Solventless, ultraviolet radiation-curable silicone coating compositions

• US 4,486,504 A
• Filed: 03/19/1982
• Issued: 12/04/1984
• Est. Priority Date: 03/19/1982
• Status: Expired due to Term

• Current Assignee: General Electric Company
• Original Assignee: General Electric Company
• Inventors: Chung, Rack H.
• Primary Examiner(s): Marquis, Melvyn I.
• Assistant Examiner(s): KOECKERT JR, ARTHUR
• Application Number:
  US06/359,989
• Time in Patent Office: 991 Days
• Field of Search: 204/159.13, 428/412
• US Class Current: 428/412
• CPC Class Codes: C08F 290/148 Polysiloxanes
• CPC Class Codes: C08F 299/08 from polysiloxanes
• CPC Class Codes: C08L 2666/28 Non-macromolecular organic substances
• CPC Class Codes: C08L 2666/54 Inorganic substances
• CPC Class Codes: C09D 183/06 containing silicon bound to oxygen-containing groups C09D183/12 takes precedence
• 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: Y10S 522/907 involving precursor of an ultraviolet absorber, e.g. monobenzoate
• CPC Class Codes: Y10T 428/31507 Of polycarbonate
• CPC Class Codes: Y10T 428/31529 Next to metal
• CPC Class Codes: Y10T 428/31663 As siloxane, silicone or silane

Abstract

An ultraviolet radiation-curable silicone coating composition is disclosed which, when applied to a solid substrate, provides an abrasion-resistant coating firmly adhered thereon. The silicone coating composition is free of residual solvent and free of toxic hydroxy acrylates, and is prepared from the hydrolysis products of acryloxy-functional silanes and/or glycidoxy-functional silanes, colloidal silica and a photoinitiator.

Claims

1. A solventless ultraviolet radiation-curable coating composition free of hydroxy acrylates comprising:

(A) 100 parts by weight silica in the form of a colloidal dispersion;

(B) 5 to 500 parts by weight of an acid hydrolysis product of

(i) an acryloxy-functional silane having a general formula;

##STR9## wherein R³ and R⁴ are the same or different monovalent hydrocarbon radicals, R⁵ is a divalent hydrocarbon radical having from 2 to 8 carbon atoms, R⁶ is hydrogen or a monovalent hydrocarbon radical, b is an integer from 1 to 3, c is an integer from 0 to 2, and d is an integer equaling 4-b-c;

or

(ii) a glycidoxy-functional silane having a general formula;

##STR10## wherein R⁷ and R⁸ are the same or different monovalent hydrocarbon radicals, R⁹ is a divalent hydrocarbon radical having from 2 to 8 carbon atoms, e is an integer from 1 to 3, f is an integer from 0 to 2, and g is an integer equaling 4-e-f;

or

(iii) a mixture of (i) and (ii); and

(C) a catalytic amount of an ultraviolet light sensitive photoinitiator or mixture of photoinitiators;

wherein residual solvent has been removed from said coating composition at reduced pressure.

2. A composition as defined in claim 1 which additionally contains 10 to 500 parts by weight of a non-silyl, non-hydroxy acrylate.

3. A composition as defined in claim 1 or 2 wherein said acryloxy-functional silane is selected from the group consisting of:

3-methacryloxypropyltrimethoxysilane

3-acryloxypropyltrimethoxysilane

2-methacryloxyethyltrimethoxysilane

2-acryloxyethyltrimethoxysilane

3-methacryloxypropyltriethoxysilane

3-acryloxypropyltriethoxysilane

2-acryloxyethyltriethoxysilane.

4. A composition as defined in claim 1 or 2 wherein said glycidoxy-functional silane is selected from the group consisting of:

3-glycidoxypropyltrimethoxysilane

2-glycidoxyethyltrimethoxysilane

3-glycidoxypropyltriethoxysilane

2-glycidoxyethyltriethoxysilane.

5. A composition as defined in claim 2 wherein said non-silyl acrylate is selected from the group consisting of:

diethylene glycol diacrylate

triethylene glycol diacrylate

tetraethylene glycol diacrylate

trimethylol propane triacrylate

tetrahydro furfuryl methacrylate

1-6-hexanediol diacrylate.

6. A composition as defined in claim 1 or 2 wherein said photoinitiator is a radiation sensitive aromatic onium salt having the formula:

##STR11## wherein X is a radical selected from I, P or S; and

M is a metal or metalloid and Q is a halogen radical selected from Cl, F, Br, or I;

R¹⁰ is hydrogen or a monovalent hydrocarbon radical having 1 to 12 carbon atoms, h is an integer having a value of 4 to 6 inclusive, and n is an integer having a value of 2 or 3.

7. A composition as defined in claim 6 wherein MQ_h^- is selected from SbF₆^-, AsF₆^-, BF₄^-, and PF₆^-.

8. A composition as defined in claim 6 wherein said photoinitiator is further combined with 0.5 to 5.0 parts of a radical-type photoinitiator.

9. A composition as in claim 8 wherein said radical-type photoinitiator is selected from ethyl benzoin ether, isopropyl benzoin ether, dimethoxyphenylacetophenone and diethoxyacetophenone.

10. A composition as defined in claim 1 or 2 which also contains a small amount of polysiloxane polyether copolymer flow control additive.

11. A composition as defined in claim 1 or 2 which additionally contains a photo-modifiable compound which is capable of converting to an ultraviolet radiation screening agent upon curing of the coating composition.

12. A composition as defined in claim 11 wherein the photo-modifiable compound has the formula:

##STR12## where R is hydrogen (H) or methyl (Me).

18. The cured product of claim 1 or 2.

19. A solid substrate having at least one surface coated with the coating composition of claim 1 or 2.

20. An article as defined in claim 19 wherein the solid substrate is comprised of a synthetic organic polymer.

21. An article as defined in claim 19 wherein said solid substrate is a metal.

22. An article as defined in claim 19 wherein said solid substrate is a synthetic organic polymer having a metallized surface.

23. An article as defined in claim 20 wherein said polymer is a transparent polymer.

24. An article as defined in claim 20 wherein said polymer is a polycarbonate.

25. An article as defined in claim 24 wherein said polycarbonate is transparent.

26. An article as defined in claim 24 wherein said polycarbonate is a poly (bisphenol-A carbonate).

27. An article as defined in claim 19 wherein the coating composition has been cured on said surface of said solid substrate by an effective amount of ultraviolet radiation.

28. An article as defined in claim 19 wherein said surface of said solid substrate has been primed with a primer composition prior to being coated.

29. An article as defined in claim 28 wherein said primer composition is comprised of a thermosetting acrylic emulsion.

30. An article as defined in claim 20 wherein said polymer is polymethylmethacrylate.

13. A process for preparing a solventless ultraviolet radiation curable coating composition free of hydroxy acrylates comprising:

(1) Combining

(A) 100 parts by weight silica in the form of a colloidal dispersion;

(B) 5 to 500 parts by weight of the acid hydrolysis product of

(i) an acryloxy-functional silane of the formula;

##STR13## wherein R³ and R⁴ are the same or different monovalent hydrocarbon radicals, R⁵ is a divalent hydrocarbon radical having from 2 to 8 carbon atoms, R⁶ is hydrogen or a monovalent hydrocarbon radical, b is an integer from 1 to 3, c is an integer from 0 to 2, and d is an integer equal to 4-b-c;

or

(ii) a glycydoxy-functional silane of the formula;

##STR14## wherein R⁷ and R⁸ are the same or different monovalent hydrocarbon radicals, R⁹ is a divalent hydrocarbon radical having from 2 to 8 carbon atoms, e is an integer from 1 to 3, f is an integer from 0 to 2, and g is an integer equal to 4-e-f;

or

(iii) mixtures of (i) and (ii);

(2) adding a catalytic amount of an ultraviolet light sensitive photoinitiator; and

thereafter

(3) removing residual solvent at reduced pressure.

14. The process of claim 13 which contains the additional step, before step (2), of adding 10-500 parts by weight of a non-silyl, non-hydroxy acrylate.

15. The process of claim 13 or 14 which also contains a small amount of polysiloxane polyether copolymer flow control additive.

16. The process of claims 13 or 14 which additionally contains a photo-modifiable compound which is capable of converting to an ultraviolet radiation screening agent upon curing of the coating composition.

17. The process of claim 16 wherein the photo-modifiable compound has the formula:

##STR15## where R is hydrogen (H) or methyl (Me).