Antisoiling coatings for antireflective surfaces and methods of preparation

• US 5,851,674 A
• Filed: 07/30/1997
• Issued: 12/22/1998
• Est. Priority Date: 07/30/1997
• Status: Expired due to Term

• Current Assignee: 3M Company
• Original Assignee: 3M Company
• Inventors: Pellerite, Mark J., Zhu, Dong-Wei, Invie, Judith M.
• Primary Examiner(s): LUSIGNAN, MICHAEL R
• Application Number:
  US08/902,666
• Time in Patent Office: 510 Days
• Field of Search: 429/162-9, 428/421, 428/422, 428/447, 428/450, 428/202, 204/192.26, 427/443.2
• US Class Current: 428/421
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: C08G 77/22 containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen C08G77/045 takes precedence
• CPC Class Codes: C08G 77/24 halogen-containing groups
• 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: G02B 1/111 using layers comprising organic materials
• CPC Class Codes: Y10T 428/3154 Of fluorinated addition polymer from unsaturated monomers
• CPC Class Codes: Y10T 428/31544 Addition polymer is perhalogenated
• CPC Class Codes: Y10T 428/31663 As siloxane, silicone or silane

Abstract

An antisoiling coating for an antireflective surface, particularly the outer surface of an antireflective film stack, wherein the antisoiling coating includes a fluorinated siloxane, preferably prepared by applying a coating composition of a fluorinated silane of the following formula:

R.sub.f --R.sup.1 --SiX.sub.3-x R.sup.2.sub.x

wherein:

R_f is a perfluorinated group optionally containing one or more heteroatoms;

R¹ is a divalent alkylene group, arylene group, or mixture thereof, substituted with one or more heteroatoms or functional groups, containing about 2 to about 16 carbon atoms;

R² is a lower alkyl group;

X is a halide, a lower alkoxy group, or an acyloxy group; and

x is 0 or 1.

Claims

1. An antireflective article comprising a substrate having an antireflective surface and an antisoiling coating of less than about 100 Angstroms thick deposited thereon;

wherein the antisoiling coating comprises a fluorinated siloxane prepared by applying a coating composition comprising a fluorinated silane of the following formula;

space="preserve" listing-type="equation">R.sub.f --R.sup.1 --SiX.sub.3-x R.sup.2.sub.x

wherein;

R_f is a perfluorinated group optionally containing one or more heteroatoms;

R¹ is a divalent alkylene group, arylene group, or mixture thereof, substituted with one or more heteroatoms or functional groups, containing about 2 to about 16 carbon atoms;

R² is a lower alkyl group;

X is a halide, a lower alkoxy group, or an acyloxy group; and

x is 0 or 1.

2. The antireflective article of claim 1 wherein the antireflective surface comprises a metal oxide film having one or more metal oxides.

3. The antireflective article of claim 2 wherein the antireflective surface comprises a sputter coated metal oxide film.

4. The antireflective article of claim 3 wherein the antisoiling coating is at least about 20 Angstroms thick.

5. The antireflective article of claim 1 wherein the antisoiling coating comprises a fluorinated siloxane base film of an approximately monolayer thickness on which is adsorbed oligomeric fluorinated siloxane material in an amount that does not significantly reduce the antireflective characteristics of the antireflective article.

6. The antireflective article of claim 1 which has a first surface antireflectivity that is less than about 0.2 percent different than that of the same article without the antisoiling coating.

7. The antireflective article of claim 1 wherein the coating is prepared by applying a coating composition comprising a fluorinated silane wherein each X is a halide.

8. The antireflective article of claim 1 wherein the coating is prepared by applying a coating composition comprising a fluorinated silane wherein R_f is a perfluoroalkyl group of the formula C_n F_2n.sbsb.+₁ wherein n is about 4 to about 20.

9. The antireflective article of claim 8 wherein the coating is prepared by applying a coating composition comprising a fluorinated silane wherein R_f is a perfluoroalkyl group of the formula C_n F_2n.sbsb.+₁ wherein n is about 7 to about 10.

10. The antireflective article of claim 1 wherein the coating is prepared by applying a coating composition comprising a fluorinated silane selected from the group of C₇ F₁₅ CH₂ OCH₂ CH₂ CH₂ SiCl₃, C₇ F₁₅ CH₂ OCH₂ CH₂ CH₂ Si(CH₃)Cl₂, C₇ F₁₅ CH₂ OCH₂ CH₂ CH₂ SiCl(OCH₃)₂, C₇ F₁₅ CH₂ OCH₂ CH₂ CH₂ SiCl₂ (OC₂ H₅), C₈ F₁₇ SO₂ N(Et)CH₂ CH₂ CH₂ SiCl₃, C₈ F₁₇ SO₂ N(Me)CH₂ CH₂ CH₂ Si(CH₃)Cl₂, and C₇ F₁₅ CH₂ OCH₂ CH₂ CH₂ Si(OAc)₃, and mixtures thereof.

11. An antireflective article comprising a substrate having an antireflective surface and an antisoiling coating deposited thereon;

wherein the antisoiling coating comprises a fluorinated siloxane base film of an approximately monolayer thickness on which is adsorbed oligomeric fluorinated siloxane material in an amount that does not substantially change the antireflective characteristics of the antireflective article;

wherein the fluorinated siloxane is prepared by applying a coating composition comprising a fluorinated silane of the following formula;

space="preserve" listing-type="equation">R.sub.f --R.sup.1 --SiX.sub.3-x R.sup.2.sub.x

wherein;

R_f is a perfluorinated group optionally containing one or more heteroatoms;

R¹ is a divalent alkylene group, arylene group, or mixture thereof, substituted with one or more heteroatoms or functional groups, containing about 2 to about 16 carbon atoms;

R² is a lower alkyl group;

X is a halide, a lower alkoxy group, or an acyloxy group; and

x is 0 or 1.

12. The antireflective article of claim 11 wherein the antireflective surface comprises a metal oxide film having one or more metal oxides.

13. The antireflective article of claim 12 wherein the antireflective surface comprises a sputter coated metal oxide film.

14. The antireflective article of claim 11 which has a first surface antireflectivity that is less than about 0.2 percent different than that of the same article without the antisoiling coating.

15. An antireflective article comprising a substrate having an antireflective surface and an antisoiling coating deposited thereon;

wherein the antisoiling coating is less than about 100 Angstroms thick and comprises a fluorinated siloxane base film of an approximately monolayer thickness on which is adsorbed oligomeric fluorinated siloxane material in an amount that does not significantly reduce the antireflective characteristics of the antireflective article.

16. A method of applying an antisoiling coating to a substrate having an antireflective surface, the method comprising treating the antireflective surface with a coating composition comprising a fluorinated silane without subsequent processing;

wherein the fluorinated silane has the following formula;

space="preserve" listing-type="equation">R.sub.f --R.sup.1 --SiX.sub.3-x R.sup.2.sub.x

wherein;

R_f is a perfluorinated group optionally containing one or more heteroatoms;

R¹ is a divalent alkylene group, arylene group, or mixture thereof, substituted with one or more heteroatoms or functional groups, containing about 2 to about 16 carbon atoms;

R² is a lower alkyl group;

X is a halide, a lower alkoxy group, or an acyloxy group; and

x is 0 or 1.

17. The method of claim 16 wherein the coating is prepared by applying a coating composition comprising a fluorinated silane selected from the group of C₇ F₁₅ CH₂ OCH₂ CH₂ CH₂ SiCl₃, C₇ F₁₅ CH₂ OCH₂ CH₂ CH₂ Si(CH₃)Cl₂, C₇ F₁₅ CH₂ OCH₂ CH₂ CH₂ SiCl(OCH₃)₂, C₇ F₁₅ CH₂ OCH₂ CH₂ CH₂ SiCl₂ (OC₂ H₅), C₈ F₁₇ SO₂ N(Et)CH₂ CH₂ CH₂ SiCl₃, C₈ F₁₇ SO₂ N(Me)CH₂ CH₂ CH₂ Si(CH₃)Cl₂, and C₇ F₁₅ CH₂ OCH₂ CH₂ CH₂ Si(OAc)₃, and mixtures thereof.

18. The method of claim 16 wherein the antisoiling coating formed comprises a fluorinated siloxane base film of an approximately monolayer thickness on which is adsorbed oligomeric fluorinated siloxane material.

19. The method of claim 16 wherein the antisoiling coating formed is less than about 100 Angstroms thick.

20. The method of claim 19 wherein the antisoiling coating formed is at least about 20 Angstroms thick.

21. The method of claim 16 wherein the step of treating is carried out at room temperature.

22. The method of claim 16 wherein the coating composition comprising the fluorinated silane comprises less than about 2.0 weight percent of the fluorinated silane.

23. The method of claim 16 wherein the antireflective substrate is treated with a coating composition comprising a fluorinated silane for less than 30 minutes.

24. The method of claim 23 wherein the antireflective substrate is treated with a coating composition comprising a fluorinated silane for less than about 10 minutes.

25. The method of claim 16 wherein the step of treating comprises immersing the substrate in the coating composition comprising the fluorinated silane and removing the coated antireflective substrate, wherein upon removal the coated substrate emerges substantially autophobic.

26. The method of claim 16 wherein the coating composition comprising the fluorinated silane further comprises a nonchlorinated solvent.

27. The method of claim 26 wherein the solvent is selected from the group of an alkane, a fluorinated alkane, an alkyl perfluoroalkyl ether, and mixtures thereof.

28. The method of claim 27 wherein the solvent is a mixture of a paraffinic solvent and an alkyl perfluoroalkyl ether.

29. A method of applying an antisoiling coating to a substrate having an antireflective surface, the method consisting essentially of treating the antireflective surface with a coating composition comprising less than about 0.5 weight percent of a fluorinated silane for less than 30 minutes;

wherein the fluorinated silane has the following formula;

space="preserve" listing-type="equation">R.sub.f --R.sup.1 --SiX.sub.3-x R.sup.2.sub.x

wherein;

R_f is a perfluorinated group optionally containing one or more heteroatoms;

R¹ is a divalent alkylene group, arylene group, or mixture thereof, substituted with one or more heteroatoms or functional groups, containing about 2 to about 16 carbon atoms;

R² is a lower alkyl group;

X is a halide, a lower alkoxy group, or an acyloxy group; and

x is 0 or 1.

30. The method of claim 29 wherein the step of treating comprises immersing the substrate in the coating composition comprising the fluorinated silane and removing the coated antireflective substrate, wherein upon removal the coated substrate emerges substantially autophobic.

31. A method of applying an antisoiling coating to a substrate having an antireflective surface, the method comprising immersing the substrate in a coating composition comprising less than about 0.5 weight percent of a fluorinated silane for less than about 20 minutes and removing the coated antireflective substrate, wherein upon removal the coated substrate emerges substantially autophobic.

32. A method of applying an antisoiling coating to a substrate having an antireflective surface, the method comprising immersing the substrate in a coating composition comprising a fluorinated silane of the following formula:

space="preserve" listing-type="equation">R.sub.f --R.sup.1 --SiX.sub.3-x R.sup.2.sub.x

wherein;

R_f is a perfluorinated group optionally containing one or more heteroatoms;

R¹ is a divalent alkylene group, arylene group, or mixture thereof, substituted with one or more heteroatoms or functional groups, containing about 2 to about 16 carbon atoms;

R² is a lower alkyl group;

X is a halide, a lower alkoxy group, or an acyloxy group; and

x is 0 or 1;

wherein the antisoiling coating formed has a thickness of less than about 100 Angstroms.

33. The method of claim 32 wherein the antireflective surface comprises a metal oxide film having one or more metal oxides.

34. The method of claim 33 wherein the antireflective surface comprises a sputter coated metal oxide film.

35. An antireflective article made by the method of claim 32.

36. A method of applying an antisoiling coating to a substrate having an antireflective surface, the method comprising immersing the substrate in a coating composition comprising a fluorinated silane of the following formula:

space="preserve" listing-type="equation">R.sub.f --R.sup.1 --SiX.sub.3-x R.sup.2.sub.x

wherein;

R_f is a perfluorinated group optionally containing one or more heteroatoms;

R¹ is a divalent alkylene group, arylene group, or mixture thereof, substituted with one or more heteroatoms or functional groups, containing about 2 to about 16 carbon atoms;

R² is a lower alkyl group;

X is a halide, a lower alkoxy group, or an acyloxy group; and

x is 0 or 1;

wherein the antisoiling coating comprises a fluorinated siloxane base film of an approximately monolayer thickness on which is adsorbed oligomeric fluorinated siloxane material in an amount that does not substantially change the antireflective characteristics of the antireflective article.

37. An antireflective article made by the method of claim 36.

38. A method of applying an antisoiling coating to a substrate having an antireflective surface, the method comprises immersing the substrate in a coating composition comprising less than about 0.5 weight percent of a fluorinated silane for less than about 5 minutes without subsequent processing;

wherein the fluorinated silane is of the following formula;

space="preserve" listing-type="equation">R.sub.f --R.sup.1 --SiX.sub.3-x R.sup.2.sub.x

wherein;

R_f is a perfluorinated group optionally containing one or more heteroatoms;

R¹ is a divalent alkylene group, arylene group, or mixture thereof, substituted with one or more heteroatoms or functional groups, containing about 2 to about 16 carbon atoms;

R² is a lower alkyl group;

X is a halide, a lower alkoxy group, or an acyloxy group; and

x is 0 or 1;

wherein the antisoiling coating formed has a thickness of less than about 100 Angstroms and comprises a fluorinated siloxane base film of an approximately monolayer thickness on which is adsorbed oligomeric fluorinated siloxane material in an amount that does not substantially change the antireflective characteristics of the antireflective article.

39. An antireflective article made by the method of claim 38.