TW201739593A - Molded articles, method of manufacture, and device comprising the molded article - Google Patents

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 article, manufacturing method, and device containing the same

The present disclosure relates to a molded article, a method of manufacturing, and a device comprising the molded article or a cover thereof.

Insert molding is a technique in which a mold is positioned in a mold and the remainder of the desired article is formed around the mold. Mold molding may be particularly useful in the manufacture of components for electronic devices. Conventional glass mold molding techniques often face the following problems, including an undesired visible interface between the glass mold core and the molding material, and limited aesthetic choices (i.e., commonly used to make the molded product). Deformation minimized fillers limit the choice of color available), surface modification limits, and poor adhesion (often using glue to create optical problems, and often requires additional processing steps). In addition, molded articles with glass mold cores are often fragile and susceptible to cracking and are prone to failure and are not designed to withstand the actual impact at the center of the glass. Thicker glass has been explored to improve impact resistance, however this treatment is often undesirable and results in thicker, heavier devices. Also completed A significant study to improve the impact properties of glass by altering the composition of the glass, chemically treating the glass, tempering the glass, and the like. However, these altered glasses tend to become brittle, especially when thin layers are used.

There continues to be a need in the art for improved molding techniques that provide molded articles, particularly molded articles suitable for use in electronic devices. It would be advantageous to provide a molded article having improved impact resistance and improved aesthetics, especially a molded article having a design such that the interface between the mold core and the molded resin is indistinguishable.

A molded article comprising a mold insert and a thermal attachment, the mold core comprising a glass layer having a first surface and a second surface opposite the first surface; at least a portion of the first surface disposed on the glass layer a first optically clear adhesive layer, wherein the 50 micron thick sample of the optically clear adhesive transports more than 90% of visible light, as determined according to ASTM D1003-00; and optical clarification having a first surface and a second surface a polymer film, wherein a first surface of the polymer film is in contact with a binder layer on a side different from the glass layer, the polymer film comprising a first thermoplastic polymer, wherein the optically clear polymer film is 100 microns thick The sample transports more than 85% of visible light, as determined in accordance with ASTM D1003-00; the thermoplastic attachment is coupled to a portion of the second surface of the polymeric film, wherein the attachment extends along the edge of the mold, and wherein The attachment comprises a second thermoplastic polymer; and wherein the difference between the refractive index of the mold core and the refractive index of the thermoplastic attachment is less than or equal to 0.07.

A method of manufacturing the molded article, comprising applying the optically clear adhesive to at least a portion of a first surface of the glass layer; and on the side different from the first surface of the glass layer, the polymer film and the polymer film An optically clear binder is coupled to form a mold, wherein the binder is sandwiched between the glass layer and the polymer film; a thermoplastic appendage is molded into the mold core to form a molded article in an injection molding process, wherein The attachment extends along at least a portion of the edge of the mold.

An electronic device and a cover for an electronic device including the molded article are also described.

The above and other features are exemplified by the following figures and detailed description.

1‧‧‧Men

2‧‧‧ glass layer

3,7‧‧‧ first surface

4,8‧‧‧second surface

5‧‧‧First optical clarifying adhesive layer

6‧‧‧ polymer film

9‧‧‧ Pipes

10‧‧‧Tool surface

11‧‧‧vacuum chuck

12‧‧‧ hole

13‧‧‧ holes or pipes

14‧‧‧Tool surface/surface in contact with the glass layer of the mold core

15‧‧‧Table frame

16‧‧‧Extended features

17‧‧‧Annex

18‧‧‧ round head

19‧‧‧Combination features

20‧‧‧ interface

The following figure is an illustrative specific example in which similar elements are numbered identically.

Figure 1 is a schematic illustration of a mold core.

Figure 2 is a cross-sectional view of a molded article.

Figure 3 is a cross-sectional view of a molded article.

Figure 4 is a cross-sectional view of a molded article.

Figure 5 is a cross-sectional view of a tool used in the manufacture of molded articles.

The inventors have found that it is particularly suitable for use in electronic devices. product. The molded article comprises a mold having a layer structure (especially a glass/plastic laminate structure). The molded article additionally includes a thermoplastic attachment coupled to the mold, such as a coupler using a glass mold molding technique. The material for the mold core and the thermoplastic attachment is preferably selected to provide a substantially seamless transition from the mold core to the attachment, thereby improving the overall aesthetics of the molded article. In another advantageous feature, the use of the glass/plastic laminate can provide a lightweight mold core (e.g., as compared to conventional glass mold cores) and additionally contribute to the enhanced impact resistance of the molded article.

Accordingly, one aspect of the present disclosure is a molded article. The molded article comprises a mold which is a glass/plastic laminate. The mold can be as shown in Figure 1. As shown in Figure 1, the mold core (1) comprises a glass layer (2) having a first surface (3) and a second surface (4) opposite the first surface, disposed on a first surface of the glass layer a first optically clear adhesive layer (5) on at least a portion, and an optically clear polymer film (6) having a first surface (7) and a second surface (8), wherein the first surface of the polymer film The adhesive layer is contacted on a side different from the glass layer.

The glass layer may be, but not limited to, chemically strengthened glass (e.g., as marketed by the Corning Inc. CORNING ^TM GORILLA ^TM glass, are commercially available from the Schott AG of XENSATION ^TM glass by Asahi Glass Company, LTD of the commercially available DRAGONTRAIL ^TM and a glass Nippon Electric glass Company, LTD of CX-01 is a commercially available glass, and the like), such as a non-reinforced glass comprising a low sodium glass unhardened glass (e.g. Corning Inc. as a commercially available glass of CORNING ^TM WILLOW ^TM And OA-10G Glass-on-Roll glass and the like, which are marketed by Nippon Electric Glass Company, LTD., tempered glass, or optically transparent synthetic crystals (also known as sapphire glass, by GT Advanced Technologies Inc.) Sold).

The glass layer may have a thickness of 50 microns to 25 mm, or 50 microns to 10 mm, or 50 microns to 1 mm, or 50 to 500 microns.

In some embodiments, one or both surfaces of the glass layer can be a textured surface that provides, for example, anti-glare properties, anti-reflective properties, antimicrobial properties, and the like, or includes at least one of the foregoing. combination.

In addition to the glass layer, the mold core 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 "optical clear binder" means that a 50 micron thick sample of the optically clear adhesive transports greater than 90% of visible light, as determined according to ASTM D1003-00. The first optically clear adhesive layer may have a thickness of from 1 to 2000 microns, or from 1 to 1000 microns, or from 1 to 500 microns, or from 1 to 100 microns, or from 10 to 100 microns, or from 10 to 50 microns, or from 12.5 to 25 microns.

The binder may include epoxy resin, acrylate, amine, urethane, polyfluorene oxide, thermoplastic urethane, ethylene vinyl acetate, ethylene vinyl acetate without hindered amine light stabilizer (excluding EVA of HALS), or a combination comprising at least one of the foregoing. In one embodiment, the binder is ethylene vinyl acetate without a hindered amine light stabilizer (EVA without HALS). In one embodiment, the adhesive is a thermoplastic urethane or an acrylate optical quality adhesive modified by UV light curing, or a polyoxyxide pressure sensitive adhesive, or an acrylate pressure sensitive adhesive. The adhesive may be applied using methods such as roller lamination, roller coating, screen printing, padding, spray coating, spin coating, dip coating, and the like, or a combination comprising at least one of the foregoing techniques. Apply.

In addition to the glass layer and the optically clear binder, the mold core additionally comprises an optically clear polymer film having a first surface and a second surface. As discussed above, the first surface of the polymeric film is in contact with the adhesive layer on a different side than the glass layer. In other words, the first optical clearing binder is sandwiched between the optically clear polymer film and the first surface of the glass layer (as shown in Figure 1). As used herein, the term "optical clear polymer film" means that a 100 micron thick sample of the optically clear polymer film transmits greater than 85% of visible light, as determined in accordance with ASTM D1003-00. In some embodiments, the optically clear polymer film can have a thickness of from 1 micrometer to 20 millimeters, or from 5 micrometers to 20 millimeters, or from 5 micrometers to 10 millimeters, or from 5 micrometers to 1 millimeter, or from 5 to 500 micrometers, or 5 to 250 microns, or 50 to 250 microns, or 5 to 100 microns, or 50 to 200 microns.

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 into a liquid state upon heating, and solidifies into a brittle vitreous state when sufficiently cooled. Thermoplastic plastics are generally high molecular weight polymers. Examples of thermoplastic polymers that can be used include polyacetals (e.g., polyoxyethylene and polyoxymethylene), polyacrylic acid (C _1-6 alkyl) esters, polyacrylamides, polyamines (e.g., aliphatic poly Amidoxime, polyphthalamide, and polyarylamines, polyamidoximines, polyanhydrides, polyarylates, polyarylethers (polyphenylene ethers), Polyarylene sulfides (polyphenylene sulfides), polyaryl sulfoniums, polybenzothiazoles, polybenzoxazoles, polybenzimidazoles, polycarbonates (including polycarbonate) Ester copolymers such as polycarbonate-methoxyalkanes, polycarbonate-esters, and polycarbonate-oxime-based, polyesters (eg, polyethylene terephthalate, poly-p-phenylene) Butane dicarboxylate, polyarylate, and polyester copolymers such as polyester-ethers, polyetheretherketones, polyetherimines (including copolymers such as polyetherimine-oxime copolymers) , polyetherketoneketones, polyetherketones, polyether oximes, polyimines (including copolymers such as polyamidiene-oxirane copolymers), polymethacrylic acid (C _1-6) Alkyl ester, polymethacrylamide, Norbornene (including copolymers containing norbornene units), polyolefins (for example, polyethylenes, polypropylenes, polytetrafluoroethylenes, and copolymers thereof, such as ethylene-α-olefin copolymers) , polyoxadiazoles, polyoxymethylene, polyphthalates, polyazanes, polyoxyalkylenes, polystyrene (including copolymers such as acrylonitrile-butadiene-styrene) (ABS) and methyl methacrylate-butadiene-styrene (MBS), polysulfide, polysulfonamide, polysulfonate, polyfluorene, polythioester, poly3 , polyureas, polyurethanes, polyvinyl alcohols, polyvinyl esters, polyvinyl ethers, polyvinyl halides, polyvinyl nitriles, polyvinyl ketones, polyethylene sulfides, poly Polyvinylidene fluorides, or the like, or a combination comprising at least one of the foregoing thermoplastic polymers.

In some embodiments, the polymer film comprises polyacetal, poly(C _1-6 alkyl) acrylate, polyarylate, polycarbonate, polyester, polyether phthalimide, polyimine, polymethyl Acrylic acid (C _1-6 alkyl) ester, polyolefin, polystyrene, polyurethane, polyvinyl alcohol, polyvinyl ester, polyvinyl ether, polyvinyl halide, polyvinyl nitrile, polyvinyl ketone, poly Fluorine or a combination comprising at least one of the foregoing thermoplastic polymers. In some embodiments, the polymer film comprises polyimide, polyetherimide, polyester, polyolefin, polycarbonate, (meth)acrylic polymer (eg, polyacrylic acid (C _1-6 alkane) An ester, a poly(meth) methacrylate (C _1-6 alkyl) ester, or a combination comprising at least one of the foregoing, preferably poly(methyl methacrylate), a vinyl polymer, a polyacetal (eg, poly Oxyethylene and polyoxymethylene), a styrenic polymer, or a combination comprising at least one of the foregoing. In some embodiments, the optically clear polymer film comprises polyimide, polyetherimide, polyester, polyolefin, polycarbonate, or a combination comprising at least one of the foregoing.

In some embodiments, the polymer film comprises poly(ethylene terephthalate), poly(ethylene naphthalate), poly(1,4-cyclohexanedimethylene terephthalate), poly( Cyclohexanedimethylene terephthalate)-co-poly(ethylene terephthalate), polyethylene, polypropylene, bisphenol A polycarbonate (including homopolymers and copolymers thereof), poly(4) , (4,4'-oxydiphenylene-pyromelliimide), or a combination comprising at least one of the foregoing.

In some embodiments, the polymeric film preferably comprises a polycarbonate. "Polycarbonate" as used herein means a polymer or copolymer having a repeating structural unit of a carbonate of the formula (1). Wherein at least 60% of the total number of R ¹ groups are aromatic, or each R ¹ contains at least one C _6-30 aromatic group. Specifically, each R ¹ may be obtained from a dihydroxy compound such as an aromatic dihydroxy compound of the formula (2) or a bisphenol of the formula (3).

In the formula (2), each R ^{h is} independently a halogen atom (e.g., bromine), a C _1-10 hydrocarbon group such as a C _1-10 alkyl group, a halogen substituted C _1-10 alkyl group, and a C _6-10 aromatic group. a C _6-10 aryl group substituted with a halo group, and n is 0 to 4.

In the formula (3), R ^a and R ^b are each independently halogen, C _1-12 alkoxy, or C _1-12 alkyl, and p and q are each independently an integer of 0 to 4 such that when p or q is less than 4, and each carbon valence of the ring is filled with hydrogen. In a specific example, each of p and q is 0, or p and q are each 1, and R ^a and R ^b are each a C _1-3 alkyl group disposed at the hydroxy group of each aryl group, especially It is a methyl group. X ^a is a bridging group linking the two hydroxy-substituted aromatic groups (wherein the bridging group and the hydroxy substituent of each C ₆ exfoliating group are adjacent to each other on the C ₆ exaryl group) Position, meta, or alignment (especially alignment), for example, single bond, -O-, -S-, -S(O)-, -S(O) ₂ -, -C(O) Or, may be a cyclic or acyclic aromatic or non-aromatic C _1-18 organic group, and may additionally contain a hetero atom such as halogen, oxygen, nitrogen, sulfur, ruthenium, or phosphorus. For example, X ^a may be substituted or unsubstituted C _3-18 cycloalkylene; C _1-25 alkylene of formula C(R ^c )(R ^d )-, wherein R ^c and R ^d are each independently Is hydrogen, C _1-12 alkyl, C _1-12 cycloalkyl, C _7-12 aralkyl, C _1-12 heteroalkyl, or cyclic C _7-12 heteroarylalkyl; or Formula C ( a group of =R ^e )-, wherein R ^e is a divalent C _1-12 hydrocarbyl group.

Examples of the bisphenol compound include 4,4'-dihydroxybiphenyl, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, bis(4-hydroxyphenyl)methane, bis(4-hydroxyphenyl) Diphenylmethane, bis(4-hydroxyphenyl)-1-naphthalene, 1,2-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)-1-benzene Ethylethane, 2-(4-hydroxyphenyl)-2-(3-hydroxyphenyl)propane, bis(4-hydroxyphenyl)phenylmethane, 2,2-bis(4-hydroxy-3-bromo) Phenyl)propane, 1,1-bis(hydroxyphenyl)cyclopentane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)isobutylene, 1 , 1-bis(4-hydroxyphenyl)cyclododecane, trans-2,3-bis(4-hydroxyphenyl)-2-butene, 2,2-bis(4-hydroxyphenyl)-gold Alkane, α,α'-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-hydroxyl) Phenyl)propane, 2,2-bis(3-secondbutyl-4-hydroxyphenyl)propane, 2,2-bis(3-tert-butyl-4-hydroxyphenyl)propane, 2,2 - bis(3-cyclohexyl-4-hydroxyphenyl)propane, 2,2-bis(3-allyl-4-hydroxyl Propane, 2,2-bis(3-methoxy-4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)hexafluoropropane, 1,1-dichloro-2,2 - bis(4-hydroxyphenyl)ethene, 1,1-dibromo-2,2-bis(4-hydroxyphenyl)ethene, 1,1-dichloro-2,2-bis(5-phenoxy 4-hydroxyphenyl)ethene, 4,4'-dihydroxybenzophenone, 3,3-bis(4-hydroxyphenyl)-2-butanone, 1,6-bis(4-hydroxyphenyl) )-1,6-hexanedione, ethylene glycol bis(4-hydroxyphenyl)ether, bis(4-hydroxyphenyl)ether, bis(4-hydroxyphenyl) sulfide, bis(4-hydroxybenzene) Athene, bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxyphenyl)fluorene, 2,7-dihydroxyindole, 6,6'-dihydroxy-3,3,3 ',3'-Tetramethylspiro(bis)decane ("spirobisoxane bisphenol"), 3,3-bis(4-hydroxyphenyl)phenenimide, 2,6-dihydroxy Dibenzo-p-dioxin, 2,6-dihydroxy thiophene, 2,7-dihydroxymorphine Thio, 2,7-dihydroxy-9,10-dimethylmorph , 3,6-dihydroxydibenzofuran, 3,6-dihydroxydibenzothiophene, and 2,7-dihydroxycarbazole; resorcinol; substituted resorcinol compound such as 5-A Resorcinol, 5-ethyl resorcinol, 5-propyl resorcinol, 5-butyl resorcinol, 5-tert-butyl resorcinol, 5-phenylisophthalic acid Diphenol, 5-cumyl resorcinol, 2,4,5,6-tetrafluororesorcinol, 2,4,5,6-tetrabromoresorcinol, or the like; catechin Phenol; hydroquinone; substituted hydroquinone such as 2-methylhydroquinone, 2-ethylhydroquinone, 2-propylhydroquinone, 2-butylhydroquinone, 2-tert-butylhydroquinone, 2- Phenylhydroquinone, 2-isopropylphenylhydroquinone, 2,3,5,6-tetramethylhydroquinone, 2,3,5,6-tetra-t-butylhydroquinone, 2,3,5, 6-tetrafluorohydroquinone, 2,3,5,6-tetrabromohydroquinone, or the like.

Specific dihydroxy compounds include resorcinol, 2,2-bis(4-hydroxyphenyl)propane ("bisphenol A" or "BPA"), 3,3-bis(4-hydroxyphenyl)benzyl Endoamine, 2-phenyl-3,3-bis(4-hydroxyphenyl)benzylcarbenamide (also known as N-phenylphenolphthalein bisphenol, "PPPBP" or 3,3-bis (4- Hydroxyphenyl)-2-phenylisoindol-1-one), 1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane, and 1,1-bis(4-hydroxyl) Phenyl)-3,3,5-trimethylcyclohexane (isophorone bisphenol).

"Polycarbonate" as used herein also includes copolymers comprising carbonate units and ester units ("poly(ester-carbonate)", also known as polyester-polycarbonate). The poly(ester-carbonate) class contains a repeating ester unit of the formula (4) in addition to the recurring carbonate chain unit of the formula (1).

Wherein J is a divalent group derived from a dihydroxy compound (including a reactive derivative thereof), and may be, for example, a C _2-10 alkylene group, a C _6-20 cycloalkylene group, or a C _6-20 extended aromatic group. Or a polyoxyalkylene group, wherein the alkylene group contains 2 to 6 carbon atoms, especially 2, 3, or 4 carbon atoms; and T is a dicarboxylic acid (including reactive derivatives thereof) A divalent group derived, and may be, for example, a C _2-20 alkylene group, a C _6-20 cycloalkylene group, or a C _6-20 extended aryl group. Copolyesters containing a combination of different T or J groups can be used. The polyester unit may be branched or linear.

Specific dihydroxy compounds include aromatic dihydroxy compounds of formula (2) (for example resorcinol), bisphenols of formula (3) (for example bisphenol A), C _1-8 aliphatic diols such as ethylene A combination of at least one of an alcohol, n-propylene glycol, isopropyl glycol, 1,4-butanediol, 1,6-cyclohexanediol, 1,6-hydroxymethylcyclohexane, or a dihydroxy compound. Aliphatic dicarboxylic acids which may be used include C _2-6 aliphatic dicarboxylic acids (including carboxyl end groups), especially linear C _8-12 aliphatic dicarboxylic acids such as sebacic acid (lactone) And α,ω-C ₁₂ dicarboxylic acid such as dodecanedioic acid (DDDA). The aromatic dicarboxylic acid which can be used includes terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, 1,6-cyclohexanedicarboxylic acid, or a combination comprising at least one of the foregoing acids. A combination of isophthalic acid and terephthalic acid may be used, wherein the weight ratio of isophthalic acid to terephthalic acid is from 91:9 to 2:98.

Specific ester units include ethylene terephthalate units, n-propylene terephthalate units, n-butylene terephthalate units, derived from isophthalic acid, terephthalic acid, and resorcinol. An ester unit (ITR ester unit), and an ester unit derived from azelaic acid and bisphenol A. In the poly(ester-carbonate) class, the molar ratio of the ester unit to the carbonate unit can vary widely, for example from 1:99 to 99:1, especially from 10:90 to 90:10, more particularly 25:75 to 75:25, or 2:98 to 15:85. In some embodiments, in the poly(ester-carbonate) class, the molar ratio of the ester unit to the carbonate unit may be from 1:99 to 30:70, especially from 2:98 to 25:75, more particularly Ground 3:97 to 20:80, or 5:95 to 15:85 change.

In a specific embodiment, the polycarbonate is a linear homopolymer containing bisphenol A carbonate unit (BPA-PC) commercially available from SABIC under the trade name LEXAN; or commercially available from SABIC Branched cyanophenol-terminated bisphenol A homopolymer containing 3 mol% 1,1,1-gin(4-hydroxyphenyl)ethane (THPE) branching agent by LEXAN CFR and interfacial polymerization Carbonate. A combination of a linear polycarbonate and a branched polycarbonate can be used. It is also possible to use polycarbonate copolymers or interpolymers instead of homopolymers. The polycarbonate copolymer may comprise a copolycarbonate comprising two or more different types of carbonate units, such as units derived from BPA and PPPBP (commercially known under the trade name XHT by SABIC) BPA and DMBPC (commercially available from SABIC under the trade name DMX); or BPA and isophorone bisphenol (commercially available from Bayer under the trade name APEC). The polycarbonate copolymer may additionally comprise non-carbonate repeating units, such as repeating ester units (polyester-carbonates), such as those comprising resorcinol isophthalate and terephthalate units and Bisphenol A carbonate units, such as those commercially available from SABIC under the trade name LEXAN SLX; depending on the relative ratio of carbonate units to ester units, bisphenol A carbonate units and isophthalate-pairs Phthalate-bisphenol A ester units, also commonly known as poly(carbonate-ester) (PCE) or poly(phthalate-carbonate) (PPC); or bisphenol A carbonate Units and C _6-12 dicarboxylate units such as phthalate units (commercially available under the trade name HFD from SABIC). Other polycarbonate copolymers may comprise repeating oxoxane units (polycarbonate-dioxane), such as those comprising bisphenol A carbonate units and oxoxane units (eg containing from 5 to 200 dimethyl oxime) Blocks of alkane units, such as those commercially available from SABIC under the trade name EXL; or both ester units and oxoxane units (polycarbonate-ester-oxanes), such as those containing bisphenol A a carbonate unit, an isophthalate-terephthalate-bisphenol A ester unit, and a oxoxane unit (for example, a block containing 5 to 200 dimethyloxane units), such as those The product sold by SABIC is called FST. Any combination of the above materials can be used.

Combinations of polycarbonates with other polymers may be used, such as a mixture of bisphenol A polycarbonate and an ester such as poly(butylene terephthalate) or poly(ethylene terephthalate), each of which It can be semi-crystalline or amorphous. This combination is commercially available from SABIC under the trade names XENOY and XYLEX.

Particular copolycarbonates include bisphenol A and macro bisphenol carbonate units, i.e., derived from bisphenols containing at least 12 carbon atoms (e.g., 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)benzyl indoleamine carbonate units (by A BPA-PPPBP copolymer commercially available from SABIC under the trade name LEXAN XHT, comprising a bisphenol A carbonate unit and a 1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane carbonate unit. a copolymer (BPA-DMBPC copolymer commercially available from SABIC under the trade name LEXAN DMC), or a copolymer comprising a bisphenol A carbonate unit and an isophorone bisphenol carbonate unit (commercially available from Bayer) Named APEC). A combination of a linear polycarbonate and a branched polycarbonate can be used. Furthermore, any combination of the above materials can be used.

The intrinsic viscosity of the polycarbonate, as determined in chloroform at 25 ° C, may be from 0.3 to 1.5 deciliters per gram (dl/gm), especially from 0.45 to 1.0 dl/gm. The polycarbonates may have a weight average molecular weight of from 10,000 to 200,000 Daltons, especially from 20,000 to 100,000 Daltons, such as by gel permeation chromatography (GPC), using crosslinked styrene-divinyl Piphenyl column and measured with polycarbonate reference correction of. The GPC sample was prepared at a concentration of 1 mg per ml and was washed at a flow rate of 1.5 ml per minute.

In some embodiments, one or both surfaces of the polymeric film can be a textualized surface that can provide, for example, anti-glare properties, anti-reflective properties, antimicrobial properties, and the like, or at least one of the foregoing. The combination.

In addition to including the glass layer, the binder layer, and the polymeric film, the mold may optionally include one or more additional layers, particularly one or more functional layers. In some embodiments, when present, the functional layer is preferably disposed on the glass layer, the polymeric film, or at least a portion of both. In some embodiments, the functional layer can be disposed on either side of the glass layer, on both sides of the polymer layer, or both. The optional functional layer may include an ultraviolet light protection layer, a touch sensing layer, a wear layer, an infrared light absorbing layer, an infrared light reflecting layer, a hydrophobic layer, a hydrophilic layer, an anti-fingerprint layer, an antifouling layer, an anti-glare layer, and an anti-glare layer. a reflective layer, an antimicrobial layer, a conductive layer, an electromagnetic radiation shielding layer (eg, an electromagnetic interference shielding layer), a defrosting layer, a defogging layer, an image forming layer (eg, an ink layer), a touch sensing layer, or at least one of the foregoing The combination. In some embodiments, the functional layer may preferably include an anti-reflection layer, an anti-glare layer, an anti-microbial layer, a conductive layer, an anti-fingerprint layer, an anti-fouling layer, a defogging layer, a touch sensing layer, or at least one of the foregoing. Combination of people. In some embodiments, the functional layer can be additionally textured. The functional layer can be disposed in any form, such as a film, coating, coextruded layer, deposited layer, molded layer, or the like.

In a specific example, the mold core additionally comprises a functional layer, The functional layer comprises a conductive layer. The conductive layer can be disposed on at least a portion of the polymeric film on a different side than the first optical clearing adhesive. In some embodiments, the lid assembly can include a first conductive layer disposed on at least a portion of the polymeric film between the first optically clear adhesive and the polymeric film, and in the first a second conductive layer disposed on at least a portion of the polymeric film on a different side of the conductive layer. In other words, in some embodiments, the polymeric film can be sandwiched between the first and second conductive layers. When present, the conductive layer is optically transparent such that a 5 micron thick sample of the conductive layer transmits greater than 80% of visible light, as determined according to ASTM D1003-00.

The transparent conductive layer may include indium tin oxide, carbon nanotubes, graphene, conductive metal nanowires, conductive metal nanoparticles (such as silver nanoparticles), conductive nano-screens (including self-conducting A rice sieve, for example formed of conductive metal nanoparticles, a transparent conductive ink, or a combination comprising at least one of the foregoing.

In some embodiments, the mold may optionally include a barrier coating disposed on the functional layer. The barrier coating can provide physical protection and preferably can additionally provide water or oxygen or both. When present, the barrier coating can comprise two or more films comprising different materials. In some embodiments, a set of materials (eg, a pair of films or a set of three or more films) are placed in alternating layers of two, three, four, or more pairs or sets. A variety of different film materials can be used to provide the desired barrier properties. For example, a pair of layers may comprise a layer of organic material (eg, a polymer) and a layer of inorganic material (eg, vermiculite, alumina, or glass); or a layer of first inorganic material and A layer of a second inorganic material (such as a vermiculite layer and a glass layer); or a layer comprising nanoparticle and a layer of inorganic material (such as vermiculite). The organic materials may include those in the optically clear polymer film described below, and may 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, polyetheretherketone, polyether oxime, polystyrene, or a combination comprising at least one of the foregoing. Materials for the inorganic layers of the barrier films are likewise selected. As long as an optically clear barrier film can be produced, examples of inorganic materials that can be used include individual metals, mixtures, mesometallics, or alloys of two or more metals, metals, and mixed metal oxides, metals, and mixtures. Metal fluorides, metals and mixed metal nitrides, metals and mixed metal carbides, metals and mixed metal carbonitrides, metals and mixed metal oxynitrides, metals and mixed metal borides, metals and mixtures a metal oxyborate, a metal and a mixed metal halide, and a combination comprising at least one of the foregoing.

The barrier coatings can be formed by known procedures such as liquid coating techniques such as solution coating, roller coating, dip coating, spray coating or spin coating; coating techniques such as sputtering, for solids Vacuum program for thermal evaporation and deposition of 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, a suitable barrier coating can be an Ultra Barrier Film available from LOTUS Applied Technology.

The barrier coating may have a thickness of from 50 micrometers to 1 millimeter, preferably from 50 micrometers to 0.7 millimeters, more preferably from 50 to 400 micrometers. Even better is 50 to 200 microns.

In some embodiments, the mold core can additionally include a decorative pattern disposed on at least a portion of the glass layer, the polymeric film, or both. The decorative pattern can be by screen printing, laser marking, digital inkjet printing, digital conductive inkjet printing, sublimation, offset printing, digital lithography, roto gravure printing, mobile printing ( A combination of at least one of pad printing, transfer printing, metallization, vacuum metallization, powder coating, spray coating, hand coating, or the aforementioned application techniques is applied to the glass layer or polymer film. In some embodiments, the pattern can be applied to provide a dead front image or display, wherein when not illuminated, the display appears to be tinted or mirrored, and when backlit, the image is displayed, or when When the display is turned on, the display is displayed. In some embodiments, the decorative pattern is provided on the edge of the lid assembly (eg, as a border).

The mold core can be applied to the optically clear adhesive by applying an optically clear adhesive to at least a portion of the first surface of the glass layer and on a side different from the first surface of the glass layer Manufacturing. Any suitable procedure (including but not limited to roller lamination, roller coating, screen printing, padding, spray coating, spin coating, dip coating, and the like, or at least one of the foregoing techniques may be used) Combination) applying the adhesive. The polymer film can be prepared by any method generally known for preparing a polymer film. For example, the polymer film can be prepared by extrusion, solution casting, melt blowing, and the like. When it exists, One or more additional layers may be applied to the desired location of the lid assembly. The layers can generally be combined in any order to provide the desired lid assembly. In some embodiments, when the lid assembly includes first and second conductive layers coated on each side of the polymeric film, the first and second conductive layers can be applied to the polymeric film (including the The conductive layer) is applied to the polymer film (simultaneously or continuously) before the first optically clear adhesive (applied on a side different from the first surface of the glass layer). In some embodiments, the mold core can be additionally polished such that at least a portion of the edge of the mold core is polished.

In addition to the above-described mold core, the molded article comprises a thermoplastic attachment coupled to a portion of the second surface of the polymer film. The attachment extends along the edge of the mold. The thermoplastic attachment can be of any shape. The attachment can be bonded to the polymer film of the mold core. In some embodiments, the attachment can surround the edge of the mold core. Exemplary molded articles can be as shown in Figures 2-4. For example, as shown in Figure 2, the attachment (17) can extend along the edge of the mold core and can be flush with the second surface of the glass layer of the mold core. In some embodiments, the molded article can include a bezel (15) or a trim strip attached to the polymeric film (6), preferably surrounding the edge of the mold core. Also, as shown in Figure 2, the attachment can have an extended feature (16) to increase the area of adhesion between the attachment (17) and the polymeric film (6). Advantageously, no additional layer of adhesive is needed to promote bonding of the attachment to the polymeric film of the mold core.

As shown in Figure 3, in some embodiments, the glass layer of the mold core can be a rounded head (18). In other words, in some specific examples, The second surface of the glass layer can optionally exhibit a curvature in a direction perpendicular to the front side of the molded article, wherein the front side of the molded article includes a second surface of the glass layer and a portion of the thermoplastic attachment. The rounded edge of the glass layer of the mold core can be prepared, for example, by machine action or any other suitable method.

As shown in Figure 4, in some embodiments, the accessory (17) can additionally be configured to include an assembly feature (19). The assembly features can facilitate the use of the molded article, for example, within an electronic device. The assembly feature can be, for example, a snap fit assembly feature, a hook, or any other suitable combination feature.

The accessory comprises a second thermoplastic polymer. The first and second thermoplastic polymers can be the same or different. In some embodiments, the second thermoplastic polymer is an optically clear high modulus extensible thermoplastic polymer composition. Advantageously, the difference between the refractive index of the mold core and the refractive index of the thermoplastic attachment is less than or equal to 0.07, preferably less than or equal to 0.05. The difference in refractive index between the mold core and the attachment is less than or equal to 0.07, or less than or equal to 0.05 to provide a so-called "seamless" molded article, wherein the interface between the edge of the mold and the accessory (in FIG. 4) The indication (20)) is basically invisible or unrecognizable to the naked eye. In some embodiments, the refractive index of the mold core is 1.49 to 1.65, or 1.50 to 1.60, and the refractive index of the thermoplastic attachment is 1.49 to 1.65, or 1.50 to 1.60, or 1.54 to 1.58.

The second thermoplastic polymer of the attachment comprises a polycarbonate, wherein the polycarbonate is as described above. In addition to including the second thermoplastic polymer, the accessory may additionally comprise at least one reinforcing filler and Intentionally flame retardant ingredients (such as phosphorus-containing flame retardants), flame retardant synergists. When present, the flame retardant component and the flame retardant synergist are as described in U.S. Patent Application Serial No. 14/317,412.

In some embodiments, the accessory may include 50 to 95 wt% polycarbonate and 5 to 50 wt% reinforcing filler, wherein wt% is based on the total weight of the accessory, and the combined weight percentage of all components is not More than 100% by weight. When present, from 3 to 7 wt% of a flame retardant can be used.

The reinforcing filler may be selected to impart additional impact strength to improve transparency, or to provide additional features based on the last selected feature of the attachment of the molded article. In some embodiments, the reinforcing filler is present in an amount of from 5 to 50% by weight, or from 5 to 35% by weight, based on the total weight of the accessory.

The reinforcing filler may be, for example, carbon fiber, glass fiber, glass beads, glass flakes, glass bubbles, polyarylene fibers, basalt fibers, quartz fibers, boron fibers, cellulose fibers, natural fibers, liquid crystal polymer fibers, High tenacity polymer fibers, or a combination comprising at least one of the foregoing. In some embodiments, the reinforcing filler is transparent and comprises glass fibers, glass beads, glass flakes, glass bubbles, carbon nanotubes, or a combination comprising at least one of the foregoing.

In some embodiments, the reinforcing filler preferably comprises glass fibers (including continuous fibers and staple fibers) including, but not limited to, E, A, C, ECR, R, S, D, and NE glass and quartz, glass. Spheres (including but not limited to hollow and solid glass spheres), glass flakes, and Like. In some embodiments, the glass fibers can have a round or flat cross section.

In some specific examples, examples of suitable glass materials are C glass [SiO ₂ (65-70%), Al ₂ O ₃ (2-6%), CaO (4-9%), MgO (0-5%). ), B ₂ O ₃ (2-7%), Na ₂ O & K ₂ O (9-13%), ZnO (1-6%)] and ECR glass [SiO ₂ (63-70%), Al ₂ O ₃ (3-6%), CaO (4-7%), MgO (1-4%), B ₂ O ₃ (2-5%), Na ₂ O (9-12%), K ₂ O ( 0-3%), TiO ₂ (0-4%), ZnO (1-5%)]. A particularly preferred glass material is an ECR glass having >0.1% TiO ₂ , especially an ECR glass of less than 1% TiO ₂ .

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

The attachment of the molded article is preferably optically clear. In this connection, the accessory composition can exhibit 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%. Transmittance. Transparency can be measured at a thickness of 2 mm according to ASTM D1003.

In some embodiments, the accessory can optionally include one or more additives, such as anti-drip agents, antioxidants, antistatic agents, chain extenders, colorants, de-molding agents, dyes, flows Promoters, flow improvers, light stabilizers, lubricants, mold release agents, pigments, quenching agents, heat stabilizers, UV absorbing materials, UV reflective materials, A UV stabilizer, or a combination comprising at least one of the foregoing.

In some embodiments, the composition preferably comprises a colorant, dye, or pigment. Preferably, when the composition of the accessory comprises a colorant, a dye, or a pigment, the polymer film of the mold core also contains a colorant, a dye, or a pigment, preferably, the colorant, dye of the polymer film Or the pigment is the same as the composition used for the attachment.

Examples of color pigments include, in particular, organic pigments selected from the group consisting of azo, methine azo, methine, hydrazine, phthalocyanine, perinone, hydrazine, diketopyrrolopyrrole. Sulfur, two Iminoisoporphyrin, two a group of iminoisoindolinones, quinophthalones, yellow ketones, indanthrones, anthrapyrindidines, and quinophine pigments, or mixtures or solids thereof Solution; especially two , diketopyrrolopyrrole, quinophthalone, phthalocyanine, indanthrene, or imidoisoindolone pigment, or mixtures or solid solutions thereof. Particularly interesting color organic pigments include CIPigment Red 202, CIPigment Red 122, CIPigment Red 179, CIPigment Red 170, CIPigment Red 144, CIPigment Red 177, CIPigment Red 254, CIPigment Red 255, CIPigment Red 264, CIPigment Brown 23, CIPigment Yellow 109, CIPigment Yellow 110, CIPigment Yellow 147, CIPigment Orange 61, CIPigment Orange 71, CIPigment Orange 73, CIPigment Orange 48, CIPigment Orange 49, CIPigment Blue 15, CI Pigment Blue 60, CIPigment Violet 23, CIPigment Violet 37, CIPigment Violet 19, CIPigment Green 7, CIPigment Green 36, or mixtures or solid solutions thereof. Suitable color pigments also include inorganic pigments; especially those selected from the group consisting of metal oxides, antimony yellow, lead chromate, lead chromate sulphate, lead molybdate, ultramarine blue, cobalt blue, manganese blue, chrome oxide green, hydrated chromium oxide Green, cobalt green, and metal sulfides (such as barium sulfide or cadmium sulfide), cadmium sulfide selenide, zinc ferrite, barium vanadate, and mixed metal oxides.

More particularly, the color pigment may be a transparent organic pigment. Of particular interest are pigment compositions wherein the color pigment is a clear organic pigment having a particle size of μ 0.2 μm (more preferably ≦ 0.1 μm). For example, of particular interest are pigment compositions containing the following pigments as transparent organic pigments: transparent quinacridones which are magenta or red, transparent yellow pigments (for example the isoindolinones or yellow quinophthalones) /quinacridone oxime solid solution), transparent bismuth cyanine blue and halogenated copper phthalocyanine, or the highly saturated transparent diketopyrrolopyrrole or two pigment. Typically, the pigment composition is prepared by blending the pigment with the filler using known dry or wet mixing techniques. For example, the ingredients are wet mixed in the final step of the pigment preparation procedure, or by blending the filler in an aqueous pigment slurry, which is then filtered, dried and micronized.

In some embodiments, the second thermoplastic polymer additionally comprises a different polymer than the polycarbonate, such as a polyester. For example, the second thermoplastic polymer comprises an aromatic polycarbonate (such as bisphenol A polycarbonate) and a polyester. In some embodiments, the polyester may include, for example, polyparaphenylene Ethylene diformate, polybutylene terephthalate, polyarylates, and polyester copolymers such as polyester ethers. In some embodiments, the polyester may include poly(ethylene terephthalate), diol modified poly(ethylene terephthalate), poly(ethylene naphthalate), poly( 1,4-cyclohexane-dimethanol-1,4-cyclohexanedicarboxylate), poly(cyclohexanedimethylene terephthalate)-co-poly-(ethylene terephthalate) Or a combination comprising at least one of the foregoing. In some embodiments, the polyester is preferably poly(1,4-cyclohexanedimethylene terephthalate). In some embodiments, the accessory comprises from 30 to 90% by weight of the aromatic polycarbonate and from 10 to 70% by weight of the poly(1,4-cyclohexanedicarboxylic acid 1) based on the total weight of the polymeric component of the accessory. , 4-cyclohexanedimethylene ester).

In some embodiments, the difference in refractive index between each component of the molded article is less than or equal to 0.07, preferably less than or equal to 0.05. In particular, the difference in refractive index between the glass layer and the polymer film of the mold and the attachment may be less than or equal to 0.07, preferably less than or equal to 0.05. If it is not desired to be limited to theory, it is believed that minimizing the difference in refractive index between each layer of the molded article contributes to the superior optical properties of the molded article.

The molded article can be manufactured by molding the accessory to the mold in a molding process. For example, the mold core can be positioned in a cavity and the polymer composition of the accessory can be injected into the mold cavity to bond with the polymer film of the mold core. The molding process can incorporate known techniques such as injection molding, injection compression molding, gas assist molding, bubble molding, multiple injection molding, multi-stage molding, compression molding, or the like including the aforementioned molding techniques. A combination of at least one. Improved flow, surface finish, and warp Tooling of the welding strength of the joining and molding parts such as induction heating or heating/cooling techniques to reduce the injection pressure, improve the surface finishing parts, and promote the improved bonding strength with the mold core. The mold core can be held in place within the cavity of the mold during the molding process using any technique known in the art. For example, the mold core can be held in place by a pressure differential such as a vacuum applied to the area of the mold core through a passage in the mold portion. The mold core can be held in place by extending from the mold portion to the tip in the mold cavity. The tips can be loaded with a spring to ensure that sufficient pressure is applied to the mold to maintain its position during the molding operation. The use of a spring loaded tip is responsible for the thickness variation between the various parts of the mold during the manufacture of multiple articles. The mold core can be held in place by electrostatic charge. The mold core can be held in place by core shutoffs from which the core shut-off body can extend and form a feature that allows the mold to fit. The mold core can be maintained in place by a combination of tips, statics, shut-off bodies, mold features, and pressure differentials as described above.

In some embodiments, the molded article can be fabricated using a mold as shown in FIG. The mold can incorporate power tool temperature control. Additionally, the mold can have a highly polished surface to maximize the desired optical properties from the accessory. Figure 5 shows a cross section of a mold that can be used to prepare the molded article. The mold includes heating and cooling conduits (9) to provide a path for heating and cooling the medium. The pipe (9) may have a diameter of 6 to 16 mm and may be spaced from the tool surface (10) by a distance of 1 to 1.5 times the diameter of the pipe. The tool surface (10) can be heated by the pipe (9) Up to the glass transition temperature (Tg) above the melted molten polymer composition. After encapsulation, the tool surface (10) can be cooled to a demold temperature. The demolding temperature can be selected by one of ordinary skill in the art and is often lower than the hot twist temperature (HDT) or the Fica softening temperature of the ejected polymer composition.

As mentioned above, the tool surface (10) can be smoothed or polished by any generally known method. The resulting glossy tool surface (10) can help provide the desired optical properties to the molded part. The tool surface (14) that is in contact with the glass layer of the mold core is also highly polished. The surface (14) may be in direct contact with the glass or may be positioned over the glass such that there is some micro space between the glass layer and the surface (14). The mold core (1) is fixed in the tool using a vacuum chuck (11). The vacuum chuck (11) may be ceramic and may additionally include a few micrometers of holes or tubes (13) as an air path. The molten resin is injected into the cavity (12) to form an attachment to the molded article. As stated above, after injection of the molten composition, the mold is cooled to a demold temperature and the molded part can be removed by the mold.

The molded articles described herein can be used in a variety of applications, including consumer electronics, electronic devices used in the transportation industry, and furniture components. Accordingly, an electronic device incorporating 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 to the device via an adhesive layer, or via one or more combination features (eg, a snap-fit assembly or hook) ) attached to the device. Examples of electronic devices that can be utilized with the molded article include but not Limited to cellular phones, smart phones, laptops, laptops, tablets, televisions, dashboards (such as electrical dashboards or car dashboards, especially automotive interior dashboards such as central stacked displays or heads up displays) ), smart whiteboards, medical devices, monitors, smart windows, public information displays, transparent displays, or wearable electronic devices or displays (eg smart watches, activity trackers, health trackers, health monitoring devices, and the like) By). In some embodiments, the display can be a heads up display, a display instrument panel, or a touch screen display. Alternatively, the electronic device used with the molded article may be a lighting device. In some embodiments in which the molded article is used in a lighting device, the molded article may additionally serve as a barrier layer for oxygen and water, so that an additional barrier layer is not required. In some embodiments, the molded article can be part of a cover or cover for an electronic device. The molded article described herein can be used as a front cover or a back cover for an electronic device or display device. In some embodiments, the molded article may have components for a furniture component, such as a furniture door or window.

The molded articles described herein provide a lightweight and seamless design for superior optical properties for electronic devices or lighting devices. The seamless design is made by carefully selecting the glass/plastic laminated mold core and the polymer composition for the thermoplastic attachment such that the difference between the refractive index of the mold core and the refractive index of the thermoplastic attachment is lower than or It is equal to 0.07 and completed. The molded article exhibits little or no birefringence due to the index matching of the different components. Accordingly, significant improvements in moldings for electronic devices are provided by the present disclosure.

The molded article, method and device are by the following non-limiting Specific examples are further described.

Specific Example 1: A molded article comprising: a mold core comprising: a glass layer having a first surface and a second surface different from the first surface; and being placed on at least a portion of the first surface of the glass layer a first optically clear adhesive layer, wherein the 50 micron thick sample of the optically clear adhesive transports more than 90% of visible light, as determined according to ASTM D1003-00; and an optically clear polymer having a first surface and a second surface a film, wherein a first surface of the polymer film is in contact with a binder layer on a side different from the glass layer, the polymer film comprising a first thermoplastic polymer, wherein the optically clear polymer film is a 100 micron thick sample Transmitting more than 85% of visible light, as determined in accordance with ASTM D1003-00; and a thermoplastic attachment coupled to a portion of the second surface of the polymeric film, wherein the attachment extends along the edge of the mold, and wherein the attachment comprises a second thermoplastic polymer; and wherein the difference between the refractive index of the mold core and the refractive index of the thermoplastic attachment is less than or equal to 0.07.

Specific Example 2: The molded article of Specific Example 1, wherein the glass layer has a thickness of 50 μm to 25 mm, preferably 50 μm to 10 mm, more preferably 50 μm to 1 mm, even more preferably 50 to 500 μm.

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

Specific example 4: The molded article of any one or more of the examples 1 to 3, wherein the optically clear adhesive has a thickness of 1 to 2000 μm. It is preferably from 10 to 100 μm, more preferably from 10 to 50 μm, even more preferably from 12.5 to 25 μm.

Specific Example 5: The molded article of any one or more of Specific Examples 1 to 4, wherein the polymer film comprises polyacetal, poly(C _1-6 alkyl) acrylate, polyarylate, polycarbonate , polyester, polyetherimide, polyimide, polymethyl methacrylate (C _1-6 alkyl) esters, polyolefins, polystyrenes, polyamines formate, polyvinyl alcohol, polyvinyl acetate, poly a combination of vinyl ether, polyvinyl halide, polyvinyl nitrile, polyvinyl ketone, polydifluoroethylene, or at least one of the foregoing thermoplastic polymers; preferably poly(ethylene terephthalate), poly( Ethylene naphthalate), poly(1,4-cyclohexanedimethylene terephthalate), poly(cyclohexanedimethylene terephthalate)-co-poly(ethylene terephthalate), Polyethylene, polypropylene, bisphenol A polycarbonate, poly(4,4'-oxydiphenylene-1,2,4,5-benzenetetramethyleneimine), or at least one of the foregoing Combination; more preferably bisphenol A polycarbonate.

Specific Example 6: The molded article of any one or more of Specific Examples 1 to 5, wherein the polymer film has a thickness of from 1 μm to 20 mm, preferably from 5 μm to 20 mm, more preferably from 5 μm to 10 mm Even more preferably from 5 micrometers to 1 millimeter, even more preferably from 5 to 250 micrometers, most preferably from 50 to 200 micrometers.

The molded article of any one or more of the specific examples 1 to 6, wherein the mold core further comprises a functional layer disposed on the glass layer, the polymer film, or at least a part of both, preferably Wherein the functional layer comprises an anti-reflective coating, an anti-glare coating, an anti-fingerprint coating, an antimicrobial coating, a conductive layer, a touch sensing layer, or the like a combination of at least one of them.

Specific Example 8: The molded article of Specific Example 7, wherein the functional layer comprises a conductive layer disposed on at least a portion of the polymer film on a side different from the first optical clear adhesive layer, wherein the conductive layer 5 The micron thick sample 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, conductivity Metal nanoparticle, conductive nanosieve, transparent conductive ink, or a combination comprising at least one of the foregoing.

Specific Example 9: The molded article of Specific Example 7 or 8, which additionally comprises a barrier coating layer disposed on the functional layer.

Specific Example 10: The molded article of any one or more of Specific Examples 1 to 9, further comprising a decorative pattern disposed on the glass layer, the polymer film or both.

Specific Example 11: The molded article of any one or more of Specific Examples 1 to 10, wherein the glass layer or the polymer film or both are textured.

Specific Example 12: The molded article of any one or more of Embodiments 1 to 11, wherein the polymer film or the thermoplastic accessory comprises a pigment.

Specific Example 13: The molded article of any one or more of Specific Examples 1 to 12, wherein the second thermoplastic polymer comprises an aromatic polycarbonate.

Specific Example 14: The molded article of any one or more of Specific Examples 1 to 13, wherein the second thermoplastic polymer comprises an aromatic polycarbonate and a polyester, preferably an aromatic polycarbonate and a poly(p-benzene) 1,4-cyclohexanedimethyl diformate).

Specific Example 15: The molded article of any one or more of Specific Examples 1 to 14, wherein the second thermoplastic polymer comprises 30 to 90% by weight of an aromatic polycarbonate and 10 to 70% by weight of poly(1,4- Cyclohexanedicarboxylic acid 1,4-cyclohexanedimethylmethane).

Specific Example 16: The molded article of any one or more of Specific Examples 1 to 15, wherein the thermoplastic accessory comprises a reinforcing filler comprising carbon fiber, glass fiber, glass beads, glass flakes, glass bubbles, polyarylene Amine 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 is Transparent and comprising glass fibers, glass beads, glass flakes, glass bubbles, carbon nanotubes, or a combination comprising at least one of the foregoing.

Specific Example 17: The molded article of Specific Example 16, wherein the reinforcing filler is contained in an amount of from 1 to 50% by weight, or from 5 to 35% by weight based on the total of the thermoplastics.

Embodiment 18: The molded article of any one or more of Embodiments 1 to 17, wherein the thermoplastic attachment forms a boundary that surrounds the mold core in at least one dimension.

The molded article of any one or more of the specific examples 1 to 18, wherein the refractive index of the mold core is 1.49 to 1.65, or 1.50 to 1.60, and the refractive index of the thermoplastic accessory is 1.49 to 1.65, or 1.50 to 1.60, or 1.54 to 1.58.

The molded article of any one or more of the specific examples 1 to 19, wherein the front side of the molded article comprises the second surface of the glass layer and One part of the thermoplastic attachment.

Specific example 21: The molded article of embodiment 20, wherein a second surface of the glass layer is flush with the thermoplastic attachment along a front side of the molded article; or a second surface of the glass layer is perpendicular to a front side of the article The curvature is expressed in the direction.

Specific Example 22: A method of producing a molded article according to one or more of Specific Examples 1 to 21, the method comprising: applying the optically clear adhesive to at least a portion of a first surface of the glass layer; On the different sides of the first surface of the layer, the polymer film is coupled with the optically clear adhesive to form a mold, wherein the adhesive is sandwiched between the glass layer and the polymer film; in injection molding A thermoplastic attachment is molded into the mold to form a molded article, wherein the attachment extends along at least a portion of the edge of the mold.

Specific Example 23: An electronic device comprising the molded article of any one or more of Examples 1 to 21, wherein the device is a cellular phone, a smart phone, a laptop, a notebook computer, a tablet computer, a television, Dashboards (such as electrical dashboards or car dashboards such as centrally stacked displays or heads up displays), smart whiteboards, wearable displays, transparent displays, medical devices, lighting fixtures, or smart windows.

Embodiment 24: The electronic device of Embodiment 23, wherein the molded article is laminated to the device, or molded onto the device, or attached to the device via an adhesive layer, or via one or more combined parts Attached to the device.

Specific Example 25: A cover for an electronic device, comprising specific The molded article of any one or more of Examples 1 to 21.

The molded articles, methods, and devices may alternatively comprise, consist of, or consist essentially of any of the components or steps disclosed herein. The compositions, methods, and articles may be additionally or alternatively formulated such that they are not or substantially free of any steps, components, or materials that are not essential to the achievement of the function or purpose of the compositions, methods, and articles in other instances. , ingredients, adjuvants, or substances.

All ranges disclosed herein are inclusive of the endpoints, and the endpoints can be independently combined with each other. "Combination" includes blends, mixtures, alloys, reaction products, and the like. "First", "second", and the like do not indicate any order, quantity, or importance, but are used to distinguish one element from another. "A" and "the" do not denote a limitation of the quantity, and are to be construed to cover both the singular and the plural, unless otherwise clearly stated herein or clearly indicated by the context. . Unless otherwise stated clearly, "or" means "and / or". The "some specific examples", "a specific example", and the like, as used throughout the specification, are intended to mean that the particular elements described in connection with the specific examples are included in at least one specific example described herein and may or may not be present in In other specific examples. Moreover, it is to be understood that the described elements can be combined in different embodiments in any suitable manner.

The technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs, unless otherwise defined. All cited patents, patent applications, and His citations are incorporated herein by reference in their entirety. However, if the words used in this application contradict or contradict the words used in the combined citation information, the terms from this application are preferred over the citations in the combined citations.

The term "alkyl" means a branched or straight-chain unsaturated aliphatic hydrocarbon group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, t-butyl, N-pentyl, second amyl, n-hexyl and second hexyl. "Alkenyl" means having at least one carbon - carbon double bond of a linear or branched monovalent hydrocarbon group (e.g., vinyl (-HC = CH _2)). "Alkoxy" means an alkyl group (eg, alkyl-O-) attached via an oxygen, such as methoxy, ethoxy, and second butoxy. "Alkyl" means a linear or branched saturated divalent aliphatic hydrocarbon group (e.g., methylene (-CH ₂ -) or propyl (-(CH ₂ ) ₃ -)). "Cycloalkyl Alkylene" means a divalent cyclic alkylene group _{(-C n H 2n-x)} , where x is the number by cyclization of substituted hydrogen. "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 (eg, cyclopentyl or cyclohexyl). "Aryl" means an aromatic hydrocarbon group containing the specified number of carbon atoms, such as phenyl, cycloheptenone, indanyl, or naphthyl. The word "halo" means a group or compound including one or more of fluorine, chlorine, bromine, or iodine substituents. Combinations of different halo groups (such as bromine and fluorine), or only chlorine groups may be present. The word "hetero" means a compound or group comprising at least one ring member that is a hetero atom (eg, 1, 2, or 3 heteroatoms), wherein the (etc.) heteroatoms are independently N, O, S, respectively. Si, or P. "Substituted" means that the compound or group is substituted with at least one (e.g., 1, 2, 3, or 4) substituents other than hydrogen, and the substituents may independently be C _1-9 alkoxy, C, respectively. _1-9 haloalkoxy, nitro (-NO ₂ ), cyano (-CN), C _1-6 alkanesulfonyl (-S(=O) ₂ -alkyl), C _6-12 aryl sulfonate Mercapto (-S(=O) ₂ -aryl), fluorenyl (-SH), thiocyano (-SCN), toluenesulfonyl (CH ₃ C ₆ H ₄ SO ₂ -), C _3-12 ring Alkyl, C _2-12 alkenyl, C _5-12 cycloalkenyl, C _6-12 aryl, C _7-13 arylalkyl, C _4-12 heterocycloalkyl, and C _3-12 heteroaryl As long as the normal price of the substituted atom is not exceeded. The number of carbon atoms indicated in the group excludes any substituent. For example, -CH ₂ CH ₂ CN is a C ₂ alkyl group substituted with a nitrile.

Although specific examples have been described, alternative, modified, variant, modified, substantially equivalent types that are currently unknown or may not be currently known are contemplated by the applicant or other skilled artisan skilled in the art. Accordingly, the appended claims are intended to cover all such alternative, modified, modified, modified, and substantial equivalents.

1‧‧‧Men

2‧‧‧ glass layer

3,7‧‧‧ first surface

4,8‧‧‧second surface

5‧‧‧First optical clarifying adhesive layer

6‧‧‧ polymer film

Claims (20)

A molded article comprising: a mold core comprising: a glass layer having a first surface and a second surface opposite the first surface; a first optically clear bond disposed on at least a portion of the first surface of the glass layer a layer of 50 μm thick of the optically clear adhesive transporting more than 90% of visible light, as determined according to ASTM D1003-00; and an optically clear polymer film having a first surface and a second surface, wherein the polymer a first surface of the film is in contact with the adhesive layer on a side different from the glass layer, the polymer film comprising a first thermoplastic polymer, wherein the optically clear polymer film transmits more than 85% of the 100 micron thick sample Visible light, as determined in accordance with ASTM D1003-00; and a thermoplastic attachment coupled to a portion of the second surface of the polymeric film, wherein the attachment extends along the edge of the mold, and wherein the attachment comprises a second thermoplastic polymer; And the difference between the refractive index of the mold core and the refractive index of the thermoplastic attachment is less than or equal to 0.07. The molded article of claim 1, wherein the glass layer has a thickness of from 50 μm to 25 mm, preferably from 50 μm to 10 mm, more preferably from 50 μm to 1 mm, even more preferably from 50 to 500 μm. The molded article of claim 1, wherein the glass layer comprises chemically strengthened glass, unreinforced glass, tempered glass, or optically transparent Synthetic crystals. The molded article of claim 1, wherein the optically clear adhesive has a thickness of from 1 to 2000 μm, preferably from 10 to 100 μm, more preferably from 10 to 50 μm, even more preferably from 12.5 to 25 μm. The molded article of claim 1, wherein the polymer film comprises polyacetal, poly(C _1-6 alkyl) acrylate, polyarylate, polycarbonate, polyester, polyether phthalate amine, polyimide, polymethyl methacrylate (C _1-6 alkyl) esters, polyolefins, polystyrenes, polyamines formate, polyvinyl alcohol, polyvinyl esters, polyvinyl ethers, polyvinyl halides, polyethylene a combination of vinyl nitrile, polyvinyl ketone, polydifluoroethylene, or at least one of the foregoing thermoplastic polymers; preferably poly(ethylene terephthalate), poly(ethylene naphthalate), poly (1,4-cyclohexanedimethylene terephthalate), poly(cyclohexanedimethylene terephthalate)-co-(ethylene terephthalate), polyethylene, polypropylene, bisphenol A Polycarbonate, poly(4,4'-oxydiphenylene-1,2,4,5-phenyltetramethyleneimine), or a combination comprising at least one of the foregoing; more preferably bisphenol A Polycarbonate. The molded article of claim 1, wherein the polymer film has a thickness of from 1 μm to 20 mm, preferably from 5 μm to 20 mm, more preferably from 5 μm to 10 mm, even more preferably from 5 μm to 1 mm, even more preferably 5 to 250 μm, most preferably 50 to 200 μm. The molded article of claim 1, wherein the mold core further comprises a glass layer, the polymer film, Or a functional layer on at least a portion of the two, preferably wherein the functional layer comprises an anti-reflective 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 polymeric film on a side different from the first optically clear adhesive layer, wherein the conducting The 5 mm thick sample of the 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 a conductive metal nanoparticle, a conductive nanosieve, a transparent conductive ink, or a combination comprising at least one of the foregoing. A molded article according to claim 7 which additionally comprises a barrier coating disposed on the functional layer. The molded article of claim 1, further comprising a decorative pattern disposed on the glass layer, the polymer film, or both, or wherein the glass layer or the polymer film or both are textured . The molded article of claim 1, wherein the polymer film and the thermoplastic accessory comprise a pigment. The molded article of claim 1, wherein the edge of the mold is polished. The molded article of claim 1, wherein the second thermoplastic polymer comprises an aromatic polycarbonate, preferably an aromatic polycarbonate and a polyester, more preferably an aromatic polycarbonate and a poly(p-benzene) 1,4-cyclohexanedicarboxylic acid Methyl ester), even more preferably 30 to 90% by weight of aromatic polycarbonate and 10 to 70% by weight of poly(1,4-cyclohexanedicarboxylic acid 1,4-cyclohexanedimethyl ester). The molded article of claim 1, wherein the thermoplastic accessory comprises a reinforcing filler comprising carbon fiber, glass fiber, glass beads, glass flakes, glass bubbles, polyarylene fibers, basalt fibers, quartz fibers, 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 is transparent and comprises glass fiber, glass beads a granule, a glass flake, a glass foam, a carbon nanotube, or a combination comprising at least one of the foregoing, and wherein the reinforcing filler is present in an amount of from 1 to 50% by weight, or from 5% by total weight of the thermoplastic accessory 35wt%. The molded article of claim 1, wherein the thermoplastic attachment forms a boundary that surrounds the mold core in at least one dimension. The molded article of claim 1, wherein the mold core has a refractive index of 1.49 to 1.65, or 1.50 to 1.60, and the thermoplastic accessory has a refractive index of 1.49 to 1.65, or 1.50 to 1.60, or 1.54 to 1.58. The molded article of claim 1, wherein the front side of the molded article comprises a second surface of the glass layer and a portion of the thermoplastic attachment, and wherein a second surface of the glass layer along the front side of the article The thermoplastic attachment is flush; or The second surface of the glass layer exhibits a curvature in a direction perpendicular to the front side of the article. A method of manufacturing a molded article according to any one or more of claims 1 to 16, comprising: applying the optically clear adhesive to at least a portion of a first surface of the glass layer; On the different side of the first surface, the polymer film is coupled with the optically clear adhesive to form a mold, wherein the adhesive is sandwiched between the glass layer and the polymer film; in the injection molding process A thermoplastic attachment is molded to the mold to form a molded article, wherein the attachment extends along at least a portion of the edge of the mold. An electronic device comprising a molded article according to any one or more of claims 1 to 16, wherein the device is a cellular phone, a smart phone, a laptop, a notebook computer, a tablet computer, a television, a meter Boards (such as electrical dashboards or car dashboards such as centrally stacked displays or heads up displays), smart whiteboards, wearable displays, transparent displays, medical devices, lighting fixtures, or smart windows. The electronic device of claim 18, wherein the molded article is laminated to the device, or molded onto the device, or attached to the device via an adhesive layer, or via one or more combined parts Attached to the device. A cover for an electronic device comprising a molded article as claimed in any one or more of claims 1 to 16.