	US 12,454,637 B2
	Silicone hybrid pressure sensitive adhesive and methods for its preparation and use in protective films for (opto)electronic device fabrication
Juyoung Yook, Chungcheongbuk-do (KR); Nanguo Liu, Midland, MI (US); Zachary Wenzlick, Midland, MI (US); Hojin Choi, Chungcheongbuk-do (KR); and Bo Kyung Bona Kim, Chungcheongbuk-do (KR)
Assigned to Dow Silicones Corporation, Midland, MI (US)
Appl. No. 17/802,272
Filed by Dow Silicones Corporation, Midland, MI (US)
PCT Filed Mar. 1, 2021, PCT No. PCT/US2021/020208 § 371(c)(1), (2) Date Aug. 25, 2022, PCT Pub. No. WO2021/225673, PCT Pub. Date Nov. 11, 2021.
Claims priority of provisional application 63/021,186, filed on May 7, 2020.
Prior Publication US 2023/0091861 A1, Mar. 23, 2023
This patent is subject to a terminal disclaimer.
Int. Cl. C09J 183/06 (2006.01); C08K 5/00 (2006.01); C08K 5/07 (2006.01); C08K 5/08 (2006.01); C08K 5/13 (2006.01); C08G 77/12 (2006.01); C08G 77/20 (2006.01)

CPC C09J 183/06 (2013.01) [C08K 5/0025 (2013.01); C08K 5/07 (2013.01); C08K 5/08 (2013.01); C08K 5/13 (2013.01); C08G 77/12 (2013.01); C08G 77/20 (2013.01); C08L 2312/06 (2013.01); C09J 2301/302 (2020.08)]

17 Claims

1. A silicone hybrid pressure sensitive adhesive composition comprising:

100 parts by weight of (A) a 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_pM″_qD_mD′_nD”₀T″_rQ_s, where

M represents a unit of formula (R¹₃SiO_1/2),

M″ represents a unit of formula (R¹₂R³SiO_1/2),

D represents a unit of formula (R¹₂SiO_2/2),

D′ represents a unit of formula (R¹R²SiO_2/2),

D″ represents a unit of formula (R¹R³SiO_2/2)

T′″ represents a unit of formula (R⁵SiO_3/2), and

Q represents a unit of formula (SiO_4/2), where

each R¹is a monovalent hydrocarbon group free of aliphatic unsaturation,

each R²is the (meth) acryloxyalkyl functional group,

each R³is the aliphatically unsaturated monovalent hydrocarbon group,

each R⁵is independently selected from the group consisting of R¹, R², and R³, and

subscripts p, q, m, n, r, and s have values such that

0≤p, 0≤q, a quantity (p+q) ≥2,

0<m<10,000, 2<n≤10,000, o ≥0, a quantity (m+n+0) is 100 to 10,000, a ratio (m+0)/n is 1/1 to 500/1,

a ratio (q+0)/(m+n) is 0≤to ≤1/5,

0≤r≤100, and 0≤s≤100; a ratio (m+n+0)/(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 1.9/1, where the polyorganosilicate resin comprises unit formula M_aM″_bM″D_dD′_eT′_fQ_hX_i, where M, M”, D, D′, and Q are as described above, M″′ represents a unit of formula (R¹₂R²SiO_1/2), T′ represents a unit of formula (R²SiO_3/2), X represents a hydroxyl group and/or alkoxy 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 in an amount sufficient to provide a molar ratio of silicon bonded hydrogen atoms in starting material (C) to reactive groups in starting materials (A) and (B) combined (SiH/reactive group ratio) of 0.3 to 2, where the reactive groups are R²and R³combined, where the polyorganohydrogensiloxane comprises unit formula M_tM^H_uD_vD^H_wT_xT^H_yQ_z, where M, D, T, and Q represent units of the formulas shown above, and

M^Hrepresents a unit of formula (HR¹₂SiO_1/2),

D^Hrepresents a unit of formula (HR¹SiO_2/2),

T^Hrepresents 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.;

(D) a hydrosilylation reaction catalyst in an amount sufficient to provide 2 ppm to 500 ppm of platinum based on combined weights of all starting materials in the composition;

1 to 20 parts by weight, per 100 parts of starting material (A), of (E) a photoradical initiator;

0.1 to 4 parts by weight, per 100 parts of starting material (A), of (F) a hydrosilylation reaction inhibitor;

0.001 to 0.1 parts by weight, per 100 parts of starting material (A), of (G) a free radical scavenger;

0 to 120 parts by weight, per 100 parts of starting material (A), of (H) a solvent; and

0 to 2 parts by weight, per 100 parts of starting material (A), of (I) an additive selected from the group consisting of a sensitizer and a synergist.