WO2017176738A1

WO2017176738A1 - Molded articles, method of manufacture, and device comprising the molded article

Info

Publication number: WO2017176738A1
Application number: PCT/US2017/025923
Authority: WO
Inventors: Michael M. Laurin; Jong-Min Choi; Xiaoyu Sun
Original assignee: Sabic Global Technologies B.V.
Priority date: 2016-04-08
Filing date: 2017-04-04
Publication date: 2017-10-12
Also published as: TW201739593A

Abstract

A molded article includes a mold insert and a thermoplastic attachment. The mold insert includes a glass layer having a first surface and a second surface opposite the first surface, a first optically clear adhesive layer disposed on at least a portion of the first surface of the glass layer, and an optically clear polymer film having a first surface and a second surface, where the first surface of the polymer film is in contact with the adhesive layer on a side opposite the glass layer. The thermoplastic attachment extends along an edge of the mold insert, and includes an optically clear high modulus ductile thermoplastic polymer. The difference between the refractive index of the mold insert and the refractive index of the thermoplastic attachment is less than or equal to 0.07. Methods for the manufacture of the molded article, and electronic devices including the molded article are also described.

Description

MOLDED ARTICLES, METHOD OF MANUFACTURE, AND DEVICE COMPRISING THE

MOLDED ARTICLE

BACKGROUND

[0001] Insert molding is a technique in which an insert is located in a mold and the remainder of the desired article is formed around the insert. Insert molding can be particularly useful in the manufacture of a component of an electronic device. Conventional glass insert molding technologies often face issues including an undesirable visible interface between the glass insert and the molded material, limited aesthetic options (i.e., fillers often used to minimize deformation of the molded product limit the available color choices), surface finish limitations, and poor adhesion (often necessitating the use of glue which creates optical issues, as well as additional processing steps). Furthermore, the molded articles having glass inserts are often brittle and susceptible to cracking and failure, and are not designed to withstand substantial impact at the center of the glass. Thicker glasses have been explored for improved resistance to impact, however this approach is often undesirable, resulting in thicker, heavier devices.

Significant research has also been done to improve the impact properties of glass through altering the glass composition, chemically treating the glass, tempering the glass, and the like. However, these altered glasses tend to be brittle, particularly when a thin layer is used.

[0002] There remains a continuing need in the art for improved molding techniques that can provide molded articles, in particular molded articles suitable for use in an electronic device. It would be advantageous to provide a molded article having improved impact resistance and improved aesthetics, in particular, having a design such that the interface between the mold insert and the molded resin in indistinguishable.

BRIEF DESCRIPTION

[0003] A molded article comprises a mold insert comprising a glass layer having a first surface and a second surface opposite the first surface; a first optically clear adhesive layer disposed on at least a portion of the first surface of the glass layer, wherein a 50 micrometer- thick sample of the optically clear adhesive transmits greater than 90% of visible light as determined according to ASTM D 1003-00; and an optically clear polymer film having a first surface and a second surface, where the first surface of the polymer film is in contact with the adhesive layer on a side opposite the glass layer, the polymer film comprising a first

thermoplastic polymer, wherein a 100 micrometer-thick sample of the optically clear polymer film transmits greater than 85% of visible light as determined according to ASTM D 1003-00; and a thermoplastic attachment coupled to a portion of the second surface of the polymer film, wherein the attachment extends along an edge of the mold insert, and wherein the attachment comprises a second thermoplastic polymer; and wherein the difference between the refractive index of the mold insert and the refractive index of the thermoplastic attachment is less than or equal to 0.07.

[0004] A method of manufacturing the molded article comprises applying the optically clear adhesive to at least a portion of the first surface of the glass layer; coupling the polymer film to the optically clear adhesive on a side opposite the first surface of the glass layer to form a mold insert, wherein the adhesive is sandwiched between the glass layer and the polymer film; molding a thermoplastic attachment to the mold insert in an injection molding process to form a molded article, wherein the attachment extends along at least a portion of an edge of the mold insert.

[0005] An electronic device and a housing for an electronic device comprising the molded article are also described.

[0006] The above described and other features are exemplified by the following figures and detailed description.

BRIEF DESCRIPTION OF THE DRAWINGS

[0007] The following figures are exemplary embodiments wherein the like elements are numbered alike.

[0008] FIG. 1 is a schematic illustration of a mold insert.

[0009] FIG. 2 is a cross-sectional view of a molded article.

[0010] FIG. 3 is a cross-sectional view of a molded article.

[0011] FIG. 4 is a cross-sectional view of a molded article.

[0012] FIG. 5 is a cross-sectional view of a tool used in the manufacture of a molded article.

DETAILED DESCRIPTION

[0013] The present inventors have discovered molded articles particularly suitable for use in electronic devices. The molded articles include a mold insert having a layered structure, in particular, a glass/plastic laminated structure. The molded articles further include a thermoplastic attachment coupled to the mold insert, for example using glass insert molding techniques. The materials for the mold insert and the thermoplastic attachment are preferably selected to provide a substantially seamless transition from the mold insert to the attachment, thus improving the overall aesthetics of the molded article. In a further advantageous feature, the use of the glass/plastic laminate can provide a lightweight mold insert (for example, compared to conventional glass mold inserts), and further can contribute enhanced impact resistance to the molded article.

[0014] Thus, one aspect of the present disclosure is a molded article. The molded article comprises a mold insert that is a glass/plastic laminate. The mold insert can be as shown in FIG. 1. As shown in FIG. 1, the mold insert (1) comprises a glass layer (2) having a first surface (3) and a second surface (4) opposite the first surface, a first optically clear adhesive layer (5) disposed on at least a portion of the first surface of the glass layer, and an optically clear polymer film (6) having a first (7) and second (8) surface, where the first surface of the polymer film is in contact with the adhesive layer on a side opposite the glass layer.

[0015] The glass layer can be, but is not limited to, chemically strengthened glass (e.g., CORNING™ GORILLA™ Glass commercially available from Corning Inc., XENSATION™ glass commercially available from Schott AG, DRAGONTRAIL™ glass commercially available from Asahi Glass Company, LTD, and CX-01 glass commercially available from Nippon Electric Glass Company, LTD, and the like), non- strengthened glass such as non- hardened glass including low sodium glass (e.g., CORNING™ WILLOW™ Glass

commercially available from Corning Inc. and OA-10G Glass-on-Roll glass commercially available from Nippon Electric Glass Company, LTD, and the like), tempered glass, or optically transparent synthetic crystal (also referred to as sapphire glass, commercially available from GT Advanced Technologies Inc.).

[0016] The glass layer can have a thickness of 50 micrometers to 25 millimeters, or 50 micrometers to 10 millimeters, or 50 micrometers to 1 millimeter, or 50 to 500 micrometers.

[0017] In some embodiments, one or both surfaces of the glass layer can be a textured surface, which can provide, for example, anti-glare properties, anti-reflective properties, antimicrobial properties, and the like, or a combination comprising at least one of the foregoing.

[0018] In addition to the glass layer, the mold insert comprises an optically clear adhesive layer disposed on at least a portion of the first surface of the glass layer. In some embodiments, the optically clear adhesive layer is in adhesive contact with the entire first surface of the glass layer. As used herein, the term "optically clear adhesive" means that a 50 micrometer-thick sample of the optically clear adhesive transmits greater than 90% of visible light as determined according to ASTM D 1003-00. The first optically clear adhesive layer can have a thickness of 1 to 2000 micrometers, or 1 to 1000 micrometers, or 1 to 500 micrometers, or 1 to 100 micrometers, or 10 to 100 micrometers, or 10 to 50 micrometers, or 12.5 to 25 micrometers.

[0019] The adhesive can include epoxy, acrylate, amine, urethane, silicone,

thermoplastic urethane, ethyl vinyl acetate, hindered amine light stabilizer free ethyl vinyl acetate (HALS free EVA), or a combination comprising at least one of the foregoing. In an embodiment, the adhesive is a hindered amine light stabilizer free ethyl vinyl acetate (HALS free EVA). In an embodiment the adhesive is a thermoplastic urethane, or an ultra violet light cured modified acrylate optical quality adhesive, or a silicone pressure sensitive adhesive, or an acrylate pressure sensitive adhesive. The adhesive can be applied using a process such as roll lamination, roller coating, screen printing, spreading, spray coating, spin coating, dip coating, and the like, or a combination comprising at least one of the foregoing techniques.

[0020] In addition to the glass layer and the optically clear adhesive, the mold insert further comprises an optically clear polymer film having a first surface and a second surface. As discussed above, the first surface of the polymer film is in contact with the adhesive layer on a side opposite the glass layer. Stated another way, the first optically clear adhesive is sandwiched between the optically clear polymer film and the first surface of the glass layer (as shown in FIG. 1). As used herein, the term "optically clear polymer film" means that a 100 micrometer- thick sample of the optically clear polymer film transmits greater than 85% of visible light as determined according to ASTM D 1003-00. In some embodiments, the optically clear polymer film can have a thickness of 1 micrometer to 20 millimeters, or 5 micrometers to 20 millimeters, or 5 micrometers to 10 millimeters, or 5 micrometers to 1 millimeter, or 5 to 500 micrometers, or 5 to 250 micrometers, or 5 to 100 micrometers, or 50 to 200 micrometers.

[0021] The optically clear polymer film comprises a first thermoplastic polymer. As used herein, the term "thermoplastic" refers to a material that is plastic or deformable, melts to a liquid when heated, and freezes to a brittle, glassy state when cooled sufficiently.

Thermoplastics are typically high molecular weight polymers. Examples of thermoplastic polymers that can be used include polyacetals (e.g., polyoxyethylene and polyoxymethylene), poly(Ci-6 alkyl)acrylates, polyacrylamides, polyamides, (e.g., aliphatic polyamides,

polyphthalamides, and polyaramides), polyamideimides, polyanhydrides, polyarylates, polyarylene ethers (e.g., polyphenylene ethers), polyarylene sulfides (e.g., polyphenylene sulfides), polyarylsulfones, polybenzothiazoles, polybenzoxazoles, polybenzimidazoles, polycarbonates (including polycarbonate copolymers such as polycarbonate-siloxanes, polycarbonate-esters, and polycarbonate-ester- siloxanes), polyesters (e.g., polyethylene terephthalates, polybutylene terephthalates, polyarylates, and polyester copolymers such as polyester-ethers), polyetheretherketones, polyetherimides (including copolymers such as polyetherimide-siloxane copolymers), polyetherketoneketones, polyetherketones,

polyethersulfones, polyimides (including copolymers such as polyimide-siloxane copolymers), poly(Ci-6 alkyl)methacrylates, polymethacrylamides, polynorbornenes (including copolymers containing norbornenyl units) polyolefins (e.g., polyethylenes, polypropylenes,

polytetraf uoroethylenes, and their copolymers, for example ethylene-alpha-olefin copolymers), polyoxadiazoles, polyoxymethylene, polyphthalides, polysilazanes, polysiloxanes, polystyrenes (including copolymers such as acrylonitrile-butadiene-styrene (ABS) and methyl methacrylate- butadiene-styrene (MBS)), polysulfides, polysulfonamides, poly sulfonates, polysulfones, polythioesters, polytriazines, polyureas, polyurethanes, polyvinyl alcohols, polyvinyl esters, polyvinyl ethers, polyvinyl halides, polyvinyl nitriles, polyvinyl ketones, polyvinyl thioethers, polyvinylidene fluorides, or the like, or a combination comprising at least one of the foregoing thermoplastic polymers.

[0022] In some embodiments, the polymer film comprises a polyacetal, poly(Ci-6 alkyl)acrylate, polyarylate, polycarbonate, polyester, polyetherimide, polyimide, poly(Ci-6 alkyl)methacrylate, polyolefin, polystyrene, polyurethane, polyvinyl alcohol, polyvinyl ester, polyvinyl ether, polyvinyl halide, polyvinyl nitrile, polyvinyl ketone, polyvinylidene fluoride, or a combination comprising at least one of the foregoing thermoplastic polymers. In some embodiments, the polymer film comprises a polyimide, a polyetherimide, a polyester, a polyolefin, a polycarbonate, a (meth)acrylic polymer (e.g., poly(Ci-6 alkyl)acrylates, poly(Ci-6 alkyl)methacrylates, or a combination comprising at least one of the foregoing, preferably poly(methyl methacrylate)), a vinyl polymer, polyacetal (e.g., polyoxyethylene and

polyoxymethylene), a styrenic polymer, or a combination comprising at least one of the foregoing. In some embodiments, the optically clear polymer film comprises a polyimide, a polyetherimide, a polyester, a polyolefin, a polycarbonate, or a combination comprising at least one of the foregoing.

[0023] In some embodiments, the polymer film comprises poly(ethylene terephthalate), poly(ethylene naphthalate), poly(l,4-cyclohexane dimethylene terephthalate),

poly(cyclohexanedimethylene terephthalate)-co-poly(ethylene terephthalate), polyethylene, polypropylene, a bisphenol A polycarbonate (including homopolymers and copolymers thereof), poly(4,4'-oxydiphenylene-pyromellitimide), or a combination comprising at least one of the foregoing. [0024] In some embodiments, the polymer film preferably comprises a polycarbonate. "Polycarbonate" as used herein means a polymer or copolymer having repeating structural carbonate units of formula (1)

O R¹— O C O (1)

wherein at least 60 percent of the total number of R¹ groups are aromatic, or each R¹ contains at least one C₆-30 aromatic group. Specifically, each R¹ can be derived from a dihydroxy compound such as an aromatic dihydroxy compound of formula (2) or a bisphenol of formula (3).

In formula (2), each R is independently a halogen atom, for example bromine, a Ci-io hydrocarbyl group such as a Ci-io alkyl, a halogen-substituted Ci-io alkyl, a C₆-io aryl, or a halogen-substituted C6-io aryl, and n is 0 to 4.

[0025] In formula (3), R^a and R^b are each independently a halogen, Ci-12 alkoxy, or Ci-12 alkyl, and p and q are each independently integers of 0 to 4, such that when p or q is less than 4, the valence of each carbon of the ring is filled by hydrogen. In an embodiment, p and q is each 0, or p and q is each 1, and R^a and R^b are each a C1-3 alkyl group, specifically methyl, disposed meta to the hydroxy group on each arylene group. X^a is a bridging group connecting the two hydroxy-substituted aromatic groups, where the bridging group and the hydroxy substituent of each Ce arylene group are disposed ortho, meta, or para (specifically para) to each other on the Ce arylene group, for example, a single bond, -0-, -S-, -S(O)-, -S(0)₂-, -C(O)-, or a Ci-is organic group, which can be cyclic or acyclic, aromatic or non-aromatic, and can further comprise heteroatoms such as halogens, oxygen, nitrogen, sulfur, silicon, or phosphorous. For example, X^a can be a substituted or unsubstituted C3-18 cycloalkylidene; a Ci-25 alkylidene of the formula - C(R^c)(R^d) - wherein R^c and R^d are each independently hydrogen, Ci-12 alkyl, Ci-12 cycloalkyl, C7-12 arylalkyl, Ci-12 heteroalkyl, or cyclic C7-12 heteroarylalkyl; or a group of the formula - C(=R^e)- wherein R^e is a divalent Ci-12 hydrocarbon group.

[0026] Examples of bisphenol compounds include 4,4'-dihydroxybiphenyl, 1,6- dihydroxynaphthalene, 2,6-dihydroxynaphthalene, bis(4-hydroxyphenyl)methane, bis(4- hydroxyphenyl)diphenylmethane, bis(4-hydroxyphenyl)-l-naphthylmethane, l,2-bis(4- hydroxyphenyl)ethane, l ,l-bis(4-hydroxyphenyl)- l-phenylethane, 2-(4-hydroxyphenyl)-2-(3- hydroxyphenyl)propane, bis(4-hydroxyphenyl)phenylmethane, 2,2-bis(4-hydroxy-3- bromophenyl)propane, 1,1 -bis (hydroxyphenyl)cyclopentane, l,l-bis(4- hydroxyphenyl)cyclohexane, 1 , 1 -bis(4-hydroxyphenyl)isobutene, 1 , 1 -bis(4- hydroxyphenyl)cyclododecane, trans-2,3-bis(4-hydroxyphenyl)-2-butene, 2,2-bis(4- hydroxyphenyl)adamantane, alpha,alpha'-bis(4-hydroxyphenyl)toluene, bis(4- hydroxyphenyl)acetonitrile, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 2,2-bis(3-ethyl-4- hydroxyphenyl)propane, 2,2-bis(3-n-propyl-4-hydroxyphenyl)propane, 2,2-bis(3-isopropyl-4- hydroxyphenyl)propane, 2,2-bis(3-sec-butyl-4-hydroxyphenyl)propane, 2,2-bis(3-t-butyl-4- hydroxyphenyl)propane, 2,2-bis(3-cyclohexyl-4-hydroxyphenyl)propane, 2,2-bis(3-allyl-4- hydroxyphenyl)propane, 2,2-bis(3-methoxy-4-hydroxyphenyl)propane, 2,2-bis(4- hydroxyphenyl)hexafluoropropane, 1 , 1 -dichloro-2,2-bis(4-hydroxyphenyl)ethylene, 1,1- dibromo-2,2-bis(4-hydroxyphenyl)ethylene, 1 , 1 -dichloro-2,2-bis(5-phenoxy-4- hydroxyphenyl)ethylene, 4,4'-dihydroxybenzophenone, 3,3-bis(4-hydroxyphenyl)-2-butanone, l,6-bis(4-hydroxyphenyl)-l,6-hexanedione, ethylene glycol bis(4-hydroxyphenyl)ether, bis(4- hydroxyphenyl)ether, bis(4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl) sulfoxide, bis(4- hydroxyphenyl)sulfone, 9,9-bis(4-hydroxyphenyl)fluorene, 2,7-dihydroxypyrene, 6,6'- dihydroxy-3,3,3',3'- tetramethylspiro(bis)indane ("spirobiindane bisphenol"), 3,3-bis(4- hydroxyphenyl)phthalimide, 2,6-dihydroxydibenzo-p-dioxin, 2,6-dihydroxythianthrene, 2,7- dihydroxyphenoxathin, 2,7-dihydroxy-9, 10-dimethylphenazine, 3,6-dihydroxydibenzofuran, 3,6-dihydroxydibenzothiophene, and 2,7-dihydroxycarbazole; resorcinol, substituted resorcinol compounds such as 5-methyl resorcinol, 5-ethyl resorcinol, 5-propyl resorcinol, 5-butyl resorcinol, 5-t-butyl resorcinol, 5-phenyl resorcinol, 5-cumyl resorcinol, 2,4,5, 6-tetrafluoro resorcinol, 2,4,5, 6-tetrabromo resorcinol, or the like; catechol; hydroquinone; substituted hydroquinones such as 2-methyl hydroquinone, 2-ethyl hydroquinone, 2-propyl hydroquinone, 2-butyl hydroquinone, 2-t-butyl hydroquinone, 2-phenyl hydroquinone, 2-cumyl hydroquinone, 2,3,5,6-tetramethyl hydroquinone, 2,3,5,6-tetra-t-butyl hydroquinone, 2,3, 5, 6-tetrafluoro hydroquinone, 2,3,5, 6-tetrabromo hydroquinone, or the like.

[0027] Specific dihydroxy compounds include resorcinol, 2,2-bis(4-hydroxyphenyl) propane ("bisphenol A" or "BPA"), 3,3-bis(4-hydroxyphenyl) phthalimidine, 2-phenyl-3,3'- bis(4-hydroxyphenyl) phthalimidine (also known as N-phenyl phenolphthalein bisphenol, "PPPBP", or 3,3-bis(4-hydroxyphenyl)-2-phenylisoindolin-l-one), l,l-bis(4-hydroxy-3- methylphenyl)cyclohexane, and l,l-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane

(isophorone bisphenol). [0028] "Polycarbonate" as used herein also includes copolymers comprising carbonate units and ester units ("poly(ester-carbonate)s", also known as polyester-polycarbonates).

Poly(ester-carbonate)s further contain, in addition to recurring carbonate chain units of formula (1), repeating ester units of formula (4)

O O

II II C T C— O J O

wherein J is a divalent group derived from a dihydroxy compound (which includes a reactive derivative thereof), and can be, for example, a C2-10 alkylene, a C₆-20 cycloalkylene a C₆-20 arylene, or a polyoxyalkylene group in which the alkylene groups contain 2 to 6 carbon atoms, specifically, 2, 3, or 4 carbon atoms; and T is a divalent group derived from a dicarboxylic acid (which includes a reactive derivative thereof), and can be, for example, a C2-20 alkylene, a C₆-20 cycloalkylene, or a C₆-20 arylene. Copolyesters containing a combination of different T or J groups can be used. The polyester units can be branched or linear.

[0029] Specific dihydroxy compounds include aromatic dihydroxy compounds of formula (2) (e.g., resorcinol), bisphenols of formula (3) (e.g., bisphenol A), a C_1-8 aliphatic diol such as ethane diol, n-propane diol, i-propane diol, 1,4-butane diol, 1,6-cyclohexane diol, 1,6- hydroxymethylcyclohexane, or a combination comprising at least one of the foregoing dihydroxy compounds. Aliphatic dicarboxylic acids that can be used include C₆-20 aliphatic dicarboxylic acids (which includes the terminal carboxyl groups), specifically linear Cs-i2 aliphatic dicarboxylic acid such as decanedioic acid (sebacic acid); and alpha, omega-Ci2 dicarboxylic acids such as dodecanedioic acid (DDDA). Aromatic dicarboxylic acids that can be used include terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, 1,6- cyclohexane dicarboxylic acid, or a combination comprising at least one of the foregoing acids. A combination of isophthalic acid and terephthalic acid wherein the weight ratio of isophthalic acid to terephthalic acid is 91:9 to 2:98 can be used.

[0030] Specific ester units include ethylene terephthalate units, n-proplyene terephthalate units, n-butylene terephthalate units, ester units derived from isophthalic acid, terephthalic acid, and resorcinol (ITR ester units), and ester units derived from sebacic acid and bisphenol A. The molar ratio of ester units to carbonate units in the poly(ester-carbonate)s can vary broadly, for example 1:99 to 99: 1, specifically, 10:90 to 90: 10, more specifically, 25:75 to 75:25, or from 2:98 to 15:85. In some embodiments the molar ratio of ester units to carbonate units in the poly(ester-carbonate)s can vary from 1:99 to 30: 70, specifically 2:98 to 25:75, more specifically 3:97 to 20:80, or from 5:95 to 15:85. [0031] In a specific embodiment, the polycarbonate is a linear homopolymer containing bisphenol A carbonate units (BPA-PC), commercially available under the trade name LEXAN from SABIC; or a branched, cyanophenol end-capped bisphenol A homopolycarbonate produced via interfacial polymerization, containing 3 mol% l,l,l-tris(4-hydroxyphenyl)ethane (THPE) branching agent, commercially available under the trade name LEXAN CFR from SABIC. A combination of a linear polycarbonate and a branched polycarbonate can be used. It is also possible to use a polycarbonate copolymer or interpolymer rather than a homopolymer. Polycarbonate copolymers can include copolycarbonates comprising two or more different types of carbonate units, for example units derived from BPA and PPPBP (commercially available under the trade name XHT from SABIC); BPA and DMBPC (commercially available under the trade name DMX from SABIC); or BPA and isophorone bisphenol (commercially available under the trade name APEC from Bayer). The polycarbonate copolymers can further comprise non-carbonate repeating units, for example repeating ester units (polyester-carbonates), such as those comprising resorcinol isophthalate and terephthalate units and bisphenol A carbonate units, such as those commercially available under the trade name LEXAN SLX from SABIC; bisphenol A carbonate units and isophthalate-terephthalate-bisphenol A ester units, also commonly referred to as poly(carbonate-ester)s (PCE) or poly(phthalate-carbonate)s (PPC), depending on the relative ratio of carbonate units and ester units; or bisphenol A carbonate units and C₆-i2 dicarboxy ester units such as sebacic ester units (commercially available under the trade name HFD from SABIC) Other polycarbonate copolymers can comprise repeating siloxane units (polycarbonate- siloxanes), for example those comprising bisphenol A carbonate units and siloxane units (e.g., blocks containing 5 to 200 dimethylsiloxane units), such as those commercially available under the trade name EXL from SABIC; or both ester units and siloxane units (polycarbonate-ester- siloxanes), for example those comprising bisphenol A carbonate units, isophthalate-terephthalate-bisphenol A ester units, and siloxane units (e.g., blocks containing 5 to 200 dimethylsiloxane units), such as those commercially available under the trade name FST from SABIC. Combinations of any of the above materials can be used.

[0032] Combinations of polycarbonates with other polymers can be used, for example an alloy of bisphenol A polycarbonate with an ester such as poly(butylene terephthalate) or poly(ethylene terephthalate), each of which can be semicrystalline or amorphous. Such combinations are commercially available under the trade name XENOY and XYLEX from SABIC.

[0033] A specific copolycarbonate includes bisphenol A and bulky bisphenol carbonate units, i.e., derived from bisphenols containing at least 12 carbon atoms, for example 12 to 60 carbon atoms or 20 to 40 carbon atoms. Examples of such copolycarbonates include

copolycarbonates comprising bisphenol A carbonate units and 2-phenyl-3,3'-bis(4- hydroxyphenyl) phthalimidine carbonate units (a BPA-PPPBP copolymer, commercially available under the trade designation LEXAN XHT from SABIC), a copolymer comprising bisphenol A carbonate units and l,l-bis(4-hydroxy-3-methylphenyl)cyclohexane carbonate units (a BPA-DMBPC copolymer commercially available under the trade designation LEXAN DMC from SABIC, or a copolymer comprising bisphenol A carbonate units and isophorone bisphenol carbonate units (commercially available under the trade name APEC from Bayer). A

combination of linear polycarbonate and a branched polycarbonate can be used. Moreover, combinations of any of the above materials may be used.

[0034] The polycarbonates can have an intrinsic viscosity, as determined in chloroform at 25°C, of 0.3 to 1.5 deciliters per gram (dl/gm), specifically 0.45 to 1.0 dl/gm. The

polycarbonates can have a weight average molecular weight of 10,000 to 200,000 Daltons, specifically 20,000 to 100,000 Daltons, as measured by gel permeation chromatography (GPC), using a crosslinked styrene-divinylbenzene column and calibrated to polycarbonate references. GPC samples are prepared at a concentration of 1 milligram per milliliter, and are eluted at a flow rate of 1.5 milliliters per minute.

[0035] In some embodiments, one or both surfaces of the polymer film can be a textured surface, which can provide, for example, anti-glare properties, anti-reflective properties, antimicrobial properties, and the like, or a combination comprising at least one of the foregoing.

[0036] In addition to the glass layer, the adhesive layer, and the polymer film, the mold insert can optionally further include one or more additional layers, specifically, one or more functional layers. In some embodiments, a functional layer, when present, is preferably disposed on at least a portion of the glass layer, the polymer film, or both. In some

embodiments, the functional layer can be disposed on both sides of the glass layer, both sides of the polymer layer, or both. The optional functional layer can include an ultraviolet light protection layer, a touch sensing layer, abrasion resistant layer, infrared absorbing layer, infrared reflecting layer, hydrophobic layer, hydrophilic layer, anti-fingerprint layer, anti-smudge layer, anti-glare layer, anti-reflection layer, antimicrobial layer, conductive layer, electromagnetic radiation shielding layer (e.g., an electromagnetic interference shielding layer), anti-frost layer, anti-fog layer, image forming layer (e.g., an ink layer), a touch sensing layer, or a combination including at least one of the foregoing. In some embodiments, the functional layer can preferably include an anti-reflection layer, an anti-glare layer, an antimicrobial layer, a conductive layer, an anti-fingerprint layer, an anti- smudge layer, an anti-fog layer, a touch sensing layer, or a combination comprising at least one of the foregoing. In some embodiments, the functional layer can further be textured. The functional layer can be disposed in any form, e.g., a film, coating, coextruded layer, deposited layer, molded layer, or the like.

[0037] In an embodiment, the mold insert further comprises a functional layer comprising conductive layer. The conductive layer can be disposed on at least a portion of the polymer film, on a side opposite the first optically clear adhesive. In some embodiments, the cover assembly can include a first conductive layer disposed on at least a portion of the polymer film between the first optically clear adhesive and the polymer film, and a second conductive layer disposed on at least a portion of the polymer film, on a side opposite the first conductive layer. In other words, in some embodiments, the polymer film can be sandwiched between a first and a second conductive layer. When present, the conductive layer is optically transparent, such that a 5 micrometer thick sample of the conductive layer transmits greater than 80% of visible light as determined according to ASTM D1003-00.

[0038] The transparent conductive layer can include indium tin oxide, carbon nanotubes, graphene, conductive metal nanowires, conductive metal nanoparticles (e.g., silver

nanoparticles), a conductive nanomesh (including a self-assembling conductive nanomesh, for example formed from conductive metal nanoparticles), a transparent conductive ink, or a combination comprising at least one of the foregoing.

[0039] In some embodiments, the mold insert can optionally further include a barrier coating disposed on the functional layer. The barrier coating can provide physical protection, and preferably can further provide protection from moisture or oxygen or both. When present, the barrier coating can comprise two or more thin films comprising different materials. In some embodiments a set of materials (e.g, a pair of films, or a set of three or more films) is layered in an alternating structure of two, three, four, or more pairs or sets. A wide variety of different film materials can be used to provide the desired barrier properties. For example, a pair of layers can include a layer of an organic material, e.g, a polymer, and an inorganic material, e.g., silica, alumina, or a glass; or a layer of a first inorganic material and a layer of a second inorganic material, e.g., a silica layer and a glass layer; or a layer including nanoparticles, and a layer of an inorganic material such as silica. The organic materials can include those used in the optically clear polymer films described below, and can be selected for their high temperature resistance, gas barrier properties, or both. Preferred materials for the organic layer of the barrier film include polyethylene naphthalate, polyether ether ketone, polyether sulfone, polystyrenes, or a combination comprising at least one of the foregoing. Materials for the inorganic layer of the barrier films are similarly selected. Examples of inorganic materials that can be used include individual metals, two or more metals as mixtures, inter-metallics or alloys, metal and mixed metal oxides, metal and mixed metal fluorides, metal and mixed metal nitrides, metal and mixed metal carbides, metal and mixed metal carbonitrides, metal and mixed metal oxynitrides, metal and mixed metal borides, metal and mixed metal oxyborides, metal and mixed metal silicides, and combinations comprising at least one of the foregoing, provided that an optically clear barrier film layer can be manufactured.

[0040] The barrier coating can be formed by known processes, for example liquid coating techniques such as solution coating, roll coating, dip coating, spray coating, or spin coating; coating techniques such as sputtering, vacuum processes for thermal evaporation and deposition of solid materials, chemical vapor deposition (CVD), chemical vapor deposition (PECVD) or atomic layer deposition (ALD). In some embodiments, the barrier coating can be prepared using ALD. In some embodiments, suitable barrier coatings can be Ultra Barrier Films available from LOTUS Applied Technology.

[0041] The barrier coating can have a thickness of 50 micrometers to 1 millimeter, preferably 50 micrometers to 0.7 millimeter, more preferably 50 to 400 micrometers, even more preferably 50 to 200 micrometers.

[0042] In some embodiments, the mold insert can further include a decorative pattern disposed on at least a portion of the glass layer, the polymer film, or both. The decorative pattern can be applied to the glass layer or the polymer film by screen printing, laser marking, digital inkjet printing, digital conductive inkjet printing, sublimation, offset printing, digital offset printing, roto gravure printing, pad printing, transfer printing, metallization, vacuum metallization, powder coating, spray painting, painting by hand, or a combination of at least one of the foregoing application techniques. In some embodiments, the pattern can be applied so as to provide a dead front graphic or display, where the display appears tinted or mirrored when not lit, and shows the graphics when backlit or a display when the display is turned on. In some embodiments, the decorative pattern is provided at an edge of the cover assembly (e.g., as a border).

[0043] The mold insert can be manufactured by applying the optically clear adhesive to at least a portion of the first surface of the glass layer, and applying the polymer film to the optically clear adhesive on a side opposite the first surface of the glass layer. The adhesive can be applied using any suitable process including, but not limited to, roll lamination, roller coating, screen printing, spreading, spray coating, spin coating, dip coating, and the like, or a combination comprising at least one of the foregoing techniques. The polymer film can be prepared using any method for preparing a polymer film that is generally known. For example, the polymer film can be prepared by extrusion, solution casting, melt blowing, and the like. When present, the one or more additional layers can be applied in the desired position in the cover assembly. The layers can generally be assembled in any order to provide the desired cover assembly. In some embodiments, when the cover assembly includes a first and a second conductive layer coating each side of the polymer film, the first and the second conductive layers can be applied to the polymer film (simultaneously or consecutively) prior to applying the polymer film (including the conductive layers) to the first optically clear adhesive on a side opposite the first surface of the glass layer. In some embodiments, the mold insert can further be polished such that at least a portion of an edge of the mold insert is polished.

[0044] In addition to the mold insert as described above, the molded article comprises a thermoplastic attachment coupled to a portion of the second surface of the polymer film. The attachment extends along an edge of the mold insert. The thermoplastic attachment can be any shape. The attachment can be bonded to the polymer film of the mold insert. In some embodiments, the attachment can surround the edge of the mold insert. Exemplary molded articles can be as shown in FIGS. 2-4. For example, as shown in FIG. 2, the attachment (17) can extend alone the edge of the mold insert and can be flush with the second surface of the glass layer of the mold insert. In some embodiments, the molded article can include a bezel (15) or trim adhered to the polymer film (6), preferably around the edges of the mold insert. Also as shown in FIG. 2, the attachment can have an extended feature (16) to provide an increased adhesion area between the attachment (17) and the polymer film (6). Advantageously, no additional adhesive layer is required to facilitate bonding the attachment to the polymer film of the mold insert.

[0045] As shown in FIG. 3, in some embodiments, the glass layer of the mold insert can be rounded (18). Stated another way, in some embodiments, the second surface of the glass layer can optionally exhibit curvature in a direction perpendicular to a front side of the molded article, where the front side of the molded article comprises the second surface of the glass layer and a portion of the thermoplastic attachment. The rounded edges of the glass layer of the mold insert can be prepared, for example, by machining or any other suitable method.

[0046] As shown in FIG. 4, in some embodiments, the attachment (17) can further be configured so as to include assembly features (19). The assembly features can facilitate use of the molded article within an electronic device, for example. The assembly features can be, for example, snap fit assembly features, a hook, or any other suitable assembly feature.

[0047] The attachment comprises a second thermoplastic polymer. The first and second thermoplastic polymer can be the same or different. In some embodiments, the second thermoplastic polymer is an optically clear high modulus ductile thermoplastic polymer composition. Advantageously, the difference between the refractive index of the mold insert and the refractive index of the thermoplastic attachment is less than or equal to 0.07, preferably less than or equal to 0.05. A difference of less than or equal to 0.07, or less than or equal to 0.05 in refractive index of the mold insert and the attachment can provide a so-called "seamless" molded article, where the interface between the edge of the mold insert and the attachment (identified as (20) in FIG. 4) is essentially invisible or unidentifiable to the naked eye. In some embodiments, the mold insert has a refractive index of 1.49 to 1.65, or 1.50 to 1.60, and the thermoplastic attachment has a refractive index of 1.49 to 1.65, or 1.50 to 1.60, or 1.54 to 1.58.

[0048] The second thermoplastic polymer of the attachment comprises a polycarbonate, where the polycarbonate can be as described above. In addition to the second thermoplastic polymer, the attachment can further include at least one reinforcing filler and optionally, a flame retardant component (e.g., a phosphorus-containing flame retardance), and a flame retardant synergist. When present, the flame retardant component and the flame retardant synergist can be as described in US Patent Application No. 14/317,412.

[0049] In some embodiments, the attachment can include 50 to 95 wt% of the polycarbonate and 5 to 50 wt% of the reinforcing filler, wherein wt% is based on the total weight of the attachment, and the combined weight percent of all components does not exceed 100 wt%. When present, a flame retardant can be used in an amount of 3 to 7 wt%.

[0050] The reinforcing filler can be selected to impart additional impact strength, to improve transparency, or to provide additional characteristics that can be based on the final selected characteristics of the attachment of the molded article. In some embodiments, the reinforcing filler can be present in an amount of 5 to 50 wt%, or 5 to 35 wt%, based on the total weight of the attachment.

[0051] The reinforcing filler can be, for example, carbon fiber, glass fiber, glass beads, glass flakes, glass bubbles, aramid fiber, basalt fiber, quartz fiber, boron fiber, cellulose fiber, natural fiber, liquid crystal polymer fiber, high tenacity polymer fiber, or a combination comprising at least one of the foregoing. In some embodiments, the reinforcing filler material is transparent and comprises glass fiber, glass beads, glass flakes, glass bubbles, carbon nanotubes, or a combination comprising at least one of the foregoing.

[0052] In some embodiments, the reinforcing filler preferably comprises glass fibers (including continuous and chopped fibers), including but not limited to E, A, C, ECR, R, S, D, and NE glasses and quartz, glass spheres including but not limited to hollow and solid glass spheres, glass flakes, and the like. In some embodiments, the glass fiber can have a cross section that is round or flat.

[0053] In some embodiments, examples of suitable glass materials are C glass [S1O2 (65- 70%), AI2O3 (2-6%), CaO (4-9%), MgO (0-5%), B2O3 (2-7%), Na₂0 & K₂0 (9-13%), ZnO (1- 6%)] and ECR glass [Si0₂ (63-70%), AI2O3 (3-6%), CaO (4-7%), MgO (1-4%), B2O3 (2-5%), Na₂0 (9-12%), K₂0 (0-3%), T1O2 (0-4%), ZnO (1-5%)]. An especially preferred glass material is ECR glass having >0.1% T1O2, especially below 1% T1O2.

[0054] The reinforcing filler preferably has a refractive index that is at least substantially similar to the refractive index of the polycarbonate of the attachment. In some embodiments, the reinforcing filler can have a refractive index that is 1.42 to 1.6, or 1.45 to 1.6, or 1.5 to 1.59, or 1.55 to 1.59.

[0055] The attachment of the molded article is preferably optically clear. To that end, the attachment composition can exhibit a level of transmittance that is greater than 50%, or greater than 60%, or greater than 70%, or greater than 80%, or greater than 85%, or greater than 90%, or greater than 95%, or greater than 99%. Transparency can be determined according to ASTM D1003 at a thickness of 2 millimeters.

[0056] In some embodiments, the attachment can optionally include one or more additives, for example an anti-drip agent, antioxidant, antistatic agent, chain extender, colorant, de-molding agent, dye, flow promoter, flow modifier, light stabilizer, lubricant, mold release agent, pigment, quenching agent, thermal stabilizer, UV absorbent substance, UV reflectant substance, UV stabilizer, or a combination comprising at least one of the foregoing.

[0057] In some embodiments, the composition preferably comprises a colorant, dye, or pigment. Preferably, when the composition of the attachment, comprises a colorant, dye, or pigment, the polymer film of the mold insert also comprises a colorant, dye, or pigment, preferably wherein the colorant, dye, or pigment of the polymer film is the same as for the composition of the attachment.

[0058] Examples of colored pigments especially include organic pigments selected from the group consisting of azo, azomethine, methine, anthraquinone, phthalocyanine, perinone, perylene, diketopyrrolopyrrole, thioindigo, dioxazine iminoisoindoline, dioxazine,

iminoisoindolinone, quinacridone, flavanthrone, indanthrone, anthrapyrimidine and quinoph- thalone pigments, or a mixture or solid solution thereof; especially a dioxazine,

diketopyrrolopyrrole, quinacridone, phthalocyanine, indanthrone or iminoisoindolinone pigment, or a mixture or solid solution thereof. Colored organic pigments of particular interest include CI. Pigment Red 202, CI. Pigment Red 122, CI. Pigment Red 179, CI. Pigment Red 170, CI. Pigment Red 144, CI. Pigment Red 177, CI. Pigment Red 254, CI. Pigment Red 255, CI. Pigment Red 264, CI. Pigment Brown 23, CI. Pigment Yellow 109, CI. Pigment Yellow 110, CI. Pigment Yellow 147, CI. Pigment Orange 61, CI. Pigment Orange 71, CI. Pigment Orange 73, CI. Pigment Orange 48, CI. Pigment Orange 49, CI. Pigment Blue 15, CI. Pigment Blue 60, CI. Pigment Violet 23, CI. Pigment Violet 37, CI. Pigment Violet 19, CI. Pigment Green 7, CI. Pigment Green 36, or a mixture or solid solution thereof. Suitable colored pigments also include inorganic pigments; especially those selected from the group consisting of metal oxides, antimony yellow, lead chromate, lead chromate sulfate, lead molybdate, ultramarine blue, cobalt blue, manganese blue, chrome oxide green, hydrated chrome oxide green, cobalt green, and metal sulfides, such as cerium or cadmium sulfide, cadmium sulfoselenides, zinc ferrite, bismuth vanadate, and mixed metal oxides.

[0059] More particularly, the colored pigment can be a transparent organic pigment. Pigment compositions wherein the colored pigment is a transparent organic pigment having a particle size of <0.2 μιη, more specifically, <0.1 μιη, are particularly interesting. For example, pigment compositions containing, as transparent organic pigment, the transparent quinacridones in their magenta and red colors, the transparent yellow pigments, like the isoindolinones or the yellow quinacridone/quinacridone quinone solid solutions, transparent copper phthalocyanine blue and halogenated copper phthalocyanine green, or the highly- saturated transparent diketopyrrolopyrrole or dioxazine pigments are particularly interesting. Typically the pigment composition is prepared by blending the pigment with the filler by known dry or wet mixing techniques. For example, the components are wet mixed in the end step of a pigment preparatory process, or by blending the filler into an aqueous pigment slurry, the slurry mixture is then filtered, dried and micropulverized.

[0060] In some embodiments, the second thermoplastic polymer further comprises a polymer different from the polycarbonate, for example a polyester. For example, the second thermoplastic polymer comprises an aromatic polycarbonate (e.g., a bisphenol A polycarbonate) and a polyester. In some embodiments, the polyester can include, for example, polyethylene terephthalates, polybutylene terephthalates, polyarylates, and polyester copolymers such as polyester-ethers). In some embodiments, the polyester can include a poly(ethylene

terephthalate), a glycol-modified poly(ethylene terephthalate), a poly(ethylene naphthalate), poly( 1 ,4-cyclohexane-dimethanol- 1 ,4-cyclohexane dicarboxylate),

poly(cyclohexanedimethylene terephthalate)-co-poly(ethylene terephthalate), or a combination comprising at least one of the foregoing polyesters. In some embodiments, the polyester is preferably poly(l,4-cyclohexane dimethylene terephthalate). In some embodiments, the attachment comprises 30 to 90 wt% of an aromatic polycarbonate and 10 to 70 wt% of poly(l,4- cyclohexane dimethylene 1,4-cyclohexanedicarboxylate), based on the total weight of the polymer components of the attachment.

[0061] In some embodiments, the difference in the refractive index between each of the components of the molded article is less than or equal to 0.07, preferably less than or equal to 0.05. Specifically, the difference in the refractive index between the glass layer and the polymer film of the mold insert and the attachment can be less than or equal to 0.07, preferably less than or equal to 0.05. Without wishing to be bound by theory, it is believed that minimizing the difference in refractive index between each of the layers of the molded article contributes to the superior optical properties of the molded article.

[0062] The molded article can be manufactured by molding the attachment to the mold insert in a molding process. For example, the mold insert can be positioned in a cavity and a polymeric composition of the attachments can be injected into the mold cavity to bond to the polymer film of the mold insert. The molding process can incorporate known technologies such as injection molding, injection compression molding, gas assist molding, foam molding, multi shot molding, multi stage molding, compression molding, or a combination comprising at least one of the foregoing molding technologies. Tooling that improves flow, surface finish, and weld strength of knit lines with a molded part such as induction heating and heat/cool technology can be used to reduce injection pressures, improve surface finishes, and promote improved bond strength to the mold insert. The mold insert can be held in position within the mold cavity during the molding process using any technique known in the art. For example, the mold insert can be held in place by a pressure differential such as vacuum applied to an area of the mold insert through passages in a mold section. The mold insert can be held in place by pins extending from a mold section into the mold cavity. The pins can be spring loaded to ensure sufficient pressure in applied to the mold insert to maintain its position during the molding operation. Spring loaded pins can account for variation in the thickness of the mold insert from part to part during production of multiple articles. The mold insert can be held in place by a static charge. The mold insert can be held in place by core shutoffs that can extend out from the cavity and can form a feature that the insert can fit over. The mold insert can be held in place by a combination of pins, static, shutoffs, mold features, and pressure differential as described in the foregoing.

[0063] In some embodiments, the molded article can be manufactured using tooling as shown in FIG. 5. The tooling can incorporate dynamic tool temperature control. Furthermore, the tooling can have a highly polished surface in order to maximize the desired optical properties from the attachment. FIG. 5 shows a cross-section of exemplary tooling that can be used to prepare the molded article. The tooling includes heating and cooling channels (9) to provide a pathway for heating and cooling medium. The channels (9) can be 6 to 16 millimeters in diameter, and can be distanced from the tool surface (10) by a distance that is 1 to 1.5 times the channel diameter. Through the channels (9), the tool surface (10) can be heated to above the glass transition temperature (Tg) of the injected molten polymer composition. After packing, the tool surface (10) can be cooled to a demolding temperature. The demolding temperature can be selected by a person having ordinary skill in the art, and is usually below the heat distortion temperature (HDT) or the Vicat softening temperature of the injected polymer composition.

[0064] As mentioned above, the tooling surface (10) can be smoothed or polished by any method that is generally known. The resulting glossy tooling surface (10) can aid in providing desirable optical properties to the molded part. The tool surface in contact with the glass layer of mold insert (14), is also highly polished. The surface (14) can be in direct contact with the glass, or can be positioned above the glass such that there is a slight space between the glass layer and the surface (14). The mold insert (1) is fixed in the tool using a vacuum chuck (11). The vacuum chuck (11) can be ceramic, and can further include several micrometer pores or channels (13) serving as an air pathway. The molten resin is injected in the cavity (12) to form the attachment of the molded article. As stated above, following injection of the molten composition, the tooling is cooled to a de-molding temperature and the molded part can be removed from the tooling.

[0065] The molded articles described herein can be useful for a wide variety of applications, including consumer electronics, electronics using in the transportation industry, and furniture components. Accordingly, an electronic device comprising the molded article represents another aspect of the present disclosure. In some embodiments, the molded article can be laminated or molded onto the device, or adhered onto the device via an adhesive layer, or attached to the device via one or more assembly features (e.g., a snap fit assembly or a hook). Examples of electronic devices that can be utilized with the molded article include, but are not limited to, a cellular telephone, a smart telephone, a laptop computer, a notebook computer, a tablet computer, a television, a console (e.g., an appliance console or an automotive console, particularly an automotive interior center console, such as a central stack display or a heads up display), a smart board, a medical device, a monitor, a smart window, public information displays, a transparent display, or a wearable electronic device or display (e.g., smart watch, activity tracker, health tracker, health monitoring devices, and the like). In some embodiments, the display can be a heads-up display, a display console, or a touch screen display. Alternatively, an electronic device for use with the molded article can be a lighting device. In some embodiments where the molded article is used for a lighting device, the molded article can further serve as a barrier layer for oxygen and moisture, such that no additional barrier layer is required. In some embodiments, the molded article can be a housing or a portion of a housing for an electronic device. The molded article described herein can be used as a front or back cover for an electronic device or a display device. In some embodiments, the molded article can be useful as a furniture component, for example a component of a furniture door or window.

[0066] The molded article described herein provides a light weight, seamless design with superior optical properties for an electronic or lighting device. The seamless design is accomplished by careful selection of the glass/plastic laminate mold insert and the polymer composition used for the thermoplastic attachment, such that the difference between the refractive index of the mold insert and the refractive index of the thermoplastic attachment is less than or equal to 0.07. The molded articles exhibit little to no birefringence due to the refractive index matching of the various components. Thus, a significant improvement in molded articles for electronic devices is provided by the present disclosure.

[0067] The molded articles, methods, and devices are further described by the following embodiments, which are non-limiting.

[0068] Embodiment 1: A molded article comprising: a mold insert comprising:

[0069] a glass layer having a first surface and a second surface opposite the first surface; a first optically clear adhesive layer disposed on at least a portion of the first surface of the glass layer, wherein a 50 micrometer-thick sample of the optically clear adhesive transmits greater than 90% of visible light as determined according to ASTM D 1003-00; and an optically clear polymer film having a first surface and a second surface, where the first surface of the polymer film is in contact with the adhesive layer on a side opposite the glass layer, the polymer film comprising a first thermoplastic polymer, wherein a 100 micrometer-thick sample of the optically clear polymer film transmits greater than 85% of visible light as determined according to ASTM D 1003-00; and a thermoplastic attachment coupled to a portion of the second surface of the polymer film, wherein the attachment extends along an edge of the mold insert, and wherein the attachment comprises a second thermoplastic polymer; and wherein the difference between the refractive index of the mold insert and the refractive index of the thermoplastic attachment is less than or equal to 0.07.

[0070] Embodiment 2: The molded article of embodiment 1, wherein the glass layer has a thickness of 50 micrometers to 25 millimeters, preferably 50 micrometers to 10 millimeters, more preferably 50 micrometers to 1 millimeter, even more preferably 50 to 500 micrometers. [0071] Embodiment 3: The molded article of embodiment 1 or 2, wherein the glass layer comprises chemically strengthened glass, non- strengthened glass, tempered glass, or optically transparent synthetic crystal.

[0072] Embodiment 4: The molded article of any one or more of embodiments 1 to 3, wherein the optically clear adhesive has a thickness of 1 to 2000 micrometers, preferably 10 to 100 micrometers, more preferably 10 to 50 micrometers, even more preferably 12.5 to 25 micrometers.

[0073] Embodiment 5: The molded article of any one or more of embodiments 1 to 4, wherein the polymer film comprises a polyacetal, poly(Ci-6 alkyl)acrylate, polyarylate, polycarbonate, polyester, polyetherimide, polyimide, poly(Ci-6 alkyl)methacrylate, polyolefin, polystyrene, polyurethane, polyvinyl alcohol, polyvinyl ester, polyvinyl ether, polyvinyl halide, polyvinyl nitrile, polyvinyl ketone, polyvinylidene fluoride, or a combination comprising at least one of the foregoing thermoplastic polymers; preferably, poly(ethylene terephthalate), poly(ethylene naphthalate), poly(l,4-cyclohexane dimethylene terephthalate),

poly(cyclohexanedimethylene terephthalate)-co-poly(ethylene terephthalate), polyethylene, polypropylene, a bisphenol A polycarbonate, poly(4,4'-oxydiphenylene-pyromellitimide), or a combination comprising at least one of the foregoing; more preferably, a bisphenol A

polycarbonate.

[0074] Embodiment 6: The molded article of any one or more of embodiments 1 to 5, wherein the polymer film has a thickness of 1 micrometer to 20 millimeters, preferably 5 micrometers to 20 millimeters, more preferably 5 micrometers to 10 millimeters, even more preferably 5 micrometers to 1 millimeter, even more preferably still 5 to 250 micrometers, most preferably still 50 to 200 micrometers.

[0075] Embodiment 7: The molded article of any one or more of embodiments 1 to 6, wherein the mold insert further comprises a functional layer disposed on at least a portion of the glass layer, the polymer film, or both, preferably wherein the functional layer comprises an anti- reflection coating, an anti-glare coating, an anti-fingerprint coating, an antimicrobial coating, a conductive layer, a touch sensing layer, or a combination comprising at least one of the foregoing.

[0076] Embodiment 8: The molded article of embodiment 7, wherein the functional layer comprises a conductive layer disposed on at least a portion of the polymer film on a side opposite the first optically clear adhesive layer, wherein a 5 micrometer-thick sample of the conductive layer transmits greater than 90% of visible light as determined according to ASTM D 1003-00, preferably wherein the transparent conductive layer comprises indium tin oxide, carbon nanotubes, graphene, conductive metal nanowires, conductive metal nanoparticles, a conductive nanomesh, a transparent conductive ink, or a combination comprising at least one of the foregoing.

[0077] Embodiment 9: The molded article of embodiments 7 or 8, further comprising a barrier coating disposed on the functional layer.

[0078] Embodiment 10: The molded article of any one or more of embodiments 1 to 9, further comprising a decorative pattern disposed on the glass layer, the polymer film, or both.

[0079] Embodiment 11: The molded article of any one or more of embodiments 1 to 10, wherein the glass layer or polymer film or both is textured.

[0080] Embodiment 12: The molded article of any one or more of embodiments 1 to 11, wherein the polymer film and the thermoplastic attachment comprise a colorant.

[0081] Embodiment 13: The molded article of any one or more of embodiments 1 to 12, wherein the second thermoplastic polymer comprises an aromatic polycarbonate.

[0082] Embodiment 14: The molded article of any one or more of embodiments 1 to 13, wherein the second thermoplastic polymer comprises an aromatic polycarbonate and a polyester, preferably an aromatic polycarbonate and poly(l,4-cyclohexane dimethylene terephthalate).

[0083] Embodiment 15: The molded article of any one or more of embodiments 1 to 14, wherein the second thermoplastic polymer comprises 30 to 90 wt% of an aromatic

polycarbonate and 10 to 70 wt% of poly(l,4-cyclohexane dimethylene 1,4- cyclohexanedicarboxylate) .

[0084] Embodiment 16: The molded article of any one or more of embodiments 1 to 15, wherein the thermoplastic attachment comprises a reinforcing filler material comprising carbon fiber, glass fiber, glass beads, glass flakes, glass bubbles, aramid fiber, basalt fiber, quartz fiber, boron fiber, cellulose fiber, natural fiber, liquid crystal polymer fiber, high tenacity polymer fiber, or a combination comprising at least one of the foregoing, preferably, wherein the reinforcing filler material is transparent and comprises glass fiber, glass beads, glass flakes, glass bubbles, carbon nanotubes, or a combination comprising at least one of the foregoing.

[0085] Embodiment 17: The molded article of embodiment 16, wherein the reinforcing filler material is present in an amount of 1 to 50 wt%, or 5 to 35 wt%, based on the total weight of the thermoplastic attachment.

[0086] Embodiment 18: The molded article of any one or more of embodiments 1 to 17, wherein the thermoplastic attachment forms a border that surrounds the mold insert in at least one dimension. [0087] Embodiment 19: The molded article of any one or more of embodiments 1 to 18, wherein the mold insert has a refractive index of 1.49 to 1.65, or 1.50 to 1.60, and the thermoplastic attachment has a refractive index of 1.49 to 1.65, or 1.50 to 1.60, or 1.54 to 1.58.

[0088] Embodiment 20: The molded article of any one or more of embodiments 1 to 19, wherein a front side of the molded article comprises the second surface of the glass layer and a portion of the thermoplastic attachment.

[0089] Embodiment 21: The molded article of embodiment 20, wherein the second surface of the glass layer and the thermoplastic attachment are flush along the front side of the article; or the second surface of the glass layer exhibits curvature in a direction perpendicular to the front side of the article.

[0090] Embodiment 22: A method of manufacturing the molded article of any one or more of embodiments 1 to 21, the method comprising, applying the optically clear adhesive to at least a portion of the first surface of the glass layer; coupling the polymer film to the optically clear adhesive on a side opposite the first surface of the glass layer to form a mold insert, wherein the adhesive is sandwiched between the glass layer and the polymer film; molding a thermoplastic attachment to the mold insert in an injection molding process to form a molded article, wherein the attachment extends along at least a portion of an edge of the mold insert.

[0091] Embodiment 23: An electronic device comprising the molded article of any one or more of embodiments 1 to 21, wherein the device is a cellular telephone, a smart telephone, a laptop computer, a notebook computer, a tablet computer, a television, a console (e.g., an appliance or automotive console such as a central stack display or a heads-up display), a smart white board, a wearable display, a transparent display, a medical device, a lighting device, or a smart window.

[0092] Embodiment 24: The electronic device of embodiment 23, wherein the molded article is laminated onto the device, or molded onto the device, or adhered onto the device via an adhesive layer, or attached to the device via one or more assembly features.

Embodiment 25: A housing for an electronic device comprising the molded article of any one or more of embodiments 1 to 21.

[0093] The molded articles, methods, and devices can alternatively comprise, consist of, or consist essentially of, any appropriate components or steps herein disclosed. The

compositions, methods, and articles can additionally, or alternatively, be formulated so as to be devoid, or substantially free, of any steps, components, materials, ingredients, adjuvants, or species that are otherwise not necessary to the achievement of the function or objectives of the compositions, methods, and articles.

[0094] All ranges disclosed herein are inclusive of the endpoints, and the endpoints are independently combinable with each other. "Combinations" is inclusive of blends, mixtures, alloys, reaction products, and the like. The terms "first," "second," and the like, do not denote any order, quantity, or importance, but rather are used to distinguish one element from another. The terms "a" and "an" and "the" do not denote a limitation of quantity, and are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly

contradicted by context. "Or" means "and/or" unless clearly stated otherwise. Reference throughout the specification to "some embodiments", "an embodiment", and so forth, means that a particular element described in connection with the embodiment is included in at least one embodiment described herein, and may or may not be present in other embodiments. In addition, it is to be understood that the described elements may be combined in any suitable manner in the various embodiments.

[0095] Unless defined otherwise, technical and scientific terms used herein have the same meaning as is commonly understood by one of skill in the art to which this application belongs. All cited patents, patent applications, and other references are incorporated herein by reference in their entirety. However, if a term in the present application contradicts or conflicts with a term in the incorporated reference, the term from the present application takes precedence over the conflicting term from the incorporated reference.

[0096] The term "alkyl" means a branched or straight chain, unsaturated aliphatic hydrocarbon group, e.g., methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, t-butyl, n-pentyl, s- pentyl, and n- and s-hexyl. "Alkenyl" means a straight or branched chain, monovalent hydrocarbon group having at least one carbon-carbon double bond (e.g., ethenyl (-HC=CH₂)). "Alkoxy" means an alkyl group that is linked via an oxygen (i.e., alkyl-O-), for example methoxy, ethoxy, and sec-butyloxy groups. "Alkylene" means a straight or branched chain, saturated, divalent aliphatic hydrocarbon group (e.g., methylene (-CH₂-) or, propylene (-(CH₂)₃- )). "Cycloalkylene" means a divalent cyclic alkylene group, -C_nH_2n-_x, wherein x is the number of hydrogens replaced by cyclization(s). "Cycloalkenyl" means a monovalent group having one or more rings and one or more carbon-carbon double bonds in the ring, wherein all ring members are carbon (e.g., cyclopentyl and cyclohexyl). "Aryl" means an aromatic hydrocarbon group containing the specified number of carbon atoms, such as phenyl, tropone, indanyl, or naphthyl. The prefix "halo" means a group or compound including one more of a fluoro, chloro, bromo, or iodo substituent. A combination of different halo groups (e.g., bromo and fluoro), or only chloro groups can be present. The prefix "hetero" means that the compound or group includes at least one ring member that is a heteroatom (e.g., 1, 2, or 3 heteroatom(s)), wherein the heteroatom(s) is each independently N, O, S, Si, or P. "Substituted" means that the compound or group is substituted with at least one (e.g., 1, 2, 3, or 4) substituents that can each independently be a C1-9 alkoxy, a C1-9 haloalkoxy, a nitro (-NO2), a cyano (-CN), a Ci-6 alkyl sulfonyl (-S(=0)₂-alkyl), a C₆-i2 aryl sulfonyl (-S(=0)₂-aryl)a thiol (-SH), a thiocyano (-SCN), a tosyl (CH3C6H₄S0₂-), a C3-12 cycloalkyl, a C2-12 alkenyl, a C5-12 cycloalkenyl, a C₆-i2 aryl, a C7-13 arylalkylene, a C_4-12 heterocycloalkyl, and a C3-12 heteroaryl instead of hydrogen, provided that the substituted atom's normal valence is not exceeded. The number of carbon atoms indicated in a group is exclusive of any substituents. For example -CH2CH2CN is a C2 alkyl group substituted with a nitrile.

[0097] While particular embodiments have been described, alternatives, modifications, variations, improvements, and substantial equivalents that are or may be presently unforeseen may arise to applicants or others skilled in the art. Accordingly, the appended claims as filed and as they may be amended are intended to embrace all such alternatives, modifications variations, improvements, and substantial equivalents.

Claims

CLAIMS What is claimed is:

1. A molded article comprising:

a mold insert comprising:

a glass layer having a first surface and a second surface opposite the first surface; a first optically clear adhesive layer disposed on at least a portion of the first surface of the glass layer, wherein a 50 micrometer-thick sample of the optically clear adhesive transmits greater than 90% of visible light as determined according to ASTM D 1003-00; and

an optically clear polymer film having a first surface and a second surface, where the first surface of the polymer film is in contact with the adhesive layer on a side opposite the glass layer, the polymer film comprising a first thermoplastic polymer, wherein a 100 micrometer-thick sample of the optically clear polymer film transmits greater than 85% of visible light as determined according to ASTM D 1003-00; and

a thermoplastic attachment coupled to a portion of the second surface of the polymer film, wherein the attachment extends along an edge of the mold insert, and wherein the attachment comprises a second thermoplastic polymer; and

wherein the difference between the refractive index of the mold insert and the refractive index of the thermoplastic attachment is less than or equal to 0.07.

2. The molded article of claim 1, wherein the glass layer has a thickness of 50 micrometers to 25 millimeters, preferably 50 micrometers to 10 millimeters, more preferably 50 micrometers to 1 millimeter, even more preferably 50 to 500 micrometers.

3. The molded article of claim 1 or 2, wherein the glass layer comprises chemically strengthened glass, non- strengthened glass, tempered glass, or optically transparent synthetic crystal.

4. The molded article of any one or more of claims 1 to 3, wherein the optically clear adhesive has a thickness of 1 to 2000 micrometers, preferably 10 to 100 micrometers, more preferably 10 to 50 micrometers, even more preferably 12.5 to 25 micrometers.

5. The molded article of any one or more of claims 1 to 4, wherein the polymer film comprises

a polyacetal, poly(Ci-6 alkyl)acrylate, polyarylate, polycarbonate, polyester,

polyetherimide, polyimide, poly(Ci-6 alkyl)methacrylate, polyolefin, polystyrene, polyurethane, polyvinyl alcohol, polyvinyl ester, polyvinyl ether, polyvinyl halide, polyvinyl nitrile, polyvinyl ketone, polyvinylidene fluoride, or a combination comprising at least one of the foregoing thermoplastic polymers;

preferably, poly(ethylene terephthalate), poly(ethylene naphthalate), poly(l,4- cyclohexane dimethylene terephthalate), poly(cyclohexanedimethylene terephthalate)-co- poly(ethylene terephthalate), polyethylene, polypropylene, a bisphenol A polycarbonate, poly(4,4'-oxydiphenylene-pyromellitimide), or a combination comprising at least one of the foregoing;

more preferably, a bisphenol A polycarbonate.

6. The molded article of any one or more of claims 1 to 5, wherein the polymer film has a thickness of 1 micrometer to 20 millimeters, preferably 5 micrometers to 20 millimeters, more preferably 5 micrometers to 10 millimeters, even more preferably 5 micrometers to 1 millimeter, even more preferably still 5 to 250 micrometers, most preferably still 50 to 200 micrometers.

7. The molded article of any one or more of claims 1 to 6,

wherein the mold insert further comprises a functional layer disposed on at least a portion of the glass layer, the polymer film, or both,

preferably wherein the functional layer comprises an anti-reflection coating, an anti-glare coating, an anti-fingerprint coating, an antimicrobial coating, a conductive layer, a touch sensing layer, or a combination comprising at least one of the foregoing,

more preferably wherein the functional layer comprises a conductive layer disposed on at least a portion of the polymer film on a side opposite the first optically clear adhesive layer, wherein a 5 micrometer-thick sample of the conductive layer transmits greater than 90% of visible light as determined according to ASTM D1003-00, preferably wherein the transparent conductive layer comprises indium tin oxide, carbon nanotubes, graphene, conductive metal nanowires, conductive metal nanoparticles, a conductive nanomesh, a transparent conductive ink, or a combination comprising at least one of the foregoing.

8. The molded article of claim 7, further comprising a barrier coating disposed on the functional layer.

9. The molded article of any one or more of claims 1 to 8 further comprising a decorative pattern disposed on the glass layer, the polymer film, or both, or wherein the glass layer or polymer film or both is textured.

10. The molded article of any one or more of claims 1 to 9, wherein the polymer film and the thermoplastic attachment comprise a colorant.

11. The molded article of any one or more of claims 1 to 10, wherein an edge of the mold insert is polished.

12. The molded article of any one or more of claims 1 to 11, wherein the second

thermoplastic polymer comprises

an aromatic polycarbonate,

preferably an aromatic polycarbonate and a polyester,

more preferably an aromatic polycarbonate and poly(l,4-cyclohexane dimethylene terephthalate),

even more preferably 30 to 90 wt% of an aromatic polycarbonate and 10 to 70 wt% of poly(l,4-cyclohexane dimethylene 1,4-cyclohexanedicarboxylate).

13. The molded article of any one or more of claims 1 to 12, wherein the thermoplastic attachment comprises a reinforcing filler material comprising carbon fiber, glass fiber, glass beads, glass flakes, glass bubbles, aramid fiber, basalt fiber, quartz fiber, boron fiber, cellulose fiber, natural fiber, liquid crystal polymer fiber, high tenacity polymer fiber, or a combination comprising at least one of the foregoing, preferably, wherein the reinforcing filler material is transparent and comprises glass fiber, glass beads, glass flakes, glass bubbles, carbon nanotubes, or a combination comprising at least one of the foregoing, and wherein the reinforcing filler material is present in an amount of 1 to 50 wt%, or 5 to 35 wt%, based on the total weight of the thermoplastic attachment.

14. The molded article of any one or more of claims 1 to 13, wherein the thermoplastic attachment forms a border that surrounds the mold insert in at least one dimension.

15. The molded article of any one or more of claims 1 to 14, wherein the mold insert has a refractive index of 1.49 to 1.65, or 1.50 to 1.60, and the thermoplastic attachment has a refractive index of 1.49 to 1.65, or 1.50 to 1.60, or 1.54 to 1.58.

16. The molded article of any one or more of claims 1 to 15,

wherein a front side of the molded article comprises the second surface of the glass layer and a portion of the thermoplastic attachment, and

wherein

the second surface of the glass layer and the thermoplastic attachment are flush along the front side of the article; or

the second surface of the glass layer exhibits curvature in a direction perpendicular to the front side of the article.

17. A method of manufacturing the molded article of any one or more of claims 1 to 16, the method comprising,

applying the optically clear adhesive to at least a portion of the first surface of the glass layer;

coupling the polymer film to the optically clear adhesive on a side opposite the first surface of the glass layer to form a mold insert, wherein the adhesive is sandwiched between the glass layer and the polymer film;

molding a thermoplastic attachment to the mold insert in an injection molding process to form a molded article, wherein the attachment extends along at least a portion of an edge of the mold insert.

18. An electronic device comprising the molded article of any one or more of claims 1 to 16, wherein the device is a cellular telephone, a smart telephone, a laptop computer, a notebook computer, a tablet computer, a television, a console (e.g., an appliance or automotive console such as a central stack display or a heads-up display), a smart white board, a wearable display, a transparent display, a medical device, a lighting device, or a smart window.

19. The electronic device of claim 18, wherein the molded article is laminated onto the device, or molded onto the device, or adhered onto the device via an adhesive layer, or attached to the device via one or more assembly features.

20. A housing for an electronic device comprising the molded article of any one or more of claims 1 to 16.