Coating composition yielding abrasion-resistant tintable coating

• US 7,037,585 B2
• Filed: 06/23/2004
• Issued: 05/02/2006
• Est. Priority Date: 08/20/1999
• Status: Expired due to Term

• Current Assignee: Walman Optical Company The
• Original Assignee: Walman Optical Company The
• Inventors: Treadway, Gerald D.
• Primary Examiner(s): Mulcahy, Peter D.
• Application Number:
  US10/875,139
• Publication Number:
  US 20040234789A1
• Time in Patent Office: 678 Days
• Field of Search: 428/413, 428/447
• US Class Current: 428/413
• CPC Class Codes: C08F 283/12 on to polysiloxanes
• CPC Class Codes: C08G 59/306 containing silicon
• CPC Class Codes: C08G 59/3254 containing atoms other than carbon, hydrogen, oxygen or nitrogen
• CPC Class Codes: C08G 77/00 Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
• CPC Class Codes: C08G 77/04 Polysiloxanes
• CPC Class Codes: C08J 2483/00 Characterised by the use 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; Derivatives of such polymers
• CPC Class Codes: C08J 7/0427 with only one layer of a composition containing a polymer binder with more layers C08J7/042
• CPC Class Codes: C08J 7/043 Improving the adhesiveness of the coatings per se, e.g. forming primers adhesives in the form of films or foils characterised by the primer layers between the polymer carriers and the adhesives C09J7/50
• CPC Class Codes: C08J 7/046 Forming abrasion-resistant coatings; Forming surface-hardening coatings
• CPC Class Codes: C08K 5/5435 containing oxygen in a ring
• CPC Class Codes: C08L 2666/28 Non-macromolecular organic substances
• CPC Class Codes: C08L 2666/44 Silicon-containing compounds
• CPC Class Codes: C09D 163/00 Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
• CPC Class Codes: C09D 183/06 containing silicon bound to oxygen-containing groups C09D183/12 takes precedence
• CPC Class Codes: C09D 4/00 Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
• 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: G02B 1/111 using layers comprising organic materials
• CPC Class Codes: G02B 1/14 Protective coatings, e.g. hard coatings
• CPC Class Codes: Y10T 428/31507 Of polycarbonate
• CPC Class Codes: Y10T 428/31511 Of epoxy ether
• CPC Class Codes: Y10T 428/31663 : As siloxane, silicone or silane
• CPC Class Codes: Y10T 428/31667 : Next to addition polymer from unsaturated monomers, or aldehyde or ketone condensation product

Abstract

A coating composition based upon at least partially hydrolyzed epoxy-functional alkoxy silanes and having particular utility in forming tintable, abrasion resistant coatings on lenses. Incorporation in the composition of a non-hydrolyzed epoxy-functional alkoxy silane provides a desired reduction in viscosity. Incorporation in the composition of a polyether surfactant provides a cured coating of the composition with increased tintability.

Claims

1. A substrate having a transparent, abrasion-resistant coating formed by the use of a coating composition comprising:

a) the hydrolysis product of an epoxy-functional alkoxy silane,

b) a curing agent for polymerizing epoxy compounds, the curing agent comprising a cationic photoinitiator,

c) an ethylenically unsaturated monomer and photoactivated free-radical initiator therefore, and

d) a viscosity-reducing amount up to 50% by weight, solids basis, of an unhydrolyzed epoxy-functional alkoxy silane,

wherein the silanes of parts a) and d) are separately prepared and blended to form the composition and the composition is photocurable.

2. The coated substrate claim 1 wherein said ethylenically unsaturated monomer comprises an acrylic monomer.

3. The coated substrate of claim 2 wherein said acrylic monomer has an acrylic functionality not greater than two.

4. The coated substrate of claim 1 including an essentially non-reactive polyether surfactant in sufficient quantity to improve tintability of a cured coating formed from said composition.

5. The coated substrate of claim 4 wherein said polyether surfactant is a siloxane.

6. The coated substrate of claim 4 wherein said polyether surfactant is a polyalkaleneoxide siloxane.

7. The coated substrate of claim 4 wherein said polyether surfactant is an alkoxy polyethylene oxyalkanol.

8. The coated substrate of claim 4 in which the surfactant is at least partially water soluble.

9. The coated substrate of claim 4 in which the surfactant is insoluble in water.

10. The coated substrate of claim 1 wherein the epoxyfunctional alkoxy silanes of parts a) and d) are independently prepared from the group consisting of glycidoxymethyl-trimethoxysilane, glycidoxymethyltriethoxysilane, glycidoxymethyl-tripropoxysilane, glycidoxymethyl-tributoxysilane, β

-glycidoxyethyltrimethoxysilane, β

-glycidoxyethyltriethoxysilane, β

-glycidoxyethyl-tripropoxysilane, β

-glycidoxyethyl-tributoxysilane, β

-glycidoxyethyltrimethoxysilane, α

-glycidoxyethyl-triethoxysilane, α

-glycidoxyethyl-tripropoxysilane, α

-glycidoxyethyltributoxysilane, γ

-glycidoxypropyl-trimethoxysilane, γ

-glycidoxypropyl-triethoxysilane, γ

-glycidoxypropyl-tripropoxysilane, γ

-glycidoxypropyltributoxysilane, β

-glycidoxypropyl-trimethoxysilane, β

-glycidoxypropyl-triethoxysilane, β

-glycidoxypropyl-tripropoxysilane, β

-glycidoxypropyltributoxysilane, α

-glycidoxypropyl-trimethoxysilane, α

-glycidoxypropyl-triethoxysilane, α

-glycidoxypropyl-tripropoxysilane, α

-glycidoxypropyltributoxysilane, γ

-glycidoxybutyl-trimethoxysilane, δ

-glycidoxybutyl-triethoxysilane, δ

-glycidoxybutyl-tripropoxysilane, δ

-glycidoxybutyl-tributoxysilane, δ

-glycidoxybutyl-trimethoxysilane, γ

-glycidoxybutyl-triethoxysilane, γ

-glycidoxybutyl-tripropoxysilane, γ

-propoxybutyl-tributoxysilane, δ

-glycidoxybutyl-trimethoxysilane, δ

-glycidoxybutyl-triethoxysilane, δ

-glycidoxybutyl-tripropoxysilane, α

-glycidoxybutyl-trimethoxysilane, α

-glycidoxybutyl-triethoxysilane, α

-glycidoxybutyl-tripropoxysilane, α

-glycidoxybutyl-tributoxysilane, (3,4-epoxycyclohexyl)-methyl-trimethoxysilane, (3,4-epoxycyclohexyl)methyl-triethoxysilane, (3,4-epoxycyclohexyl)methyl-tripropoxysilane, (3,4-epoxycyclohexyl)-methyl-tributoxysilane, (3,4-epoxycyclohexyl)ethyl-trimethoxysilane, (3,4-epoxycyclohexyl)ethyl-triethoxysilane, (3,4-epoxycyclohexyl)ethyl-tripropoxysilane, (3,4-epoxycyclohexyl)-ethyl-tributoxysilane, (3,4-epoxycyclohexyl)propyl-trimethoxysilane, (3,4-epoxycyclohexyl)propyl-triethoxysilane, (3,4-epoxycyclohexyl)propyl-tripropoxysilane, (3,4-epoxycyclohexyl)propyl-tributoxysilane, (3,4-epoxycyclohexyl)butyl-trimethoxysilane, (3,4-epoxycyclohexy) butyl-triethoxysilane, (3,4-epoxycyclohexyl)-butyl-tripropoxysilane, and (3,4-epoxycyclohexyl)butyl-tributoxysilane.

11. The coated substrate of claim 1 wherein the silane of part a) is added in an amount sufficient to provide a concentration in the composition, based on weight (solids basis), of between about 10% to about 75%, and the silane of part d) is added in an amount sufficient to provide a concentration of not less than about 10%.

12. The coated substrate of claim 1 wherein the ethylenically unsaturated monomers comprise acrylic monomers and oligomers having acrylic functionalities of not greater than two.

13. The coated substrate of claim 11 wherein the monomers are selected from the group consisting of ethyl acrylate, butyl acrylate, 2-hydroxypropyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, neopentylglycol diacrylate, pentaerythritol triacrylate, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, tetraethylene glycol diacrylate, 1,3-butylene glycol diacrylate, trimethylolpropane trimethacrylate, 1,3-butylene glycol dimethacrylate, ethylene glycol dimethacrylate, pentaerythritol tetraacrylate, tetraethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, glycerol diacrylate, glycerol triacrylate, 1,3-propanediol diacrylate, 1,3-propanediol dimethacrylate, 1,2,4-butanetriol trimethacrylate, 1,4-cyclohexanediol diacrylate, 1,4-cyclohexanediol dimethacrylate, pentaerythritol diacrylate, and 1,5-pentanediol dimethacrylate.

14. The coated substrate of claim 12 wherein the monomers are employed at a weight concentration in the composition from about 10% to about 25%, on a solids basis.

15. The coated substrate of claim 1 wherein the cationic photoinitiator is selected from the group consisting of salts of Group Va elements, salts of Group VIa elements, and salts of Group VIIa elements.

16. The coated substrate according to claim 14 wherein the cationic photoinitiator comprises a diaryl iodonium hexafluoroantimonate.

17. The coated substrate according to claim 1 wherein the photoactivated free-radical initiator is selected from the group consisting of haloalkylated aromatic ketones, chloromethylbenzophenones, benzoin ethers, and acetophenone derivatives.

18. The coated substrate according to claim 16 wherein the initiator is selected from the group consisting of diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzil ketals, α

,α

-dimethoxy-α

-phenyl acetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, ethyl benzoin ether, isopropyl benzoin ether, dimethoxyphenyl acetophenone, diethoxy acetophenone, and benzophenone.

19. The coated substrate according to claim 1 wherein the composition is substantially free of volatile solvents.

20. The coated substrate according to claim 1 wherein the composition can be cured using ultraviolet radiation.

21. The coated substrate of claim 1 wherein the epoxyfunctional alkoxy silanes of parts a) and d) are independently prepared from the group consisting of glycidoxymethyl-trimethoxysilane, glycidoxymethyltriethoxysilane, glycidoxymethyl-tripropoxysilane, glycidoxymethyl-tributoxysilane, β

-glycidoxyethyltrimethoxysilane, β

-glycidoxyethyltriethoxysilane, β

-glycidoxyethyl-tripropoxysilane, β

-glycidoxyethyl-tributoxysilane, β

-glycidoxyethyltrimethoxysilane, α

-glycidoxyethyl-triethoxysilane, α

-glycidoxyethyl-tripropoxysilane, α

-glycidoxyethyltributoxysilane, γ

-glycidoxypropyl-trimethoxysilane, γ

-glycidoxypropyl-triethoxysilane, γ

-glycidoxypropyl-tripropoxysilane, γ

-glycidoxypropyltributoxysilane, β

-glycidoxypropyl-trimethoxysilane, β

-glycidoxypropyl-triethoxysilane, β

-glycidoxypropyl-tripropoxysilane, β

-glycidoxypropyltributoxysilane, α

-glycidoxypropyl-trimethoxysilane, α

-glycidoxypropyl-triethoxysilane, α

-glycidoxypropyl-tripropoxysilane, α

-glycidoxypropyltributoxysilane, γ

-glycidoxybutyl-trimethoxysilane, δ

-glycidoxybutyl-triethoxysilane, δ

-glycidoxybutyl-tripropoxysilane, δ

-glycidoxybutyl-tributoxysilane, δ

-glycidoxybutyl-trimethoxysilane, γ

-glycidoxybutyl-triethoxysilane, γ

-glycidoxybutyl-tripropoxysilane, γ

-propoxybutyl-tributoxysilane, δ

-glycidoxybutyl-trimethoxysilane, δ

-glycidoxybutyl-triethoxysilane, δ

-glycidoxybutyl-tripropoxysilane, α

-glycidoxybutyl-trimethoxysilane, α

-glycidoxybutyl-triethoxysilane, α

-glycidoxybutyl-tripropoxysilane, α

-glycidoxybutyl-tributoxysilane, (3,4-epoxycyclohexyl)-methyl-trimethoxysilane, (3,4-epoxycyclohexyl)methyl-triethoxysilane, (3,4-epoxycyclohexyl)methyl-tripropoxysilane, (3,4-epoxycyclohexyl)-methyl-tributoxysilane, (3,4-epoxycyclohexyl)ethyl-trimethoxysilane, (3,4-epoxycyclohexyl)ethyl-triethoxysilane, (3,4-epoxycyclohexyl)ethyl-tripropoxysilane, (3,4-epoxycyclohexyl)-ethyl-tributoxysilane, (3,4-epoxycyclohexyl)propyl-trimethoxysilane, (3,4-epoxycyclohexyl)propyl-triethoxysilane, (3,4-epoxycyclohexyl)propyl-tripropoxysilane, (3,4-epoxycyclohexyl)propyl-tributoxysilane, (3,4-epoxycyclohexyl)butyl-trimethoxysilane, (3,4-epoxycyclohexy) butyl-triethoxysilane, (3,4-epoxycyclohexyl)-butyl-tripropoxysilane, and (3,4-epoxycyclohexyl)butyl-tributoxysilane,

and wherein the ethylenically unsaturated monomers are selected from the group consisting of ethyl acrylate, butyl acrylate, 2-hydroxypropyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, neopentylglycol diacrylate, pentaerythritol triacrylate, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, tetraethylene glycol diacrylate, 1,3-butylene glycol diacrylate, trimethylolpropane trimethacrylate, 1,3-butylene glycol dimethacrylate, ethylene glycol dimethacrylate, pentaerythritol tetraacrylate, tetraethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, glycerol diacrylate, glycerol triacrylate, 1,3-propanediol diacrylate, 1,3-propanediol dimethacrylate, 1,2,4-butanetriol trimethacrylate, 1,4-cyclohexanediol diacrylate, 1,4-cyclohexanediol dimethacrylate, pentaerythritol diacrylate, and 1,5-pentanediol dimethacrylate,

and wherein the cationic photoinitiator is selected from the group consisting of salts of Group Va elements, salts of Group VIa elements, and salts of Group VIIa elements,

and wherein the photoactivated free-radical initiator is selected from the group consisting of diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzil ketals, α

,α

-dimethoxy-α

-phenyl acetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, ethyl benzoin ether, isopropyl benzoin ether, dimethoxyphenyl acetophenone, diethoxy acetophenone, and benzophenone,

and wherein the composition is substantially free of volatile solvents and can be cured using ultraviolet radiation.

22. A coated substrate according to claim 1 wherein the substrate comprises an eyeglass lens.

23. A coated substrate according to claim 22 wherein the lens is prepared from a material selected from polycarbonate or poly(methylmethacrylate).

24. A coated substrate according to claim 10 wherein the substrate comprises an eyeglass lens.

25. A coated substrate according to claim 24 wherein the lens is prepared from a material selected from polycarbonate or poly(methylmethacrylate).

26. A coated substrate according to claim 21 wherein the substrate comprises an eyeglass lens.

27. A coated substrate according to claim 26 wherein the lens is prepared from a material selected from polycarbonate or poly(methylmethacrylate).