Granted Patent B2

US 12,466,982 · App. 18/552,309 · Granted Nov 11, 2025

Inventors: Jingui Jiang (Shanghai, CN); Jiayin Zhu (Shanghai, CN); Chengrong Zhu (Shanghai, CN); Zhihua Liu (Shanghai, CN); Qing Cao (Shanghai, CN); Yan Zhou (Shanghai, CN)

Assignee: Dow Silicones Corporation

C09J183/04C08G77/08C08G77/12C08G77/20C08K5/5435C09J7/38C09J2301/302C09J2483/00Y10T428/28Y10T428/2852

Abstract

Claims (124)

1 . A silicone pressure sensitive adhesive composition comprising:

30 weight % to less than 80 weight %, based on combined weights of starting materials (A) to (G), of (A) an alkenyl-functional polydiorganosiloxane comprising unit formula:

(R M 2 R U SiO 1/2 ) a (R M 3 SiO 1/2 ) b (R M 2 SiO 2/2 ) c (R M R U SiO 2/2 ) a (R M SiO 3/2 ) e (R U SiO 3/2 ) f (SiO 4/2 ) g , where

each R M is an independently selected alkyl group of 1 to 30 carbon atoms;

each R U is an independently selected alkenyl group of 2 to 30 carbon atoms; and

subscripts a, b, c, and d represent average numbers of each unit per molecule,

subscript a≥0,

subscript b≥0,

subscript c≥0,

subscript d≥0,

subscript e≥0,

subscript f≥0,

a quantity (a+d+f)≥2,

subscript g≥0, and

a quantity (a+b+c+d+e+f+g) is 4 to 10,000;

0.5 weight % to 5 weight %, based on combined weights of starting materials (A) to (G), of (B) a polyorganohydrogensiloxane comprising unit formula (R M 3 SiO 1/2 ) dd (H cc R M (3-cc) SiO 1/2 ) h (SiO 4/2 ) i (ZO 1/2 ) ee ,

where R M is as described above,

each Z is independently selected from the group consisting of hydrogen and R M

subscripts dd and h represent relative weights of monofunctional siloxane units in the formula,

subscript i represents relative weight of tetrafunctional siloxane units in the formula,

subscript dd≥0,

subscript h>0,

subscript i>0,

subscripts dd, h, and i have values sufficient to provide the

polyorganohydrogensiloxane with a weight ratio of monofunctional units: tetrafunctional units {(dd+h):i} of 0.4:1 to 2:1,

subscript ee represents relative weight of hydrolyzable groups in the formula,

subscript ee≥0,

subscript ee has a value sufficient to provide 0 to 2 weight % of hydrolyzable groups based on weight of the polyorganohydrogensiloxane;

subscript cc represents the number of silicon bonded hydrogen atoms in each monofunctional unit,

2≥cc≥1; and

where the starting material (B) is present in a sufficient amount to provide a molar ratio of silicon bonded hydrogen atoms to alkenyl groups in the starting material (A) (SiH:Vi ratio) of 0.5 to 20;

a sufficient amount of (C) a platinum group metal hydrosilylation reaction catalyst to provide 1 ppm to 5,200 ppm of the platinum group metal, based on combined weights of starting materials (A) to (G);

10 to 50 weight %, based on combined weights of the starting materials (A) to (G), of (D) a polyorganosilicate resin;

>0.4 weight % to 20 weight %, based on combined weights of the starting materials (A) to (G), of (E) a polyfluoropolyether silane;

0.01 weight % to 5 weight %, based on combined weights of the starting materials (A) to (G), of (F) an anchorage additive;

0.01 weight % to 5 weight %, based on combined weights of the starting materials (A) to (G), of (G) a hydrosilylation reaction catalyst inhibitor; and

0 to 90 weight %, based on combined weights of all starting materials in the composition, of (H) a solvent.

2 . The composition of claim 1 , where (A) the alkenyl-functional polydiorganosiloxane is selected from the group consisting of:

(A1) an alkenyl-functional polydiorganosiloxane gum of unit formula

(R M 2 R U SiO 1/2 ) j (R M 2 SiO 2/2 ) k (R M R U SiO 2/2 ) m (R M 3 SiO 1/2 ) n , where

each R M is an independently selected alkyl group of 1 to 30 carbon atoms; each R U is an independently selected alkenyl group of 2 to 30 carbon atoms are as described above;

subscripts j, k, m, and n represent average numbers of each unit per molecule;

subscript j is 0, 1, or 2;

subscript n is 0, 1, or 2;

a quantity (j+n)=2;

subscript k≥0;

subscript m≥0;

a quantity (k+m) is 3,000 to 10,000; and

a quantity (j+m)≥2;

(A2) an alkenyl-functional polydiorganosiloxane polymer of unit formula

(R M 2 R U SiO 1/2 ) o d(R M 2 SiO 2/2 ) p (R M R U SiO 2/2 ) q (R M 3 SiO 1/2 ) r , where

R M and R U are as described above;

subscripts o, p, q and r, represent average numbers of each unit per molecule;

subscript o is 0, 1, or 2;

subscript r is 0, 1, or 2;

a quantity (r+o)=2;

subscript p≥0;

subscript q≥0;

a quantity (p+q) is 100 to 1,200; and

a quantity (o+q)≥2;

(A3) a branched alkenyl-functional polyorganosiloxane of unit formula

(R M 3 SiO 1/2 ) u (R M 2 R U SiO 1/2 ) v (R M 2 SiO 2/2 ) s (SiO 4/2 ) t , where

R M and R U are as described above;

subscripts s, t, u, and v represent average numbers of each unit per molecule;

2≥u≥0;

4≥v≥0;

995≥s≥4;

t=1;

(u+v)=4; and

(u+v+s+t) has a value sufficient to impart a viscosity >100 mPa·s measured at room temperature by rotational viscometry to the branched alkenyl-functional polyorganosiloxane;

(A4) an alkenyl-functional silsesquioxane polymer of unit formula

(R M 3 SiO 1/2 ) ii (R U R M 2 SiO 1/2 ) jj (R M 2 SiO 2/2 ) kk (R U R M SiO 2/2 ) mm (R M 2 SiO 3/2 ) nn , where

R M and R U are as described above;

Subscripts ii, jj, kk, mm, and nn represent average numbers of each unit per molecule;

subscript 12≥ ii≥0,

subscript 12≥ jj>0,

subscript 995≥ kk≥15,

subscript 10≥ nn>0, and

subscript 800≥ mm≥0; and

(A5) a combination of two or more of (A1), (A2), (A3), and (A4).

3 . The composition of claim 1 , where starting material (B), the polyorganohydrogensiloxane, comprises unit formula (HR M 2 SiO 1/2 ) h (SiO 4/2 ) i , where

R M is as described above; and

a weight ratio (h:i) is 1:1 to 2:1.

4 . The composition of claim 1 , where starting material (C), the hydrosilylation reaction catalyst, comprises a platinum-organosiloxane complex.

5 . The composition of claim 1 , where starting material (D) the polyorganosilicate resin, comprises unit formula: (R M 3 SiO 1/2 ) w (R M 2 R U SiO 1/2 ) x (SiO 4/2 ) y (ZO 1/2 ) z , where

each R M is an independently selected alkyl group of 1 to 30 carbon atoms; each R U is an independently selected alkenyl group of 2 to 30 carbon atoms; each Z is independently selected from the group consisting of hydrogen and the R M ;

subscripts w, x, and y represent mole fractions of each unit in the formula, and have values such that

w>0;

x≥0;

y>1;

with the proviso that a quantity (w+x+y) has a value sufficient to provide the polyorganosilicate resin with a number average molecular weight of 1,000 g/mol to 10,000 g/mol; and

subscript z is 0 to a value sufficient to give (D) the polyorganosilicate resin a hydrolyzable group content of up 4 weight % based on weight of the polyorganosilicate resin.

6 . The composition of claim 1 , where starting material (E), the polyfluoropolyether silane has general formula (E1): Y—Z a —[(OC 3 F 6 ) b —(OCF(CF 3 )CF 2 ) c —(OCF 2 CF(CF 3 )) d —(OC 2 F 4 ) e —(CF(CF 3 )) f —(OCF 2 ) g ]—(CH 2 ) h —X—(C n H 2n —((SiR 2 —O) m —SiR 2 ) i —(C j H 2j )—Si—(X′) 3-z (R 1 ) z , where

the groups represented by subscripts b to g in the general formula (E1) are present in any order within the polyfluoropolyether silane, including a different order as that which is represented in the general formula (E1);

each Z is independently selected from the group consisting of —(CF 2 )—, —(CF(CF 3 ) CF 2 O)—,

(CF 2 CF(CF 3 )O)—, —(CF(CF 3 )O)—, —(CF(CF 3 )—CF 2 )—, —(CF 2 —CF(CF 3 ))—, and —(CF(CF 3 ))—,

with the proviso that Z and the moiety represented by —[(OC 3 F 6 ) b —(OCF(CF 3 )CF 2 ) c —(OCF 2 CF(CF 3 )) d —(OC 2 F 4 ) e —(CF(CF 3 )) f —(OCF 2 ) g ]— are selected such that Z and this moiety do not form a peroxide;

subscript a is an integer from 1 to 200;

subscripts b, c, d, e, f, and g are integers each independently selected from 0 to 200;

subscripts h, n, and j are integers each independently selected from 0 to 20,

subscripts i and m are integers each independently selected from 0 to 5;

subscript z is an integer independently selected from 0 to 2;

X is a bivalent organic group or an oxygen atom;

each R is an independently selected hydrocarbon group having from 1 to 22 carbon atoms, optionally substituted with a heteroatom;

each X′ is an independently selected hydrolysable group;

each R 1 is an independently selected hydrocarbon group having from 1 to 22 carbon atoms which is free of aliphatic unsaturation;

Y is selected from the group consisting of F and Si—(X′) 3-z (R 1 ) z (C j H 2j )—((SiR 2 —O) m —SiR 2 )—(C n H 2n )—X—(CH 2 ) h —; wherein X′, z, R 1 , j, m, i, n and h are as defined above.

7 . The composition of claim 1 , where each R M is methyl and each R U is independently selected from the group consisting of vinyl, allyl, and hexenyl.

8 . The composition of claim 1 , where starting material (F), the anchorage additive, is selected from the group consisting of (F-1) vinyltriacetoxysilane, (F-2) glycidoxypropyltrimethoxysilane, (F-3) a combination of (F-1) and (F-2), and (F-4) a combination of (F-3) and a polydimethylsiloxane terminated with hydroxyl groups, methoxy groups, or terminated with both a hydroxy group and a methoxy group.

9 . The composition of claim 1 , where starting material (G), the hydrosilylation reaction inhibitor, is selected from the group consisting of 1-ethynyl-1-cyclohexanol, methyl butynol, and diallyl maleate.

10 . The composition of claim 1 , where starting material (H), the solvent, is present and is selected from the group consisting of toluene, xylene, heptane, ethyl benzene, ethyl acetate, and a combination of two or more thereof.

11 . A silicone pressure sensitive adhesive prepared by curing the composition of claim 1 .

12 . A protective film comprising:

1) the silicone pressure sensitive adhesive of claim 11 ,

2) A substrate having a surface, where the silicone pressure sensitive adhesive is coated on the surface of the substrate.

13 . A method comprising:

optionally 1) treating a surface of a substrate,

2) Coating the silicone pressure sensitive adhesive composition of claim 1 on the surface of the substrate,

optionally 3) removing some or all of the solvent, when present, and

4) Curing the pressure sensitive adhesive composition, thereby preparing a topside protective film comprising a silicone pressure sensitive adhesive having a first surface adhered to the surface of the substrate, the silicone pressure sensitive adhesive having a second surface opposite the first surface.

14 . The method of claim 13 , further comprising:

5) Applying the second surface of the silicone pressure sensitive adhesive to an anti-fingerprint hard coating in a display device.

15 . The method of claim 14 , further comprising:

6) Removing the silicone pressure sensitive adhesive from the anti-fingerprint hard coating in a display device with a dynamic coefficient of friction <0.5.

Assignments (2)

Continuity (1)

References Cited (55)