Low-color scratch-resistant articles with a multilayer optical film

• US 10,444,408 B2
• Filed: 04/29/2016
• Issued: 10/15/2019
• Est. Priority Date: 05/07/2013
• Status: Active Grant

• Current Assignee: Corning Incorporated
• Original Assignee: Corning Incorporated
• Inventors: Bellman, Robert Alan, Hart, Shandon Dee, Koch, III, Karl William, Paulson, Charles Andrew, Price, James Joseph
• Primary Examiner(s): Kakalec, Kimberly N.
• Application Number:
  US15/142,508
• Publication Number:
  US 20160238743A1
• Time in Patent Office: 1,264 Days
• CPC Class Codes: C03C 17/3435 comprising a nitride, oxynitride, boronitride or carbonitride
• CPC Class Codes: C03C 2217/734 comprising an alternation of high and low refractive indexes
• CPC Class Codes: C03C 2217/78 Coatings specially designed to be durable, e.g. scratch-resistant
• CPC Class Codes: G02B 1/10 Optical coatings produced by application to, or surface treatment of, optical elements G02B1/08 takes precedence
• CPC Class Codes: G02B 1/113 using inorganic layer materials only
• CPC Class Codes: G02B 1/115 Multilayers
• CPC Class Codes: G02B 1/14 Protective coatings, e.g. hard coatings
• CPC Class Codes: Y10T 428/24942 including components having same physical characteristic in differing degree
• CPC Class Codes: Y10T 428/315 Surface modified glass [e.g., tempered, strengthened, etc.]

Abstract

Embodiments of this disclosure pertain to articles that exhibit scratch-resistance and improved optical properties. In some examples, the article exhibits a color shift of about 2 or less, when viewed at an incident illumination angle in the range from about 0 degrees to about 60 degrees from normal under an illuminant. In one or more embodiments, the articles include a substrate, and an optical film disposed on the substrate. The optical film includes a scratch-resistant layer and an optical interference layer. The optical interference layer may include one or more sub-layers that exhibit different refractive indices. In one example, the optical interference layer includes a first low refractive index sub-layer and a second a second high refractive index sub-layer. In some instances, the optical interference layer may include a third sub-layer.

Claims

1. A device comprising:

a display comprising a user interface; and

a cover article disposed over the display, the cover article comprising a substrate having a surface, and an optical film disposed on the substrate surface forming a coated surface, the optical film comprising a scratch-resistant layer and an optical interference layer disposed between the scratch-resistant layer and the substrate, the scratch-resistant layer having a physical thickness from 0.2 microns to 3 microns, and comprising oxygen and nitrogen, the optical interference layer comprises a first low refractive index RI sub-layer and a second high RI sub-layer, wherein the high RI sub-layer comprises oxygen and nitrogen,

wherein the cover article comprises a maximum hardness of 12 GPa or greater, as measured by a Berkovich Indenter Hardness Test along indentation depths of about 100 nm or greater, an average transmittance of 85% or greater over a visible spectrum, and a color shift of 2 or less, when viewed at an incident illumination angle in the range from about 2 degrees to about 60 degrees from normal incidence under an illuminant comprising CIE A illuminants, CIE B illuminants CIE C illuminants, CIE D illuminants or CIE F illuminants,

wherein color shift is determined by the equation √

((a*₂−

a*₁)²+(b*₂−

b*₁)²), where a*₁ and b*₁ are coordinates of the article when viewed at normal incidence and a*₂, and b*₂ are coordinates of the article viewed at the incident illumination angle, and wherein the coordinates of the article when viewed at normal incidence and at the incident illumination angle are both in transmittance or reflectance.

2. The device of claim 1, further comprising an electronic article, an architectural article, a transportation article or an appliance article.

3. The device of claim 2, wherein the electronic article comprises a mobile device selected from the group consisting of a smart phone, mp3 player, and computer tablet.

4. The device of claim 2, wherein the transportation article comprises an automobile, a train, aircraft, or sea craft.

5. The device of claim 1, wherein the difference between the refractive index of the first low RI sub-layer and the refractive index of the second high RI sub-layer is about 0.01 or greater.

6. The device of claim 1, wherein the optical interference layer comprises a plurality of sub-layer sets, the plurality of sub-layer sets comprising a first low RI sub-layer and a second high RI sub-layer.

7. The device of claim 6, wherein the optical interference layer further comprises a third sub-layer disposed between at least one of:

the plurality of sub-layer sets and the scratch-resistant layer; and

the substrate and the plurality of sub-layer sets, or wherein the third sub-layer has a RI between the refractive index of the first low RI sub-layer and the refractive index of the second high RI sub-layer.

8. The device of claim 6, wherein the optical interference film comprises up to about 10 sub-layer sets.

9. The device of claim 6, wherein at least one of the first low RI sub-layer or the second high RI sub-layer comprises an optical thickness (n*d) in the range from about 2 nm to about 200 nm.

10. The device of claim 1, wherein the optical interference layer comprises a thickness of about 800 nm or less.

11. The device of claim 1, wherein the optical interference layer comprises an average light reflection of about 0.5% or less over the optical wavelength regime.

12. The device of claim 1, wherein the cover article comprises an average transmittance or average reflectance having an average oscillation amplitude of about 5 percentage points or less over the optical wavelength regime.

13. The device of claim 1, wherein the optical film comprises a sensor layer.

14. The device of claim 1, wherein the substrate comprises an amorphous substrate or a crystalline substrate.

15. The device of claim 14, wherein the amorphous substrate comprises a glass selected from the group consisting of soda lime glass, alkali aluminosilicate glass, alkali containing borosilicate glass and alkali aluminoborosilicate glass.

16. The device of claim 15, wherein the glass is chemically strengthened and comprises a compressive stress (CS) layer with a surface CS of at least 250 MPa extending within the chemically strengthened glass from a surface of the chemically strengthened glass to a depth of layer (DOL) of at least about 10 μ

m.

17. A device comprising:

a display comprising a user interface; and

a cover article disposed over the display, the cover article comprising a substrate comprising a substrate surface, and an optical film disposed on the substrate surface forming a coated surface,

wherein the optical film comprises a scratch-resistant layer and an optical interference layer disposed between the scratch-resistant layer and the substrate, the optical interference layer comprising at least one set of sub-layers, the set of sub-layers comprising a first low RI sub-layer and a second high RI sub-layer, the scratch-resistant layer having a physical thickness from 0.2 microns to 3 microns and comprising nitrogen and oxygen, the high RI sub-layer comprising nitrogen and oxygen,

wherein the cover article comprises a maximum hardness in the range from 12 GPa to about 50 GPa, as measured by a Berkovich Indenter Hardness Test along indentation depths of about 100 nm or greater, and

wherein the cover article comprises a color shift of less than 2, when viewed at an incident illumination angle in the range from about 2 degrees to about 60 degrees from normal incidence under an illuminant comprising CIE A illuminants, CIE B illuminants CIE C illuminants, CIE D illuminants or CIE F illuminants,

wherein color shift is determined by the equation √

((a*₂−

a*₁)²+(b*₂−

b*₁)²), where a*₁ and b*₁ are coordinates of the article when viewed at normal incidence and a*₂, and b*₂ are coordinates of the article viewed at the incident illumination angle, and wherein the coordinates of the article when viewed at normal incidence and at the incident illumination angle are both in transmittance or reflectance.

18. The device of claim 17, wherein the first low RI sub-layer comprises at least one of SiO₂, Al₂O₃, GeO₂, SiO, AlO_xN_y, SiO_xN_y, Si_uAl_vO_xN_y, MgO, MgF₂, BaF₂, CaF₂, DyF₃, YbF₃, YF₃, or CeF₃, and wherein the second high RI sub-layer comprises at least one of Si_uAl_vO_xN_y, AlO_xN_y, or SiO_xN_y.

19. The device of claim 17, wherein the scratch-resistant layer comprises at least one of AlO_xN_y, SiO_xN_y, TiO_xN_y, or Si_uAl_vO_xN_y.

20. The device of claim 17, wherein the article further comprises a crack mitigating layer.

21. An article comprising:

a substrate having a surface; and

an optical film disposed on the substrate surface forming a coated surface, the optical film comprising a scratch-resistant layer and an optical interference layer disposed between the scratch-resistant layer and the substrate, the scratch-resistant layer having a physical thickness from 0.2 microns to 3 microns, and comprising oxygen and nitrogen, the optical interference layer comprises a first low refractive index RI sub-layer and a second high RI sub-layer, wherein the high RI sub-layer comprises oxygen and nitrogen;

wherein the article comprises a color shift of about 2 or less, when viewed at an incident illumination angle in the range from about 0 degrees to about 60 degrees from normal incidence under an illuminant,

wherein the article comprises an abrasion resistance comprising about 1% haze or less, as measured using a hazemeter having an aperture, wherein the aperture has a diameter of about 8 mm, and

wherein the abrasion resistance is measured after a 500-cycle abrasion using a Taber Test.

22. The article of claim 21, wherein the difference between the refractive index of the first low RI sub-layer and the refractive index of the second high RI sub-layer is about 0.01 or greater.

23. The article of claim 21, wherein the substrate comprises an amorphous substrate or a crystalline substrate.

24. A device comprising:

a display comprising a user interface; and

the article of claim 21 disposed over the display.

25. An article comprising:

a substrate having a surface; and

an optical film disposed on the substrate surface forming a coated surface, the optical film comprising a scratch-resistant layer and an optical interference layer disposed between the scratch-resistant layer and the substrate, the scratch-resistant layer having a physical thickness from 0.2 microns to 3 microns, and comprising oxygen and nitrogen, the optical interference layer comprises a first low refractive index RI sub-layer and a second high RI sub-layer, wherein the high RI sub-layer comprises oxygen and nitrogen;

wherein the article comprises a color shift of about 2 or less, when viewed at an incident illumination angle in the range from about 0 degrees to about 60 degrees from normal incidence under an illuminant,

wherein the article comprises an abrasion resistance comprising a scattered light intensity of about 0.1 (in units of 1/steradian) or less, at a polar scattering angle in the range from about 15°

to about 60°

, as measured at normal incidence in transmission using an imaging sphere for scatter measurements, with a 2 mm aperture at 600 nm wavelength, and

wherein the abrasion resistance is measured after a 500-cycle abrasion using a Taber Test.

26. The article of claim 25, wherein the abrasion resistance comprises any one or more of:

a scattered light intensity of about 0.05 (in units of 1/steradian) or less, at a polar scattering angle of about 40 degrees or less, as measured at normal incidence in transmission using an imaging sphere for scatter measurements, with a 2 mm aperture at 600 nm wavelength, and

a scattered light intensity of about 0.1 (in units of 1/steradian) or less, at a polar scattering angle of about 20 degrees or less, as measured at normal incidence in transmission using an imaging sphere for scatter measurements, with a 2 mm aperture at 600 nm wavelength.

27. The article of claim 25, wherein the difference between the refractive index of the first low RI sub-layer and the refractive index of the second high RI sub-layer is about 0.01 or greater.

28. The article of claim 25, wherein the substrate comprises an amorphous substrate or a crystalline substrate.

29. A device comprising:

a display comprising a user interface; and

the article of claim 25 disposed over the display.