Adhesives having improved chemical resistance and curable silicone compositions for preparing the adhesives

1. A composition prepared by mixing components comprising:

(I) a polyorganosiloxane having an average of at least two unsaturated organic groups per molecule,

where component (I) is free of fluorine atoms;

(II) an organohydrogenpolysiloxane having an average of at least two silicon-bonded hydrogen atoms per molecule,

where component (II) is free of fluorine atoms;

(III) a hydrosilylation catalyst;

(IV) a fluoroorganosilicone having at least one functional group reactive with component (I), component (II), or both;

(V) an unsaturated ester-functional compound comprising

v) a combination thereof; where

in formula i), each R 18 is independently a hydrogen atom, a monovalent hydrocarbon group of 1 to 4 carbon atoms, or CF 3 ,

each R 19 is independently a divalent organic group of 1 to 20 carbon atoms,

each R 20 is independently a hydrogen atom or a monovalent hydrocarbon group of 1 to 20 carbon atoms,

in formula ii), n has an average value of 0 to 2 and m =4−n,

each R 21 is independently a hydroxyl group, or CF 3 .

each R 22 is independently a hydrogen atom, a monovalent hydrocarbon group of 1 to 4 carbon atoms, or CF 3 ,

each R 23 is independently a hydrogen atom or a monovalent hydrocarbon group of 1 to 20 carbon atoms,

in formula iii), each R 24 is independently a fluoroalkyl group, an epoxy functional group, or a polyether group with the proviso that at least one of R 24 or R 25 is unsaturated, each R 25 is independently an oxygen-bridged monovalent organic group or a carbon-bridged carbonyl group,

in formula iv), each R 26 is independently a monovalent organic group or a hydrogen atom, with the proviso that at least one R 26 is an aliphatically unsaturated monovalent organic group or a hydrogen atom, and

each R 27 is independently an oxygen atom or a divalent organic group; and

(VI) an adhesion promoter.

2. The composition of claim 1 , where component (I) comprises a polyorganosiloxane of the formula:

(a) R 1 3 SiO(R 1 2 SiO) α (R 1 R 2 SiO) βSiR 1 3 ,

(b) R 3 2 R 4 SiO(R 3 2 SiO) χ(R 3 R 4 SiO) δ SiR 3 2 R 4 , or

(c) a combination thereof, where

α has an average value of 0 to 2000,

β has an average value of 2 to 2000,

each R 1 is independently a monovalent organic group,

each R 2 is independently an unsaturated monovalent organic group,

χ has an average value of 0 to 2000,

δ has an average value of 0 to 2000,

each R 3 is independently a monovalent organic group, and

each R 4 is independently an unsaturated monovalent organic group.

3. The composition of claim 1 , where component (I) comprises:

i) dimethylvinylsiloxy-terminated polydimethylsiloxane,

ii) dimethylvinylsiloxy-terminated poly(dimethylsiloxane/methylvinylsiloxane),

iii) dimethylvinylsiloxy-terminated polymethylvinylsiloxane,

iv) trimethylsiloxy-terminated poly(dimethylsiloxane/methylvinylsiloxane),

v) trimethylsiloxy-terminated polymethylvinylsiloxane,

vi) dimethylvinylsiloxy-terminated poly(dimethylsiloxane/methylphenylsiloxane),

vii) dimethylvinylsiloxy-terminated poly(dimethylsiloxane/diphenylsiloxane),

viii) phenyl,methyl,vinyl-siloxy-terminated polydimethylsiloxane,

ix) dimethyl-acryloyloxypropyl-siloxy-terminated polydimethylsiloxane,

x) dimethyl-methacryloyloxypropyl-siloxy-terminated polydimethylsiloxane,

xi) dimethylhexenylsiloxy-terminated polydimethylsiloxane,

xii) dimethylhexenylsiloxy-terminated poly(dimethylsiloxane/methylhexenylsiloxane),

xiii) dimethylhexenylsiloxy-terminated polymethylhexenylsiloxane,

xiv) trimethylsiloxy-terminated poly(dimethylsiloxane/methylhexenylsiloxane),

xv) dimethylvinylsiloxy-terminated poly(dimethylsiloxane/methylcyanopropylsiloxane), or

xvi) combinations thereof.

4. The composition of claim 1 , where component (I) comprises an MQ resin consisting essentially of R 5 3 SiO 1/2 units and SiO 4/2 units, a TD resin consisting essentially of R 5 SiO 3/2 units and R 5 2 SiO 2/2 units, an MT resin consisting essentially of R 5 3 SiO 1/2 units and R 5 SiO 3/2 units, an MTD resin consisting essentially of R 5 3 SiO 1,2 units, R 5 SiO 3/2 units, and R 5 2 SiO 2/2 units, or a combination thereof, where

each R 5 is a monovalent organic group of 1 to 20 carbon atoms, and

the resin contains an average of 3 to 30 mole percent of unsaturated organic groups.

5. The composition of claim 1 , where component (II) comprises siloxane units selected from HR 6 3 SiO 1/2 , R 6 3 SiO 1/2 , HR 6 SiO 2/2 , R 6 2 SiO 2/2 , R 6 SiO 3/2 , SiO 4/2 , or combinations thereof; where each R 6 is independently selected from monovalent organic groups free of aliphatic unsaturation.

6. The composition of claim 1 , where component (II) comprises a compound of the formula:

(a) R 7 3 SiO(R 7 2 SiO) ε (R 7 HSiO) φ SiR 7 3 , or

(b) R 8 2 HSiO(R 8 2 SiO) γ (R 8 HSiO) η SiR 8 2 H,

(c) a combination thereof, where

ε has an average value of 0 to 2000,

φ has an average value of 2 to 2000,

each R 7 is independently a monovalent organic group free of aliphatic unsaturation,

γ has an average value of 0 to 2000,

η has an average value of 0 to 2000, and

each R 8 is independently a monovalent organic group free of aliphatic unsaturation.

7. The composition of claim 1 , where component (II) comprises:

i) dimethylhydrogensiloxy-terminated polydimethylsiloxane,

ii) dimethylhydrogensiloxy-terminated poly(dimethylsiloxane/methylhydrogensiloxane),

iii) dimethylhydrogensiloxy-terminated polymethylhydrogensiloxane,

iv) trimethylsiloxy-terminated poly(dimethylsiloxane/methylhydrogensiloxane),

v) trimethylsiloxy-terminated polymethylhydrogensiloxane,

vi) a resin consisting essentially of H(CH 3 ) 2 SiO 1/2 units and SiO 4/2 units, and

vii) combinations thereof.

8. The composition of claim 1 , where component (II) comprises a combination of more than one organohydrogenpolysiloxane.

9. The composition of claim 1 , where component (III) comprises a platinum metal, a rhodium metal, or an organometallic compound.

10. The composition of claim 1 , where component (III) comprises a microencapsulated hydrosilylation catalyst.

11. The composition of claim 1 , where component (IV) comprises a compound of the formula:

(a) R 9 3 SiO(R 9 2 SiO) ι (R 9 R 10 SiO) φ SiR 9 3 ,

(b) R 11 2 R 12 SiO(R 11 2 SiO) κ (R 11 R 12 SiO) λ SiR 11 2 R 12 ,

(c) F 3 C(CF 2 ) ν R 13 —Si—[O—Si(R 14 ) 2 (R 15 )] 3 ,

(d) a resinous or branched structure consisting essentially of R 15 R 14 SiO 1/2 units,

CF 3 (CF 2 ) ν R 13 SiO 3/2 units, and optionally SiO 4/2 units, or

(e) a combination thereof; where

ι has an average value of 0 to 2000,

φ has an average value of 1 to 500,

each R 9 is independently a hydrogen atom or a monovalent organic group, with the proviso that at least one R 9 is a hydrogen atom or an unsaturated monovalent organic group;

each R 10 is independently a fluoro-functional organic group;

κ has an average value of 0 to 2000;

λ has an average value of 0 to 500;

each R 11 is independently a hydrogen atom or a monovalent organic group, with the proviso that at least one R 11 is a hydrogen atom or an unsaturated monovalent organic group;

each R 12 is independently a fluoro-functional organic group;

each R 13 is independently a divalent organic group;

each R 14 is independently a monovalent hydrocarbon group free of aliphatic unsaturation;

ν is 0 to 10; and

each R 15 is independently a hydrogen atom or an unsaturated monovalent organic group.

12. The composition of claim 1 , where component (IV) comprises

i) dimethylvinylsiloxy-terminated polymethyl3,3,3-trifluoropropyl siloxane,

ii) dimethylvinylsiloxy-terminated poly(methylhydrogensiloxane/methyl-6,6,6,5,5,4,4,3,3-nonafluorohexylsiloxane),

iii) trimethylsiloxy-terminated poly(methylhydrogensiloxane/methyl-6,6,6,5,5,4,4,3,3-nonafluorohexylsiloxane),

iv) trimethylsiloxy-terminated poly(methylhydrogensiloxane/methyl-3,3,3-trifluoropropyl),

v) trimethylsiloxy-terminated poly(methylvinylsiloxane/methyl-6,6,6,5,5,4,4,3,3-nonafluorohexylsiloxane) or

vi) combinations thereof.

13. The composition of claim 1 , where component (VI) comprises a transition metal chelate, an alkoxysilane, a combination of an alkoxysilane and a hydroxy-functional polyorganosiloxane, or a combination thereof.

14. The composition of claim 1 , where component (VI) comprises an unsaturated alkoxysilane, an epoxy-functional alkoxysilane, an epoxy-functional siloxane, or a combination thereof.

15. The composition of claim 1 , where component (VI) comprises an alkoxysilane of the formula R 28 μ Si(OR 29 ) (4-μ) , where

μ is 1, 2, or 3,

each R 28 is independently a monovalent organic group, with the proviso that at least one R 28 is an unsaturated organic group or an epoxy-functional group, and

each R 29 is independently an unsubstituted, saturated hydrocarbon group of at least 1 carbon atom.

16. The composition of claim 1 , where component (VI) comprises 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, (epoxycyclohexyl)ethyldimethoxysilane, (epoxycyclohexyl)ethyldiethoxysilane, vinyltrimethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, hexenyltrimethoxysilane, undecylenyltrimethoxysilane, 3-methacryloyloxypropyl trimethoxysilane, 3-methacryloyloxypropyl triethoxysilane, 3-acryloyloxypropyl trimethoxysilane, 3-acryloyloxypropyl triethoxysilane, or combinations thereof.

17. The composition of claim 1 , further comprising (VII) a void reducing agent, (VIII) a pigment, (IX) a filler, (X) a cure modifier, (XI) a rheology modifier, (XII) a spacer or a combination thereof.

18. The composition of claim 1 , further comprising an acid acceptor, an anti-oxidant, a stabilizer, a flame retardant, a flow control additive, a reactive diluent, an anti-settling agent, a silylating agent, a desiccant, a blowing agent, or combinations thereof.

19. The composition of claim 1 , where the composition adheres to metals.

20. The composition of claim 1 , where the composition has SiH tot /Vi tot of 1.05 to 5.0.

21. A kit comprising Part A and Part B, where

Part A comprises

(I) a polyorganosiloxane having an average of at least two unsaturated organic groups per molecule,

(III) a hydrosilylation catalyst,

optionally (IV) a fluoroorganosilicone having at least one functional group reactive with component (I),

optionally (V) an unsaturated ester-functional compound,

optionally (VI) an adhesion promoter,

optionally (VII) a void reducing agent,

optionally (VIII) a pigment,

optionally (IX) a filler,

optionally (X) an cure modifier,

optionally (XI) a rheology modifier,

optionally (XII) a spacer; and

Part B comprises

optionally (I) a polyorganosiloxane having at least two terminally-unsaturated organic groups per molecule,

(II) an organohydrogenpolysiloxane having an average of at least two silicon-bonded hydrogen atoms per molecule,

optionally (IV) a fluoroorganosilicone having at least one functional group reactive with component (I), component (II), or both,

optionally (V) an unsaturated ester-functional compound,

optionally (VI) an adhesion promoter,

optionally (VII) a void reducing agent,

optionally (VIII) a pigment,

optionally (IX) a filler,

optionally (X) an cure modifier,

optionally (XI) a rheology modifier, and

optionally (XII) a spacer,

with the provisos that

at least one of Part A and Part B contains component (IV),

at least one of Part A and Part B contains component (V),

component (V) comprises

or

v) a combination thereof; where

in formula i), each R 18 is independently a hydrogen atom, a monovalent hydrocarbon group of 1 to 4 carbon atoms, or CF 3 .

each R 19 is independently a divalent organic group of 1 to 20 carbon atoms,

each R 20 is independently a hydrogen atom or a monovalent hydrocarbon group of 1 to 20 carbon atoms,

in formula ii), n has an average value of 0 to 2 and m=4−n,

each R 21 is independently a hydroxyl group, or CF 3 ,

each R 22 is independently a hydrogen atom, a monovalent hydrocarbon group of 1 to 4 carbon atoms, or CF 3 ,

each R 23 is independently a hydrogen atom or a monovalent hydrocarbon group of 1 to 20 carbon atoms,

in formula iii), each R 24 is independently a fluoroalkyl group, an epoxy functional group, or a polyether group with the proviso that at least one of R 24 or R 25 is unsaturated, each R 25 is independently an oxygen-bridged monovalent organic group or a carbon-bridged carbonyl group,

in formula iv), each R 26 is independently a monovalent organic group or a hydrogen atom, with the proviso that at least one R 26 is an aliphatically unsaturated monovalent organic group or a hydrogen atom, and each R 27 is independently an oxygen atom or a divalent organic group; and

at least one of Part A and Part B contains component (VI).

22. The kit of claim 21 , further comprising information or instructions or both as how to use the kit, how to combine Part A and Part B, or how to cure the resulting combination, or combinations thereof.