# US 11,028,284 B2 · Polymer substrate with hardcoat layer, and manufacturing method for same

> Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt

- Number: US 11,028,284 B2
- Document ID: US11028284B2
- Status: Granted
- Kind: B2
- Application number: 15/761,348
- Filed: 2016-09-23
- Published: 2018-09-20
- Granted: 2021-06-08
- Earliest claimed: 2015-09-25
- Assignees: Teijin Limited; Tsukishima Kikai Co., Ltd.
- Applicants: Teijin Limited; Tsukishima Kikai Co., Ltd.
- Inventors: Tatsuya Ekinaka; Tatsuichirou Kon; Takehiro Suga; Hiroshi Kishimoto; Yume Morita; Satoshi Ogata; Masato Nakagomi
- Web page: https://patentgrep.com/patent/US11028284B2

## CPC

- C08J 7/043: Improving the adhesiveness of the coatings per se, e.g. forming primers (adhesives in the form of films or foils characterised by the primer layers between the polymer carriers and the adhesives C09J7/50)
- B32B 9/00: Layered products comprising a {layer of a} particular substance not covered by groups B32B11/00 - B32B29/00
- C08J 7/04: Coating
- C08J 7/0427: {with only one layer of a composition containing a polymer binder (with more layers C08J7/042)}
- C08J 7/044: Forming conductive coatings; Forming coatings having anti-static properties
- C08J 7/046: Forming abrasion-resistant coatings; Forming surface-hardening coatings
- C09D 7/40: Additives
- C09D 7/62: modified by treatment with other compounds
- C09D 133/10: Homopolymers or copolymers of methacrylic acid esters
- C09D 133/12: Homopolymers or copolymers of methyl methacrylate
- C23C 16/0218: {in a reactive atmosphere (C23C16/0227 takes precedence)}
- C23C 16/0272: {Deposition of sub-layers, e.g. to promote the adhesion of the main coating}
- C23C 16/401: {containing silicon}
- C23C 16/402: {Silicon dioxide}
- C23C 16/42: Silicides
- C23C 16/50: using electric discharges {(generation and control of plasma in discharge tubes for surface treatment H01J37/32, H01J37/34)}
- C23C 16/5096: {Flat-bed apparatus}
- C23C 16/56: After-treatment
- C23C 28/00: Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C08J 2369/00: Characterised by the use of polycarbonates; Derivatives of polycarbonates
- C08J 2433/00: Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J: WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H (working, e.g. shaping, of plastics B29)
- B32B: LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- 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)
- C23C: COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL (making metal-coated products by extrusion B21C23/22; covering with metal by connecting pre-existing layers to articles, see the relevant places, e.g. B21D39/00, B23K; metallising of glass C03C; metallising mortars, concrete, artificial stone, ceramics or natural stone C04B41/00; enamelling of, or applying a vitreous layer to, metals C23D; treating metal surfaces or coating of metals by electrolysis or electrophoresis C25D; single-crystal film growth C30B; by metallising textiles D06M11/83; decorating textiles by locally metallising D06Q1/04)

## Abstract

The present invention provides a polymer substrate with a hardcoat layer exhibiting excellent environmental resistance and wear resistance. A polymer substrate (60) is 1-20 mm thick and a hardcoat layer (70, 80) on the surface thereof comprises: an underlayer cured layer (70) with a thickness of 1-20 μm, and including 10-90 parts by weight of a multifunctional acrylate, and 90-10 parts by weight of inorganic oxide fine particles and/or a silicon compound hydrolytic condensate; and a silicon oxide layer (80) which is in direct contract with the underlayer cured layer, is formed by PE-CVD with an organosilicon compound as the starter material, and satisfies all of the following conditions (a)-(c): (a) the film thickness of the silicon oxide layer is 3.5-9.0 μm; (b) the maximum indentation depth of the surface of the silicon oxide layer by nanoindentation measurement at a maximum load of 1 mN is 150 nm or less; and (c) the limit compression ratio K of the silicon oxide layer is at most 0.975 in a 3-point bending test of the polymer substrate with a hardcoat layer having been subjected to indentation deformation that causes the surface on which the silicon oxide layer is layered to be indented.

## Claims

### Claim 1

A polymer substrate with hard coating layer comprising a polymer substrate having a thickness of 1 mm to 20 mm and a hard coating layer on the surface thereof; wherein,
the hard coating layer comprises:
a cured underlayer laminated on the surface of the polymer substrate, containing 10 to 90 parts by weight of multifunctional acrylate and 90 to 10 parts by weight of inorganic oxide fine particles and/or a hydrolysis-condensation product of an organic silicon compound, and having a thickness of 1 μm to 20 μm, and
a silicon oxide layer that makes direct contact with the cured underlayer on the opposite side from the polymer substrate, is formed by PE-CVD using an organic silicon compound selected from an organosiloxane, organosilane or (organo)silazane as raw material, and satisfies all of the following requirements (a) to (c):
(a) film thickness of the silicon oxide layer is within the range of 3.5 to 9.0 μm,
(b) maximum indentation depth of the surface of the silicon oxide layer, as determined by measuring nanoindentation under conditions of a maximum load of 1 mN, is 150 nm or less, and
(c) the value of critical compression ratio K of the silicon oxide layer, as defined by formula (1) in a 3-point bending test of the polymer substrate with hard coating layer that imparts indentation displacement in which the surface laminated with the silicon oxide layer becomes concave, is 0.975 or less:
K=(R−D/2)/R−(0.00215×d) Formula (1)
(wherein,
D represents the total thickness (mm) of the polymer substrate with hard coating layer,
d represents the film thickness (μm) of the silicon oxide layer, and
R represents the bend radius (mm) of the polymer substrate with hard coating layer, measured when the silicon oxide layer begins to separate from a cut line (separation starting line) drawn in advance at the location of the central fulcrum point where a weight is applied in a 3-point bending test),
wherein the ratio of infrared absorbance of the silicon oxide layer at a wave number of 1280 cm−1 to that at a wave number of 1020 cm−1 (α1280/α1020) is within the range of 0.002 to 0.020, and
the inorganic oxide fine particles and/or the hydrolysis-condensation product of the organic silicon compound of the cured underlayer is reacted with a (meth)acrylic resin having alkoxysilyl groups, hydroxyl groups, amino groups, or carboxyl groups in a side chain thereof.

### Claim 2 (depends on 1)

The polymer substrate with hard coating layer according to claim 1, wherein the ratio of infrared absorbance of the silicon oxide layer at a wave number of 930 cm−1 to that at a wave number of 1020 cm−1 (α930/α1020) is 0.30 or less.

### Claim 3 (depends on 1)

The polymer substrate with hard coating layer according to claim 1, wherein indentation hardness of the surface of the silicon oxide layer as determined by measuring nanoindentation under conditions of a maximum load of 1 mN is 3.0 GPa or more.

### Claim 4 (depends on 1)

The polymer substrate with hard coating layer according to claim 1, wherein surface roughness (Ra) of the silicon oxide layer when measured using the dynamic force mode (DFM) of a scanning probe microscope under conditions of observing by 5.0 μm square is 5.0 nm or less.

### Claim 5 (depends on 1)

The polymer substrate with hard coating layer according to claim 1, wherein the (meth)acrylic resin contains 0.1 to 5 mol/kg of the hydroxyl groups, amino groups, carboxyl groups, alkoxysilyl groups or a combination thereof in the compound thereof.

### Claim 6 (depends on 1)

A method for producing the polymer substrate with hard coating layer according to claim 1, comprising: forming the cured underlayer by coating a precursor material composition containing 10 to 90 parts by weight of a multi-functional acrylate and 90 to 10 parts by weight of an inorganic oxide fine particle and/or silicon compound hydrolysis-condensation product onto the polymer substrate followed by drying and heat curing or active energy ray curing.

### Claim 7 (depends on 6)

The method for producing the polymer substrate with hard coating layer according to claim 6, wherein the surface of the cured underlayer is adjusted by plasma excitation or colliding an ionized inert gas with the surface of the cured underlayer.

### Claim 8 (depends on 6)

The method for producing the polymer substrate with hard coating layer according to claim 6, wherein the silicon oxide layer is formed by making the average deposition rate (nm/sec) from the start of deposition to 30 seconds after the start of deposition to be 1 nm/sec or less.

### Claim 9 (depends on 8)

The method for producing the polymer substrate with hard coating layer according to claim 8, wherein the silicon oxide layer is formed by making the average deposition rate (nm/sec) starting from 30 seconds after the start of deposition to be 2 nm/sec or more.

### Claim 10 (depends on 9)

The method for producing the polymer substrate with hard coating layer according to claim 9, wherein the deposition rate of the silicon oxide layer is increased continuously or incrementally in two or more steps.