US20200215572A1 - Polymer Plastic Front Plate And Method For Manufacturing The Same - Google Patents

Polymer Plastic Front Plate And Method For Manufacturing The Same Download PDF

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Publication number
US20200215572A1
US20200215572A1 US16/734,327 US202016734327A US2020215572A1 US 20200215572 A1 US20200215572 A1 US 20200215572A1 US 202016734327 A US202016734327 A US 202016734327A US 2020215572 A1 US2020215572 A1 US 2020215572A1
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Prior art keywords
layer
hard coating
front plate
polymer plastic
coating layer
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US16/734,327
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English (en)
Inventor
Hsin Yuan Chen
Chun Kai Wang
Yu Ling Chien
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Enflex Corp Taiwan
Enflex Corp
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Enflex Corp Taiwan
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Assigned to ENFLEX CORPORATION reassignment ENFLEX CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: CHEN, HSIN YUAN, CHIEN, YU LING, WANG, CHUN KAI
Publication of US20200215572A1 publication Critical patent/US20200215572A1/en
Priority to US18/381,053 priority Critical patent/US12109587B2/en
Abandoned legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/02—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber
    • B05D7/04—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber to surfaces of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings
    • H05K3/284—Applying non-metallic protective coatings for encapsulating mounted components
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2333/00—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
    • C08J2333/04—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 esters
    • C08J2333/06—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 esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C08J2333/10—Homopolymers or copolymers of methacrylic acid esters
    • C08J2333/12—Homopolymers or copolymers of methyl methacrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2475/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2475/04—Polyurethanes
    • C08J2475/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/28—Nitrogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
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    • G—PHYSICS
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    • G06F—ELECTRIC DIGITAL DATA PROCESSING
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    • G06F2203/041—Indexing scheme relating to G06F3/041 - G06F3/045
    • G06F2203/04103—Manufacturing, i.e. details related to manufacturing processes specially suited for touch sensitive devices

Definitions

  • the invention refers to a polymer plastic front plate and a method for manufacturing the same, especially refers to a polymer plastic front plate which is suitable for bonding on the surface of automotive touch panels.
  • a touch panel on a touch-sensitive electronic device for a car is usually fitted with a front panel, not only because the front panel can protect the touch panel from scratches, but also because the front panel can also be printed with specific patterns or text for marking a specific touch area on the touch panel so as to improve the convenience of the user to operate the touch panel.
  • FIG. 1 is a schematic diagram of a typical example of a conventional technology, in which a front panel is attached to the front surface of a touch panel.
  • the front panel 10 currently used for laminating on a touch panel is usually composed of a polymer plastic material, which comprises a plastic substrate 11 primary made of polymethyl methacrylate (PMMA) or polycarbonate (PC), a protective layer 12 disposed on an operation surface (outer surface) of the plastic substrate 11 , and a hard coating layer 13 disposed on a bonding surface (inner surface) of the plastic substrate 11 .
  • PMMA polymethyl methacrylate
  • PC polycarbonate
  • the protective layer 12 and the hard coating layer 13 are applied to two different surfaces of the plastic substrate 11 by a hard coating (HC) technology.
  • HC hard coating
  • HC materials include UV-curable multifunctional high surface tension oligomers (Oligomer) or high surface tension monomer formulations, which can be formed as a thin film on the surface of the plastic substrate 11 for increasing the hardness thereof, so as to provide a scratch-resistant effect.
  • HC technology is mainly used on the surface of soft substrates, such as PC or PMMA plastic substrates 11 . These kinds of plastic substrate 11 are relatively soft. After the surface is hardened by hard coating, the hardness can be as hard as glass, which is easy to be wiped clean and uneasy to be scratched.
  • an ink layer 21 of a specific pattern or text can be printed on the surface of the hard coating layer 13 formed on the bonding surface of the plastic substrate 11 by means of ink printing; after that, an optical clear adhesive 22 (OCA) is applied to the hard coating layer 13 formed on the bonding surface of the plastic substrate 11 , and then the front panel 10 is attached to the touch panel 23 , letting the hard coating layer 13 and the ink layer 21 to be sandwiched between the plastic substrate 11 and the touch panel 23 and are adhesively bonded by the optical clear adhesive 22 .
  • OCA optical clear adhesive 22
  • the composition of HC materials of the hard coating layer 13 formed on the bonding surface of the conventional plastic substrate 11 is a highly cross-linked ultraviolet light curing typed (UV-curable) resin formulation, for example, a multifunctional high surface tension oligomer formulation or a high surface tension monomer formulation.
  • UV-curable resin formulation for example, a multifunctional high surface tension oligomer formulation or a high surface tension monomer formulation.
  • the highly cross-linked UV-curable resin formulation is coated on the OCA bonding surface of PC or PMMA plastic substrate 11 , which not only can provide ink-printability and scratch resistance abilities to the bonding surface of the plastic substrate 11 , but also can avoid surface damage caused by ink printing process.
  • composition of HC materials of the hard coating layer 13 of the conventional plastic substrate 11 has a high surface dyne value (>38 dyne), which is capable of ink printing and suitable for optical clear adhesive 22 (OCA) bonding, and has good adhesion with the optical clear adhesive 22 (OCA); however, because the ordinary multifunctional high surface tension oligomer and high surface tension monomer formula are not effective in blocking gas diffusion, therefore, it is still impossible to pass the environmental tests of harsh high-temperature, high-temperature and high-humidity, and high-low temperature (hot and cold) thermal shocks for the front panel 10 of the touch panel of vehicle electronic device in the automotive industry. Thus, the front panel 10 will suffer problems such as outgassing, delay bubbles caused by moisture intrusion, and delamination after the environmental tests.
  • FIG. 2 is a schematic diagram of another typical example of a conventional front panel.
  • one approach is to additionally provide a “single-layer” continuous gas barrier layer 14 on the hard coating layer 13 formed on the bonding surface of the front panel 10 a.
  • the material of the single-layer continuous gas barrier layer 14 can be an air-impermeable material such as alumina, and is completely covering the entire surface of the hard coating layer 13 .
  • OCA optical clear adhesive 22
  • the continuous gas barrier layer 14 is subjected to the environmental tests with high-low temperature (hot and cold) thermal shocks, many micro or nano cracks will be generated, and thus, the gas barrier effect becomes poor after the environmental tests; in addition, the continuous gas barrier layer 14 must be formed by using vacuum coating process, the costs is high, and the production efficiency is low; furthermore, the printability of ink of the continuous gas barrier layer 14 is poor (poor adhesion between the inorganic layer material and the ink); therefore, such approach is not a good solution.
  • FIG. 3 is a schematic diagram of a further typical example of a conventional front panel.
  • Another approach of the prior art is to add a plurality of dispersed spherical nano gas barrier particles 212 into the hard coating layer 210 formed on the bonding surface of the front panel 20 .
  • These spherical nano gas barrier particles 212 can be made of air-impermeable material such as alumina, and are discontinuously dispersed in the highly cross-linked UV-curable resin material 211 included in the entire hard coating layer 210 , in order to form a discontinuous gas barrier structure in the hard layer 210 .
  • the advantages of this approach are that the adhesion between the hard coating layer 210 and the optical clear adhesive (OCA) is good, and the printability of ink is also good; in addition, the material of spherical nano gas barrier particles 212 is also easy to get.
  • OCA optical clear adhesive
  • the gas barrier structure included in the hard coating layer 210 is discontinuous, there are many gaps between these spherical nano gas barrier particles 212 , therefore the initial gas barrier effect for blocking the gas diffusion is not good, and the effect for blocking the gas diffusion after the environmental test is also poor, and thus leaves a room for further improvements.
  • the primary objective of the invention is to provide a polymer plastic front plate suitable for bonding on the surface of automotive touch panels, which can form a gas barrier hard coating layer with high surface dyne value (>44 dyne) on the adhesion surface of the plastic substrate. It not only has good ink printability and OCA adhesiveness, but also inhibits the diffusion of fugitive gas from polymer plastic front plates during high-temperature, high-temperature and high-humidity, high-low temperature (hot and cold) thermal shocks and other harsh automotive industry environmental tests. The gas can be avoided from entering the OCA layer, thereby solving the problems of bubbles and delamination after the environmental tests are performed.
  • Another objective of the invention is to provide a method for manufacturing a polymer plastic front plate suitable for bonding on the surface of automotive touch panels, which can apply a hard coating layer on the bonding surface of the plastic substrate by using a hard coating (HC) technology.
  • the hard coating layer contains a plurality of dispersed nano-scale flaky inorganic substances arranged in a randomly distributed horizontal direction in the hard coating layer, so as to form a discontinuously layered dispersed gas barrier layer in the hard coating layer. Not only can provide good gas barrier effect but also can prevent cracks from happening.
  • the invention provides a polymer plastic front plate which comprises: a plastic substrate having an operation surface and a bonding surface, a protective layer furnished on the operation surface, and a hard coating layer furnished on the bonding surface; wherein the hard coating layer comprises: a first weight percentage of organic-inorganic hybrid UV-curable oligomer, a second weight percentage of UV-curable resin additives with high glass transition temperature (Tg) value, a plurality of dispersed nano-scale flaky inorganic substances, and a photo initiator; wherein, the plurality of dispersed nano-scale flaky inorganic substances are arranged in a randomly distributed horizontal direction in the hard coating layer to form a discontinuously layered dispersed gas barrier layer in the hard coating layer.
  • Tg glass transition temperature
  • the organic-inorganic hybrid UV-curable oligomer includes a polyurethane resin and a sol-gel silica hybrid mixture.
  • the glass transition temperature (Tg) value of the UV-curable resin additives is not less than 120° C. ; in addition, the UV-curable resin additives contain at least one of the following: UV-curable oligomer with high glass transition temperature (high Tg UV oligomer) and UV-curable monomer with high glass transition temperature (high Tg UV monomer).
  • the UV-curable oligomer with high glass transition temperature is polyurethane acrylate, which has a glass transition temperature (Tg) value not less than 120° C.; in addition, the UV-curable monomer with high glass transition temperature is Tris(2-hydroxy ethyl) isocyanuratetriacrylate (THEICTA), which has a glass transition temperature (Tg) value not less than 240° C.
  • Tg glass transition temperature
  • Tg Tris(2-hydroxy ethyl) isocyanuratetriacrylate
  • the nano-scale flaky inorganic substances are composed of at least one of the following materials: SiO 2 , Al 2 O 3 , Si 3 N 4 , SiO x N y , and AlO x N y .
  • each of the nano-scale flaky inorganic substances has a thickness (t), a longitudinal width (w 1 ) and a lateral width (w 2 ); wherein, the measuring directions of the thickness (t), the longitudinal width (w 1 ) and the lateral width (w 2 ) are perpendicular to each other, and w 1 ⁇ w 2 ⁇ t; wherein, the thickness (t) is between 0.1 nm and 50 nm, the longitudinal width (w 1 ) is between 100 nm and 1000 nm, and the ratio of the lateral width to the longitudinal width (w 2 /w 1 ) is between 0.01 and 1.
  • the value of the first weight percentage is ranged between 50% and 70%
  • the value of the second weight percentage is ranged between 30% and 50%
  • the value of the weight percentage of the nano-scale flaky inorganic substances in the hard coating layer is between 5% and 15%.
  • the plastic substrate is one of the following: polymethyl methacrylate (PMMA) plate, polycarbonate (PC) plate, PMMA/PC double-layer composite plate, and PMMA/PC/PMMA three-layer composite plate; in addition, the surface of the hard coating layer can be applied with an ink layer and an optical clear adhesive (OCA) layer for attaching to the surface of the touch panel.
  • PMMA polymethyl methacrylate
  • PC polycarbonate
  • OCA optical clear adhesive
  • the invention provides a method for manufacturing a polymer plastic front plate, comprising: Step (A): providing a plastic substrate and a coating material;
  • the plastic substrate having a bonding surface; said coating material including: a first weight percentage of organic-inorganic hybrid UV-curable oligomer, a second weight percentage of UV-curable resin additives with high glass transition temperature (Tg) value, a plurality of dispersed nano-scale flaky inorganic substances, and a photo initiator; Step (B): applying the coating material onto the bonding surface of the plastic substrate; and Step (C): curing the coating material to form a hard coating layer on the bonding surface of the plastic substrate; wherein, during the curing process, the plurality of dispersed nano-scale flaky inorganic substances will be affected by the gravity and hydrodynamics, and randomly dispersed and arranged along a horizontal direction in a parallel manner within the hard coating layer, such that the plurality of dispersed nano-scale flaky inorganic substances can form a discontinuously layered dispersed gas barrier layer in the hard coating layer.
  • Tg glass transition temperature
  • the process for providing the coating material described in Step (A) comprises the following steps: Step (A1): forming an inorganic layer on a carrier plate; Step (A2): detaching and braking the inorganic layer into a plurality of tiny inorganic fragments; Step (A3): smoothing and dispersing the plurality of tiny inorganic fragments in order to transform the plurality of tiny inorganic fragments into the plurality of dispersed nano-scale flaky inorganic substances; and Step (A4): adding and mixing the plurality of dispersed nano-scale flaky inorganic substances into a solution of the organic-inorganic hybrid UV-curable oligomer, the UV-curable resin additive and the photo initiator to form the coating material.
  • the carrier plate is a glass carrier plate, and a release film is provided on a surface of the glass carrier plate; an inorganic material is plated on the release film by a vacuum sputtering process in order to form a whole piece of the inorganic layer on the surface of the release film; in Step (A2), the inorganic layer is broken by shaking, vibrating or striking the carrier plate, such that the broken inorganic layer can be detached from the release film of the carrier plate and be broken into the plurality of tiny inorganic fragments; in Step (A3), the plurality of tiny inorganic fragments are mixed and stirred by a nano dispersion equipment, so that the plurality of tiny inorganic fragments can collide with each other to gradually smooth their sharp edges and also disperse them evenly and individually, so as to form the plurality of dispersed nano-scale flaky inorganic substances.
  • FIG. 1 is a schematic diagram of a typical example of a conventional front panel
  • FIG. 2 is a schematic diagram of another typical example of a conventional front panel
  • FIG. 3 is a schematic diagram of a further typical example of a conventional front panel
  • FIG. 4 is a schematic diagram of a preferred embodiment of a polymer plastic front panel suitable for a sunroof of vehicle according to the present invention
  • FIG. 5 is a flow chart showing an embodiment of the method for manufacturing the polymer plastic front plate in accordance with the invention.
  • FIG. 6 is a flowchart of an embodiment of the process for providing the coating material of the hard coating layer in accordance with the method for manufacturing the polymer plastic front panel of the present invention
  • FIGS. 7A to 7C respectively are some schematic diagrams of several different steps of the flowchart shown in FIG. 6 , in accordance with the method for manufacturing the polymer plastic front panel of the present invention
  • FIG. 8A to FIG. 8C respectively are the schematic diagrams of the hard coating layer at some different stages during the curing process of coating material in accordance with the manufacturing method of the polymer plastic front panel of the present invention.
  • the polymer plastic front plate of the invention is suitable for bonding on the surface of automotive touch panels.
  • a gas barrier hard coating layer with high surface dyne value (>44 dyne) can be formed on the adhesion surface of the plastic substrate.
  • FIG. 4 is a schematic diagram of a preferred embodiment of a polymer plastic front panel suitable for a sunroof of vehicle according to the present invention.
  • the polymer plastic front panel 30 of the present invention can be bonded on a touch panel (not shown in the figure) of a touch-sensitive typed electronic device for a vehicle by using optical clear adhesive (not shown in the figure), which comprises: a plastic substrate 11 , a protective layer 12 and a hard coating layer 31 .
  • the polymer plastic front panel 30 of the present invention can be made into a polymer plastic sheet with high hardness, high wear resistance, high impact resistance, high flexibility, and extremely low gas transmission rate, or be used to replace traditional tempered glass as the cover material of touch panel, which is particularly suitable for cover materials of automotive touch panels in order to meet the harsh high-temperature or high-temperature high-humidity environmental testing specifications.
  • the plastic substrate 11 is one of the following: polymethyl methacrylate (PMMA) plate, polycarbonate (PC) plate, PMMA/PC double-layer composite plate, PMMA/PC/PMMA three-layer composite plate, or other kind of single-layer or multi-layer co-extruded plate made of polymer materials.
  • PMMA polymethyl methacrylate
  • PC polycarbonate
  • the plastic substrate is a multilayer plate
  • PC polycarbonate
  • PC can be used as the material of the main-layer with a thickness accounting for 60%-99.99% of the total thickness of the plastic substrate.
  • each of the sub-layers located on either one side or two opposite (outer and inner) sides of the main-layer may have a thickness accounting for 0.01%-40% of the total thickness of the plastic substrate, and the material of the sub-layer may be chosen from one of the following: PMMA, Modified PMMA, Modified PC, PMMI, PET, PEN, PES, PI, and etc.
  • the plastic substrate 11 has a corresponding operation surface (outer surface) and a bonding surface (inner surface); in which, the side of the operation surface is for the user to touch and operate the touch panel, while the side of the bonding surface is for printing an ink layer and for applying an optical clear adhesive in order to bond to the touch panel.
  • the protective layer 12 is furnished on the operation surface (outer surface) of the plastic substrate 11
  • the hard coating layer 31 is furnished on the bonding surface (inner surface) of the plastic substrate 11
  • the protective layer 12 and the hard coating layer 31 are respectively applied to the operation surface (outer surface) and the bonding surface (inner surface) of the plastic substrate 11 by a hard coating (HC) technology.
  • HC hard coating
  • the surface of the hard coating layer 31 of the invention can also be applied with both an ink layer and an optical clear adhesive (OCA) layer for attaching to the surface of the touch panel.
  • the thickness of the plastic substrate 11 is between 100 ⁇ m and 1000 ⁇ m.
  • the thickness of the hard coating layer 31 can be between 0.1 ⁇ m and 100 ⁇ m, and is better between 1 ⁇ m and 50 ⁇ m, and is best between 5 ⁇ m and 30 ⁇ m.
  • the hard coating layer 31 is composed of a mixture of: a coating material 32 , a plurality of dispersed nano-scale flaky inorganic substances 33 , and a photo initiator; wherein, the resin formulation of the coating material 32 includes a first weight percentage of organic-inorganic hybrid UV-curable oligomer, and a second weight percentage of UV-curable resin additives with high glass transition temperature (Tg) value.
  • the plurality of dispersed nano-scale flaky inorganic substances 33 are arranged in a randomly distributed horizontal direction in the coating material 32 of the hard coating layer 31 , so as to form a discontinuously layered dispersed gas barrier layer in the hard coating layer 31 .
  • These randomly and horizontally distributed nano-scale flaky inorganic substances 33 not only can provide good gas barrier effect but also can prevent cracks from happening in the hard coating layer 31 .
  • the organic-inorganic hybrid UV-curable oligomer includes a polyurethane resin and a sol-gel silica hybrid mixture.
  • the glass transition temperature (Tg) value of the UV-curable resin additives is not less than 120 ; in addition, the UV-curable resin additives contain at least one of the following: UV-curable oligomer with high glass transition temperature (high Tg UV oligomer) and/or UV-curable monomer with high glass transition temperature (high Tg UV monomer).
  • the UV-curable oligomer with high glass transition temperature is polyurethane acrylate, which has a glass transition temperature (Tg) value not less than 120° C.
  • the UV-curable monomer with high glass transition temperature is Tris(2-hydroxy ethyl) isocyanuratetriacrylate (THEICTA), which has a glass transition temperature (Tg) value not less than 240° C.
  • TBEICTA glass transition temperature
  • the nano-scale flaky inorganic substances 33 are composed of at least one of the following materials: SiO 2 , Al 2 O 3 , Si 3 N 4 , SiO x N y , and/or AlO x N y .
  • the value of the first weight percentage is ranged between 50% and 70%
  • the value of the second weight percentage is ranged between 30% and 50%
  • the value of the weight percentage of the nano-scale flaky inorganic substances 33 in the hard coating layer is between 5% and 15%.
  • the organic-inorganic hybrid UV oligomer contained in the hard coating layer 31 can provide the optical clear adhesive (OCA) bonding surface of the polymer plastic front panel 30 with high hardness and high wear resistance.
  • the high Tg UV oligomer ( ⁇ 120° C.) and/or high Tg UV monomer ( ⁇ 240° C.) contained in the hard coating layer 31 can provide the optical clear adhesive (OCA) bonding surface of the polymer plastic front panel 30 with high impact resistance, high flexibility, and stability at high temperatures, which can reduce the air chamber space during the high-temperature and high-humidity environmental tests, reduce polymer pores, and thus reduce gas permeability.
  • the polymer plastic front panel 30 of the present invention contains a material with a high Tg (above 120° C.) is that, when the temperature of working environment of the polymer plastic front panel 30 is close to the Tg point (glass transition temperature) of the polymer material, the porosity of the polymer material will increase, which will cause water vapor to enter.
  • the highest testing temperature of the environmental tests for vehicles is 90° C. If the Tg of the material is lower than or close to 90° C., when the working temperature of 90° C. is reached, the polymer segment will soften and the porosity will increase, which will cause water vapor to penetrate more easily and fail to provide the effect of blocking water vapor.
  • the randomly and horizontally distributed nano-scale flaky inorganic substances 33 contained in the coating material 32 of the hard coating layer 31 can provide the polymer plastic front panel 30 with a very low gas transmission rate, and can also maintain high transparency and low haze.
  • these nano-scale flaky inorganic substances 33 can form a discontinuously layered dispersed gas barrier layer in the hard coating layer 31 , which inhibits the diffusion of fugitive gas from the polymer plastic front plate during the high-temperature, high-temperature and high-humidity, high-low temperature (hot and cold) thermal shocks and other harsh automotive industry environmental tests, prevents the gas from entering the OCA layer, solves the problems of bubbles and delamination after the environmental tests, and thereby indeed effectively improves the various shortcomings of the aforementioned conventional techniques.
  • FIG. 5 is a flow chart showing an embodiment of the method for manufacturing the polymer plastic front plate in accordance with the invention.
  • the method for manufacturing the polymer plastic front plate of the invention comprises the following steps.
  • Step 51 providing a plastic substrate and a coating material of hard coating layer.
  • the plastic substrate of the polymer plastic front plate of the invention has a bonding surface and an operation surface.
  • the coating material of the hard coating layer is a paint-like liquid mixture including: a first weight percentage of organic-inorganic hybrid UV-curable oligomer, a second weight percentage of UV-curable resin additives with high glass transition temperature (Tg) value, a plurality of dispersed nano-scale flaky inorganic substances, a photo initiator, and volatile solvents.
  • Tg glass transition temperature
  • a protective layer has been formed on the operation surface of the plastic substrate in advance before performing the following Step 52.
  • Step 52 applying the paint-like liquid coating material of the hard coating layer onto the entire bonding surface of the plastic substrate by using a hard coating technology.
  • Step 53 curing the coating material to form the hard coating layer on the bonding surface of the plastic substrate.
  • the volatile solvent contained in the coating material is volatilized by a baking or far-infrared (IR) irradiating process, and the organic-inorganic hybrid UV-curable oligomer and the UV-curable resin additive contained in the coating material is hardened by an irradiating process of ultraviolet (UV) light with a specific wavelength.
  • UV ultraviolet
  • the plurality of dispersed nano-scale flaky inorganic substances will be affected by the gravity and hydrodynamics, and thus randomly dispersed and arranged along a horizontal direction in a parallel manner within the hard coating layer, such that the plurality of dispersed nano-scale flaky inorganic substances can form a discontinuously layered dispersed gas barrier layer in the hard coating layer after the curing process is completed.
  • a hard coating layer including a discontinuously layered dispersed gas barrier layer composed of the plurality of dispersed nano-scale flaky inorganic substances can be formed on the bonding surface of the plastic substrate.
  • FIG. 6 and FIGS. 7A to 7C respectively are the flowchart of an embodiment of the process for providing the coating material of the hard coating layer, and some schematic diagrams of several different steps thereof, in accordance with the method for manufacturing the polymer plastic front panel of the present invention.
  • the process for providing the coating material of the hard coating layer comprises the following steps.
  • Step 511 forming an inorganic layer 62 on a carrier plate 61 .
  • the carrier plate 61 is a glass carrier plate 61
  • a release film 611 is provided on a surface of the glass carrier plate 61 .
  • An inorganic material is plated on the release film 611 by a vacuum sputtering process in order to form a whole piece of the inorganic layer 62 on the surface of the release film 611 .
  • the material of the inorganic material comprises one of the following: silicon dioxide (SiO 2 ), aluminum oxide (Al 2 O 3 ), silicon nitride (Si 3 N 4 ), silicon oxynitride (SiO x N y ), and aluminum oxynitride (AlO x N y ).
  • the inorganic material is preferably made of aluminum oxide (Al 2 O 3 ).
  • Step 512 detaching and braking the inorganic layer 62 into a plurality of tiny inorganic fragments 621 .
  • the entire inorganic layer 62 is broken by shaking, vibrating or striking the carrier plate 61 , such that the broken inorganic layer 62 can be detached from the release film 611 of the carrier plate 61 , and the released inorganic layer 62 can be broken into the plurality of tiny inorganic fragments 621 .
  • the plurality of the tiny inorganic fragments 621 obtained are irregular in shape and have sharp edges, but the size of each tiny inorganic fragment 621 does not differ much.
  • Step 513 smoothing and dispersing the plurality of tiny inorganic fragments 621 in order to transform the plurality of tiny inorganic fragments 621 into the plurality of dispersed nano-scale flaky inorganic substances 622 .
  • the plurality of tiny inorganic fragments 621 are mixed and stirred by a nano dispersion equipment 63 , so that the plurality of tiny inorganic fragments 621 will collide with each other to gradually smooth their sharp edges and also disperse them evenly and individually, so as to form the plurality of dispersed nano-scale flaky inorganic substances 622 .
  • FIG. 7B in this step, the plurality of tiny inorganic fragments 621 are mixed and stirred by a nano dispersion equipment 63 , so that the plurality of tiny inorganic fragments 621 will collide with each other to gradually smooth their sharp edges and also disperse them evenly and individually, so as to form the plurality of dispersed nano-scale flaky inorganic substances 622 .
  • each of the nano-scale flaky inorganic substances 622 will have a thickness (t), a longitudinal width (w 1 ) and a lateral width (w 2 ); wherein, the measuring directions of the thickness (t), the longitudinal width (w 1 ) and the lateral width (w 2 ) are perpendicular to each other, and w 1 ⁇ w 2 ⁇ t.
  • the thickness (t) is between 0.1 nm and 50 nm
  • the longitudinal width (w 1 ) is between 100 nm and 1000 nm
  • the ratio of the lateral width to the longitudinal width (w 2 /w 1 ) is between 0.01 and 1.
  • a best effect can be achieved when 10 nm ⁇ t ⁇ 30 nm, 300 nm ⁇ w 1 ⁇ 800 nm, and 0.1 ⁇ (w 2 /w 1 ) ⁇ 1.
  • Step 514 adding and mixing the plurality of dispersed nano-scale flaky inorganic substances 622 into the solution of organic-inorganic hybrid UV-curable oligomer, the UV-curable resin additive, the photo initiator, and the volatile solvent to form the coating material of the hard coating layer.
  • the organic-inorganic hybrid UV-curable oligomer comprises polyurethane resin and sal-gel silica hybrid mixture.
  • the glass transition temperature (Tg) value of the UV-curable resin additive is not less than 120° C.
  • the UV-curable resin additive comprises at least one of the following: high Tg UV-curable oligomer or high Tg UV-curable monomer.
  • the high Tg UV-curable oligomer is polyurethane acrylate, which has a Tg value not less than 120° C.
  • the high Tg UV-curable monomer is Tris(2-hydroxy ethyl) isocyanuratetriacrylate (THEICTA), which has a Tg value not less than 240° C.
  • TEICTA Tris(2-hydroxy ethyl) isocyanuratetriacrylate
  • the weight percentage of the organic-inorganic hybrid UV oligomer in the coating material is ranged between 50% and 70%
  • the weight percentage of the high Tg UV-curable resin additive is ranged between 30% and 50%
  • the weight percentage of the nano-scale flaky inorganic substances in the coating material of the hard coating layer is between 5% and 15%
  • the weight percentage of the photo initiator is about 5% or so.
  • FIG. 8A to FIG. 8C respectively are the schematic diagrams of the hard coating layer at some different stages during the curing process of coating material in accordance with the manufacturing method of the polymer plastic front panel of the present invention.
  • the initial status of the plastic substrate 11 will be similar to the one shown in FIG. 8A that, the coating material 32 applied on the bonding surface of the plastic substrate 11 is still in a liquid state, and the thickness of the coating material 32 is relatively thick because the amount of the solvent contained in the coating material 32 is still large.
  • the plurality of dispersed nano-scale flaky inorganic substances 33 will form a discontinuously layered dispersed gas barrier layer in the cured hard coating layer 31 .
  • Such kind of structure of the discontinuously layered dispersed gas barrier layer not only can provide a good gas barrier effect similar to the continuous gas barrier layer shown in FIG.
  • the polymer plastic front plate 30 made by the manufacturing method of the invention described above can effectively reduce the diffusion of gas from polymer plastic plates, avoid spilled gas from entering the optical clear adhesive (OCA) layer, solve the problems of bubbles and delamination after the environmental tests are performed, and thereby indeed effectively improve the various shortcomings of the aforementioned conventional techniques.
  • OCA optical clear adhesive
  • Each sample of the front panel is composed of different resin formulations and solid ingredient ratios and is tested by using the same harsh regulations as the aforementioned automotive industry environmental tests.
  • the results of tests are shown in the Table 1 and Table 2 below.
  • Table 1 lists the information of the resin formulations and solid ingredient ratios of a total of twelve samples including sample numbers “Sample1” to “Sample11” and a “Comparative Sample”.
  • Table 2 lists a comparison table of the testing results and performances of these samples shown in Table 1 after conducting the environmental tests.
  • composition column A indicates the weight percentage of the organic-inorganic hybrid UV-curable oligomer (including polyurethane resin and sol-gel silica hybrid mixture) contained in the coating material of the hard coating layer;
  • the value in the composition column B indicates the weight percentage of the High Tg UV-curable oligomer (e.g., Polyurethane acrylate or High Tg UV-curable monomer such as THEICTA) contained in the coating material of the hard coating layer;
  • the High Tg UV-curable oligomer e.g., Polyurethane acrylate or High Tg UV-curable monomer such as THEICTA
  • the value in the composition column C indicates the weight percentage of the conventional Spherical Inorganic Nano Gas Barrier Particles (e.g., Spherical Nano Al 2 O 3 ) contained in the coating material of the hard coating layer;
  • the value in the composition column D indicates the weight percentage of the Dispersed Nano-scale Flaky Inorganic Substances (e.g., Laminar Nano Al 2 O 3 ) of the invention contained in the coating material of the hard coating layer;
  • the value in the composition column E indicates the weight percentage of the Photo Initiator contained in the coating material of the hard coating layer
  • the “Comparative Sample” is a sample of front panel formed with a single continuous gas barrier layer on the bonding surface of plastic substrate by a vacuum sputtering process as which shown in FIG. 2 .
  • compositions A and composition B are the primary materials for the hard coating layer, while the compositions C, D, and E are merely additives; therefore, in practice, when calculating the solid ingredient ratios contained in the resin formulation of the hard coating layer, the sum of the weight percentages of the composition A and the composition B (primary materials) should be equal to 100%, while the weight percentages of the compositions C, D, E are considered to be an additional amount of additives which is not calculated within the aforementioned 100%.
  • Pencil hardness test using Mitsubishi special pencils for hardness test, with 750 g loading, performing sliding tests of pencils with different pencil hardness on the surface of the material; if there is no scratch, it is defined as the hardness of the surface (specification: HS K5600).
  • Wear-resistance of surface nail scratch resistance under simulated use of touch panels (specification: defined by Applicant). The meanings of symbols shown in this column are: ⁇ : Excellent (no scratch), ⁇ : Good (very minor scratches, less than 3 scratches), ⁇ : Normal (minor scratches, with 3 to 5 scratches), X: Fail (serious scratches, more than 5 scratches).
  • OCA bonding environmental test after the material is bonded to the hard coating layer with OCA, performing various environmental tests on it, and then observing whether there are bubbles or delamination occurred in the bonding surface after the environmental tests (specification: defined by Applicant). The meanings of symbols shown in this column are: ⁇ : No Bubble Observed, ⁇ : Few Small Bubbles, ⁇ : Some Big Bubbles, X: Lamination Failure.
  • the samples “Sample9”, “Sample10” and “Sample11” produced according to the technology of the present invention have obtained the best test results. It is proved that, the polymer plastic front plate of the invention is suitable for bonding on the surface of automotive touch panels.
  • the polymer plastic front plate of the invention is suitable for bonding on the surface of automotive touch panels.
  • organic-inorganic high Glass Transition Temperature (Tg) UV oligomers and nano-scale flake-like inorganic oxides By means of the addition of organic-inorganic high Glass Transition Temperature (Tg) UV oligomers and nano-scale flake-like inorganic oxides, a gas barrier hard coating layer with high surface dyne value (>44 dyne) can be formed on the adhesion surface of the plastic substrate.
  • Tg Glass Transition Temperature
  • the weight percentage of the organic-inorganic hybrid UV oligomer contained in the coating material of the hard coating layer is ranged between 50% and 70%
  • the weight percentage of the high Tg UV-curable resin additive is ranged between 30% and 50%
  • the weight percentage of the nano-scale flaky inorganic substances in the coating material of the hard coating layer is between 5% and 15%
  • the weight percentage of the photo initiator is about 5% or so.

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