Composition containing fluoroalkyl silicone and hydrosilicone

• US 7,407,710 B2
• Filed: 04/14/2006
• Issued: 08/05/2008
• Est. Priority Date: 04/14/2006
• Status: Expired due to Fees

• Current Assignee: 3M Innovative Properties Company (3M Company)
• Original Assignee: 3M Innovative Properties Company (3M Company)
• Inventors: Qiu, Zai-Ming, Walker, Christopher B. Jr., Liu, Lan Hong
• Primary Examiner(s): Gulakowski; Randy
• Assistant Examiner(s): LOEWE, ROBERT S
• Application Number:
  US11/279,803
• Publication Number:
  US 20070254167A1
• Time in Patent Office: 844 Days
• Field of Search: 525/477
• US Class Current: 428/447
• CPC Class Codes: C08F 222/103 of trialcohols, e.g. trimethylolpropane tri(meth)acrylate
• CPC Class Codes: C08F 230/08 containing silicon
• CPC Class Codes: C08F 283/128 on to reaction products of polysiloxanes having at least one Si-H bond and compounds having carbon-to-carbon double bonds
• CPC Class Codes: C08G 77/12 containing silicon bound to hydrogen C08G77/045 takes precedence
• CPC Class Codes: C08G 77/24 halogen-containing groups
• CPC Class Codes: C08K 5/56 Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
• CPC Class Codes: C08L 83/00 Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
• CPC Class Codes: C09D 183/04 Polysiloxanes
• CPC Class Codes: C09D 4/06 Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
• CPC Class Codes: Y10T 428/31663 As siloxane, silicone or silane

Abstract

Described is a free-radically curable composition comprising a fluoroalkyl silicone having at least two ethylenically unsaturated groups, silicone having at least two Si—H, a polyethylenically unsaturated component having at least two ethylenically unsaturated groups, a hydrosilylation catalyst, and a free radical initiator.

Claims

1. A free-radically curable composition comprising:

a) 80 to 99.5 parts by weight of a polyethylenically unsaturated component having at least two ethylenically unsaturated groups,

b) a fluoroalkyl silicone having at least two ethylenically unsaturated groups,

c) a hydrosilicone having at least two Si—

H groups, the total of b) and c) being at least 0.5 parts by weight,

d) a hydrosilylation catalyst, and

e) a free radical polymerization catalyst.

2. The composition of claim 1 comprising:

a hydrosilylation reaction product of the fluoroalkyl silicone having at least two ethylenically unsaturated groups, and the hydrosilicone having at least two Si—

H groups.

3. The composition of claim 1 wherein the fluoroalkyl silicone is of the formula:

4. The composition of claim 3 wherein R_f is of the formula C_nF_2n+1(C_mH_2mO)_dC_pH_2p—

, or C_nF_2n+1CHFCF₂(C_mH_2mO)_dC_pH_2p—

or C_nF_2n+1OCHFCF₂(C_mH_2mO)_dC_pH_2p—

wherein n is an integer of 1 to 12, m is an integer of 1 to 12, d is 0 or 1, and p is an integer of 2 to 12.

5. The composition of claim 4 where n is 3 to 6.

6. The composition of claim 3 wherein Z is selected from alkenyl groups, alkynyl groups, vinyloxyalkylene, allyloxyalkylene, and (meth)acryloyl groups.

7. The composition of claim 3 wherein the fluoroalkyl silicone is of the formula:

8. The composition of claim 3 wherein the fluoroalkyl silicone is of the formula:

9. The composition of claim 1 wherein said polyethylenically unsaturated component is of the formula

R⁴(Z′

)_p, wherein R⁴ is a non-urethane organic moiety of valency p, p is at least 2, and Z′

is an ethylenically unsaturated polymerizable group, reactive with said ethylenically unsaturated group of said fluoroalkyl silicone.

10. The composition of claim 9 wherein R⁴ is an aliphatic moiety of valency p.

11. The composition of claim 1 wherein said polyethylenically unsaturated component is an acrylated polyol.

12. The composition of claim 11 wherein said hydrosilicone having at least two Si—

H groups is of the formula;

13. The composition of claim 1 wherein the hydrosilicone having at least two Si—

H groups is of the formula;

14. The composition of claim 13 wherein said hydrosilicone having at least two Si—

H groups is of the formula;

15. The composition of claim 13 wherein said hydrosilicone having at least two Si—

H groups is of the formula;

16. The composition of claim 1 wherein said a polyethylenically unsaturated component comprises surface functionalized inorganic nanoparticles, having a plurality of ethylenically unsaturated groups.

17. The composition of claim 16, wherein said inorganic nanoparticles comprise a plurality of (meth)acryloyl surface functional groups.

18. The composition of claim 1, further comprising a mono (meth)acryloyl compound having a functional group.

19. The composition of claim 1 wherein the molar ratio of Si—

H groups is less than or equal to the molar amount of ethylenically unsaturated groups of said fluoroalkyl silicone and the ethylenically unsaturated groups of the polyethylenically unsaturated component.

20. The composition of claim 1 wherein said polyethylenically unsaturated component comprises surface modified zirconia nanoparticles.

21. A method of providing a coating onto a substrate comprising the steps of:

a) coating a substrate with the composition of claim 1 and curing the coating with a hydrosilylation catalyst and a free radical initiator.

22. The method of claim 21 wherein composition comprises the reaction product of fluoroalkyl silicone having at least two ethylenically unsaturated groups, and the hydrosilicone having at least two Si—

H, effected by the hydrosilylation catalyst.

23. The method of claim 21 wherein the coating is cured by UV.

24. The method of claim 21 wherein the substrate is selected from vinyl, wood, glass, stone, metals, ceramics, masonry, paint, plastics and thermoplastic resins.

25. A coated substrate comprising the cured composition of claim 1.

26. The coated substrate of claim 25, wherein the substrate is selected from vinyl, wood, glass, stone, metals, ceramics, masonry, paint, plastics and thermoplastic resins.

27. The coated substrate of claim 25 wherein said coating has an index of refraction of at least 1.6.