Silicone gel-forming compositions and hysteretic silicone gel and device comprising the gel
View Patent ↗There is provided silicone gel-forming composition comprising a unique combination of polyorganosiloxane and organohydrogenpolysiloxane, which can produce silicone gel with improved hysteresis.
1. A curable hysteretic silicone gel-forming composition comprising:
(A) at least one organopolysiloxane containing at least two silicon-bonded alkenyl groups per molecule;
(B) at least one organohydrogenpolysiloxane containing at least two silicon-bonded hydrogen atoms per molecule, said organohydrogenpolysiloxane (B) being used in an amount such that the mole ratio of total amount of silicon-bonded hydrogen atoms contained in organohydrogenpolysiloxane (B) to one silicon-bonded alkenyl group contained in organopolysiloxane (A) is of from about 0.20 to about 0.79;
(C) filler in an amount of from about 25 to about 100 parts per hundred of organopolysiloxane (A);
(D) catalyst; and,
(E) inhibitor; wherein the recovery time of a hysteretic silicone gel obtained from said curable hysteretic silicone gel-forming composition is greater than about 3 seconds,
where each organopolysiloxane (A) has the formula:
M a M vi b D c D vi d T e T vi f Q g
where
M=R 7 R 8 R 9 SiO 1/2 ;
M vi =R 10 R 11 R 12 SiO 1/2 ;
D=R 13 R 14 SiO 2/2 ;
D vi =R 15 R 16 SiO 2/2 ;
T=R 17 SiO 3/2 ;
T vi =R 18 SiO 3/2 ; and
Q=SiO 4/2 ;
where R 7 , R 8 , R 9 , R 13 , R 14 and R 17 are independently monovalent hydrocarbon radicals having from one to sixty carbon atoms; R 10 is a monovalent unsaturated hydrocarbon radical having from two to ten carbon atoms, and R 11 and R 12 are independently monovalent hydrocarbon radicals having from one to sixty carbon atoms; R 15 is a monovalent unsaturated hydrocarbon radical having from two to ten carbon atoms, and R 16 is a monovalent hydrocarbon radical having from one to sixty carbon atoms; R 17 is a monovalent unsaturated hydrocarbon radical having from two to ten carbon atoms; the stoichiometric subscripts a, b, c, d, e, f, and g are either zero or positive subject to the following limitations: c is greater than 10; d is from zero to about 40; when d=0, b=2; b is from zero to two provided that when b=0, d=2; b+d is of from 2 to about 40; when b=1, a=1; a+b≧2; e+f+g>0, and a+b+c+d≧e+f+g, and wherein said at least one organopolysiloxane (A) comprises a combination of (A-i) vinyl organopolysiloxane having a viscosity of from about 20,000 to about 60,000 centipoise at 25 degrees celsius, and (A-ii) vinyl organopolysiloxane having a viscosity of from about 250 to about 750 centipoise at 25 degrees celsius; organohydrogenpolysiloxane (B) is at least one organohydrogenpolysiloxane having terminal and/or non-terminal silicon-bonded hydrogen atoms and having a viscosity of from about 15 to about 60 centipoise at 25 degrees celsius.
2. The curable hysteretic silicone gel-forming composition of claim 1 further comprising a non-alkenyl containing polyorganosiloxane selected from the group consisting of linear polyorganosiloxane, a non-network branched polyorganosiloxane, three-dimensional network polyorganosiloxane, non-network resinous polyorganosiloxane and combinations thereof where each polyorganosiloxane does not contain any alkenyl groups.
3. The curable hysteretic silicone gel-forming composition of claim 1 where at least two silicon-bonded alkenyl groups contain from 2 to about 6 carbon atoms.
4. The curable hysteretic silicone gel-forming composition of claim 1 where organo groups of organopolysiloxane (A) comprise methyl and/or phenyl.
5. The curable hysteretic silicone gel-forming composition of claim 1 which further comprises non-hydrogen containing organopolysiloxane selected from the group consisting of linear organopolysiloxane, non-network branched organopolysiloxane, cyclic organopolysiloxane, three-dimensional network organopolysiloxane, non-network resinous organopolysiloxane and combinations thereof where each organopolysiloxane does not contain any silicon-bonded hydrogen atoms.
6. The curable hysteretic silicone gel-forming composition of claim 1 where organohydrogenpolysiloxane (B) is substantially resinous organohydrogenpolysiloxane and comprises no less than about 30 weight percent of T and/or Q units, where T=R 24 SiO 3/2 and Q=SiO 4/2 , where R 24 is selected from the group consisting of a monovalent hydrocarbon radical of from one to about sixty carbon atoms; a hydrogen atom; and combinations thereof.
7. The curable hysteretic silicone gel-forming composition of claim 1 where organohydrogenpolysiloxane (B) has the formula:
M h M H i D j D H k T L T H m Q n
where
M=R 27 R 28 R 29 SiO 1/2 ;
M H =R 30 R 31 HSiO 1/2 ;
D=R 32 R 33 SiO 2/2 ;
D H =R 34 HSiO 2/2 ;
T=R 35 SiO 3/2 ;
T H =HSiO 3/2 ; and
Q=SiO 4/2 ;
where R 27 , R 28 , R 29 , R 32 , R 33 , and R 35 are independently monovalent hydrocarbon radicals having from one to sixty carbon atoms and are substantially free of aliphatic unsaturation; R 30 , R 31 , and R 34 are independently monovalent hydrocarbon radicals having from one to sixty carbon atoms or hydrogen and are substantially free of aliphatic unsaturation the stoichiometric subscripts h, i, j, k, L, m and n being zero or positive subject to the following limitations: J is greater than 0; k is of from zero to about 20, when k=0, i=2; h is of from zero to about 2; subject to the further limitation that i+k is of from 2 to about 20, when i=1, h=1; h+i≧2; and in at least one substantially straight chain organohydrogenpolysiloxane if L+m+n>0 then h+i+j+k>L+m+n; and organohydrogenpolysiloxane (B) contains at least two silicon-bonded hydrogen atoms per molecule.
8. The curable hysteretic silicone gel-forming composition of claim 1 where each organohydrogenpolysiloxane (B) has a viscosity of from about 0.1 to about 2000 centipoise at 25 degrees celsius.
9. The curable hysteretic silicone gel-forming composition of claim 1 where each organohydrogenpolysiloxane (B) has a viscosity of from about 0.5 to about 1000 centipoises at 25 degrees celsius.
10. The curable hysteretic silicone gel-forming composition of claim 1 where each organohydrogenpolysiloxane (B) has a viscosity of from about 1 to about 500 centipoise at 25 degrees celsius.
11. The curable hysteretic silicone gel-forming composition of claim 1 where the mole ratio of total amount of silicon-bonded hydrogen atoms contained in organohydrogenpolysiloxane (B) to one silicon-bonded alkenyl group contained in organopolysiloxane (A) is of from about 0.25 to about 0.75.
12. The curable hysteretic silicone gel-forming composition of claim 1 where the mole ratio of total amount of silicon-bonded hydrogen atoms contained in organohydrogenpolysiloxane (B) to one silicon-bonded alkenyl group contained in organopolysiloxane (A) is of from about 0.30 to about 0.65.
13. The curable hysteretic silicone gel-forming composition of claim 1 where filler (C) is present in an amount of from about 35 to about 80 parts by weight per 100 parts of organopolysiloxane (A).
14. The curable hysteretic silicone gel-forming composition of claim 1 where filler (C) is present in an amount of from about 40 to about 65 parts by weight per 100 parts of organopolysiloxane (A).
15. The curable hysteretic silicone gel-forming composition of claim 1 where filler is selected from the group consisting of silica, fumed silica, precipitated silica, titania, alumina, clay, wollastonite, quartz and combinations thereof.
16. The curable hysteretic silicone gel-forming composition of claim 1 where catalyst (D) is at least one Group VIIIB catalyst.
17. The curable hysteretic silicone gel-forming composition of claim 1 where inhibitor (E) has aliphatic=saturation and is selected from the group consisting of diallyl maleate, D-4 vinyl, 2-methyl-3-butene-2-ol, 1-ethynyl-1-cyclohexanol, 3,5,-dimethyl-1-hexyn-3-ol and combinations thereof.
18. A hysteretic silicone gel obtained from the curing of curable hysteretic silicone gel-forming composition of claim 1 .
19. The hysteretic gel of claim 18 having a recovery time of specifically greater than about 3 seconds.
20. A hand-grippable device having an external surface at least a portion of which comprises hysteretic silicone gel of claim 19 .
21. The hand-grippable device of claim 20 which is a writing implement, a razor, a toothbrush, a utensil, sport equipment, a tool, a motor-driven device, or a steering wheel.
22. A curable hysteretic silicone gel-forming composition comprising:
(A) at least one organopolysiloxane containing at least two silicon-bonded alkenyl groups per molecule;
(B) at least one organohydrogenpolysiloxane containing at least two silicon-bonded hydrogen atoms per molecule, said organohydrogenpolysiloxane (B) being used in an amount such that the mole ratio of total amount of silicon-bonded hydrogen atoms contained in organohydrogenpolysiloxane (B) to one silicon-bonded alkenyl group contained in organopolysiloxane (A) is of from about 0.20 to about 0.79;
(C) filler in an amount of from about 25 to about 100 parts per hundred of organopolysiloxane (A);
(D) catalyst; and,
(E) inhibitor; wherein the recovery time of a hysteretic silicone gel obtained from said curable hysteretic silicone gel-forming composition is greater than about 3 seconds,
where organopolysiloxane (A) is a combination of (A-i) vinyl organopolysiloxane having a viscosity of from about 20,000 to about 60,000 centipoise at 25 degrees celsius, being present in an amount of from about 60 to about 75 weight percent, and (A-ii) vinyl organopolysiloxane having a viscosity of from about 250 to about 750 centipoise at 25 degrees celsius being present in an amount of from about 5 to 15 about weight percent; organohydrogenpolysiloxane (B) is at least one organohydrogenpolysiloxane having terminal and/or non-terminal silicon-bonded hydrogen atoms and having a viscosity of from about 15 to about 60 centipoise at 25 degrees celsius, being present in an amount of from about 0.2 to about 0.5 weight percent; filler (C) being fumed silica with a surface area of from about 200 to about 350 m 2 /g, said fumed silica having been treated with silane, where filler (C) is present in an amount of from about 15 to about 25 weight percent; catalyst (D) is a platinum catalyst where catalyst (D) is present in an amount of from about 10 to about 20 parts per million; and, inhibitor (E) is 1-ethynyl-1-cyclohexanol where inhibitor (E) is present in an amount of from about 0.05 to about 0.1 weight percent, with all weight percents being based upon the total weight of the curable hysteretic silicone gel-forming composition.
23. A curable hysteretic silicone gel-forming composition comprising:
(A) at least one organopolysiloxane containing at least two silicon-bonded alkenyl groups per molecule;
(B) at least one organohydrogenpolysiloxane containing at least two silicon-bonded hydrogen atoms per molecule, said organohydrogenpolysiloxane (B) being used in an amount such that the mole ratio of total amount of silicon-bonded hydrogen atoms contained in organohydrogenpolysiloxane (B) to one silicon-bonded alkenyl group contained in organopolysiloxane (A) is of from about 0.20 to about 0.79;
(C) filler in an amount of from about 25 to about 100 parts per hundred of organopolysiloxane (A);
(D) catalyst; and,
(E) inhibitor; wherein the recovery time of a hysteretic silicone gel obtained from said curable hysteretic silicone gel-forming composition is greater than about 3 seconds,
where organopolysiloxane (A) is a combination of (A-i) vinyl organopolysiloxane having a viscosity of from about 20,000 to about 60,000 centipoise at 25 degrees celsius, and (A-ii) vinyl organopolysiloxane having a viscosity of from about 250 to about 750 centipoise at 25 degrees celsius; organohydrogenpolysiloxane (B) is at least one organohydrogenpolysiloxane having terminal and/or non-terminal silicon-bonded hydrogen atoms and having a viscosity of from about 15 to about 60 centipoise at 25 degrees celsius.