WO2018026601A1 - Laminés pour une structuration directe par laser, procédé permettant de fabriquer ces derniers, articles moulés préparés à partir de ces derniers et dispositif comprenant l'article moulé - Google Patents

Laminés pour une structuration directe par laser, procédé permettant de fabriquer ces derniers, articles moulés préparés à partir de ces derniers et dispositif comprenant l'article moulé Download PDF

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Publication number
WO2018026601A1
WO2018026601A1 PCT/US2017/043941 US2017043941W WO2018026601A1 WO 2018026601 A1 WO2018026601 A1 WO 2018026601A1 US 2017043941 W US2017043941 W US 2017043941W WO 2018026601 A1 WO2018026601 A1 WO 2018026601A1
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layer
polymer film
laminate
substrate
polymer
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PCT/US2017/043941
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English (en)
Inventor
Michael M. Laurin
Wei Zhao
Xiaoyu Sun
Wei FENG
Shijie Song
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Sabic Global Technologies B.V.
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Publication of WO2018026601A1 publication Critical patent/WO2018026601A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B21/00—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board
    • B32B21/04—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board comprising wood as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B21/08—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board comprising wood as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/04—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B25/08—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/10—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of paper or cardboard
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/288—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyketones
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B32B27/365—Layered products comprising a layer of synthetic resin comprising polyesters comprising polycarbonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/267—Marking of plastic artifacts, e.g. with laser
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/101—Glass fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
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    • B32B2457/00—Electrical equipment
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2605/00—Vehicles
    • B32B2605/003—Interior finishings

Definitions

  • LDS Laser-direct structuring
  • MIDs molded injection devices
  • 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).
  • the spacing between the conductive paths can also be small.
  • 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.
  • laser-direct structuring methods can provide short development cycles, facile variation in design, cost reducting, miniaturization, and product functionality.
  • MIDs manufactured using a LDS process also have inherent disadvantages.
  • 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.
  • LDS additives expensive, but they also can adversely affect other performance parameters of the bulk materials, such as long-term stability and ductility.
  • 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.
  • 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.
  • 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.
  • 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.
  • FIG. 1 shows a cross-sectional view of a single layer polymer film.
  • FIG. 2 shows a cross-sectional view of a multilayer polymer film.
  • FIG. 3 shows a cross-sectional view of a multilayer polymer film.
  • FIG. 4 shows a cross-sectional view of a multilayer polymer film.
  • FIG. 5 shows a cross-sectional view of a single layer polymer film having a three- dimensional configuration after thermoforming.
  • FIG. 6 shows a cross-sectional view of a laminate.
  • FIG. 7 shows a cross-sectional view of a laminate.
  • FIG. 8 shows a cross-sectional view of a laminate.
  • FIG. 9 shows a cross-sectional view of a molded article comprising the laminate.
  • 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.
  • LDS laser-direct structuring
  • 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.
  • the laminates described herein can withstand high temperatures and humid environments.
  • 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.
  • the polymer film can be a monolayer polymer film, or a multilayered polymer film.
  • 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.
  • the polymer film (1) comprises the first layer (2).
  • the first layer can have a first side (2a).
  • the polymer film is a monolayer, in particular an extruded monolayer polymer film
  • 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).
  • thermoplastic polymer can generally be any suitable thermoplastic polymer.
  • 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.
  • 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
  • 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
  • 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.
  • the polymer film preferably comprises a polycarbonate.
  • Polycarbonate as used herein means a polymer or copolymer having repeating structural carbonate units of formula (1)
  • each R 1 can be derived from a dihydroxy compound such as an aromatic dihydroxy compound of formula (2) or a bisphenol of formula (3).
  • 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 C 6 -io aryl, or a halogen-substituted C6-io aryl, and n is 0 to 4.
  • a Ci-io hydrocarbyl group such as a Ci-io alkyl, a halogen-substituted Ci-io alkyl, a C 6 -io aryl, or a halogen-substituted C6-io aryl
  • n is 0 to 4.
  • 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.
  • p and q is each
  • 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.
  • 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.
  • X a can be a substituted or unsubstituted C3-18 cycloalkylidene; a C 1 -2 5 alkylidene of the formula -
  • R c and R d are each independently hydrogen, C 1-12 alkyl, C 1-12 cycloalkyl, C 7-
  • 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-hydroxypheny
  • 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
  • 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)
  • 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 C 6 -20 cycloalkylene a C 6 -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 C 6 -20 cycloalkylene, or a C 6 -20 arylene.
  • Copolyesters containing a combination of different T or J groups can be used.
  • the polyester units can be branched or linear.
  • 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.
  • 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
  • Aliphatic dicarboxylic acids that can be used include C 6 -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.
  • 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.
  • 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.
  • 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.
  • BPA-PC bisphenol A carbonate units
  • LEXAN 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.
  • THPE t-hydroxyphenyl)ethane
  • 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;
  • poly(carbonate-ester)s PCE
  • poly(phthalate-carbonate)s PPC
  • bisphenol A carbonate units and C 6 -i2 dicarboxy ester units such as sebacic ester units (commercially available under the trade name HFD from SABIC)
  • PCE poly(carbonate-ester)s
  • PPC poly(phthalate-carbonate)s
  • 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 si
  • 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.
  • 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.
  • ester such as poly(butylene terephthalate) or poly(ethylene terephthalate)
  • 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
  • a copolymer comprising bisphenol A carbonate units and isophorone bisphenol carbonate units commercially available under the trade name APEC from Bayer.
  • 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
  • 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.
  • 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.
  • the first layer of the polymer film comprises a laser-direct structuring (LDS) additive.
  • 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.
  • 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.
  • the LDS additives can also be provided having spinel-type crystal structures.
  • 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.
  • 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.
  • 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 (Cr 2 03, Cr 2 0 4 2" , Cr 2 07 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.
  • 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.
  • each LDS -containing layer 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.
  • LDS additive independently include the LDS additive in an amount of 2 to 30 weight percent, or 5 to 20 weight percent.
  • 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).
  • 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).
  • the side of the second layer opposite the first layer forms the first side of the polymer film (la).
  • 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.
  • 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.
  • 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.
  • the side of the third layer opposite the second layer forms the first side of the polymer film (la).
  • 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.
  • the side of the fourth layer opposite the third layer forms the first side of the polymer film (la).
  • 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.
  • 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.
  • 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.
  • 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.
  • each layer of the polymer film comprises the same thermoplastic polymer.
  • 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.
  • the multilayered structure can be formed by coextrusion of each polymer layer.
  • 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.
  • the process chosen for making each layer of the polymer film can depend on the desired configuration of the resulting polymer film.
  • a two-dimensional film i.e., a flat polymer film
  • the layer or layers can be formed by extrusion or coextrusion.
  • 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.
  • 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.
  • each layer of the polymer film can have, for example, a thickness of 3 to 100 micrometers, or 5 to 50 micrometers.
  • the laminate of the present disclosure further comprises a substrate.
  • 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.
  • the substrate is preferably a glass substrate.
  • the glass substrate can be, but is not limited to, chemically strengthened glass (e.g., CORNINGTM GORILLATM Glass commercially available from Corning Inc., XENSATIONTM glass commercially available from Schott AG, DRAGONTRAILTM 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., CORNINGTM WILLOWTM 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.).
  • chemically strengthened glass e.g., CORNINGTM GORILLATM Glass commercially available from Corning Inc., XENSATIONTM glass commercially available from Schott AG, DRAGONTRAILTM glass commercially available from As
  • 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.
  • 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.
  • the polymer film and the substrate can be laminated together via an adhesive layer to form the laminate of the present disclosure.
  • the laminate further comprises an adhesive layer disposed between the polymer film and the substrate.
  • 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).
  • 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).
  • the laminate can be as shown in FIG.
  • 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).
  • 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.
  • 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).
  • 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.
  • 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.
  • the adhesive is a hindered amine light stabilizer free ethyl vinyl acetate (HALS free EVA).
  • 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.
  • 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.
  • 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.
  • the laminate 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.
  • a functional layer when present, is preferably disposed on at least a portion of the substrate, the polymer film, or both.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the polymer film can be prepared by thermoforming.
  • the polymer film can be prepared by thermoforming an extruded or coextruded polymer film, specifically when a three-dimensionally configured polymer film is desired.
  • 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.
  • 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.
  • 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.
  • a laser is used to form an activated/conductive path during a laser structuring step.
  • laser-direct structuring comprises laser etching, and in a further embodiment, laser etching is carried out to provide an activated surface.
  • 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.
  • 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.
  • the metallizing step can be any conventional metallizing techniques.
  • an electroless copper plating bath is used during the
  • depositing the metal layer comprises plating a metal layer onto an activated path.
  • the LDS additive can remain present at the surface of the polymer film in the areas not irradiated by the laser.
  • the molded article comprises a mold insert comprising the laminate described above.
  • 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.
  • 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).
  • an adhesive can be used to couple the attachment to the insert.
  • 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.
  • 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.
  • 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.
  • the attachment comprises polycarbonate.
  • 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.
  • a flame retardant component e.g., a phosphorus- containing flame retardant
  • the flame retardant component and the flame retardant synergist can be as described in US Patent Application No. 14/317,142.
  • 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.
  • the reinforcing filler material is present in an amount of 1 to 50 wt%, based on the total weight of the thermoplastic attachment.
  • 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%.
  • a flame retardant can be used in an amount of 3 to 7 wt%.
  • the attachment does not include a reinforcing filler (i.e., a reinforcing filler can be excluded from the attachment).
  • the reinforcing filler when present, 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.
  • the glass fiber can have a cross section that is round or flat.
  • examples of suitable glass materials are C glass [S1O2 (65- 70%), AI2O3 (2-6%), CaO (4-9%), MgO (0-5%), B2O3 (2-7%), Na 2 0 & K 2 0 (9-13%), ZnO (1- 6%)] and ECR glass [S1O2 (63-70%), AI2O3 (3-6%), CaO (4-7%), MgO (1-4%), B2O3 (2-5%), Na 2 0 (9-12%), K 2 0 (0-3%), T1O2 (0-4%), ZnO (1-5%)].
  • An especially preferred glass material is ECR glass having >0.1% T1O2, especially below 1% T1O2.
  • 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.
  • 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.
  • no additives are present in the attachment.
  • the molded article can be manufactured by molding the attachment to the mold insert in a molding process.
  • 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.
  • 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.
  • 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.
  • the mold can be cooled to a de-molding temperature, and the molded articles can be removed.
  • 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.
  • 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).
  • the display can be a heads-up display, a display console, or a touch screen display.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • Embodiment 12 The laminate of any one or more of embodiments 1 to 11, wherein the polymer film has a three dimensional configuration.
  • 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.
  • 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.
  • Embodiment 15 The method of embodiment 14, further comprising
  • thermoforming the polymer film to provide a polymer film having a three dimensional configuration.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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
  • 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.
  • 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.
  • 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.
  • a console e.g., an appliance or automotive console such as a central stack display or a heads-up display
  • a smart white board e.g., a central stack display or a heads-up display
  • a wearable display e.g., a transparent display
  • a medical device e.g., a portable lighting device, or a smart window.
  • 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.
  • 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.
  • 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 (-CH 2 -) or, propylene
  • Cycloalkylene means a divalent cyclic alkylene group, -C n H 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.
  • 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.
  • 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.

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  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Laminated Bodies (AREA)

Abstract

La présente invention concerne un stratifié qui comprend un film polymère, un substrat et une couche adhésive disposée entre le film polymère et le substrat. Le film polymère comprend une première couche comprenant un polymère thermoplastique et un additif de structuration directe au laser. Un article moulé comprend un insert de moule comprenant le stratifié, et une fixation thermoplastique couplée à au moins une partie d'un second côté du substrat du stratifié. La fixation s'étend le long d'un bord de l'insert de moule et comprend un polymère thermoplastique. Les articles moulés de la présente invention peuvent être particulièrement utiles pour des composants ou des boîtiers pour des dispositifs électriques et électroniques.
PCT/US2017/043941 2016-08-05 2017-07-26 Laminés pour une structuration directe par laser, procédé permettant de fabriquer ces derniers, articles moulés préparés à partir de ces derniers et dispositif comprenant l'article moulé WO2018026601A1 (fr)

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US201662371291P 2016-08-05 2016-08-05
US62/371,291 2016-08-05
US201662433454P 2016-12-13 2016-12-13
US62/433,454 2016-12-13

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CN109504053A (zh) * 2018-07-12 2019-03-22 江苏华信新材料股份有限公司 一种智能卡用聚碳酸酯激光刻蚀膜及其制备方法
CN109575584A (zh) * 2018-11-20 2019-04-05 贵州航天天马机电科技有限公司 一种3d打印用尼龙线材及其制备方法
WO2020194196A1 (fr) 2019-03-28 2020-10-01 Sabic Global Technologies B.V. Feuilles multicouches, procédés de fabrication et articles formés à partir de celles-ci
RU2737262C2 (ru) * 2019-03-27 2020-11-26 Акционерное общество "Средне-Невский судостроительный завод" Термопластичная полиэфиримидная композиция с базальтовым волокном
JP2021014549A (ja) * 2019-07-16 2021-02-12 Ｍｃｐｐイノベーション合同会社 レーザーダイレクトストラクチャリング用熱可塑性樹脂組成物及び成形体
CN112708235A (zh) * 2019-10-24 2021-04-27 中国石油化工股份有限公司 一种lds电路制件及其制备方法
US11258184B2 (en) 2019-08-21 2022-02-22 Ticona Llc Antenna system including a polymer composition having a low dissipation factor
CN114950458A (zh) * 2022-07-01 2022-08-30 宁夏清研高分子新材料有限公司 一种lcp基lds复合材料和激光催化剂及其制备方法
US11555113B2 (en) 2019-09-10 2023-01-17 Ticona Llc Liquid crystalline polymer composition
US11637365B2 (en) 2019-08-21 2023-04-25 Ticona Llc Polymer composition for use in an antenna system
US11646760B2 (en) 2019-09-23 2023-05-09 Ticona Llc RF filter for use at 5G frequencies
US11721888B2 (en) 2019-11-11 2023-08-08 Ticona Llc Antenna cover including a polymer composition having a low dielectric constant and dissipation factor
US11728559B2 (en) 2021-02-18 2023-08-15 Ticona Llc Polymer composition for use in an antenna system
US11729908B2 (en) 2020-02-26 2023-08-15 Ticona Llc Circuit structure
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US11917753B2 (en) 2019-09-23 2024-02-27 Ticona Llc Circuit board for use at 5G frequencies
US12035467B2 (en) 2023-06-27 2024-07-09 Ticona Llc Circuit structure

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WO2015091447A1 (fr) * 2013-12-20 2015-06-25 Ems-Patent Ag Matière à mouler en plastique et utilisation de ladite matière
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Cited By (21)

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Publication number Priority date Publication date Assignee Title
CN109504053A (zh) * 2018-07-12 2019-03-22 江苏华信新材料股份有限公司 一种智能卡用聚碳酸酯激光刻蚀膜及其制备方法
CN109575584A (zh) * 2018-11-20 2019-04-05 贵州航天天马机电科技有限公司 一种3d打印用尼龙线材及其制备方法
CN109575584B (zh) * 2018-11-20 2021-02-12 贵州航天天马机电科技有限公司 一种3d打印用尼龙线材及其制备方法
RU2737262C2 (ru) * 2019-03-27 2020-11-26 Акционерное общество "Средне-Невский судостроительный завод" Термопластичная полиэфиримидная композиция с базальтовым волокном
WO2020194196A1 (fr) 2019-03-28 2020-10-01 Sabic Global Technologies B.V. Feuilles multicouches, procédés de fabrication et articles formés à partir de celles-ci
CN113840725A (zh) * 2019-03-28 2021-12-24 高新特殊工程塑料全球技术有限公司 多层片材、制造方法和由其形成的制品
JP2021014549A (ja) * 2019-07-16 2021-02-12 Ｍｃｐｐイノベーション合同会社 レーザーダイレクトストラクチャリング用熱可塑性樹脂組成物及び成形体
JP7381232B2 (ja) 2019-07-16 2023-11-15 Ｍｃｐｐイノベーション合同会社 レーザーダイレクトストラクチャリング用熱可塑性樹脂組成物及び成形体
US11637365B2 (en) 2019-08-21 2023-04-25 Ticona Llc Polymer composition for use in an antenna system
US11258184B2 (en) 2019-08-21 2022-02-22 Ticona Llc Antenna system including a polymer composition having a low dissipation factor
US11705641B2 (en) 2019-08-21 2023-07-18 Ticoan Llc Antenna system including a polymer composition having a low dissipation factor
US11555113B2 (en) 2019-09-10 2023-01-17 Ticona Llc Liquid crystalline polymer composition
US11912817B2 (en) 2019-09-10 2024-02-27 Ticona Llc Polymer composition for laser direct structuring
US11646760B2 (en) 2019-09-23 2023-05-09 Ticona Llc RF filter for use at 5G frequencies
US11917753B2 (en) 2019-09-23 2024-02-27 Ticona Llc Circuit board for use at 5G frequencies
CN112708235A (zh) * 2019-10-24 2021-04-27 中国石油化工股份有限公司 一种lds电路制件及其制备方法
US11721888B2 (en) 2019-11-11 2023-08-08 Ticona Llc Antenna cover including a polymer composition having a low dielectric constant and dissipation factor
US11729908B2 (en) 2020-02-26 2023-08-15 Ticona Llc Circuit structure
US11728559B2 (en) 2021-02-18 2023-08-15 Ticona Llc Polymer composition for use in an antenna system
CN114950458A (zh) * 2022-07-01 2022-08-30 宁夏清研高分子新材料有限公司 一种lcp基lds复合材料和激光催化剂及其制备方法
US12035467B2 (en) 2023-06-27 2024-07-09 Ticona Llc Circuit structure

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