.00 g, OH FLUID) along with 0.23 g of (G-1) MEHQ were added to the reaction solution. The magnetic stir bar was removed and a Teflon paddle with a glass stir rod was used to mix the solution. Vacuum was pulled to ~5 mmHg and the reaction was heated to 80℃ for 1.5 hours. The simple distillation glassware setup was dissembled, and a Dean Stark distillation setup was used for the last reaction step. To the reaction solution, (H-1) toluene (300 g, Sigma-Aldrich) and bis-dimethylvinylsiloxy- terminated polydimethylsiloxane (2.2 g, End-blocker) were added. The solution was then heated to 111- 115℃, with 0.4 mL of phosphazene catalyst being added at 90℃. The overheads were collected in the Dean Stark trap and an additional 0.4 mL of phosphazene catalyst was added. The solution was held at toluene reflux for 1 hour. The heat was removed, and the solution was cooled. At ~60℃, DVTMDZ (1 g, Sigma Aldrich) was added to the reaction solution and mixed for 2 hours. And, the solution was heated to 120°C with nitrogen/2% oxygen gas bubbling for 1 hours and cooled to RT with gas bubbling. The solid content of the solution was adjusted to 75% by adding additional toluene. Then, the product dissolved in toluene was obtained. Based on 13 C- and 29 Si-NMR analysis, the obtained bis-vinyldimethylsiloxy- terminated poly(dimethyl/methyl,methacryloxypropyl)siloxane copolymer comprised the following average unit formula: (R4 3 SiO 1/2 ) 0.00035 (R4 2 SiO 2/2 ) 0.99965 ; where each R4 was independently selected from methyl, methacryloxypropyl, and vinyl; and the subscripts represent mole fractions. The methacryl content was 0.876 mole % of total R 4 , the vinyl content was 0.006 mole % of total R 4 , and the methyl content was 99.1187 mole% of total R 4 . The (m+o)/n ratio is 56/1. [Methacryl Content = 0.230 mmol/g, Vi Content = 0.005 mmol/g, Total Reactive group = 0.235 mmol/g]. Alternatively, the obtained a bis- vinyldimethylsiloxy-terminated poly(dimethyl/methyl,methacryloxypropyl)siloxane copolymer could be shown as: (ViMe 2 SiO) 2 (MaMeSiO) 100 (Me 2 SiO) 5610 . [0071] In this Reference Example 4, a bis-vinyl-terminated poly(dimethyl/methyl,methacryloxypropyl)siloxane copolymer shown as Starting Material A-4 in Table 1, above, was synthesized as follows. To a 4-neck 1 liter round bottom flask 3-methacryloxypropyl methyl dimethoxysilane (13.7 g, DOWSIL™ Z-6033) and 0.1N HCl (24.37 g) were added and mixed using a magnetic stir bar at ~23℃. Using a simple distillation glassware setup vacuum was pulled to ~20 mmHg for 1.5 hours. After 1.5 hours the vacuum was released and bis-hydroxyl-terminated polydimethylsiloxane (1179.49 g, OH FLUID) along with 0.34 g of (G-1) MEHQ were added to the reaction solution. The magnetic stir bar was removed and a Teflon paddle with a glass stir rod was used to mix the solution. Vacuum was pulled to ~5 mmHg and the reaction was heated to 80℃ for 1.5 hours. The simple distillation glassware setup was dissembled, and a Dean Stark distillation setup was used for the last reaction step. To the reaction solution, (H-1) toluene (550 g, Sigma-Aldrich) and bis-dimethylvinylsiloxy-terminated polydimethylsiloxane (2.2 g, End-blocker) were added. The solution was then heated to 111-115℃, with 0.1 mL of phosphazene catalyst being added at 90℃. The overheads were collected in the Dean Stark trap and an additional 0.1 mL of phosphazene catalyst was added. The solution was held at toluene reflux for 1 hour. The heat was removed, and the solution was cooled. At ~60℃, DVTMDZ (0.3 g, Sigma Aldrich) was added to the reaction solution and mixed for 2 hours. And, the solution was heated to 120°C with nitrogen/2% oxygen gas bubbling for 1 hour and cooled to RT. The solid content of the solution was adjusted to 75% by adding additional toluene. Then, the product dissolved in toluene was obtained. Based on 13 C- and 29 Si-NMR analysis, the obtained bis-vinyldimethylsiloxy-terminated poly(dimethyl/methyl,methacryloxypropyl)siloxane copolymer comprised the following average unit formula: (R4 3 SiO 1/2 ) 0.00074 (R4 2 SiO 2/2 ) 0.99926 ; where each R4 was independently selected from methyl, methacryloxypropyl, and vinyl; and the subscripts represented mole fractions. The methacryl content was 0.192 mole % of total R 4 , the vinyl content was 0.012 mole % of total R 4 , and the methyl content was 99.796 mole% of total R 4 . The (m+o)/n ratio is 260/1. [Methacryl Content = 0.051 mmol/g, Vi Content = 0.010 mmol/g, Total Reactive group = 0.061 mmol/g]. Alternatively, the obtained bis- vinyldimethylsiloxy-terminated poly(dimethyl/methyl,methacryloxypropyl)siloxane copolymer could be shown as (ViMe 2 SiO) 2 ViMe 2 SiO(MaMeSiO) 10 (Me 2 SiO) 2679 . [0072] In this Reference Example 5, a bis-vinyldimethylsiloxy-terminated poly(dimethyl/methyl,methacryloxypropyl)siloxane copolymer shown as Starting Material A-5 in Table 1, above, was synthesized as follows. To a 4-neck 1 liter round bottom flask 3-methacryloxypropyl methyl dimethoxysilane (4.5 g, DOWSIL™ Z-6033) and 0.1N HCl (4.55 g) were added and mixed using a magnetic stir bar at room temperature (~23℃). Using a simple distillation glassware setup vacuum was pulled to ~20 mmHg for 1.5 hours. After 1.5 hours the vacuum was released and dimethyl siloxane, silanol terminated (786.5 g, OH FLUID) along with 0.23 g of (G-1) MEHQ were added to the reaction solution. The magnetic stir bar was removed and a Teflon paddle with a glass stir rod was used to mix the solution. Vacuum was pulled to ~5 mmHg and the reaction was heated to 80℃ for 1.5 hours. The simple distillation glassware setup was dissembled, and a Dean Stark distillation setup was used for the last reaction step. To the reaction solution, (H-1) toluene (450 g, Sigma-Aldrich) and bis-dimethylvinylsiloxy- terminated polydimethylsiloxane (5 g, End-blocker) were added. The solution was then heated to 111- 115℃, with 0.1 mL of phosphazene catalyst being added at 90℃. The overheads were collected in the Dean Stark trap and an additional 0.1 mL of phosphazene catalyst was added. The solution was held at toluene reflux for 1 hour. There was ~80 g of overheads collected. The heat was removed, and the solution was cooled. At ~60℃, DVTMDZ (0.3 g, Sigma Aldrich) was added to the reaction solution and mixed for 2 hours. The solid content of the solution was adjusted to 75% by adding additional toluene. Then, the product dissolved in toluene was obtained. Based on 13 C- and 29 Si-NMR analysis, the obtained bis-vinyldimethylsiloxy-terminated poly(dimethyl/methyl,methacryloxypropyl)siloxane copolymer comprised the following average unit formula: (R4 3 SiO 1/2 ) 0.00074 (R4 2 SiO 2/2 ) 0.99926 , where each R4 was independently selected from methyl, methacryloxypropyl, and vinyl, and the subscripts represented mole fractions. The methacryl content was 0.097 mole % of total R 4 , the vinyl content was 0.022 mole % of total R 4 , and the methyl content was 99.881 mole% of total R 4 . The (m+o)/n ratio is 512/1. [Methacryl Content = 0.025 mmol/g, Vi Content = 0.017 mmol/g, Total Reactive group = 0.043 mmol/g] The obtained bis-vinyldimethylsiloxy-terminated poly(dimethyl/methyl,methacryloxypropyl)siloxane copolymer can also be expressed as unit formula: (ViMe 2 SiO) 2 (MaMeSiO) 3 (Me 2 SiO) 1536 . [0073] In this Reference Example 6, a bis-vinyldimethylsiloxy-terminated poly(dimethyl/methyl,methacryloxypropyl)siloxane copolymer shown as Starting Material A-6 in Table 1, above, was synthesized as follows.900 g of dimethyl siloxane, silanol terminated (786.5 g, OH FLUID) ,63 g of 3-methacryloxypropylmethyldimethoxysilane (DOWIL™ Z-6033), 6.3 of hexamethyldisiloxane, and 180 g of heptane were charged into a 4-neck 2 L flask equipped with a thermal couple, a mechanical stirrer, a Dean Stark adapted to water cooled condenser and air bubbler. With vigorous stirring, 0.53 ml triflic acid (Sigma-Aldrich) was added into the flask. Heat was applied, and the pot temperature rose to 73°C. Water, methanol, and heptane began` to distill out and collected in the Dean Stark. The refluxing temperature gradually rose to 90°C after ~1 hour.3 g of water was added into the flask and continue the azeotropic distillation process.30 minutes later, the pot temperature rose to ~90°C and another 2.5 g of water was added into the flask. The refluxing temperature rose to 96°C after 1 hour and 40 minutes. During the above process, water/methanol collected in the Dean Stark was drained out. Heat source was removed and 36 g of Kyowaad™ 500SN (Kytowa Chemical Industry Co,, Ltd) were added into the flask. The pot temperature was cooled down to RT. Solids were filtered out through a 0.45µm filter membrane after stirred for 3 hours. The filtrate was rotovaped at 110°C and < 1 torr for 1 hour. Then, the product was obtained. Based on 13 C- and 29 Si-NMR analysis, the obtained bis-vinyldimethylsiloxy-terminated poly(dimethyl/methyl,methacryloxypropyl)siloxane copolymer comprised the following average unit formula: (R4 3 SiO 1/2 ) 0.00689 (R4 2 SiO 2/2 ) 0.99311 , where each R4 was independently selected from methyl, methacryloxypropyl, and vinyl, and the subscripts represented mole fractions. The methacryl content was 1.383 mole % of total R 4 , the vinyl content was 0.115 mole % of total R 4 , and the methyl content was 98.502 mole% of total R 4 . The (m+o)/n ratio is 35/1. [Methacryl Content = 0.355 mmol/g, Vi Content = 0.089 mmol/g, Total Reactive group = 0.443 mmol/g] The obtained bis-vinyldimethylsiloxy- terminated poly(dimethyl/methyl,methacryloxypropyl)siloxane copolymer can also be expressed as unit f ormula: (ViMe 2 SiO) 2 (MaMeSiO) 8 (Me 2 SiO) 280 . [0074] In this Reference Example 7, a bis-vinyldimethylsiloxy-terminated poly(dimethyl/methyl,methacryloxypropyl)siloxane copolymer shown as Starting Material A-7 in Table 1, above, was synthesized as follows. To a 4-neck 1 liter round bottom flask 3-methacryloxypropyl methyl dimethoxysilane (30 g, DOWSIL™ Z-6033), dimethyl, methylvinyl siloxane, sianol termeidated (9.5 g, ME2/MeVi Diol) and 0.1N HCl (4.55 g) were added and mixed using a magnetic stir bar at room temperature (~23℃). Using a simple distillation glassware setup vacuum was pulled to ~20 mmHg for 1.5 hours. After 1.5 hours the vacuum was released and dimethyl siloxane, silanol terminated (300 g, OH FLUID) along with 0.03 g of (G-1) MEHQ were added to the reaction solution. The magnetic stir bar was removed and a Teflon paddle with a glass stir rod was used to mix the solution. Vacuum was pulled to ~5 mmHg and the reaction was heated to 80℃ for 1.5 hours. The simple distillation glassware setup was dissembled, and a Dean Stark distillation setup was used for the last reaction step. To the reaction solution, (H-1) toluene (200 g, Sigma-Aldrich). The solution was then heated to 111-115℃, with 0.1 mL of phosphazene catalyst being added at 90℃. The overheads were collected in the Dean Stark trap and an additional 0.1 mL of phosphazene catalyst was added. The solution was held at toluene reflux for 1 hour. There was ~80 g of overheads collected. The heat was removed, and the solution was cooled. At <50℃, HMDZ (1.31 g, Sigma Aldrich) was added to the reaction solution and mixed for 1 hours. Water was added and mixed for 30 min. and then the temperature was elevated to 110⁰C to remove water, volaille residuals and ammonia gas for 1 hours. The solid content of the solution was adjusted to 40%. Then, the product dissolved in toluene was obtained. Based on 13 C- and 29 Si-NMR analysis, the obtained bis- trimethylsiloxy-terminated poly(dimethyl/methyl,vinyl/methyl,methacryloxypropyl)siloxan e copolymer comprised the following average unit formula: (R4 3 SiO 1/2 ) 0.00004 (R4 2 SiO 2/2 ) 0.99916 , where each R4 was independently selected from methyl, methacryloxypropyl, and vinyl, and the subscripts represented mole fractions. The methacryl content was 1.55 mole % of total R 4 , the vinyl content was 0.4 mole % of total R 4 , and the methyl content was 98.05 mole% of total R 4 . The (m+o)/n ratio is 31/1. [Methacryl Content = 0.339 mmol/g, Vi Content = 0.106 mmol/g, Total Reactive group = 0.505 mmol/g] The obtained bis-vinyldimethylsiloxy-terminated poly(dimethyl/methyl,vinyl/methyl,methacryloxypropyl)siloxan e copolymer can also be expressed as unit formula: (Me 3 SiO) 2 (MaMeSiO) 155 (ViMeSiO) 40 (Me 2 SiO) 4795 . [0075] In this Reference Example 8, a both methacryloxy and vinyl-functional polyorganosilicate resin shown as Starting Material B-1 in Table 4, was synthesized as follow. The following starting materials were charged into a 3-neck 2 L flask equipped with a thermal couple, a mechanical stirrer, a Dean Stark adapted to water cooled condenser and N 2 bubbler: 742.2 g of 75% of (B-3) dimethylvinylated and trimethylated silica (Mn = 4830, Mw = 5030) in xylene, 39.5 g of 3- methacryloxypropylmethyldimethoxysilane, 0.20 g of 4-methoxyphenol, and 120 g of toluene. With vigorous stirring, 1.2 g of trifluoromethane sulfonic acid (from Sigma-Aldrich) was slowly added, and heated to 60°C. After 1 hours.9.18 g of water was added and stirred for 2 hours. The refluxing temperature gradually rose to 90°C after 1 hour to collect methanol. The refluxing temperature gradually rose to 127°C. During the above process, water/methanol collected in the Dean Stark was drained out. After no water was distilled out, the flask contents were additionally refluxed for 2 hours with maintaining the temperature. Thereafter, the heat source was removed, and 22.8 g of calcium carbonate (from Sigma-Aldrich) and 50 g of sodium sulfate (from Sigma-Aldrich) were added into the flask. The flask was cooled down to RT. Solids were filtered out through a 0.45 µm filter membrane after stirring for 3 hours. The resulting methacryloxy-functional polyorganosilicate resin was a liquid in solvent (xylene and toluene) (Solid contents = 68.4%). The methacryloxy-functional polyorganosilicate resin was represented by the following average formula:(Me 3 SiO 1/2 ) 0.40 (ViMe 2 SiO 1/2 ) 0.039 (MaMeSiO 2/2 ) 0.024 (SiO 4/2 ) 0.537 (OH) 0.01 , with Methacryl Content = 1.79 mol% of total R 4 ; Vinyl Content = 2.86 mol% of total R 4 ; Methyl content = 95.36 mole% of total R 4 [Methacryl Content = 0.332 mmol/g, Vi Content = 0.532 mmol/g, Total Reactive group = 0.864 mmol/g] [0076] In this Reference Example 9, a methacryloxy-functional polyorganosilicate resin shown as Starting Material B-4 in Table 4, was synthesized as follow. The following starting materials were charged into a 3-neck 2 L flask equipped with a thermal couple, a mechanical stirrer, a Dean Stark adapted to water cooled condenser and N 2 bubbler: 450.37 g of 75% of (B-2) trimethylated silica (Mn = 3065, Mw = 5664) in xylene, 55.76 g of 3-methacryloxypropylmethyldimethoxysilane, 0.13 g of (G-1) MEHQ, and 120 g of toluene. With vigorous stirring, 0.6 g of triflic acid (Sigma-Aldrich) was slowly added, and heated to 60°C. After 1 hours.9 g of water was added and stirred for 1 hours at RT. Then, 60 g of methanol and 1.73 g of 11N KOH were added subsequently. The temperature gradually rose to 90°C after 1 hour to collect methanol. The refluxing temperature gradually rose to 115°C. During the above process, water/methanol collected in the Dean Stark was drained out. After no water was distilled out, the flask contents were additionally refluxed for 1 hours with maintaining the temperature. Thereafter, the heat source was removed, and 0.94 g of acetic acid (Sigma-Aldrich) were added into the flask. The flask was cooled down to RT. Solids were filtered out through a 0.45 µm filter membrane after stirring for 3 hours. The resulting methacryloxy-functional polyorganosilicate resin was a liquid in solvent (xylene and toluene) (Solid contents = 68.2 %). The methacryloxy-functional polyorganosilicate resin was represented by the following average formula:(Me 3 SiO 1/2 ) 0.476 (MaMeSiO 2/2 ) 0.048 (SiO 4/2 ) 0.476 , with Methacryl Content = 3.13 mol% of total R 4 ; Methyl content = 96.88 mole% of total R 4 [Methacryl Content = 0.626 mmol/g, , Total Reactive group = 0.626 mmol/g] [0077] In this Reference Example 10, silicone hybrid pressure sensitive adhesive compositions and comparative compositions were made. Starting material (A) and (B) may be dissolved in solvents. The general procedure was as follows: For preparing the sample labelled Inv.1, a solution was prepared by mixing the following starting materials in a mixer: 133.33 g of the 100 g of starting material (A-1) dissolved in toluene (H-1) with ~ 300 ppm of (G-1); 140 g of the 95.76 g of the staring material (B-3) dissolved in solvents; 10.8 g of polyorganohydrogensiloxane (C-2); 8.3 g of photoradical initiator (E-1); 0.2 g of hydrosilylation reaction inhibitor (F-1). After mixing of above starting materials, the obtained solution was further mixed with 0.3 g of hydrosilylation reaction catalyst (D-1). Mixing of the above starting materials with the aforementioned solution produced a silicone hybrid pressure sensitive adhesive composition. The obtained composition was used for manufacturing an adhesive tape. The produced adhesive tape was evaluated with regard to the lamination property and adhesive force. Comparative examples and Inv. 2 – 25 were prepared in the same manner using the starting materials and amounts in the tables. For preparing the solventless sample labelled Inv.26, a solution was prepared by mixing the following starting materials in a mixer: 100 g of the starting material (A-6) with ~ 300 ppm of (G-1) and 458.21 g of the 312.5 g of the staring material (B-4), and xylene and toluene were evaporated under reduced pressure at 110°C. Then, 2.8 g of polyorganohydrogensiloxane (C-2); 6.2 g of photoradical initiator (E-1); 0.1 g of hydrosilylation reaction inhibitor (F-1) were added. After mixing of above starting materials, the obtained fluid was further mixed with 0.1 g of hydrosilylation reaction catalyst (D-1). Inv.27 – 29 were prepared in the same manner using the starting materials and amounts in the tables. Tables 2 – 5 show the starting materials (described in detail in Table 1) and their amounts [based on solids in grams and (solution in grams)] used. The values (solution in grams) indicate that the starting material was first dissolved in solvent, and represents the weight in grams of the solution. The values based on solids indicate the amount of the starting material excluding solvent. [0078] In this Reference Example 11, the silicone hybrid pressure sensitive adhesive compositions prepared according to Reference Example 9 were used to form silicone hybrid pressure sensitive adhesive tapes. Solvent-included composition (Comp.1 – 12, and Inv.1 – 25) was coated onto a polyethylene terephthalate (PET) film (50 µm), and then was dried by heating the coated film for 20 min at 110°C, followed by 4 min at 150°C to have 200 µm. On the dried surface, each composition was coated repeatedly, and then was dried by heating the coated film for 20 min at 110°C, followed by 6 min at 150°C. The silicone hybrid pressure sensitive adhesive layer had a total thickness after curing is 400 µm. Solvent-less composition (Inv.26 – 29) was coated onto a polyethylene terephthalate (PET) film (50 µm), and then was dried by heating the coated film for 20 min at 110°C, followed by 5 min at 150°C to have 400 µm. The obtained silicone hybrid pressure sensitive adhesive sheet was pasted onto a fluoro-coated polyethylene terephthalate film (release linear) by means of a laminator, and then the resulting product was aged for 1 day at room temperature. [0079] In this Reference Example 11, the silicone hybrid pressure sensitive adhesive tapes prepared according to Reference Example 10 were evaluated for adhesion on an uneven surface. Then, the obtained silicone hybrid pressure sensitive adhesive sheet was cut into 1-inch wide tape strips, which were placed on an uneven surface. A ball grid array (or BGA Package) with a substrate size= 27 mm X 27 mm X 2.46 mm, having 320-pin (ball) array on the surface; ball diameter = 0.75 mm, ball height = 0.35 mm, center pitch =1.27 mm, supplied from Fujitsu Semiconductor Limited, Product name: BGA-320P- M06, was used as the uneven surface. The tape strips were bonded to the BGA packages using a laminator at the condition of RT for 30 minutes or 90˚C for 30 minutes. The pressure of 0.5 MPa was applied on the laminate under vacuum at <1 torr (Vacuum Laminator purchased from Shindo Eng. Lab. Ltd.). After pulling out the laminate from the chamber, it was transferred to UV curing machine, and were then UV irradiated from the top of base film. The light source was 365 nm LED (FireJet™ FJ100). Power = 0.6 mW, Time = 30 seconds. Finally, visual inspection by microscope was conducted to check whether the silicone hybrid pressure sensitive adhesive tape was well-laminated, without delamination and/or voids. Visual inspection results are shown in Tables 2-4, below. A value of ‘A’ means the sample had no delamination and no voids. A value of ‘B’ means the sample had partial delamination and/or a void. A value of ‘C’ means the sample completely delaminated. [0080] In this Reference Example 12, the silicone hybrid pressure sensitive adhesive tapes prepared according to Reference Example 10, were evaluated for adhesion to an even surface. Each silicone hybrid pressure sensitive adhesive tape was placed on a stainless steel (SUS) plate and bonded thereto by moving a rubber-lined pressure roller of 2 kg weight on the strip twice back and forth. The assembly was held at RT temperature for 1 hour. The tape was then irradiated with UV from the top of the base film. The light source was 365 nm LED (FireJet™ FJ100). Power = 0.6 mW, time = 30 seconds. Finally, the adhesion force (g/inch) required to peel the tape off from the stainless steel plate by pulling at a speed of 300 mm/min and an angle of 180˚ was measured and recorded below in Tables 2 – 5. All recorded adhesion force in Table 2 – 5 were values when “Adhesive Failure” occurred. “Adhesion Failure” indicates the pressure sensitive adhesive on the base film was removed from the steel plate without adhesive residuals. “Fail to measure” means the pressure sensitive adhesive was torn or left on both fluoro-coated film (release linear) and base film when removing (stripping) from fluoro-coated film due to insufficient crosslinking, prepared in Reference Example 10. “Cohesive Failure” indicates that pressure sensitive adhesive was left on both base film and stainless steel plate (or adherend) after removing the tape. [0081] In this Reference Example 13, the silicone hybrid pressure sensitive adhesive tapes prepared according to Reference Example 10, were evaluated for adhesion change to an even surface at three different condition; before/after UV radiation, and after UV radiation followed by thermal treatment. Each silicone hybrid pressure sensitive adhesive tape was placed on a stainless steel (SUS) plate and bonded thereto by moving a rubber-lined pressure roller of 2 kg weight on the strip twice back and forth. The assembly was held at RT temperature for 1 hour. Then, the adhesion force (g/inch) required to peel the tale off from the stainless steel plate by at a speed of 300 mm/min and an angle of 180˚ were measured at three different condition; 1) the adhesion force before UV radiation, 2) the adhesion force after UV radiation (The light source was 365 nm LED (FireJet™ FJ100). Power = 0.6 mW, time = 30 seconds.), 3) the adhesion force after UV radiation, followed by exposed to 125ºC for 1 hours at a convection oven, and cooled to RT. All recorded adhesion force in Table 7 were values when “Adhesive Failure” occurred. [0082] Tables 2 - 5 show the starting materials (described in detail above) and their amounts (in grams) used, as well as the test results after laminating onto uneven surfaces as described in Reference Example 9. The tables also show adhesion to an even, stainless steel (SUS) surface after UV irradiation cure as described in Reference Example 10.
Table 2 – Comparative Examples 1 – 11 (Comp.1 – Comp.11) Table 3 – Comparative Examples 12 (Comp.12) & Working Examples 1 – 8 (Inv.1 to Inv.8) Table 4 –Working Examples 9 – 16 (Inv.9 to Inv.16) Table 5 –Working Examples 17 – 23 (Inv.17 to Inv.23) Table 6 – Adhesion Force Change of Comparative Examples 2 and 4 and Working Examples 1,9,18, 20, and 21. Initial Adhesion (g/in), before UV irradiation
80.8 19.4 54.0 64.9 22.2 88.0 28.4
Subsequent Adhesion (g/in), after UV irradiation
81.0 19.5 11.6 6.7 3.1 4.4 11.3
Subsequent Adhesion (g/in), after UV irradiation and heat treatment (125 °C, 1 hrs)
201.0 319.5 13.0 20.9 12.2 27.3 26.3
[0083] Comparative Examples 1 – 5 show the effect of not using any (meth)acryloxyalkyl functional siloxanes in pressure sensitive adhesive compositions. Comparative examples 1, 2, 4, and 5 failed to adhere to the uneven surface or had voids. Comparative example 3 showed that the pressure sensitive adhesive failed to have sufficient crosslink density as shown by the cohesive failure on the stainless steel (even) surface although it was laminated without voids; cohesive failure indicated that pressure sensitive adhesive was torn and left behind on the surface after removing the tape. [0084] Comparative Examples 6 and 9 showed that when SiH/Vi ratio were too low (<0.2), then the sample failed to measure adhesion force because inadequate crosslinking on base film caused pressure sensitive adhesive to be flowable or torn when removing fluoro-coated film, prepared in Reference Example 10. Comparative Examples 7, 8, 10, and 11 showed that when SiH/Reactive Group ratio were too high (>0.34), the sample failed to adhere to the uneven surface or had voids. Working Example 1 and 2 (which contained the same starting materials as Comparative Example 6 and 7), with different SiH/Vi ratio, SiH/Reactive Group ratio showed that when SiH/Vi ratio was 0.845 and 0.554, SiH/Reactive Group ratio was 0.331 and 0.217, a silicone hybrid pressure sensitive adhesive laminated without voids to an uneven surface could be prepared by lamination at 90˚C for 30 minutes and then irradiating with UV under the conditions described in Reference Example 11. After UV irradiation, further crosslinking reaction occurred, adhesion force could be measured without cohesive failure, which is a contrasting behavior with Comparative Example 3. Working Examples 1 and 2 showed re-workable property without remaining residuals on the surface after UV irradiation. [0085] Comparative Example 8 showed that when SiH/Reactive Group ratio was 0.423 (>0.34), the sample failed to adhere to the uneven surface or had voids. In contrast, Working Example 3 and 4 with the same starting materials when SiH/Reactive Group ratio was 0.317 and 0.183, respectively, a silicone hybrid pressure sensitive adhesive laminated without voids to an uneven surface could be prepared by lamination at 90˚C for 30 minutes and then irradiating with UV under the conditions described in Reference Example 11. Working Example 4 when lower SiH/Reactive Group than Working Example 3, the sample was laminated without void at RT without heating for 30 minutes, and then irradiation with UV. After UV radiation, further crosslinking reaction occurred, adhesion force could be measured without cohesive failure. [0086] Comparative Example 10 and 11 showed that when SiH/Reactive Group ratio was 0.401 and 0.604, respectively, the samples failed to adhere to the uneven surface or had voids. In contrast, Working Example 5 to 11 with the same starting materials when SiH/Reactive Group ratio was 0.110 to 0.279, a silicone hybrid pressure sensitive adhesive laminated without voids to an uneven surface could be prepared by lamination at 90˚C for 30 minutes and then irradiating with UV under the conditions described in Reference Example 11. Moreover, Working Example 14 to 20 with the different crosslinker (C-2) when SiH/Vi ratio was 0.331 and 0.597, SiH/Reactive Group Ratio was 0.176 and 0.262, a silicone hybrid pressure sensitive adhesive laminated without voids to an uneven surface could be prepared by lamination at 90˚C for 30 minutes and then irradiating with UV under the conditions described in Reference Example 9. [0087] Working Examples 2, 4, 6, 8-12, and 17-20 showed that when SiH/Reactive Group was 0.111 to 0.223, the samples were successfully laminated on an uneven surface at RT without heating. Working Examples 1, 3, 5, 7, 14-16 had a slightly higher crosslinking density when SiH/Reactive Group 0.25 to 0.40 showed that applying heating during lamination, for example 90 ˚C, helped to laminate on an uneven surface without voids. [0088] Working Examples 19, 21, and 22 showed when SiH/Vi ratio was 0.241 to 0.331, SiH/Reactive Group ratio was 0.176 to 0.216, the sample laminated on an uneven surface without voids. However, Comparative Example 12 using the starting material (A-5) when (m+o)/n Ratio was 521/1 showed cohesive failure even after UV irradiation, which indicated sufficient further crosslinking did not occur by UV irradiation under the conditions tested. Meanwhile, Working Examples 19, 21, and 22 using the starting material (A-2 to A-5) having (m+o)/n Ratio = 37/1 to 260/1 showed ‘adhesion failure’ without remaining residuals on the surface after UV irradiation. [0089] Optional starting materials such as (I) the additive and (J) the filler, which did not influence crosslinking density when preparing silicone hybrid pressure sensitive adhesive layers, can be used for needs of industrial field, as shown in Working Example 23 to 25. [0090] Without wishing to be bound by theory, it is thought that to laminate on an uneven surface, SiH/Vi ratio and SiH/Reactive Group representing a degree of crosslinking density control regardless of Resin/Polymer Ratio because Resin/Polymer Ratio itself does not influence crosslinking density. It is further thought that as the factor of Resin/Polymer Ratio is mainly related with adhesion property, adhesion force can be modified with maintaining lamination performance. For example, Working Examples Inv.5, 13, and 26 when Resin/Polymer Ratio was 2.41 to 3.13 showed relatively higher adhesion and good lamination without voids, which demonstrates that the silicone hybrid pressure sensitive adhesive composition is also useful in the application field requiring high adhesion for long-term protection of surface of electronic device. For some samples, heating during lamination helped to laminate onto an uneven surface as shown by Inv.7 and Inv.13. [0091] Table 6 demonstrated the other advantageous of silicone hybrid pressure sensitive adhesive for use in processing film. As conventional pressure sensitive adhesive according to Comp.2 and Comp.4 showed almost no change before and after UV irradiation. Especially, when exposed to high temperature such as 125ºC, adhesion force highly increased, which meant that adhesion stability was poor and it would be difficult to detach from (opto)electric device after processing. As Working Example 9, 18, 20, 21 are shown in Table 6, adhesion force was reduced after UV irradiation and maintain low level of adhesion force even after exposed to high temperature. Industrial Applicability [0092] The silicone hybrid pressure sensitive adhesive composition described herein can cure to form a silicone hybrid pressure sensitive adhesive. One purpose herein is to provide a reactive, deformable silicone hybrid pressure sensitive adhesive curable via hydrosilylation to a B-staged cure, e.g., that is non-flowable and deformable by pressure at room temperature or elevated temperature, and that can be formed into a desired shape, and that can be further cured by light irradiation, such as an ultraviolet (UV) ray (C-staged cure), while its shape is maintained. An additional purpose is to provide control of adhesion strength in accordance with each application field requiring easy to peel off or permanent bonding after UV irradiation. And, the silicone hybrid pressure sensitive adhesive may also be useful for protection of certain area of complex electronic parts during device processing by conforming on an uneven surface. Usage of Terms [0093] The BRIEF SUMMARY OF THE INVENTION and ABSTRACT are hereby incorporated by reference. All amounts, ratios, and percentages are by weight unless otherwise indicated by the context of the specification. The articles ‘a’, ‘an’, and ‘the’ each refer to one or more, unless otherwise indicated by the context of the specification. The disclosure of ranges includes the range itself and also anything subsumed therein, as well as endpoints. For example, disclosure of a range of >0.3 to 0.8 includes not only the range of >0.3 to 0.8, but also 0.4, 0.55, 0.6, 0.7, 0.78, and 0.8 individually, as well as any other number subsumed in the range. Furthermore, disclosure of a range of, for example, >0.3 to 0.8 includes the subsets of, for example, 0.4 to 0.6, 0.35 to 0.78, 0.41 to 0.75, 0.78 to 0.8, 0.32 to 0.41, 0.35 to 0.5 as well as any other subset subsumed in the range. Similarly, the disclosure of Markush groups includes the entire group and also any individual members and subgroups subsumed therein. For example, disclosure of the Markush group a vinyl, allyl or hexenyl includes the member vinyl individually; the subgroup vinyl and hexenyl; and any other individual member and subgroup subsumed therein. [0094] Abbreviations used in this application are as defined below in Table 5. Table 5 Test Methods [NMR Analysis] [0095] An average molecular formula of starting materials (A) and (B), such as those mentioned in the Reference Example 1 to 6 was determined based on the following 29 Si-NMR and 13 C-NMR analysis: NMR apparatus: Fourier Transform Nuclear Magnetic Resonance Spectrometer JEOL (JEOL is a registered trademark of JEOL Ltd. Japan) JNM-EX400 (the product of JEOL Ltd.). Determination method: Integrated values of the peaks were calculated based on signals derived from 29 Si for various siloxane units shown below. An average molecular formula was identified by finding ratios of the integrated signal values obtained for various siloxane units (M, D, T, and Q units) and then finding siloxane-unit ratios based on the determined signal ratios. Due to overlap of chemical shift of Me2SiO 2/2 units and MaMeSiO 2/2 unit in 28Si-NMR, the ratio of Me 2 SiO 2/2 (D) and MaMeSiO 2/2 (D’) to obtain m/n ratio was determined by 13 C-NMR. The contents of Reactive Group including unsaturated bonds and (meth)acryl groups was derived from an average molecular formula. [SiH/Vi Ratio and SiH/Reactive Group Ratio] [0096] SiH/Vi Ratio was calculated from the following equation. SiH/ Vi Ratio SiH/Reactive Group Ratio [Gel Permeation Chromatography] [0097] Molecular weight was measured by gel permeation chromatography according to the following method; Samples were prepared in toluene at 0.5% w/v concentration, filtered with a 0.45 µm PTFE syringe filter, and analyzed against polystyrene standards. The relative calibration (3rd order fit) used for molecular weight determination was based on 16 polystyrene standards ranging in molecular weights from 580 to 2,610,000 Daltons. The chromatographic equipment consisted of a Waters 2695 Separations Module equipped with a vacuum degasser, a Waters 2414 differential refractometer and two (7.8 mm X 300 mm) styragel HR columns (molecular weight separation range of 100 to 4,000,000) preceded by a styragel guard column (4.6 X 30 mm). The separation was performed using toluene programmed to flow at 1.0 mL/min., injection volume was set at 100 µL and columns and detector were heated to 45 °C. Data collection was 60 min and processing was performed using Empower software. As used herein for resins, Mw (Weight Average Molecular Weight) and Mn (Number Average Molecular Weight) [Lamination Test on uneven surface] [0098] Lamination performance on uneven surface were observed as described above in Example 11. [Adhesion Force] [0099] Adhesive Force were measured as described above in Reference Example 12. Embodiments of the Invention [0100] In a first embodiment of the invention, a silicone hybrid pressure sensitive adhesive composition comprises: 100 parts by weight of (A) a linear, or substantially linear, polydiorganosiloxane having reactive groups comprising a silicon bonded (meth)acryloxyalkyl-functional group in a pendant position and optionally a silicon bonded aliphatically unsaturated hydrocarbon group in a terminal position, wherein starting material (A) comprises unit formula M p M” q D m D’ n D” o T”’ r Q s , where M represents a unit of formula (R 1 3 SiO 1/2 ), M” represents a unit of formula (R 1 2 R 3 SiO 1/2 ), D represents a unit of formula (R 1 2 SiO 2/2 ), D’ represents a unit of formula (R 1 R 2 SiO 2/2 ), D” represents a unit of formula (R 1 R 3 SiO 2/2 ), T”’ represents a unit of formula (R 5 SiO 3/2 ), and Q represents a unit of formula (SiO 4/2 ), where each R 1 is a monovalent hydrocarbon group free of aliphatic unsaturation, each R 2 is the (meth)acryloxyalkyl functional group, each R 3 is the aliphatically unsaturated monovalent hydrocarbon group, each R 5 is independently selected from the group consisting of R 1 , R 2 , and R 3 ; and subscripts p, q, m, n, o, r, and s have values such that 0 ≤ p, 0 ≤ q, 0 ≤ o , a quantity (p + q) ≥ 2, a quantity (q+o) ≥ 2, 0 < m < 10,000, 2 < n ≤ 10,000, o ≥ 0, a quantity (m + n + o) is 100 to 10,000, a ratio (m+o)/n is 1/1 to 500/1, a ratio (q + o)/(m+n) is 0 ≤ to 1/5, 0 ≤ r ≤ 100, and 0 ≤ s ≤ 100, a ratio (m + n + o)/(r+s) is 50/1 to 10,000/1 if 0 < r or if 0 < s; (B) a polyorganosilicate resin in an amount sufficient to provide a weight ratio of the polyorganosilicate resin to (A) the polydiorganosiloxane (Resin/Polymer Ratio) of 0.15/1 to 4/1, where the polyorganosilicate resin comprises unit formula M a M” b M”’ c D d D’ e T”’ f Q h X i , where M”, D, D’, T”’, and Q are as described above, M”’ represents a unit of formula (R 1 2 R 2 SiO 1/2 ), where R 1 and R 2 are as described above, X represents a hydroxyl group, and subscripts a, b, c, d, e, f, h, and i, have values such that a ≥ 0, b ≥ 0, c ≥ 0 and a quantity (a + b + c) > 10 mole %; d ≥ 0, e ≥ 0, and a quantity (d + e) is 0 to a number sufficient to provide 30 mole % of D units and D’ units combined to the resin; f ≥ 0, with the proviso that subscript f has a maximum value sufficient to provide 30 mole % of T”’ units to the resin; h > 0, with the proviso that subscript h has a value sufficient to provide 30 mole % to 60 mole % of Q units to the resin; a quantity (a + b + c + d + e + f + h) = 100 mole % i ≥ 0 is not included in the molar ratio, with the proviso that subscript i has a maximum value sufficient to provide 5 mole % of hydroxyl groups to the resin; (C) a polyorganohydrogensiloxane comprising unit formula M t M H u D v D H w T x T H y Q z , where M, D, and Q represent units of the formulas shown above, and M H represents a unit of formula (HR 1 2 SiO 1/2 ), D H represents a unit of formula (HR 1 SiO 2/2 ), T represents a unit of formula (R 1 SiO 3/2 ), represents a unit of formula (HSiO 3/2 ), and subscripts t, u, v, w, x, y, and z have values such that t ≥ 0, u ≥ 0, v ≥ 0, w ≥ 0, x ≥ 0, y ≥ 0, z ≥ 0, a quantity (u + w + y) ≥ 3, and a quantity (t + u + v + w + x + y + z) is sufficient to give the polyorganohydrogensiloxane a viscosity of 3 mPa·s to 1,000 mPa·s at 25˚C; , with the provisos that starting materials (A), (B), and (C), and amounts of each, are sufficient to provide: i) a molar ratio of silicon bonded hydrogen atoms in starting material (C) to aliphatically unsaturated monovalent hydrocarbon groups R 3 in starting materials (A) and/or (B) (SiH/Vi ratio) of > 0.2/1, ii) a molar ratio of silicon bonded hydrogen atoms in starting material (C) to reactive groups in starting materials (A) and/or (B) (SiH/reactive group ratio) of <0.34, where the reactive groups are R 2 and R 3 combined; (D) a hydrosilylation reaction catalyst in an amount sufficient to provide 2 ppm to 500 ppm of platinum based on combined weights of starting materials (A), (B), and (C); 0.1 weight % to 10 weight %, based on combined weights of starting materials (A), (B), and (C), of (E) a photoradical initiator; 10 ppm to 5,000 ppm, based on combined weights of starting materials (A), (B), and (C), of (F) a hydrosilylation reaction inhibitor; 5 ppm to 2,000 ppm, based on combined weights of starting materials (A) and (B), of (G) a free radical scavenger; 0 to 90 weight %, based on combined amounts of all starting materials in the composition, of (H) a solvent; and 0 to 5 weight % based on combined weights of starting materials (A) and (B), of (I) an additive selected from the group consisting of a sensitizer and a synergist. 0 to 30 weight % based on combined weights of starting materials (A) and (B), of (J) filler selected from the group consisting of a fumed silica or participated silica. [0101] In a second embodiment, starting material (A) in the composition of the first embodiment comprises unit formula M” 2 D m D’ n , a quantity (m + n) is 100 to 9,900, and a ratio m/n is 10/1 to 500/1. [0102] In a third embodiment, starting material (A) in the composition of the second embodiment has the quantity (m + n) = 200 to 9,900. [0103] In a fourth embodiment, starting material (A) in the composition of the third embodiment has the quantity (m + n) = 300 to 7,000. [0104] In a fifth embodiment, starting material (A) in the composition of any one of the second to fourth embodiments has R 2 present in a mole % of 0.1% to 25% based on combined amounts of R 1 , R 2 , and R 3 . [0105] In a sixth embodiment, starting material (A) in the composition of the fifth embodiment has R 2 present in a mole % of 0.8% to 12 %. [0106] In a seventh embodiment, starting material (A) in the composition of the sixth embodiment has R 2 present in a mole % of 1.5% to 6 %. [0107] In an eighth embodiment, starting material (B) in the composition of the seventh embodiment comprises a unit formula selected from the group consisting of M a Q h , M a M” b Q h , M a M” b M”’ c Q h , M a M”’ c Q h , M a D d Q h , M a D’ e Q h , M a M” b D’ e Q h , M a M” b T”’ f Q h, M a M” b T’” f Q h , where subscript a is 20 to 65 mole %, subscript b and c is 1 to 30 mole %, subscript d and e is 1 to 20 mole %, subscript f is 1 to 25 mole %, and subscript h is 35 to 55 mole %. [0108] In a ninth embodiment, in starting materials (A) and (B) in any one of the first to eighth embodiments, each R 5 is independently selected from the group consisting of R , R 2 and R 3 . [0109] In a tenth embodiment, in starting materials (A) and (B) in the ninth embodiment, R 5 is R 1 . [0110] In an eleventh embodiment, starting material (C) in any one of the first to tenth embodiments comprises unit formula M t M H u D v D H w , where a quantity (t + u) = 2, and a quantity (u + w) ≥ 3. [0111] In a twelfth embodiment, in the composition of any one of the first to eleventh embodiments, each monovalent hydrocarbon group for R 1 is selected independently from the group consisting of alkyl groups and aryl groups. [0112] In a thirteenth embodiment, in the composition of the twelfth embodiment the alkyl group is methyl and the aryl group is phenyl. [0113] In a fourteenth embodiment, in the composition of the twelfth embodiment or the thirteenth embodiment, each R 1 is the alkyl group. [0114] In a fifteenth embodiment, in the composition of any one of the first to fourteenth embodiments, each (meth)acryloxyalkyl functional group for R 2 is independently selected from the group consisting of acryloxypropyl and methacryloxypropyl. [0115] In a sixteenth embodiment, in the composition of any one of the first to fifteenth embodiments, each aliphatically unsaturated monovalent hydrocarbon group for R 3 is an independently selected alkenyl group. [0116] In a seventeenth embodiment, in the composition of the sixteenth embodiment, the alkenyl group is selected from the group consisting of vinyl and hexenyl. [0117] In an eighteenth embodiment, in the composition of any one of the first to seventeenth embodiments, Resin/Polymer Ratio is 0.2/1 to 3/1. [0118] In a nineteenth embodiment, the composition of the eighteenth embodiment has Resin/Polymer Ratio = 0.3/1 to 2.5/1. [0119] In a twentieth embodiment, in the composition of any one of the first to nineteenth embodiments, SiH/Vi ratio is 0.21/1 to 22.0/1. [0120] In a twenty-first embodiment, the composition of the nineteenth embodiment has SiH/Vi ratio of 0.23/1 to < 12.5/1. [0121] In a twenty-second embodiment, the composition of the twenty-first embodiment has SiH/Vi ratio of 0.23/1 to 0.9/1. [0122] In a twenty-third embodiment, in the composition of any one of the first to twenty-second embodiments, the SiH/reactive group ratio is 0.03 to 0.30. [0123] In a twenty-fourth embodiment, in the composition of the twenty-third embodiment the SiH/ reactive group ratio is 0.04 to 0.28. [0124] In a twenty-fifth embodiment, starting material (D) in the composition of any one of the first to twenty-fourth embodiments is selected from the group consisting of: i) a platinum group metal, ii) a compound of said metal, iii) a complex of said metal or said compound, v) the complex microencapsulated in a matrix or coreshell type structure. [0125] In a twenty-sixth embodiment, starting material (D) in the composition of the twenty-fifth embodiment is present in an amount sufficient to provide 10 ppm to 100 ppm of the platinum group metal based on combined weights of starting materials (A), (B), and (C). [0126] In a twenty-seventh embodiment, starting material (E) in the composition of any one of the first to twenty-sixth embodiments is selected from the group consisting of benzophenone, a substituted benzophenone compound, acetophenone, a substituted acetophenone compound, benzoin, an alkyl ester of benzoin, xanthone, and a substituted xanthone. [0127] In a twenty-eighth embodiment, starting material (E) in the composition of the twenty-seventh embodiment is a substituted acetophenone. [0128] In a twenty-ninth embodiment, starting material (E) in the composition of the twenty-eighth embodiment 1-hydroxycyclohexyl phenyl ketone. [0129] In a thirtieth embodiment, in the composition of any one of the first to twenty-ninth embodiments, starting material (E) is present in an amount of 1 weight % to 5 weight %. [0130] In a thirty-first embodiment, starting material (F) in the composition of any one of the first to thirtieth embodiments is present and is selected from the group consisting of acetylenic alcohols, cycloalkenylsiloxanes, ene-yne compounds, triazoles, phosphines, mercaptans, hydrazines, amines, fumarates, maleates, nitriles, ethers, carbon monoxide, alcohols, and silylated acetylenic alcohols. [0131] In a thirty-second embodiment, in the composition of the thirty-first embodiment, the acetylenic alcohol is ethynyl cyclohexanol. [0132] In a thirty-third embodiment, in the composition of any one of the first to thirty-second embodiments, starting material (F), the inhibitor is present in an amount of 20 ppm to 2,000 ppm. [0133] In a thirty-fourth embodiment, starting material (G) the radical scavenger is present in the composition of any one of the first to thirty-third embodiments, and the radical scavenger is selected from the group consisting of acetylenic alcohols, cycloalkenylsiloxanes, ene-yne compounds, triazoles, phosphines, mercaptans, hydrazines, amines, fumarates, maleates, nitriles, ethers, carbon monoxide, alcohols, and silylated acetylenic alcohols. [0134] In a thirty-fifth embodiment, in the composition of the thirty-fourth embodiment, the radical scavenger is selected from the group consisting of a phenolic compound, phenothiazine and an anaerobic inhibitor. [0135] In a thirty-sixth embodiment, in the composition of the thirty-fifth embodiment, the radical scavenger is a phenolic compound. [0136] In a thirty-seventh embodiment, in the composition of any one of the first to thirty-sixth embodiments, starting material (G), the radical scavenger is present in an amount of 10 ppm to 1,500 ppm. [0137] In a thirty-eighth embodiment, in the composition of any one of the first to thirty-seventh embodiments, starting material (H), the solvent, is present and is selected from the group consisting of an aliphatic hydrocarbon and an aromatic hydrocarbon. [0138] In a thirty-ninth embodiment, in the composition of any one of the first to thirty-eighth embodiments, starting material (H) the solvent is present in an amount of > 0 to 60 weight %. [0139] In a fortieth embodiment, in the composition of any one of the first to fortieth embodiments, (I) the additive is present in an amount of 0.05 weight % to 3 weight %. [0140] In a forty-first embodiment, in the composition of any one of the first to fortieth embodiments, starting material (J) the filler is present in an amount of 1 weight % to 30 weight %, based on combined weights of starting materials (A) and (B). [0141] In a forty-second embodiment, in the composition of any one of the first to forty-first embodiments, starting material (K) a bis-SiH-terminated polydiorganosiloxane is present in a weight ratio of starting material (K) to starting material (C) [(K)/(C) ratio] of 0.25/1 to 4/1. [0142] In a forty-third embodiment, in the composition of any one of the first to forty-second embodiments, the filler is present and is selected from the group consisting of fumed silica, precipitated silica, and both fumed silica and precipitated silica. [0143] In a forty-fourth embodiment, a method for preparing an adhesive article comprising a pressure sensitive adhesive layer on a surface of a substrate comprises the steps of: optionally 1) treating the surface of the substrate; 2) coating the silicone hybrid pressure sensitive adhesive composition of any one of the preceding embodiments on the surface, optionally 3) removing all or a portion of the solvent, if present, 4) heating the silicone hybrid pressure sensitive adhesive composition to form a silicone hybrid pressure sensitive adhesive layer on the surface of the substrate. [0144] In a forty-fifth embodiment, a method for adhering an adhesive article to an uneven surface comprises: optionally 1) treating the surface of the substrate; 2) coating the silicone hybrid pressure sensitive adhesive composition of any one of the preceding embodiments on the surface, optionally 3) removing all or a portion of the solvent, if present, 4) heating the silicone hybrid pressure sensitive adhesive composition to form a silicone hybrid pressure sensitive adhesive layer on the surface of the substrate, 5) applying the adhesive article to an uneven surface such that the silicone hybrid pressure sensitive adhesive layer contacts the uneven surface opposite the substrate, optionally 6) applying heat and/or pressure to the adhesive article and the uneven surface, and 7) exposing the silicone hybrid pressure sensitive adhesive layer to UV radiation; thereby conforming the silicone hybrid pressure sensitive adhesive layer to the uneven surface. [0145] In a forty-sixth embodiment, the method of the forty-fifth embodiment further comprises, before step 1), forming the silicone hybrid pressure sensitive adhesive composition by mixing the starting materials. [0146] In a forty-seventh embodiment, in the method of the forty-fifth or the forty-sixth embodiment, the uneven surface is all or a portion of a ball grid array.