WO2018026601A1

WO2018026601A1 - Laminates for laser-direct structuring, method for the manufacture thereof, molded articles prepared therefrom, and device comprising the molded article

Info

Publication number: WO2018026601A1
Application number: PCT/US2017/043941
Authority: WO
Inventors: Michael M. Laurin; Wei Zhao; Xiaoyu Sun; Wei FENG; Shijie Song
Original assignee: Sabic Global Technologies B.V.
Priority date: 2016-08-05
Filing date: 2017-07-26
Publication date: 2018-02-08

Abstract

A laminate includes a polymer film, a substrate, and an adhesive layer disposed between the polymer film and the substrate. The polymer film includes a first layer including a thermoplastic polymer and a laser-direct structuring additive. A molded article includes a mold insert including the laminate, and a thermoplastic attachment coupled to at least a portion of a second side of the substrate of the laminate. The attachment extends along an edge of the mold insert, and includes a thermoplastic polymer. The molded articles described herein can be particularly useful for components or housings for electrical and electronic devices.

Description

LAMINATES FOR LASER-DIRECT STRUCTURING, METHOD FOR THE

MANUFACTURE THEREOF, MOLDED ARTICLES PREPARED THEREFROM, AND

DEVICE COMPRISING THE MOLDED ARTICLE

BACKGROUND

[0001] Laser-direct structuring (LDS) materials have been explored for use in making molded injection devices (MIDs) via single-shot injection molding. In a typical LDS process, a computer-controlled laser beam travels over MIDs to activate the plastic surface at locations where the conductive path is to be situated. The LDS fillers release metallic nuclei, which can be reduced to metal to form conductive paths in a subsequent chemical plating process. With the LDS process, it is possible to obtain small conductive path-widths (for example of 150 micrometers or less). In addition, the spacing between the conductive paths can also be small. As a result, MIDs from this process save space and weight in end-use applications. Another advantage of laser direct structuring is its flexibility. If the design of a circuit or other patterned substrate is changed, it is simply a matter of reprogramming the computer that controls the laser. Thus laser-direct structuring methods can provide short development cycles, facile variation in design, cost reducting, miniaturization, and product functionality.

[0002] However, MIDs manufactured using a LDS process also have inherent disadvantages. For example, a key challenge in this area is to develop laser-direct structured materials with robust plating performance while also maintaining good mechanical properties. Laser-direct structuring only happens on the surface of the injected part, thus, most bulk material beneath the surface does not require presence of LDS additives, but they are present regardless. Not only are LDS additives expensive, but they also can adversely affect other performance parameters of the bulk materials, such as long-term stability and ductility.

[0003] Accordingly, there remains a need in the art for improved materials suitable for LDS processing techniques that can be used for various articles, including molded articles. Such laminates and molded articles would be particularly useful for the automotive, consumer electronics, home appliance, and healthcare industries.

BRIEF DESCRIPTION

[0004] A laminate comprises a polymer film comprising a first layer comprising a thermoplastic polymer and a laser direct structuring additive; a substrate; and an adhesive layer disposed between the polymer film and the substrate. [0005] A method of making the laminate comprises applying the adhesive to at least a portion of the first side of the substrate; and coupling the polymer film to the adhesive layer on a side opposite the first side of the substrate to form the laminate.

[0006] A molded article comprises a mold insert comprising the above laminate; and a thermoplastic attachment coupled to a portion of a second side of the substrate, wherein the attachment extends along an edge of the mold insert, the attachment comprises a second thermoplastic polymer, and the article further comprises a conductive path formed on a surface of the molded article, wherein the conductive path comprises a metal layer deposited on an activated path.

[0007] A method of manufacturing the molded article comprises forming an activated path on at least a portion of a second side of the polymer film, depositing a metal layer onto the activated path to provide a conductive path, applying the adhesive to at least a portion of the first side of the substrate, coupling a first side of polymer film to the adhesive layer on a side opposite the first side of the substrate to form the mold insert, and molding a thermoplastic attachment to the mold insert in an injection molding process to form the molded article, wherein the attachment extends along at least a portion of an edge of the mold insert.

[0008] An electronic device comprising the laminate or the molded article is also described.

[0009] The above described and other features are exemplified by the following figures and detailed description.

BRIEF DESCRIPTION OF THE DRAWINGS

[0010] The following figures are exemplary embodiments wherein the like elements are numbered alike.

[0011] FIG. 1 shows a cross-sectional view of a single layer polymer film.

[0012] FIG. 2 shows a cross-sectional view of a multilayer polymer film.

[0013] FIG. 3 shows a cross-sectional view of a multilayer polymer film.

[0014] FIG. 4 shows a cross-sectional view of a multilayer polymer film.

[0015] FIG. 5 shows a cross-sectional view of a single layer polymer film having a three- dimensional configuration after thermoforming.

[0016] FIG. 6 shows a cross-sectional view of a laminate.

[0017] FIG. 7 shows a cross-sectional view of a laminate.

[0018] FIG. 8 shows a cross-sectional view of a laminate.

[0019] FIG. 9 shows a cross-sectional view of a molded article comprising the laminate. DETAILED DESCRIPTION

[0020] The present inventors have discovered that laminates can be prepared which are suitable for use with a laser-direct structuring (LDS) process to provide a conductive pathway on the surface of the laminate. The laminates described herein can be particularly useful as mold inserts in the preparation of molded articles. The laminates and molded articles described herein have potential for use in a variety of applications, including, for example, automotive, electronics, and telecommunications. In a further advantageous feature, the laminates described herein can withstand high temperatures and humid environments.

[0021] Accordingly, one aspect of the present disclosure is a laminate comprising a polymer film, a substrate, and an adhesive layer disposed between the polymer film and the substrate.

[0022] The polymer film can be a monolayer polymer film, or a multilayered polymer film. In some embodiments, the polymer film can be prepared by extrusion. The polymer film comprises at least a first layer comprising a thermoplastic polymer and a laser-direct structuring additive. For example, as shown in FIG. 1, the polymer film (1) comprises the first layer (2). The first layer can have a first side (2a). In some embodiments, where the polymer film is a monolayer, in particular an extruded monolayer polymer film, the polymer film consists of the first layer. Thus, in embodiments where the polymer film consists of the first layer, the first layer has a first side (2a), which can be the same as the first side of the polymer film itself (la).

[0023] The thermoplastic polymer can generally be any suitable 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,

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

[0024] In some embodiments, the thermoplastic polymer comprises polyamide, polyarylate, poly(arylene ether), polycarbonate, polyester, polyetheretherketone, polyetherimide, polyimide, polyolefin, polystyrene, liquid crystal polymer, polyphthalamide, or a combination comprising at least one of the foregoing.

[0025] 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

R ,¹— O C II 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.

[0026] 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 C 1-3 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 C_{1 -2}5 alkylidene of the formula -

C(R^c)(R^d) - wherein R^c and R^d are each independently hydrogen, C_1-12 alkyl, C_1-12 cycloalkyl, C_7-

₁₂ arylalkyl, C_1-12 heteroalkyl, or cyclic C7-12 heteroarylalkyl; or a group of the formula -C(=R^e)- wherein R^e is a divalent C_1-12 hydrocarbon group.

[0027] 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.

[0028] 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).

[0029] "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.

[0030] 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-Cn 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.

[0031] 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.

[0032] 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.

[0033] 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.

[0034] 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.

[0035] 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.

[0036] In addition to the thermoplastic polymer, the first layer of the polymer film comprises a laser-direct structuring (LDS) additive. As used herein, a laser-direct structuring additive is a metal-containing additive suitable for use in a laser-direct structuring process. A LDS additive can be selected such that, after activating with a laser, a conductive path can be formed by a subsequent standard metallization or plating process. When the LDS additive is exposed to a laser, elemental metal is released or activated. The laser thus draws a pattern (e.g., a circuit pattern) onto the polymer film containing the LDS additive, and leaves behind a roughened surface containing embedded metal particles (an "activated path"). These particles can act as nuclei for the crystal growth during a subsequent metallization or plating process, such as a copper or other metal plating process, including for example gold plating, nickel plating, silver plating, zinc plating, tin plating, and the like.

[0037] Accordingly, the laser-direct structuring additive can comprise laser-sensitive materials (e.g., materials sensitive to a wavelength of about 1064 nanometers), including, for example, metal oxides or salts of antimony (Sb), copper (Cu), lead (Pb), nickel (Ni), iron (Fe), tin (Sn), chromium (Cr), manganese (Mn), silver (Ag), gold (Au), cobalt (Co), or a combination comprising at least one of the foregoing. In some embodiments, the LDS additives can also be provided having spinel-type crystal structures. In some embodiments, the LDS additive comprises a copper chromium oxide spinel, a copper salt, a copper hydroxide phosphate, a copper phosphate, a copper sulfate, a cuprous thiocyanate, a spinel based metal oxide, a copper chromium oxide, an organic metal complex, a palladium/palladium-containing heavy metal complex, a metal oxide, a metal oxide-coated filler, antimony doped tin oxide coated on mica, a copper containing metal oxide, a zinc containing metal oxide, a tin containing metal oxide, a magnesium containing metal oxide, an aluminum containing metal oxide, a gold containing metal oxide, a silver containing metal oxide, or a combination comprising at least one of the foregoing. In some embodiments, the LDS additive preferably comprises a copper chromium oxide spinel, a copper hydroxide phosphate, a copper phosphate, or a combination comprising at least one of the foregoing.

[0038] An exemplary and non-limiting example of a commercially available laser-direct structuring additive includes PK3095 black pigment, commercially available from Ferro Corp., USA. PK3095, for example, comprises chromium oxides (Cr₂03, Cr₂0₄ ^2", Cr₂07^2") and oxides of copper (CuO), as determined using X-ray photoelectron spectroscopy (XPS). The PK3095 black pigment also has a spinel type crystal structure. Another exemplary commercially available laser-direct structuring additive is the Black 1G pigment black 28 commercially available from The Shepherd Color company. The Black 1G pigment black 28 comprises copper chromate and has a pH of about 7.3. The Black 1G pigment also has a spinel type crystal structure.

[0039] In some embodiments, the laser-direct structuring additive can be present in an amount of 2 to 30 weight percent, preferably 5 to 20 weight percent, based on the weight of the thermoplastic polymer and the laser-direct structuring additive in each layer of the polymer film. Stated another way, when the polymer film comprises a multilayer polymer film including more than one LDS -containing layer, as discussed below, each LDS -containing layer can

independently include the LDS additive in an amount of 2 to 30 weight percent, or 5 to 20 weight percent.

[0040] In some embodiments, the polymer film can further comprise one or more additional layers (i.e., the polymer film can be a monolayer or a multilayer polymer film). For example, in some embodiments, the polymer film (1) can further comprise a second layer (5) comprising a thermoplastic polymer, for example as shown in FIG. 2. The second layer is preferably devoid of a laser-direct structuring additive. The second layer is in direct contact with a first side of the first layer (2a). In this embodiment, the side of the second layer opposite the first layer forms the first side of the polymer film (la).

[0041] In some embodiments, the polymer film (1) can further comprise a second layer (5) and a third layer (6), as shown in FIG. 3. The second layer comprises a thermoplastic polymer and is devoid of a laser-direct structuring additive. The third layer can comprise a thermoplastic polymer and a laser-direct structuring additive, which can each be the same or different from the thermoplastic polymer and the laser-direct structuring additive of the first layer. In some embodiments, the third layer can be a functional layer, for example, a thermally conductive layer, a metal plated layer, a colored layer, a magnetic layer, or the like. When the third layer is a functional layer, the third layer can also further include a thermoplastic polymer as a base material. The second layer is in direct contact with a first side of the first layer (2a) and the third layer is in direct contact with the second layer on a side opposite from the first layer. In this embodiment, the side of the third layer opposite the second layer forms the first side of the polymer film (la).

[0042] In some embodiments, the polymer film (1) can further comprise a second layer (5), a third layer (6), and a fourth layer (7), as shown in FIG. 4. The second and third layers are as described above, and the fourth layer comprises a thermoplastic polymer and is devoid of a laser-direct structuring additive. The second layer (5) is in direct contact with a first side of the first layer (2a) and the third layer (6) is in direct contact with the second layer on a side opposite the first layer. The fourth layer (7) is in direct contact with the third layer on a side opposite the second layer. In this embodiment, the side of the fourth layer opposite the third layer forms the first side of the polymer film (la).

[0043] The various layers (i.e., the first, second, third, and fourth layers) of the polymer film can be the same or different in terms of chemical and physical composition. For example, each layer can have the same or different thermoplastic polymer, the same or different LDS additive, the same or different concentration of LDS additive, or the same or different thickness. In some embodiments, the thermoplastic polymers and the laser-direct structuring additives of the second, third, and fourth layers can be the same or different as the thermoplastic polymers and the laser-direct structuring additives described above for the first layer of the polymer film. Generally, the thermoplastic polymer of each layer of the polymer film should be selected such that the layers will have good compatibility for adhesion when forming or processing the polymer film, as well as when using the polymer film. In some embodiments, each layer of the polymer film comprises the same thermoplastic polymer. In some embodiments, the laser-direct structuring additive of the first and third layers is the same. In some embodiments, the laser- direct structuring additive of the first and third layers is different.

[0044] In embodiments where the polymer film is a multilayered polymer film, the multilayered structure can be formed by coextrusion of each polymer layer. Alternatively, each layer of the polymer film can be formed individually and subsequently fused together. The various layers of the polymer film can be made on an individual basis by any suitable film making process including, for example, thermoforming, extruding, injection molding, compression molding, solution casting, resin transfer molding including vacuum resin-transfer molding, melt-casting, extrusion coating, calender rolling, skiving, and the like. The process chosen for making the each layer can depend on the thermoplastic polymer used in each layer.

[0045] In some embodiments, the process chosen for making each layer of the polymer film can depend on the desired configuration of the resulting polymer film. For example, in some embodiments, where a two-dimensional film is desired (i.e., a flat polymer film), such as those shown in FIG. 1-4, the layer or layers can be formed by extrusion or coextrusion. In some embodiments, the polymer film can have a three dimensional configuration, for example as shown in FIG. 5. Such a three dimensionally configured film can be prepared, for example, by thermoforming an extruded or coextruded layer.

[0046] In some embodiments, the polymer film can have a total thickness of 3 micrometers to 5 millimeters, or 5 micrometers to 5 millimeters, preferably 25 to 250 micrometers. When the polymer film comprises more than one layer, each layer of the polymer film can have, for example, a thickness of 3 to 100 micrometers, or 5 to 50 micrometers.

[0047] In addition to the polymer film, the laminate of the present disclosure further comprises a substrate. In some embodiments, the substrate comprises glass, sapphire, metal, wood, a thermoplastic sheet, bamboo, paper, a textile, rubber, a composite sheet (e.g., a printed circuit board comprising glass fiber and epoxy or a carbon fiber-reinforced laminate), or a combination comprising at least one of the foregoing. In some embodiments, the substrate is preferably a glass substrate. The glass substrate 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.).

[0048] In some embodiments, the substrate can have a thickness of 50 micrometers to 25 millimeters, or 50 micrometers to 10 millimeters, or 50 micrometers to 5 millimeters, or 50 micrometers to 1 millimeter, or 50 to 500 micrometers.

[0049] In some embodiments, one or both surfaces of the substrate 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.

[0050] The polymer film and the substrate can be laminated together via an adhesive layer to form the laminate of the present disclosure. Thus, the laminate further comprises an adhesive layer disposed between the polymer film and the substrate. In some embodiments, where the polymer film is a single layer consisting of the above-described first layer, the laminate can be as shown in FIG. 6, where the adhesive layer (4) is in direct contact with at least a portion of a first side of the polymer film (la) and with at least a portion of a first side (3a) of the substrate (3) to form the laminate (8). In some embodiments, where the polymer film is a three-dimensionally configured layer (i.e., from a thermoforming process), the adhesive layer can be in direct contact with at least a portion of a first side of the substrate, and with a portion of the first side of the polymer film to form a three-dimensional laminate (i.e., the polymer film can be partially laminated onto the substrate and three dimensionally configured where the film is not in direct contact with the substrate via the adhesive layer). In some embodiments, where the polymer film comprises the first layer and the second layer, the laminate can be as shown in FIG.

7, wherein the adhesive layer (4) is in direct contact with at least a portion of a side of the second layer (5) of the polymer film (5) opposite the first layer (2) of the polymer film, and with at least a portion of a first side (3a) of the substrate (3) to form laminate (8). In some embodiments, wherein the polymer film comprises, the first layer, the second layer, and the third layer, the adhesive layer is in direct contact with at least a portion of a side of the third layer opposite the second layer, and with at least a portion of a first side of the substrate. In some embodiments, where the polymer film comprises the first layer, the second layer, the third layer, and the fourth layer, the laminate can be as shown in FIG. 8, where the adhesive layer (4) is in direct contact with at least a portion of a side of the fourth layer (7) opposite the third layer (6) and with at least a portion of a first side (3a) of the substrate (3) to form the laminate (8).

[0051] In some embodiments, the adhesive layer comprises a pressure sensitive adhesive, a heat curable adhesive, a UV curable adhesive, or a combination comprising at least one of the foregoing. In some embodiments, 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), polyvinyl butyral, 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.

[0052] In some embodiments, the adhesive layer can have a total thickness of 1 to 2000 micrometers, or 10 to 200 micrometers, or 10 to 100 micrometers, or 10 to 50 micrometers.

[0053] In some embodiments, the laminate can have a total thickness of 55 micrometers to 35 millimeters, or 85 micrometers to 15 millimeters, or 100 micrometers to 10 millimeters.

[0054] In some embodiments, in addition to the polymer film, the substrate, and the adhesive layer, the laminate can optionally further comprise 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 substrate, the polymer film, or both. In some embodiments, the functional layer can be disposed on both sides of the substrate, 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., as a film, coating, coextruded layer, deposited layer, molded layer, or the like.

[0055] The laminate can be manufactured by applying the adhesive to at least a portion of the first side of the substrate, and coupling the polymer film to the adhesive layer on a side opposite the first side of the substrate to form the laminate. 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, thermoforming, and the like. Preferably, the polymer film is prepared by extrusion, for example by melt-mixing the thermoplastic polymer, and (when present) the laser-direct structuring additive, and extruding the mixture to provide the polymer film. In some embodiments, the polymer film can be prepared by thermoforming. In particular, the polymer film can be prepared by thermoforming an extruded or coextruded polymer film, specifically when a three-dimensionally configured polymer film is desired. When present, the one or more additional layers can be applied in the desired position in the laminate. The layers can generally be assembled in any order to provide the desired laminate structure.

[0056] In some embodiments, the laminate further includes one or more conductive pathways on a surface of the laminate (i.e., on the exposed, second surface of the polymer film, opposite the first side (la) of the polymer film, as shown in FIG. 6). The conductive pathways can comprise a metal layer deposited on an activated path. Thus in some embodiments, the method of manufacturing the laminate further includes forming an activated path on at least a portion of an outer surface of the polymer film and depositing a metal layer on the activated path to provide a conductive path on at least a portion of the outer surface of the polymer film.

Forming the conductive path on the surface of the polymer film can be carried out prior to or after laminating the polymer film to the substrate via the adhesive layer. In some embodiments, forming the conductive pathway occurs prior to coupling the polymer film to the substrate via the adhesive layer. The presence of the LDS additives facilitates the production of the conductive path. Typically, a laser is used to form an activated/conductive path during a laser structuring step. In some embodiments, laser-direct structuring comprises laser etching, and in a further embodiment, laser etching is carried out to provide an activated surface. In some embodiments, at least one laser beam draws at least one pattern on the surface of the coating layer during the laser structuring step. The LDS additive can release at least one metallic nucleus. The at least one metallic nucleus that has been released can further act as a catalyst for a reductive copper plating process.

[0057] In some embodiments, laser etching is carried out at a power of 1 to 10 watts with a frequency of 30 to 110 kilohertz (kHz), or 40 to 100 kHz, and a speed of 1 to 5 meters per second (m/s), or 2 to 4 m/s. In some embodiments, laser etching is carried out at a power of 3.5 watts with a frequency of 40 kHz and a speed of 2 m/s.

[0058] The metallizing step can be any conventional metallizing techniques. For example, in some embodiments, an electroless copper plating bath is used during the

metallization step in the LDS process. Thus, in some embodiments, depositing the metal layer comprises plating a metal layer onto an activated path.

[0059] In some embodiments, the LDS additive can remain present at the surface of the polymer film in the areas not irradiated by the laser.

[0060] Another aspect of the present disclosure is a molded article. The molded article comprises a mold insert comprising the laminate described above. In addition to the mold insert, the article comprises a thermoplastic attachment coupled to a portion of a second side of the substrate, and extending along an edge of the mold insert. The thermoplastic attachment can be any shape. The attachment can be bonded to the substrate 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 FIG. 9, where a thermoplastic attachment (10) extends along an edge of the mold insert/laminate (8), forming the molded article (9). In some embodiments, an adhesive can be used to couple the attachment to the insert. In some embodiments, the attachment can further be configured so as to include one or more assembly features. 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. The molded article further includes a conductive path formed on at least a portion of a surface of the molded article, the conductive path comprising a metal layer deposited on an activated path.

[0061] The attachment comprises a second thermoplastic polymer. The second thermoplastic polymer can be the same or different as the thermoplastic polymer described above for use in the polymer film. In some embodiments, the attachment preferably comprises polyamide, polyester, polycarbonate, polyetheretherketone, polyetherimide, polyimide, polyolefin, polystyrene, liquid crystal polymer, polyphthalamide, or a combination comprising at least one of the foregoing. In some embodiments, the attachment comprises polycarbonate. In addition to the second thermoplastic polymer, the attachment can optionally further include at least one reinforcing filler and optionally, a flame retardant component (e.g., a phosphorus- containing flame retardant), 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. 14/317,142. In some embodiments, the reinforcing filler material comprises talc, mica, 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. When present, the reinforcing filler material is present in an amount of 1 to 50 wt%, based on the total weight of the thermoplastic attachment. In some embodiments, the attachment can include 50 to 99 wt% of the polycarbonate and 1 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%. In some embodiments, the attachment does not include a reinforcing filler (i.e., a reinforcing filler can be excluded from the attachment).

[0062] In some embodiments, when present, 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.

[0063] 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 [S1O2 (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.

[0064] 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. In some embodiments, no additives are present in the attachment. [0065] 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.

[0066] Thus, in some embodiments, the method for manufacturing the molded article includes forming an activated path on at least a portion of a second side of the polymer film (i.e., on the side of the polymer film opposite the adhesively coupled substrate), and depositing a metal layer onto the activated path to form a conductive path on at least a portion of the second side of the polymer film. The method further comprises coupling a first side of the polymer film (i.e., the side opposite the side containing the conductive path) to a first side of the substrate via an adhesive layer to form a mold insert (e.g., laminate). The adhesive layer can be applied to at least a portion of the first side of the substrate prior to coupling the polymer film. The method further comprises molding a thermoplastic attachment to the mold insert in an injection molding process to form the molded article. The injection molding process can include, for example, injecting a molten thermoplastic polymer, for example a polycarbonate, into the mold cavity behind the laminate/mold insert to produce a single piece, bonded, three-dimensional molded article. Following injection of the molten thermoplastic polymer to form the attachment, the mold can be cooled to a de-molding temperature, and the molded articles can be removed.

[0067] The laminates and 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 laminate or 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 welded 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 laminate or the molded article include, but are not limited to, a cellular telephone, a smart telephone, an antenna, 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.

[0068] The laminates, molded articles, methods, and devices of the present disclosure are further illustrated by the following embodiments, which are non-limiting.

[0069] Embodiment 1 : A laminate, comprising a polymer film comprising a first layer comprising a thermoplastic polymer and a laser direct structuring additive; a substrate; and an adhesive layer disposed between the polymer film and the substrate.

[0070] Embodiment 2: The laminate of embodiment 1, wherein the adhesive layer is in direct contact with at least a portion of a first side of the polymer film and with at least a portion of a first side of the substrate.

[0071] Embodiment 3: The laminate of embodiment 1, wherein the polymer film further comprises a second layer comprising a thermoplastic polymer, wherein the second layer is devoid of a laser structuring additive; the second layer is in direct contact with a first side of the first layer; and the adhesive layer is in direct contact with at least a portion of a side of the second layer of the polymer film opposite the first layer of the polymer film, and with at least a portion of a first side of the substrate.

[0072] Embodiment 4: The laminate of embodiment 1, wherein the polymer film further comprises a second layer comprising a thermoplastic polymer and a third layer comprising a thermoplastic polymer and a laser direct structuring additive; wherein the second layer is devoid of a laser structuring additive; the second layer is in direct contact with a first side of the first layer; the third layer is in direct contact with the second layer on a side opposite the first layer; and the adhesive layer is in direct contact with at least a portion of a side of the third layer opposite the second layer, and with at least a portion of a first side of the substrate.

[0073] Embodiment 5: The laminate of embodiment 1, wherein the polymer film further comprises a second layer comprising a thermoplastic polymer, a third layer comprising a thermoplastic polymer and a laser direct structuring additive, and a fourth layer comprising a thermoplastic polymer; wherein the second and fourth layers are devoid of a laser structuring additive; the second layer is in direct contact with a first side of the first layer; the third layer is in direct contact with the second layer on a side opposite the first layer; the fourth layer is in direct contact with the third layer on a side opposite the second layer; and the adhesive layer is in direct contact with at least a portion of a side of the fourth layer opposite the third layer and with at least a portion of a first side of the substrate.

[0074] Embodiment 6: The laminate of any one or more of embodiments 1 to 5, wherein the polymer film is an extruded polymer film, and the thermoplastic polymer comprises polyamide, polyarylate, poly(arylene ether), polycarbonate, polyester, polyetheretherketone, polyetherimide, polyimide, polyolefin, polystyrene, liquid crystal polymer, polyphthalamide, or a combination comprising at least one of the foregoing.

[0075] Embodiment 7: The laminate of any one or more of embodiments 1 to 6, wherein the laser direct structuring additive comprises a copper chromium oxide spinel, a copper salt, a copper hydroxide phosphate, a copper phosphate, a copper sulfate, a cuprous thiocyanate, a spinel based metal oxide, a copper chromium oxide, an organic metal complex, a

palladium/palladium-containing heavy metal complex, a metal oxide, a metal oxide-coated filler, antimony doped tin oxide coated on mica, a copper containing metal oxide, a zinc containing metal oxide, a tin containing metal oxide, a magnesium containing metal oxide, an aluminum containing metal oxide, a gold containing metal oxide, a silver containing metal oxide, or a combination comprising at least one of the foregoing, preferably a copper chromium oxide spinel, a copper hydroxide phosphate, a copper phosphate, or a combination comprising at least one of the foregoing.

[0076] Embodiment 8: The laminate of any one or more of embodiments 1 to 7, wherein the laser direct structuring additive is present in an amount of 2 to 30 weight percent, or 5 to 20 weight percent, based on the weight of the thermoplastic polymer and the laser direct structuring additive. [0077] Embodiment 9: The laminate of any one or more of embodiments 1 to 8, wherein the substrate comprises glass, sapphire, metal, wood, a thermoplastic sheet, bamboo, paper, a textile, rubber, a composite sheet, or a combination comprising at least one of the foregoing.

[0078] Embodiment 10: The laminate of any one or more of embodiments 1 to 9, wherein the polymer film has a thickness of 3 micrometers to 5 millimeters, or 5 micrometers to 5 millimeters, preferably 25 to 250 micrometers; the substrate has a thickness of 50 micrometers to 25 millimeters, preferably 50 micrometers to 10 millimeters, more preferably 50 micrometers to 5 millimeters; the adhesive layer has a thickness of 1 to 2000 micrometers, preferably 10 to 200 micrometers; and the laminate has a total thickness of 55 micrometers to 35 millimeters.

[0079] Embodiment 11: The laminate of any one or more of embodiments 1 to 10, wherein the adhesive layer comprises a pressure sensitive adhesive, a heat curable adhesive, a UV curable adhesive, or a combination comprising at least one of the foregoing.

[0080] Embodiment 12: The laminate of any one or more of embodiments 1 to 11, wherein the polymer film has a three dimensional configuration.

[0081] Embodiment 13: A method of making the laminate of any one or more of embodiments 1 to 12, the method comprising, applying the adhesive to at least a portion of the first side of the substrate; and coupling the polymer film to the adhesive layer on a side opposite the first side of the substrate to form the laminate.

[0082] Embodiment 14: The method of embodiment 13, further comprising, melt-mixing the thermoplastic polymer and the laser direct structuring additive; and extruding the mixture to provide the polymer film.

[0083] Embodiment 15: The method of embodiment 14, further comprising

thermoforming the polymer film to provide a polymer film having a three dimensional configuration.

[0084] Embodiment 16: The method of any one or more of embodiments 13 or 15, further comprising forming an activated path on at least a portion of an outer surface of the polymer film and depositing a metal layer on the activated path to provide a conductive path on at least a portion of the outer surface of the polymer film.

[0085] Embodiment 17: A molded article comprising, a mold insert comprising the laminate of any one or more of embodiments 1 to 12; and a thermoplastic attachment coupled to a portion of a second side of the substrate, the thermoplastic attachment extending along an edge of the mold insert; wherein the attachment comprises a second thermoplastic polymer; and wherein the molded article further comprises a conductive path formed on a surface of the molded article, the conductive path comprising a metal layer deposited on an activated path. [0086] Embodiment 18: The molded article of embodiment 17, wherein the second thermoplastic polymer comprises polyamide, polyester, polycarbonate, polyetheretherketone, polyetherimide, polyimide, polyolefin, polystyrene, liquid crystal polymer, or a combination comprising at least one of the foregoing.

[0087] Embodiment 19: The molded article of embodiment 17 or 18, wherein the thermoplastic attachment further comprises a reinforcing filler material comprising talc, mica, 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, and wherein the reinforcing filler material is present in an amount of 1 to 50 wt%, based on the total weight of the thermoplastic attachment.

[0088] Embodiment 20: The molded article of any one or more of embodiments 17 to 19, wherein the thermoplastic attachment forms a border that surrounds the mold insert in at least one dimension.

[0089] Embodiment 21: A method of manufacturing the molded article of any one or more of embodiments 17 to 20, the method comprising, forming an activated path on at least a portion of a second side of the polymer film; depositing a metal layer onto the activated path to form a conductive path on at least a portion of the second side of the polymer film; applying the adhesive to at least a portion of the first side of the substrate; coupling a first side of polymer film to the adhesive layer on a side opposite the first side of the substrate to form the mold insert; and molding a thermoplastic attachment to the mold insert in an injection molding process to form the molded article, wherein the attachment extends along at least a portion of an edge of the mold insert.

[0090] Embodiment 22: An electronic device comprising the laminate of any one or more of embodiments 1 to 12 or the molded article of any one or more of embodiments 17 to 20, preferably 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.

[0091] The laminates, molded articles, methods, and devices can alternatively comprise, consist of, or consist essentially of, any appropriate components or steps herein disclosed. The laminates, molded articles, methods, and devices 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 laminates, molded articles, methods, and devices.

[0092] 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.

[0093] 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.

[0094] 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.

[0095] 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

1. A laminate, comprising

a polymer film comprising a first layer comprising a thermoplastic polymer and a laser direct structuring additive;

a substrate; and

an adhesive layer disposed between the polymer film and the substrate.

2. The laminate of claim 1, wherein the adhesive layer is in direct contact with at least a portion of a first side of the polymer film and with at least a portion of a first side of the substrate.

3. The laminate of claim 1, wherein the polymer film further comprises a second layer comprising a thermoplastic polymer,

wherein

the second layer is devoid of a laser structuring additive;

the second layer is in direct contact with a first side of the first layer; and the adhesive layer is in direct contact with at least a portion of a side of the second layer of the polymer film opposite the first layer of the polymer film, and with at least a portion of a first side of the substrate.

4. The laminate of claim 1, wherein the polymer film further comprises a second layer comprising a thermoplastic polymer and a third layer comprising a thermoplastic polymer and a laser direct structuring additive;

wherein

the second layer is devoid of a laser structuring additive;

the second layer is in direct contact with a first side of the first layer; the third layer is in direct contact with the second layer on a side opposite the first layer; and

the adhesive layer is in direct contact with at least a portion of a side of the third layer opposite the second layer, and with at least a portion of a first side of the substrate.

5. The laminate of claim 1, wherein the polymer film further comprises a second layer comprising a thermoplastic polymer, a third layer comprising a thermoplastic polymer and a laser direct structuring additive, and a fourth layer comprising a thermoplastic polymer;

wherein

the second and fourth layers are devoid of a laser structuring additive; the second layer is in direct contact with a first side of the first layer; the third layer is in direct contact with the second layer on a side opposite the first layer;

the fourth layer is in direct contact with the third layer on a side opposite the second layer; and

the adhesive layer is in direct contact with at least a portion of a side of the fourth layer opposite the third layer and with at least a portion of a first side of the substrate.

6. The laminate of any one or more of claims 1 to 5, wherein the polymer film is an extruded polymer film, and the thermoplastic polymer comprises polyamide, polyarylate, poly(arylene ether), polycarbonate, polyester, polyetheretherketone, polyetherimide, polyimide, polyolefin, polystyrene, liquid crystal polymer, polyphthalamide, or a combination comprising at least one of the foregoing.

7. The laminate of any one or more of claims 1 to 6, wherein

the laser direct structuring additive comprises a copper chromium oxide spinel, a copper salt, a copper hydroxide phosphate, a copper phosphate, a copper sulfate, a cuprous thiocyanate, a spinel based metal oxide, a copper chromium oxide, an organic metal complex, a palladium/palladium-containing heavy metal complex, a metal oxide, a metal oxide-coated filler, antimony doped tin oxide coated on mica, a copper containing metal oxide, a zinc containing metal oxide, a tin containing metal oxide, a magnesium containing metal oxide, an aluminum containing metal oxide, a gold containing metal oxide, a silver containing metal oxide, or a combination comprising at least one of the foregoing, preferably a copper chromium oxide spinel, a copper hydroxide phosphate, a copper phosphate, or a combination comprising at least one of the foregoing; and

the laser direct structuring additive is present in an amount of 2 to 30 weight percent, or 5 to 20 weight percent, based on the weight of the thermoplastic polymer and the laser direct structuring additive.

8. The laminate of any one or more of claims 1 to 7, wherein

the substrate comprises glass, sapphire, metal, wood, a thermoplastic sheet, bamboo, paper, textile, rubber, a composite sheet or a combination comprising at least one of the foregoing, preferably glass; and

the adhesive layer comprises a pressure sensitive adhesive, a heat curable adhesive, a UV curable adhesive, or a combination comprising at least one of the foregoing.

9. The laminate of any one or more of claims 1 to 8, wherein

the polymer film has a thickness of 3 micrometers to 5 millimeters, or 5 micrometers to 5 millimeters, preferably 25 to 250 micrometers;

the substrate has a thickness of 50 micrometers to 25 millimeters, preferably 50 micrometers to 10 millimeters, more preferably 50 micrometers to 5 millimeters;

the adhesive layer has a thickness of 1 to 2000 micrometers, preferably 10 to 200 micrometers; and

the laminate has a total thickness of 55 micrometers to 35 millimeters.

10. The laminate of any one or more of claims 1 to 9, wherein the polymer film has a three dimensional configuration.

11. A method of making the laminate of any one or more of claims 1 to 10, the method comprising,

applying the adhesive to at least a portion of the first side of the substrate; and

coupling the polymer film to the adhesive layer on a side opposite the first side of the substrate to form the laminate.

12. The method of claim 11, further comprising,

melt-mixing the thermoplastic polymer and the laser direct structuring additive; and extruding the mixture to provide the polymer film.

13. The method of claim 12, further comprising thermoforming the polymer film to provide a polymer film having a three dimensional configuration.

14. The method of any one or more of claims 11 to 13, further comprising forming an activated path on at least a portion of an outer surface of the polymer film and depositing a metal layer on the activated path to provide a conductive path on at least a portion of the outer surface of the polymer film.

15. A molded article comprising,

a mold insert comprising the laminate of any one or more of claims 1 to 10; and a thermoplastic attachment coupled to a portion of a second side of the substrate, the thermoplastic attachment extending along an edge of the mold insert;

wherein the attachment comprises a second thermoplastic polymer; and

wherein the molded article further comprises a conductive path formed on a surface of the molded article, the conductive path comprising a metal layer deposited on an activated path.

16. The molded article of claim 15, wherein the second thermoplastic polymer comprises polyamide, polyester, polycarbonate, polyetheretherketone, polyetherimide, polyimide, polyolefin, polystyrene, liquid crystal polymer, or a combination comprising at least one of the foregoing.

17. The molded article of claim 15 or 16, wherein the thermoplastic attachment further comprises a reinforcing filler material comprising talc, mica, 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, and wherein the reinforcing filler material is present in an amount of 1 to 50 wt%, based on the total weight of the thermoplastic attachment.

18. The molded article of any one or more of claims 15 to 17, wherein the thermoplastic attachment forms a border that surrounds the mold insert in at least one dimension.

19. A method of manufacturing the molded article of any one or more of claims 15 to 18, the method comprising,

forming an activated path on at least a portion of a second side of the polymer film;

depositing a metal layer onto the activated path to form a conductive path on at least a portion of the second side of the polymer film;

applying the adhesive to at least a portion of the first side of the substrate; coupling a first side of polymer film to the adhesive layer on a side opposite the first side of the substrate to form the mold insert; and

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

20. An electronic device comprising the laminate of any one or more of claims 1 to 10 or the molded article of any one or more of claims 15 to 18, preferably 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.