# US 10,371,868 B2 · Process for the manufacturing of an optical article and optical article

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- Number: US 10,371,868 B2
- Document ID: US10371868B2
- Status: Granted
- Kind: B2
- Application number: 14/906,814
- Filed: 2013-07-23
- Published: 2016-06-16
- Granted: 2019-08-06
- Earliest claimed: 2013-07-23
- Assignees: Essilor International
- Applicants: Essilor International (Compagnie Generale D'Optique)
- Inventors: Haipeng Zheng
- Web page: https://patentgrep.com/patent/US10371868B2

## CPC

- G02B 1/111: using layers comprising organic materials
- B05D 7/50: {Multilayers}
- C09D 5/006: {Anti-reflective coatings}
- C09D 7/61: inorganic
- G02B 27/0006: {with means to keep optical surfaces clean, e.g. by preventing or removing dirt, stains, contamination, condensation (G02B1/18 takes precedence; cleaning in general B08B)}
- C08K 3/22: of metals
- C08K 3/34: Silicon-containing compounds
- G02B: OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- B05D: PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL (conveying articles or workpieces through baths of liquid B65G, e.g. B65G49/02)
- C09D: COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR (cosmetics A61K; processes for applying liquids or other fluent materials to surfaces, in general, B05D; staining wood B27K5/02; glazes or vitreous enamels C03C; natural resins, French polish, drying-oils, driers, turpentine, per se, C09F; polishing compositions other than French polish, ski waxes C09G; adhesives or use of materials as adhesives C09J; materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12; processes for the electrolytic or electrophoretic production of coatings C25D)
- C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09)

## Abstract

The invention relates to a process for the manufacturing of an optical article comprising forming a multilayered coating on at least one face of an uncoated or coated substrate,and forming on the outermost layer of said multilayered coating, a layer-by-layer (LbL) coating exposed to environment, said LbL coating comprising at least two bilayers, each bilayer being formed successively by: i) applying a first layer composition comprising at least one compound A having a first electrical charge; ii) applying, directly onto the first layer resulting from i), a second layer composition comprising at least one compound B having a second electrical charge, said second electrical charge being opposite to said first electrical charge; iii) repeating at least once steps i) and ii), with the provisos that: -each of compounds A and B is independently chosen from polysaccharide polymers and colloids of metal oxide such as TiO2 and ZrO2 or silicon oxide, with the proviso that at least one of the compounds A and B is a polysaccharide polymer, -each of said compounds A and B is positively or negatively charged respectively, and d) crosslinking the first and second layers of said bilayers of the LbL coating by treatment with an aqueous composition comprising at least tetrakis(2-hydroxyethyl) orthosilicate (THEOS) as crosslinking agent to induce chemical linkages between compounds A and B. The invention also relates to the optical substrate obtained according to this process.

## Claims

### Claim 1

A process for the manufacturing of an optical article comprising:
a) providing an uncoated or coated substrate,
b) forming on at least one face of said substrate a multilayered coating,
c) forming on an outermost layer of said multilayered coating, a layer-by-layer (LbL) coating exposed to environment, said LbL coating comprising at least two bilayers, each bilayer being formed successively by:
i) applying a first layer composition comprising at least one compound A having a first electrical charge;
ii) applying, directly onto the first layer resulting from i), a second layer composition comprising at least one compound B having a second electrical charge, said second electrical charge being opposite to said first electrical charge;
iii) repeating at least once steps i) and ii),
with the provisos that:
each of compounds A and B is independently a polysaccharide polymer or colloid of metal oxide, with the proviso that at least one of the compounds A and B is a polysaccharide polymer;
each of said compounds A and B is positively or negatively charged respectively; and
d) crosslinking the first and second layers of said bilayers of the LbL coating by treatment with an aqueous composition comprising at least from 0.2 to 5 weight % of the total weight of said composition of tetrakis(2-hydroxyethyl) orthosilicate (THEOS) as a crosslinking agent to induce chemical linkages between compounds A and B.

### Claim 2 (depends on 1)

The process of claim 1, wherein at least one compound A or B is a colloid of metal oxide further defined as comprising TiO2, and ZrO2, or silicon oxide.

### Claim 3 (depends on 2)

The process of claim 2, wherein said colloid of metal oxide is further defined as silicon oxide comprising surface amino- functionalized SiO2 nanoparticles and/or surface negatively charged SiO2 nanoparticles.

### Claim 4 (depends on 1)

The process of claim 1, wherein said polysaccharide polymers comprise at least one polysaccharide comprising a glucosamine unit or polysaccharide comprising a carboxylic acid group.

### Claim 5 (depends on 4)

The process of claim 4, wherein said polysaccharide comprises a glucosamine unit and is further defined chitosan or poly(1,3-β-D-glucosamine-alt-1,4-β-D-glucuronic acid).

### Claim 6 (depends on 4)

The process of claim 4, wherein said polysaccharide comprises a carboxylic acid group and is further defined as comprising carboxyalkylcellulose, alginate, and/or xanthan.

### Claim 7 (depends on 6)

The process of claim 6, the polysaccharide is a carboxyalkylcellulose further defined as carboxymethyl cellulose, carboxyethyl cellulose, or carboxypropyl cellulose.

### Claim 8 (depends on 1)

The process of claim 1, wherein each bilayer of said LbL coating comprises:
a first layer of chitosan as compound A and a second layer of carboxymethyl cellulose as compound B; or
a first layer of aminopropyl-functionalized SiO2 nanoparticles as compound A and a second layer of carboxymethyl cellulose as compound B; or
a first layer of chitosan as compound A and a second layer of SiO2 as compound B.

### Claim 9 (depends on 1)

The process of claim 1, wherein the amount of THEOS in said crosslinking aqueous solvent-based composition ranges from 0.5 to 1 weight % of the total weight of said composition.

### Claim 10 (depends on 1)

The process of claim 1, wherein said crosslinking step d) is carried out by thermal annealing at a temperature ranging from 30° C. to 120° C. for a period of 0.5 to 12 hours.

### Claim 11 (depends on 10)

The process of claim 10, wherein said crosslinking step d) is carried out by thermal annealing at a temperature ranging from 30° C. to 120° C. for a period of 1 to 3 hours.

### Claim 12 (depends on 11)

The process of claim 11, wherein said crosslinking step d) is carried out by thermal annealing at a temperature ranging from 50 to 70° C.

### Claim 13 (depends on 10)

The process of claim 10, wherein said crosslinking step d) is carried out by thermal annealing at a temperature ranging from 40° C. to 100° C.

### Claim 14 (depends on 1)

The process of claim 1, wherein the LbL coating is at least partially dried before the crosslinking step d) is carried out.

### Claim 15 (depends on 1)

The process of claim 1, wherein said multilayered coating is an antireflecting coating further comprising a stack of low refractive index layers (LI layers) having a refractive index n ≤1.55 and high refractive index layer (HI layers) having a refractive index n′ >1.55, said multilayered coating being deposited onto the substrate through a vacuum evaporation process.

### Claim 16 (depends on 15)

The process of claim 15, wherein:
the LI layers are made of SiO2, SiOx, with 1≤x<2, MgF2, ZrF4, AlF3, chiolote (Na5Al3F14), cryolite (Na3AlF6), mixtures of SiO2 and/or SiOx with at most 10% by weight of A12O3, and mixtures thereof; and
the HI layers are made of ZrO2, TiO2, Ta2O5, Na2O5, Pr2O3, PrTiO3, La2O3, Dy2O5, Nb2O5, Y2O3, mixtures thereof, and mixtures of these oxides with silica and/or alumina.

### Claim 17 (depends on 1)

An optical article formed by the process of claim 1.

### Claim 18 (depends on 17)

The optical article of claim 17, wherein each bilayer of said LbL coating comprises a first layer of chitosan as compound A and a second layer of carboxymethyl cellulose as compound B.

### Claim 19 (depends on 17)

The optical article of claim 17, wherein each bilayer of said LbL coating comprises a first layer of aminopropyl- functionalized SiO2 nanoparticles as compound A and a second layer of carboxymethyl cellulose as compound B.

### Claim 20 (depends on 17)

The optical article of claim 17, wherein each bilayer of said LbL coating comprises a first layer of chitosan as compound A and a second layer of SiO2 as compound B.

### Claim 21 (depends on 17)

The optical article of claim 17, wherein the amount of THEOS in said crosslinking aqueous solvent-based composition ranges from 0.5 to 1.0 weight % of the total weight of said composition.