US4736048A
Expired / Lapsed
US
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Pressure sensitive adhesive release liner and fluorosilicone compounds, compositions and method therefor
Assignee: Dow Silicones Corp
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Filing: 1986-06-04
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Granted: 1988-04-05
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Expires: 2006-06-04
Abstract
Abstract Pressure sensitive adhesives can be protected with a releasable liner having a cured fluoroalkyl silicone coating which contains as little as two percent fluoroalkyl-substituted siloxane units. In a preferred embodiment of this invention silicone pressure sensitive adhesives can be solvent-cast, and even cured, directly onto the release surface of the liner and can be removed from the protective liner with a force of no more than 400 grams per inch. The fluoroalkyl silicone copolymers of this invention are prepared by a process which involves the preparation of a cohydrolyzate of fluoroalkyl-containing and fluoroalkyl-free siloxane units, followed by further polymerization of the cohydrolyzate with other siloxane units.
Inventors
- 👤 Paul L. Brown
- 👤 David L. Stickles
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-30 15:58
CPC Classifications
C; C08; C08L; C08L83/00; C08L83/04; C08L83/08; C09; C09J; C09J7/00; C09J7/40; C09J7/401; C09J2427/00; C09J2427/005; C09J2483/00; C09J2483/005
Claims Analysis
Total Claims: 25
Claim 1
Independent Claim
222 words
A coating composition comprising a curable mixture consisting essentially of (A) a fluorosilicone polymer containing an average of at least two silicon-bonded curing radicals per molecule selected from the group consisting of hydrogen, hydroxyl and alkenyl and at least 2 mol percent, based on the total number of siloxane units in the fluorosilicone polymer, of fluorinated siloxane units, any remaining siloxane units in the polymer being nonfluorinated siloxane units; said fluorinated siloxane units having the formula (RQ)(R').sub.a (Z).sub.b SiO.sub.(3-a-b)/2 and said non-fluorinated siloxane units having the formula (R').sub.c (Z).sub.d SiO.sub.(4-c-d)/2 where, in said fluorinated and non-fluorinated siloxane units, R denotes a perfluoroalkyl radical having from 4 to 8 carbon atoms and, additionally, 2 to 3 carbon atoms when the fluorosilicone polymer contains less than 90 mol percent fluorinated siloxane units and 1 carbon atom when the fluorosilicone polymer contains from 7 to 10 mol percent fluorinated siloxane units, Q denotes a divalent hydrocarbon, hydrocarbon ether or hydrocarbon thioether radical linking the R radical to a silicon atom through at least 2 carbon atoms, R' denotes a silicon-bonded, monovalent hydrocarbon radical free of aliphatic unsaturation, Z denotes said silicon-bonded curing radical, a=0 to 2, b=0 to 2, a+b=0 to 2, c=0 to 3, d=0 to 3 and c+d=0 to 3 and, (B) an effective amount of a curing agent for the fluorosilicone polymer.
Claim 2
Dependent Claim
222 words
A coating composition comprising a curable mixture consisting essentially of (A) a fluorosilicone polymer containing an average of at least two silicon-bonded curing radicals per molecule selected from the group consisting of hydrogen, hydroxyl and alkenyl and at least 2 mol percent, based on the total number of siloxane units in the fluorosilicone polymer, of fluorinated siloxane units, any remaining siloxane units in the polymer being nonfluorinated siloxane units; said fluorinated siloxane units having the formula (RQ)(R').sub.a (Z).sub.b SiO.sub.(3-a-b)/2 and said non-fluorinated siloxane units having the formula (R').sub.c (Z).sub.d SiO.sub.(4-c-d)/2 where, in said fluorinated and non-fluorinated siloxane units, R denotes a perfluoroalkyl radical having from 4 to 8 carbon atoms and, additionally, 2 to 3 carbon atoms when the fluorosilicone polymer contains less than 90 mol percent fluorinated siloxane units and 1 carbon atom when the fluorosilicone polymer contains from 7 to 10 mol percent fluorinated siloxane units, Q denotes a divalent hydrocarbon, hydrocarbon ether or hydrocarbon thioether radical linking the R radical to a silicon atom through at least 2 carbon atoms, R' denotes a silicon-bonded, monovalent hydrocarbon radical free of aliphatic unsaturation, Z denotes said silicon-bonded curing radical, a=0 to 2, b=0 to 2, a+b=0 to 2, c=0 to 3, d=0 to 3 and c+d=0 to 3 and, (B) an effective amount of a curing agent for the fluorosilicone polymer.
Claim 3
Dependent Claim
66 words
A coating composition according to claim 1 wherein the fluorosilicone polymer consists of siloxane units selected from the group consisting of YMe 2 SiO 1/2 siloxane units, RQMeYSiO 1/2 siloxane units, MeYSiO 2/2 siloxane units and RQYSiO 2/2 siloxane units; wherein Y denotes Me or A, A denotes an omega-alkenyl radical and Me denotes the methyl radical and the curing agent comprises an organohydrogen silicon compound.
Claim 4
Dependent Claim
97 words
A coating composition according to claim 2 wherein the fluorosilicone polymer has the formula YMe.sub.2 SiO(Me.sub.2 SiO).sub.x [RCH.sub.2 CH.sub.2 Si(Me)O].sub.y (MeASiO).sub.z SiMe.sub.2 Y wherein the values of x, y and z are each greater than zero and are such that the fluorosilicone polymer contains from 1 to 10 mol percent alkenyl-containing siloxane units, at least 5 mol percent fluorinated siloxane units and the balance dimethylsiloxane units, and the curing agent comprises a platinum-containing hydrosilylation catalyst and a methylhydrogenpolysiloxane having the formula Me 3 SiO(MeHSiO) e SiMe 3 wherein e has a value of from 30 to 70.
Claim 5
Dependent Claim
26 words
A coating composition according to claim 3 wherein the ratio of silicon-bonded hydrogen atoms to silicon-bonded alkenyl radicals has a value of from 1/1 to 4/1.
Claim 6
Dependent Claim
27 words
A coating composition according to claim 4 wherein the fluorinated siloxane units have the formula (CF.sub.3 CF.sub.2 CF.sub.2 CF.sub.2 CH.sub.2 CH.sub.2)(CH.sub.3)SiO.sub.2/2 and all A radicals are vinyl.
Claim 7
Dependent Claim
111 words
A coating composition according to claim 2 wherein the fluorosilicone polymer has the formula YMe.sub.2 SiO(Me.sub.2 SiO).sub.x [RCH.sub.2 CH.sub.2 Si(Me)O].sub.y (MeASiO).sub.z SiMe.sub.2 Y wherein the values of x, y and z are each greater than zero and are such that the fluorosilicone polymer contains from 3 to 7 mol percent alkenyl-containing siloxane units, from 20 to 50 mol percent fluorinated siloxane units and the balance dimethylsiloxane units, and has a viscosity of from 100 to 1,000 centistokes at 25° C. and the curing agent comprises a platinum-containing hydrosilylation catalyst and a methylhydrogenpolysiloxane having the formula Me 3 SiO(MeHSiO) e SiMe 3 wherein e has a value of from 30 to 70.
Claim 8
Dependent Claim
26 words
A coating composition according to claim 6 wherein the ratio of silicon-bonded hydrogen atoms to silicon-bonded alkenyl radicals has a value of from 1/1 to 4/1.
Claim 9
Dependent Claim
27 words
A coating composition according to claim 7 wherein the fluorinated siloxane units have the formula (CF.sub.3 CF.sub.2 CF.sub.2 CF.sub.2 CH.sub.2 CH.sub.2)(CH.sub.3)SiO.sub.2/2 and all A radicals are vinyl.
Claim 10
Dependent Claim
135 words
A fluorosilicone copolymer having the formula YMe 2 SiO(Me 2 SiO) x {RCH 2 CH 2 Si(Me)O} y (MeASiO) z SiMe 2 Y wherein Y denotes Me or A, A denotes an omega-alkenyl radical, Me denotes the methyl radical, R denotes a perfluoroalkyl radical having from 4 to 8 carbon atoms and, additionally, 2 to 3 carbon atoms when the fluorosilicone polymer contains less than 90 mol percent fluorinated siloxane units and 1 carbon atoms when the fluorosilicone polymer contains from 7 to 10 mol percent fluorinated siloxane units, the values of x, y and z are each greater than zero and are such that the fluorosilicone polymer contains from 1 to 10 mol percent, but at least 2, alkenyl-containing siloxanes units, at least 5 mol percent fluorinated siloane units and the balance dimethylsiloxane units.
Claim 11
Dependent Claim
135 words
A fluorosilicone copolymer having the formula YMe 2 SiO(Me 2 SiO) x {RCH 2 CH 2 Si(Me)O} y (MeASiO) z SiMe 2 Y wherein Y denotes Me or A, A denotes an omega-alkenyl radical, Me denotes the methyl radical, R denotes a perfluoroalkyl radical having from 4 to 8 carbon atoms and, additionally, 2 to 3 carbon atoms when the fluorosilicone polymer contains less than 90 mol percent fluorinated siloxane units and 1 carbon atoms when the fluorosilicone polymer contains from 7 to 10 mol percent fluorinated siloxane units, the values of x, y and z are each greater than zero and are such that the fluorosilicone polymer contains from 1 to 10 mol percent, but at least 2, alkenyl-containing siloxanes units, at least 5 mol percent fluorinated siloane units and the balance dimethylsiloxane units.
Claim 12
Dependent Claim
25 words
A fluorosilicone polymer according to claim 9 wherein R is CF 3 CF 2 CF 2 CF 2 -- and all A radicals are vinyl.
Claim 13
Dependent Claim
64 words
A fluorosilicone polymer according to claim 9 wherein the values of x, y and z are each greater than zero and are such that the fluorosilicone polymer contains from 3 to 7 mol percent alkenyl-containing siloxane units, from 20 to 50 mol percent fluorinated siloxane units and the balance dimethylsiloxane units, and has a viscosity of from 100 to 1,000 centistokes at 25° C.
Claim 14
Dependent Claim
25 words
A fluorosilicone polymer according to claim 11 wherein R is CF 3 CF 2 CF 2 CF 2 -- and all A radicals are vinyl.
Claim 15
Dependent Claim
187 words
A process for synthesizing a fluorosilicone polymer, said process comprising (I) hydrolyzing a mixture comprising one or more fluorinated silanes having the formula (RQ)(R").sub.f SiX.sub.(3-f) and one or more non-fluorinated silanes having the formula R".sub.g SiX.sub.(4-g) where, in said fluorinated and non-fluorinated silanes, R denotes a perfluoroalkyl radical having from 1 to 8 carbon atoms, Q denotes a divalent hydrocarbon, hydrocarbon ether or hydrocarbon thioether radical linking the R radical to the silicon atom through at least 2 carbon atoms, R" denotes a silicon-bonded radical selected from the group consisting of monovalent hydrocarbon radicals and hydrogen atoms, f has a value of 0, 1 or 2, g has a value of 0, 1, 2, or 3 and X denotes a silicon-bonded hydrolyzable radical, (II) mixing with the hydrolyzed mixture obtained in (I) an organopolysiloxane having the average unit formula R" h SiO.sub.(4-h)/2 wherein R" has the meaning noted above and h has an average value of from 1 to 3 and (III) contacting the mixture of (II) with an effective amount of a siloxane-equilibrating catalyst for a period of time sufficient to form the desired fluorosilicone polymer.
Claim 16
Dependent Claim
187 words
A process for synthesizing a fluorosilicone polymer, said process comprising (I) hydrolyzing a mixture comprising one or more fluorinated silanes having the formula (RQ)(R").sub.f SiX.sub.(3-f) and one or more non-fluorinated silanes having the formula R".sub.g SiX.sub.(4-g) where, in said fluorinated and non-fluorinated silanes, R denotes a perfluoroalkyl radical having from 1 to 8 carbon atoms, Q denotes a divalent hydrocarbon, hydrocarbon ether or hydrocarbon thioether radical linking the R radical to the silicon atom through at least 2 carbon atoms, R" denotes a silicon-bonded radical selected from the group consisting of monovalent hydrocarbon radicals and hydrogen atoms, f has a value of 0, 1 or 2, g has a value of 0, 1, 2, or 3 and X denotes a silicon-bonded hydrolyzable radical, (II) mixing with the hydrolyzed mixture obtained in (I) an organopolysiloxane having the average unit formula R" h SiO.sub.(4-h)/2 wherein R" has the meaning noted above and h has an average value of from 1 to 3 and (III) contacting the mixture of (II) with an effective amount of a siloxane-equilibrating catalyst for a period of time sufficient to form the desired fluorosilicone polymer.
Claim 17
Dependent Claim
28 words
A process according to claim 13 wherein the amount of fluorinated and non-fluorinated silanes that are hydrolyzed in step (I) has a molar ratio of 2/1 or less.
Claim 18
Dependent Claim
29 words
A process according to claim 14 wherein an organic solvent for the silanes is present in the hydrolysis step and the solvent is removed after hydrolysis has been completed.
Claim 19
Dependent Claim
46 words
A process according to claim 15 wherein said fluorinated and non-fluorinated silanes are selected from the group consisting of YMe 2 SiX, RQMeYSiX, MeYSiX 2 and RQYSiX 2 ; wherein Y denotes Me or A, A denotes an omega-alkenyl radical and Me denotes the methyl radical.
Claim 20
Dependent Claim
55 words
A process according to claim 16 wherein the organopolysiloxane which is mixed in (II) comprises cyclopolysiloxanes having the formulae (Me 2 SiO) i and (MeASiO) i , wherein i has a value of at least 3 and Me 3 SiO(Me 2 SiO) j SiMe 3 , wherein j has a value of zero or more.
Claim 21
Dependent Claim
23 words
A process according to claim 17 wherein the fluorinated silane is RQMeSiCl 2 and the non-fluorinated silane is Me 2 SiCl 2 .
Claim 22
Dependent Claim
28 words
A process according to claim 18 wherein RQ is CF 3 CF 2 CF 2 CF 2 CH 2 CH 2 -- and A is CH 2 ═CH--.
Claim 23
Dependent Claim
14 words
A process according to claim 15 wherein the siloxane-equilibrating catalyst comprises a fluoroalkanesulfonic acid.
Claim 24
Dependent Claim
25 words
A process according to claim 20 wherein said contacting is done, at least during a portion of the time, at a temperature above 25° C.
Claim 25
Dependent Claim
12 words
A process according to claim 21 further comprising neutralizing the fluoroalkanesulfonic acid.
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USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1991-04-05 | 1991-10-05 | 1992-04-05 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1995-04-05 | 1995-10-05 | 1996-04-05 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1999-04-05 | 1999-10-05 | 2000-04-05 | $7700.00 | Window Closed / Lapsed |