Multilayer composite article

Patent metadata

Field	Value
Publication number	US-10213993-B2
Application number	US-201415105913-A
Country	US
Kind code	B2
Filing date	Dec 16, 2014
Priority date	Dec 19, 2013
Publication date	Feb 26, 2019
Grant date	Feb 26, 2019

Abstract

Described herein is composite article comprising a substrate; and on at least one face of the substrate a multilayered coating disposed thereon. The multilayered coating comprises (i) an abrasion-resistant layer adjacent to the substrate, wherein the abrasion-resistant layer comprises inorganic oxide nanoparticles and a polymer binder; and (ii) an antireflection layer adjacent to the abrasion-resistant layer opposite the substrate, wherein the antireflection layer comprises a fluorosilane polymer, wherein the fluorosilane polymer comprises: at least one monomeric unit A represented by the formula (I) wherein R 1 represents H or methyl, L 1 represents a covalent bond or a divalent aliphatic group having from 1 to 10 carbon atoms, each Y 1 independently represents a hydrocarbyl group having from 1 to 6 carbon atoms, each Y 2 independently represents a hydrolyzable group, g is 0, 1, or 2; and at least one divalent monomeric unit B represented by the formula (I) wherein R 2 , R 3 , and R 4 represent H, methyl, trifluoromethyl, or F, wherein at least one of R 2 , R 3 , and R 4 is F, R f 1 represents a covalent bond or a divalent group selected from the group consisting of —(CF 2 O) a —, —(CF 2 CF 2 O) b —, —(CF 2 CF 2 CF 2 O) c —, —(CF 2 CF 2 CF 2 CF 2 O) d —, —(CF 2 CF(CF 3 )O) e —, and combinations thereof, wherein a, b, c, d, and e represent integers in the range of from 0 to 130, and wherein 1≤a+b+c+d+e≤130, and R f 2 is a perfluoroalkyl group.

First claim

What is claimed is:

1. A composite article comprising:
a substrate; and on at least one face of the substrate, a multilayered coating is disposed, wherein the multilayered coating comprises:
(i) an abrasion-resistant layer adjacent to the substrate, wherein the abrasion-resistant layer has an index of refraction greater than 1.55, wherein the abrasion-resistant layer comprises inorganic oxide nanoparticles and a polymer binder, wherein the abrasion-resistant layer has a thickness of at least 0.5 microns; and
(ii) an antireflection layer adjacent to the abrasion-resistant layer opposite the substrate, wherein the antireflection layer has an index of refraction less than 1.48, and wherein the antireflection layer comprises a fluorosilane polymer, wherein the fluorosilane polymer comprises:
at least one monomeric unit A represented by the formula

wherein
R 1 represents H or methyl,
L 1 represents a covalent bond or a divalent aliphatic group having from 1 to 10 carbon atoms,
each Y 1 independently represents a hydrocarbyl group having from 1 to 6 carbon atoms,
each Y 2 independently represents a hydrolyzable group,
g is 0, 1, or 2; and

at least one divalent monomeric unit B represented by the formula

wherein
R 2 , R 3 , and R 4 represent H, methyl, trifluoromethyl, or F, wherein at least one of R 2 , R 3 , and R 4 is F,
R f 1 represents a covalent bond or a divalent group selected from the group consisting of —(CF 2 O) a —, —(CF 2 CF 2 O) b —, —(CF 2 CF 2 CF 2 O) c —, —(CF 2 CF 2 CF 2 CF 2 O) d —, —(CF 2 CF(CF 3 )O) e —, and combinations thereof, wherein a, b, c, d, and e represent integers in the range of from 0 to 130, and wherein 2≤a+b+c+d+e≤130, and
R f 2 is a perfluoroalkyl group.

2. A composite article according to claim 1 , wherein the fluorosilane polymer contains less than or equal to 0.49 percent by weight of fluorinated alkene.

3. A composite article according to claim 1 , wherein the weight ratio of the at least one monomeric unit B to the at least one monomeric unit A is at least 0.8.

4. A composite article according to claim 1 , wherein the average molar ratio of the at least one monomeric unit A to the at least one monomeric unit B is at least 1.

5. A composite article according to claim 1 , wherein the substrate is a curved film or a complex curve.

6. A composite article according to claim 1 , wherein the substrate comprises at least one of a plastic film, an eyewear lens, eyewear protection, and a safety shield.

7. A composite article according to claim 1 , wherein the antireflection layer further comprises anisotropic silica nanoparticles.

8. A composite article according to claim 1 , wherein the inorganic oxide nanoparticles comprise zirconia nanoparticles.

9. A composite article according to claim 1 , wherein the polymer binder comprises an acrylic polymer comprising a quaternary ammonium group.

10. A composite article according to claim 1 , wherein R f 1 represents a covalent bond or a divalent group selected from the group consisting of —(CF 2 O) a —, —(CF 2 CF 2 O) b —, —(CF 2 CF 2 CF 2 O) c —, —(CF 2 CF 2 CF 2 CF 2 O) d —, —(CF 2 CF(CF 3 )O) e —, and combinations thereof, wherein a, b, c, d, and e represent integers in the range of from 0 to 130, and wherein 2≤a+b+c+d+e≤130.

11. A composite article according to claim 1 , wherein the fluorosilane polymer further comprises:
p monomeric units C represented by the formula

wherein R 5 represents H or methyl, wherein p is a positive integer.

12. A composite article according to claim 11 , wherein on a relative molar basis, the fluorosilane polymer comprises from 9 to 11 moles of monomeric unit A, 8 to 10 moles of monomeric unit B, and 0.5 to 1.5 moles of monomeric unit C.

13. The composite article of claim 11 , wherein the inorganic nanoparticles are silica.

14. A composite article according to claim 1 , wherein Y 2 is selected from the group consisting of alkoxy groups having from 1 to 4 carbon atoms, alkanoyloxy groups having from 2 to 4 carbon atoms, a hydroxyl group, and Cl.

15. A composite article according to according to claim 1 , wherein R 2 , R 3 , and R 4 represent F.

16. A composite article according to according to claim 1 , wherein the at least one divalent monomeric unit B has an average sum of a+b+c+d+e in the range of from 30 to 40.

17. A composite article according to claim 1 , wherein the Rq value for the surface topography of the antireflection layer is greater than 0.3 nm after a Fourier spatial filter with a high pass cutoff frequency of 10000 mm −1 is applied.

18. A method of making a composite article, the method comprising:
providing a substrate;
disposing an abrasion-resistant layer on at least a portion of the substrate, wherein the abrasion-resistant layer has an index of refraction greater than 1.55, wherein the abrasion-resistant layer comprises inorganic oxide nanoparticles and a polymer binder; and
disposing an antireflection layer on at least a portion of the abrasion-resistant layer opposite the substrate, wherein the antireflection layer has an index of refraction less than 1.48, and wherein the antireflection layer comprises a fluorosilane polymer, wherein the fluorosilane polymer comprises:
at least one monomeric unit A represented by the formula

wherein
R 1 represents H or methyl,
L 1 represents a covalent bond or a divalent aliphatic group having from 1 to 10 carbon atoms,
each Y 1 independently represents a hydrocarbyl group having from 1 to 6 carbon atoms,
each Y 2 independently represents a hydrolyzable group,
g is 0, 1, or 2; and

at least one divalent monomeric unit B represented by the formula

wherein
R 2 , R 3 , and R 4 represent H, methyl, trifluoromethyl, or F, wherein at least one of R 2 , R 3 , and R 4 is F,
R f 1 represents a covalent bond or a divalent group selected from the group consisting of —(CF 2 O) a —, —(CF 2 CF 2 O) b —, —(CF 2 CF 2 CF 2 O) c —, —(CF 2 CF 2 CF 2 CF 2 O) d —, —(CF 2 CF(CF 3 )O) e —, and combinations thereof, wherein a, b, c, d, and e represent integers in the range of from 0 to 130, and wherein 2≤a+b+c+d+e≤130, and
R f 2 is a perfluoroalkyl group.

19. A composition comprising:
a) a fluorosilane polymer comprising:
at least one monomeric unit A represented by the formula

wherein
R 1 represents H or methyl,
L 1 represents a covalent bond or a divalent aliphatic group having from 1 to 10 carbon atoms,
each Y 1 independently represents a hydrocarbyl group having from 1 to 6 carbon atoms,
each Y 2 independently represents a hydrolyzable group,
g is 0, 1, or 2; and

at least one divalent monomeric unit B represented by the formula

wherein
R 2 , R 3 , and R 4 represent H, methyl, trifluoromethyl, or F, wherein at least one o

Assignees

• 3M Innovative Properties Co

Inventors

• Chen-Ho Kui
• Ylitalo Caroline M
• Yang Yu
• Lu Yongshang
• Levin Alan L
• Lechuga Hyacinth L
• Kong Steven H
• Iyer Suresh S
• Haugan Ingrid N
• Ali Mahfuza B

Classifications

• B32B37/14

  characterised by the properties of the layers · CPC title

• B32B7/02

  Physical, chemical or physicochemical properties · CPC title

• C09D143/04

  Homopolymers or copolymers of monomers containing silicon · CPC title

• B32B2551/00

  Optical elements · CPC title

• B32B27/308

  comprising acrylic (co)polymers · CPC title