EP3231193A1 - Multi-layer composite for acoustic membranes - Google Patents

Multi-layer composite for acoustic membranes

Info

Publication number
EP3231193A1
EP3231193A1 EP15804082.4A EP15804082A EP3231193A1 EP 3231193 A1 EP3231193 A1 EP 3231193A1 EP 15804082 A EP15804082 A EP 15804082A EP 3231193 A1 EP3231193 A1 EP 3231193A1
Authority
EP
European Patent Office
Prior art keywords
layer
multilayer composite
composite according
cover
layers
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP15804082.4A
Other languages
German (de)
French (fr)
Inventor
Michael Egger
Gero Maatz
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tesa SE
Original Assignee
Tesa SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Tesa SE filed Critical Tesa SE
Publication of EP3231193A1 publication Critical patent/EP3231193A1/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • B32B27/28—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
    • B32B27/285—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 polyethers
    • 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
    • B32B27/286—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 polysulphones; polysulfides
    • 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
    • B32B27/32—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
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • 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
    • H—ELECTRICITY
    • H04—ELECTRIC COMMUNICATION TECHNIQUE
    • H04R—LOUDSPEAKERS, MICROPHONES, GRAMOPHONE PICK-UPS OR LIKE ACOUSTIC ELECTROMECHANICAL TRANSDUCERS; DEAF-AID SETS; PUBLIC ADDRESS SYSTEMS
    • H04R7/00—Diaphragms for electromechanical transducers; Cones
    • H04R7/02—Diaphragms for electromechanical transducers; Cones characterised by the construction
    • H—ELECTRICITY
    • H04—ELECTRIC COMMUNICATION TECHNIQUE
    • H04R—LOUDSPEAKERS, MICROPHONES, GRAMOPHONE PICK-UPS OR LIKE ACOUSTIC ELECTROMECHANICAL TRANSDUCERS; DEAF-AID SETS; PUBLIC ADDRESS SYSTEMS
    • H04R7/00—Diaphragms for electromechanical transducers; Cones
    • H04R7/02—Diaphragms for electromechanical transducers; Cones characterised by the construction
    • H04R7/04—Plane diaphragms
    • H04R7/06—Plane diaphragms comprising a plurality of sections or layers
    • H—ELECTRICITY
    • H04—ELECTRIC COMMUNICATION TECHNIQUE
    • H04R—LOUDSPEAKERS, MICROPHONES, GRAMOPHONE PICK-UPS OR LIKE ACOUSTIC ELECTROMECHANICAL TRANSDUCERS; DEAF-AID SETS; PUBLIC ADDRESS SYSTEMS
    • H04R7/00—Diaphragms for electromechanical transducers; Cones
    • H04R7/02—Diaphragms for electromechanical transducers; Cones characterised by the construction
    • H04R7/04—Plane diaphragms
    • H04R7/06—Plane diaphragms comprising a plurality of sections or layers
    • H04R7/10—Plane diaphragms comprising a plurality of sections or layers comprising superposed layers in contact
    • 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
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/26—Polymeric coating
    • 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
    • B32B2307/10—Properties of the layers or laminate having particular acoustical properties
    • 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
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/546—Flexural strength; Flexion stiffness
    • 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
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/56—Damping, energy absorption
    • 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
    • B32B2307/70—Other properties
    • B32B2307/732—Dimensional properties
    • 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
    • B32B2307/70—Other properties
    • B32B2307/738—Thermoformability
    • 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
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16C—SHAFTS; FLEXIBLE SHAFTS; ELEMENTS OR CRANKSHAFT MECHANISMS; ROTARY BODIES OTHER THAN GEARING ELEMENTS; BEARINGS
    • F16C2208/00—Plastics; Synthetic resins, e.g. rubbers
    • F16C2208/20—Thermoplastic resins
    • F16C2208/52—Polyphenylene sulphide [PPS]
    • H—ELECTRICITY
    • H04—ELECTRIC COMMUNICATION TECHNIQUE
    • H04R—LOUDSPEAKERS, MICROPHONES, GRAMOPHONE PICK-UPS OR LIKE ACOUSTIC ELECTROMECHANICAL TRANSDUCERS; DEAF-AID SETS; PUBLIC ADDRESS SYSTEMS
    • H04R2307/00—Details of diaphragms or cones for electromechanical transducers, their suspension or their manufacture covered by H04R7/00 or H04R31/003, not provided for in any of its subgroups
    • H04R2307/025—Diaphragms comprising polymeric materials
    • H—ELECTRICITY
    • H04—ELECTRIC COMMUNICATION TECHNIQUE
    • H04R—LOUDSPEAKERS, MICROPHONES, GRAMOPHONE PICK-UPS OR LIKE ACOUSTIC ELECTROMECHANICAL TRANSDUCERS; DEAF-AID SETS; PUBLIC ADDRESS SYSTEMS
    • H04R2499/00—Aspects covered by H04R or H04S not otherwise provided for in their subgroups
    • H04R2499/10—General applications
    • H04R2499/11—Transducers incorporated or for use in hand-held devices, e.g. mobile phones, PDA's, camera's

Definitions

  • the invention relates to a multilayer composite comprising at least one outer polyphenylene sulfide film for use as a membrane for electroacoustic transducers.
  • micro-speakers The generation of sound in mobile phones and smartphones for the reproduction of speech, ringtones, music, etc. is done by small electro-acoustic transducers, so-called micro-speakers.
  • microspeakers are becoming ever smaller and flatter due to the design requirements for the corresponding electronic devices, but are also intended to be operated at a higher output, the temperature load on the microspeaker, and in particular its membrane, is increasing more and more.
  • the demands on the acoustic properties of the loudspeakers which are increasingly being used, for example, in smartphones for the loud playing of music and at the same time have a good sound quality, are also increasing.
  • the demands on the mechanical strength and acoustic quality of the micro speaker membrane have increased enormously in recent years.
  • a loudspeaker diaphragm should generally be stiff and light on the one hand in order to produce a high sound pressure and to cover a wide frequency range, but on the other hand be well damped at the same time to show the smoothest possible frequency response. Since the properties stiff, light and well damped give a constructive contradiction and not all can be fulfilled simultaneously (the higher the stiffness, the lower the damping and vice versa) In general, compromises are made in terms of stiffness and damping of the membrane material in each membrane or rigid materials combined with good damping materials. Therefore, multi-layer composites (in particular multi-layer laminates) are often used, which are then formed into the membrane. The multi-layer composites usually comprise the membrane stiffening or stabilizing layers and damping layers. The rigid films used in today's multi-layer composites themselves contribute very little to the damping.
  • US Pat. No. 7,726,441 B describes a membrane composed of a multilayer composite of two rigid polymer films and a damping adhesive layer lying between these films.
  • polyphenylene sulfide plastics are known in the prior art (for polyphenylene sulfide, the term PPS is also common and is used in this document).
  • PPS polyphenylene sulfide
  • cover layer material usually have unsatisfactory acoustic distortions, so that there is aural impairment of the acoustic signals.
  • total harmonic distortion commonly referred to in the art as “Total Harmony Distortion” or “THD” for short Designation is therefore also used in the context of this document.
  • the THD is defined as the ratio of the summed powers Ph of all harmonics to the power of the fundamental vibration Pi and is usually given as a percentage:
  • THD [%] (P h / Pi) * 100 Plastics used for the realization of optimized acoustic properties of loudspeaker membranes as cover sheet material, such as polyetherimide (PEI), polyarylate (PAR) or polyetheretherketone (PEEK), are considerably more expensive than PPS.
  • PEI polyetherimide
  • PAR polyarylate
  • PEEK polyetheretherketone
  • PPS preparation of PPS, even for such films as are used for membranes of the aforementioned type, is usually carried out by polycondensation of phenylenedihalides, in particular dichlorobenzene, and sodium sulfide in a high-boiling, dipolar aprotic solvent such as N-methylpyrrolidone.
  • phenylenedihalides in particular dichlorobenzene
  • sodium sulfide in a high-boiling, dipolar aprotic solvent such as N-methylpyrrolidone.
  • EP 0737705 A An alternative method is shown in EP 0737705 A, in which the preparation of the polymer is carried out from a prepolymer having halogen end groups.
  • halogen-containing (by-products) The manufacturing process requires that a relatively high proportion of halogen-containing (by-products) remain, which remains in the polymer in considerable quantities, as a result of which commercially available polyphenylene sulfide films have a relatively high content of halogen, which is quantitatively determined by conventional analysis methods This is usually chlorine.
  • halogen contents of more than 600 ppm, generally even more than 900 ppm.
  • One ppm corresponds to one milligram of the halogen per kilogram of the analyzed PPS film material as used.
  • the object of the invention was to provide composite film systems for the production of loudspeaker membranes (acoustic membranes), which are inexpensive and therefore economically interesting, but in which the acoustic membranes produced therefrom have improved acoustic properties compared to commercially available PPS films ,
  • the membranes should not lose their good properties in terms of high flexural stiffness, low density and high internal damping.
  • the object is achieved if, as material for the cover films of such membranes, although PPS continues to be used, but here selects a PPS having a total halogen content of not more than 550 ppm.
  • PPS a PPS having a total halogen content of not more than 550 ppm.
  • the invention relates to a multilayer composite for use as or for producing a membrane for electroacoustic transducers, comprising at least a first and a second outer layer (hereinafter referred to as cover layer), optionally a damping layer disposed between these cover layers, wherein at least one of Cover layers (“first cover layer”) consists of a polyphenylene sulfide plastic, and wherein the halogen content of the polyphenylene sulfide plastic (“PPS plastic”) does not exceed 550 ppm.
  • first cover layer consists of a polyphenylene sulfide plastic, and wherein the halogen content of the polyphenylene sulfide plastic (“PPS plastic”) does not exceed 550 ppm.
  • the multilayer composite may be a two-layer composite (excluding cover layers), it may be a three-layer composite (in particular cover layer damping layer cover layer), or it may comprise more than three layers, wherein advantageously at least one of the layers located between the cover layers is a cushioning layer.
  • the at least one damping layer in a three-layer or multi-layer composite is particularly advantageously adhesive layers, in particular PSA layers.
  • the first cover layer has a thickness of 1 to 50 ⁇ , very preferably from 1 to 5 ⁇ .
  • Suitable films for use as a second cover layer are, for example, films of polyetheretherketone (PEEK), commercial polyphenylene sulphide (PPS), polyethylene naphthalate (PEN), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyarylate (PAR), polyimide (PI), polyetherimide ( PEI), Polyphenylsulfone (PPSU), Polyethersulfone (PES), Polysulfone (PSU) or Thermoplastic Polyurethane (TPU)
  • PEEK polyetheretherketone
  • PPS polyethylene naphthalate
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • PAR polyarylate
  • PI polyimide
  • PEI polyetherimide
  • PEI Polyphenylsulfone
  • PES Polyethersulfone
  • PSU Polysulfone
  • TPU Thermoplastic Polyurethane
  • the second cover layer is particularly advantageous according to the invention to also produce the second cover layer from low-halogen PPS, so that both cover layers of the multi-layer composite consist of polyphenylene sulfide plastic whose halogen content does not exceed 550 ppm in each case.
  • the second cover layer has a thickness of 1 to 50 ⁇ , preferably from 1 to 5 ⁇ on.
  • both cover layers are made of the identical low-halogen PPS plastic, and / or the thicknesses of both cover layers are the same, so that in particular a symmetrical - or at least symmetrical with respect to the outer cover layers - multi-layer composite is present.
  • the multilayer composite of the invention consists of two laminated plastic films, of which at least one of the films - optionally also both films - consists of polyphenylene sulfide plastic whose halogen content does not exceed 550 ppm.
  • Such two-sheet systems can be used particularly well for membranes when the two-layer composite has sufficient damping properties without additional damping layer and / or the requirements for the damping in the application are low.
  • one of the films can be softened and / or melted in order to improve the adhesion to the other film.
  • a film of thermoplastic polyurethane is particularly advantageous.
  • a particularly advantageous embodiment of a two-layer composite is therefore one comprising a TPU film and a film of halogen-reduced PPS.
  • the membrane should be well damped to show the smoothest possible frequency response.
  • a damping layer which may be constructed in one layer or in turn multi-layered.
  • the damping layer therefore comprises a single-layer or multi-layer double-sided adhesive tape, in particular pressure-sensitive adhesive tape;
  • the damping layer is formed by a single-layer or multilayer double-sided adhesive tape, in particular pressure-sensitive adhesive tape.
  • Pressure-sensitive adhesive tape in addition to its damping effect, is able to cause the cohesion of the layers in the composite due to its (self) adhesive properties.
  • the damping layer itself is single-layered, so that the multi-layer composite is a three-layer composite.
  • the damping layer is then preferably a layer of a pressure-sensitive adhesive.
  • the multi-layer composite has a symmetrical three-layer structure of the kind of topcoat pressure-sensitive adhesive topcoat in which the outer cover layers are identical in chemical composition and thickness.
  • the layer thickness of the (adhesive) adhesive layer in three-layer composites is advantageously 2 ⁇ m to 100 ⁇ m, preferably 5 ⁇ m to 50 ⁇ m, particularly preferably 10 ⁇ m to 30 ⁇ m.
  • a further variant of the invention is represented by a - five-layer structure - symmetrical or asymmetrical, wherein the cover layer has an inner support or stabilization layer, for example of a film of polyetheretherketone (PEEK), commercial polyphenylene sulfide (PPS), polyethylene naphthalate (PEN), Polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyarylate (PAR), polyimide (PI), polyetherimide (PEI), polyphenylsulfone (PPSU), polyethersulfone (PES), polysulfone (PSU) or thermoplastic polyurethane (TPU), or which are particularly preferred also formed from a film of a low halogenated polyphenylene sulfide (PPS) having a halogen content of less than 550 ppm.
  • PEEK polyetheretherketone
  • PPS polyetheretherketone
  • PEN polyethylene naphthalate
  • PET Polyethylene
  • both adhesive (adhesive) layers are chemically identical and / or the same thickness.
  • the (adhesive) adhesive layers can also be selected differently with regard to their chemical nature and / or their thickness.
  • the thickness of the inner carrier or stabilizing layer is preferably 1 to 50 ⁇ m, preferably 1 to 30 ⁇ m, particularly preferably 1 to 5 ⁇ m.
  • the thicknesses of the (adhesive) adhesive layer layers are preferably 1 to 100 ⁇ , preferably 1 to 50 ⁇ , particularly preferably 2 to 40 ⁇ .
  • pressure-sensitive adhesives also referred to as self-adhesives or PSA from English: "pressure sensitive adhesives”
  • PSA pressure sensitive adhesives
  • those polymeric compositions are referred to - optionally by suitable addition with other components, such as adhesive resins - at the application temperature (unless otherwise defined, in Room temperature) are permanently tacky and permanently tacky and adhere to a variety of surfaces on contact, in particular adhere immediately (a so-called “tack” [stickiness or Anutzklebrtechnik] have). They are able, even at the application temperature without activation by solvents or by heat - but usually by the influence of a more or less high pressure - sufficient to wet a substrate to be bonded so that between the mass and the substrate for the adhesion can form sufficient interactions. Factors influencing this process include pressure and contact time.
  • the special properties of the PSAs are due in particular to their viscoelastic properties.
  • acrylate PSAs are used for the adhesive layers.
  • These are adhesives whose polymer base are polymers of acrylic monomers - these are in particular acrylic and methacrylic acid, the esters of the aforementioned acids and the copolymerizable further derivatives of the aforementioned acids understood -, the acrylic monomers - optionally together with other comonomers - in the polymerization at least be used in an amount that the properties of the adhesive are thereby determined significantly.
  • pressure-sensitive adhesives having an acrylic monomer content in the polymerization of at least 50% by weight, of at least 80% by weight or of 100% by weight (pure acrylate systems) can be used.
  • adhesives which are familiar to the person skilled in the art, in particular pressure-sensitive adhesives, are likewise possible and can be used in the context of the invention, with particular preference being given to those which have good adhesion to PPS and, moreover, have good damping properties.
  • silicone adhesives and / or polyurethane adhesives and / or rubber adhesives in particular silicone pressure-sensitive adhesives, polyurethane pressure-sensitive adhesives or rubber pressure-sensitive adhesives, can also be used in particular.
  • the PSA is applied either directly to one of the two outer layers in the desired layer thickness using the application method familiar to those skilled in the art, or indirectly by coating a temporary transfer support such as siliconized paper or siliconized film, laminating with the first of the two film layers and masking the temporary transfer support.
  • the second of the two film layers can be fed directly to the pressure-sensitive adhesive side of the one-sided laminated composite.
  • laminating devices that connect the webs of material between rubber cylinders or a steel and a rubber cylinder with variably adjustable contact pressure continuously.
  • membranes for electroacoustic transducers in particular loudspeaker membranes
  • embossing or thermoforming of a multilayer composite according to the invention whereby this composite is brought into a specific three-dimensional form.
  • the multi-layer composite is heated, for example in a thermoform and pressed by applying pressure and / or vacuum in the form of the finished membrane.
  • the multilayer composites according to the invention can be used excellently in a process for the production of membranes for electroacoustic transducers, wherein they are subjected to the process of multicavity thermoforming.
  • the multilayer laminate is placed on the heatable thermoforming, which contains recesses with the negative impression of the membrane to be formed.
  • the multi-layer laminate is e.g. heated by IR radiation and thereby softened and then pressed from above with compressed air into the recesses.
  • the softened multi-layer laminate can also be pressed into the molds with a stamp made of silicone or foamed silicone.
  • the halogen content of a halogen-reduced PPS film was 532 ppm.
  • three-layer composites each consisted of a 4 ⁇ m thick PPS film, each of a 10 ⁇ m acrylate or silicone damping layer (each standard pressure-sensitive adhesive, identical in each case in Example 1 and Comparative Example 1 and in Example 2 and Comparative Example) 2) and 4 ⁇ thick PPS film produced, wherein for the inventive examples, halogen-reduced PPS films and for comparative experiments standard PPS films were used (see Table 1).
  • the resonant frequency of both loudspeakers is 450 Hz.
  • the THD curves of the loudspeakers with the multi-layer composite diaphragms made of halogen-reduced PPS foil was between 0 and 0 for the composites with acrylate damping layer as well as for the composites with silicone damping layer. 1 and 10 kHz below the THD curves of the speakers with the membranes made of commercially available PPS film.
  • Table 1 shows examples of THD values at frequencies below the resonant frequency. Table 1 . Results of the THD determination.

Abstract

The invention relates to a multi-layer composite for use as a membrane for electroacoustic transducers, comprising at least one first and one second outer layer (cover layer ), at least one of the cover layers (first cover layer) being made from a polypropylene sulfide-plastic, characterized such that the halogen content of the polyphenylene sulfide plastic (PPS-plastic ) does not exceed 550 ppm.

Description

tesa SE  tesa SE
Quickbornstraße 24  Quickbornstraße 24
20253 Hamburg  20253 Hamburg
Mehrschicht-Verbund für akustische Membranen Multi-layer composite for acoustic membranes
Die Erfindung betrifft einen Mehrschicht-Verbund umfassend zumindest eine außenliegende Polyphenylensulfid-Folie zur Verwendung als Membran für elektroakustische Wandler. The invention relates to a multilayer composite comprising at least one outer polyphenylene sulfide film for use as a membrane for electroacoustic transducers.
Die Schallerzeugung in Mobiltelefonen und Smartphones zur Wiedergabe von Sprache, Klingeltönen, Musik etc. erfolgt durch kleine elektroakustische Wandler, sogenannte Mikrolautsprecher. Die Größe der Membranen solcher Mikrolautsprecher, die auch in Kopfhörern, Notebooks, LCD-Fernsehern oder Personal Digital Assistants (PDAs) eingesetzt werden, liegt typischerweise im Bereich 20 mm2 bis 900 mm2. The generation of sound in mobile phones and smartphones for the reproduction of speech, ringtones, music, etc. is done by small electro-acoustic transducers, so-called micro-speakers. The size of the membranes of such microspeakers, which are also used in headphones, notebooks, LCD TVs or personal digital assistants (PDAs), is typically in the range of 20 mm 2 to 900 mm 2 .
Da Mikrolautsprecher aufgrund der Design-Anforderungen an die entsprechenden elektronischen Geräte immer kleiner und flacher werden, dabei aber zusätzlich mit höherer Leistung betrieben werden sollen, nimmt die Temperaturbelastung des Mikrolautsprechers und insbesondere seiner Membran immer mehr zu. Gleichzeitig steigen auch die Anforderungen an die akustischen Eigenschaften der Lautsprecher, die zum Beispiel in Smartphones vermehrt auch zum lauten Abspielen von Musik eingesetzt werden und dabei auch eine gute Klangqualität haben sollten. Die Anforderungen an die mechanische Belastbarkeit und akustische Güte der Mikrolautsprecher-Membran sind dadurch in den letzten Jahren enorm gestiegen. Since microspeakers are becoming ever smaller and flatter due to the design requirements for the corresponding electronic devices, but are also intended to be operated at a higher output, the temperature load on the microspeaker, and in particular its membrane, is increasing more and more. At the same time, the demands on the acoustic properties of the loudspeakers, which are increasingly being used, for example, in smartphones for the loud playing of music and at the same time have a good sound quality, are also increasing. The demands on the mechanical strength and acoustic quality of the micro speaker membrane have increased enormously in recent years.
Eine Lautsprechermembran sollte allgemein einerseits möglichst steif und leicht sein, um einen hohen Schalldruck zu erzeugen und einen breiten Frequenzbereich abzudecken, andererseits aber gleichzeitig gut gedämpft sein, um einen möglichst glatten Frequenzgang zu zeigen. Da die Eigenschaften steif, leicht und gut gedämpft einen konstruktiven Widerspruch ergeben und nicht alle gleichzeitig erfüllt werden können (je höher die Steifigkeit, desto geringer die Dämpfung und umgekehrt), müssen generell bei jeder Membran Kompromisse bezüglich der Steifigkeit und der Dämpfung des Membranmaterials eingegangen werden oder steife Materialien mit gut dämpfenden Materialien kombiniert werden. Daher werden vielfach Mehrschicht- Verbunde (insbesondere Mehrschichtlaminate) eingesetzt, die dann zur Membran ausgeformt werden. Die Mehrschicht-Verbunde umfassen dabei in der Regel die Membran versteifende bzw. stabilisierende Schichten sowie dämpfende Schichten. Die in den heute marktüblichen Mehrschicht-Verbunden verwendeten steifen Folien tragen selber sehr wenig zur Dämpfung bei. A loudspeaker diaphragm should generally be stiff and light on the one hand in order to produce a high sound pressure and to cover a wide frequency range, but on the other hand be well damped at the same time to show the smoothest possible frequency response. Since the properties stiff, light and well damped give a constructive contradiction and not all can be fulfilled simultaneously (the higher the stiffness, the lower the damping and vice versa) In general, compromises are made in terms of stiffness and damping of the membrane material in each membrane or rigid materials combined with good damping materials. Therefore, multi-layer composites (in particular multi-layer laminates) are often used, which are then formed into the membrane. The multi-layer composites usually comprise the membrane stiffening or stabilizing layers and damping layers. The rigid films used in today's multi-layer composites themselves contribute very little to the damping.
So beschreibt die US 7,726,441 B eine Membran aus einem Mehrschicht-Verbund aus zwei steifen Polymerfolien und einer zwischen diesen Folien liegenden dämpfenden Klebmasse-Schicht. US 8,189,851 B beschreibt die Verwendung von weichen Haftklebmassen als Dämpfungsschichten in Mehrschicht-Verbunden und nennt als Maß für die Dämpfung des mehrschichtigen Membran-Gesamtaufbaues den mechanischen Verlustfaktor (Tangens delta; tan δ) ausgehend vom Elastizitätsmodul E (Youngscher Modul). Dieser ist definiert als das Verhältnis von Verlustmodul E" und Speichermodul E': tan δ = E7E' und soll in einem relevanten Frequenzintervall einen Mindestwert haben.  For example, US Pat. No. 7,726,441 B describes a membrane composed of a multilayer composite of two rigid polymer films and a damping adhesive layer lying between these films. US Pat. No. 8,189,851 B describes the use of soft pressure-sensitive adhesives as damping layers in multilayer composites and mentions the mechanical loss factor (tangent delta; tan δ) as a measure of the attenuation of the multilayer overall membrane structure starting from the modulus of elasticity E (Young's modulus). This is defined as the ratio of loss modulus E "and storage modulus E ': tan δ = E7E' and should have a minimum value in a relevant frequency interval.
Als Polymerfolienmaterial für die steifen Polymerfolien (Deckschichten der Membran) sind nach dem Stand der Technik unter anderem Polyphenylensulfid-Kunststoffe bekannt (für Polyphenylensulfid ist auch die Bezeichnung PPS gebräuchlich und wird im Rahmen dieser Schrift verwendet). (Mikro-)Lautsprecher, deren Membranen mit PPS als Deckschichtmaterial hergestellt sind, besitzen jedoch üblicherweise unbefriedigende akustische Verzerrungen, so dass es zur klanglichen Beeinträchtigung der akustischen Signale kommt. Eine Größe, die die nichtlineare Verzerrung des Lautsprechers quantifiziert und am Lautsprecher einfach bestimmt werden kann, ist die sogenannte„Gesamte harmonische Verzerrung", in Fachkreisen üblicherweise mit dem englischen Ausdruck„Total Harmonie Distortion" oder kurz „THD" bezeichnet. Diese in Fachkreisen übliche Bezeichnung wird daher auch im Rahmen dieser Schrift verwendet. As polymer film material for the stiff polymer films (cover layers of the membrane), inter alia, polyphenylene sulfide plastics are known in the prior art (for polyphenylene sulfide, the term PPS is also common and is used in this document). However, (micro-) speakers whose membranes are made with PPS as cover layer material, usually have unsatisfactory acoustic distortions, so that there is aural impairment of the acoustic signals. A quantity that can be used to quantify the loudspeaker's nonlinear distortion and can be easily determined on the loudspeaker is the so-called "total harmonic distortion", commonly referred to in the art as "Total Harmony Distortion" or "THD" for short Designation is therefore also used in the context of this document.
Die THD ist definiert als das Verhältnis der summierten Leistungen Ph aller Oberschwingungen zur Leistung der Grundschwingung Pi und wird üblicherweise in Prozent angegeben:  The THD is defined as the ratio of the summed powers Ph of all harmonics to the power of the fundamental vibration Pi and is usually given as a percentage:
THD [%] = (Ph/Pi) * 100 Kunststoffe, die für die Realisierung optimierter akustischer Eigenschaften der Lautsprechermembranen als Deckfolienmaterial verwendet werden, wie etwa Polyetherimid (PEI), Polyarylat (PAR) oder Polyetheretherketon (PEEK), sind erheblich teurer als PPS. THD [%] = (P h / Pi) * 100 Plastics used for the realization of optimized acoustic properties of loudspeaker membranes as cover sheet material, such as polyetherimide (PEI), polyarylate (PAR) or polyetheretherketone (PEEK), are considerably more expensive than PPS.
Die Herstellung von PPS, auch für solche Folien, wie sie für Membranen der vorgenannten Art eingesetzt werden, erfolgt üblicherweise durch Polykondensation aus Phenylendihalogeniden, insbesondere Dichlorbenzol, und Natriumsulfid in einem hochsiedenden, dipolar aprotischen Lösungsmittel wie beispielsweise N- Methylpyrrolidon. Ein solcher Prozess wird beispielsweise in US 4,910,294 beschrieben. Ein alternatives Verfahren zeigt die EP 0737705 A, hier erfolgt die Herstellung des Polymers aus einem Präpolymer mit Halogen-Endgruppen. Durch das Herstellverfahren ist bedingt, dass ein relativ hoher Anteil an halogenhaltigen (Nebenprodukten entsteht, die in beträchtlicher Menge im Polymer verbleiben. Dies hat zur Folge, dass handelsübliche Polyphenylensulfid-Folien einen relativ hohen Anteil an Halogen aufweisen, das durch übliche Analyseverfahren quantitativ bestimmt werden kann. In der Regel handelt es sich dabei um Chlor. The preparation of PPS, even for such films as are used for membranes of the aforementioned type, is usually carried out by polycondensation of phenylenedihalides, in particular dichlorobenzene, and sodium sulfide in a high-boiling, dipolar aprotic solvent such as N-methylpyrrolidone. Such a process is described, for example, in US 4,910,294. An alternative method is shown in EP 0737705 A, in which the preparation of the polymer is carried out from a prepolymer having halogen end groups. The manufacturing process requires that a relatively high proportion of halogen-containing (by-products) remain, which remains in the polymer in considerable quantities, as a result of which commercially available polyphenylene sulfide films have a relatively high content of halogen, which is quantitatively determined by conventional analysis methods This is usually chlorine.
Industrieübliche PPS-Produkte haben regelmäßig Halogenanteile von mehr als 600 ppm, in der Regel sogar von mehr als 900 ppm. Ein ppm entspricht dabei einem Milligramm des Halogens auf ein Kilogramm des analysierten PPS-Folien-Materials wie eingesetzt.  Industry-standard PPS products regularly have halogen contents of more than 600 ppm, generally even more than 900 ppm. One ppm corresponds to one milligram of the halogen per kilogram of the analyzed PPS film material as used.
Ein Zusammenhang des Halogengehalts von PPS-Folien, die in akustischen Membranen eingesetzt werden, mit den Eigenschaften dieser Membranen für die Verwendung als Lautsprecher wurde bisher nicht diskutiert.  A correlation of the halogen content of PPS films used in acoustic membranes with the properties of these membranes for use as loudspeakers has not previously been discussed.
Aufgabe der Erfindung war es, Folien-Verbundsysteme für die Herstellung von Lautsprecher-Membranen (akustischen Membranen) anzubieten, die zwar preiswert und daher wirtschaftlich interessant sind, bei denen die daraus hergestellten akustischen Membranen aber im Vergleich zu handelsüblichen PPS-Folien verbesserte akustische Eigenschaften aufweisen. Die Membranen sollen dabei ihre guten Eigenschaften bezüglich hoher Biegesteifigkeit, geringer Dichte sowie hoher innerer Dämpfung nicht verlieren. The object of the invention was to provide composite film systems for the production of loudspeaker membranes (acoustic membranes), which are inexpensive and therefore economically interesting, but in which the acoustic membranes produced therefrom have improved acoustic properties compared to commercially available PPS films , The membranes should not lose their good properties in terms of high flexural stiffness, low density and high internal damping.
In überraschender Weise wird die Aufgabe gelöst, wenn man als Material für die Deckfolien solcher Membranen zwar weiterhin PPS einsetzt, hier aber ein PPS mit einem Gesamt-Halogengehalt von nicht mehr als 550 ppm wählt. Messungen haben ergeben, dass die durch die THD beschriebene Verzerrung eines Lautsprechers bei Verwendung einer solchen Membran signifikant geringer war als bei Verwendung einer Membran, deren Deckschicht aus handelsüblichem PPS besteht. Ein solcher Einfluss war für den Fachmann nicht vorhersehbar. Surprisingly, the object is achieved if, as material for the cover films of such membranes, although PPS continues to be used, but here selects a PPS having a total halogen content of not more than 550 ppm. Have measurements revealed that the distortion of a loudspeaker described by the THD when using such a membrane was significantly lower than when using a membrane whose top layer consists of commercial PPS. Such an influence was unforeseeable for the skilled person.
Dementsprechend betrifft die Erfindung einen Mehrschicht-Verbund zur Verwendung als bzw. zur Herstellung einer Membran für elektroakustische Wandler, zumindest umfassend eine erste und eine zweite außenliegende Schicht (im folgenden als Deckschicht bezeichnet), gegebenenfalls eine zwischen diesen Deckschichten angeordnete Dämpfungsschicht, wobei zumindest eine der Deckschichten („erste Deckschicht") aus einem Polyphenylensulfid-Kunststoff besteht, und wobei der Halogengehalt des Polyphenylensulfid-Kunststoffs („PPS-Kunststoff") 550 ppm nicht übersteigt. Accordingly, the invention relates to a multilayer composite for use as or for producing a membrane for electroacoustic transducers, comprising at least a first and a second outer layer (hereinafter referred to as cover layer), optionally a damping layer disposed between these cover layers, wherein at least one of Cover layers ("first cover layer") consists of a polyphenylene sulfide plastic, and wherein the halogen content of the polyphenylene sulfide plastic ("PPS plastic") does not exceed 550 ppm.
Optional können zwischen den Deckschichten weitere Schichten angeordnet sein. Der Mehrschichtverbund kann ein Zweischichtverbund (ausschließlich Deckschichten) sein, er kann ein Dreischichtverbund (insbesondere Deckschicht-Dämpfungsschicht- Deckschicht) sein, oder er umfasst mehr als drei Schichten, wobei vorteilhaft zumindest eine der zwischen den Deckschichten befindliche Schicht eine Dämpfungsschicht ist. Bei der zumindest einen Dämfungsschicht (im Drei- oder Mehrschichtverbund) handelt es sich insbesondere vorteilhaft um Klebemassenschichten, insbesondere Haftklebemassenschichten.  Optionally, further layers may be arranged between the cover layers. The multilayer composite may be a two-layer composite (excluding cover layers), it may be a three-layer composite (in particular cover layer damping layer cover layer), or it may comprise more than three layers, wherein advantageously at least one of the layers located between the cover layers is a cushioning layer. The at least one damping layer (in a three-layer or multi-layer composite) is particularly advantageously adhesive layers, in particular PSA layers.
Bevorzugt hat die erste Deckschicht eine Dicke von 1 bis 50 μηη, sehr bevorzugt von von 1 bis 5 μηη. Preferably, the first cover layer has a thickness of 1 to 50 μηη, very preferably from 1 to 5 μηη.
Geeignete Folien für den Einsatz als zweite Deckschicht sind beispielsweise Folien aus Polyetheretherketon (PEEK), handelsüblichem Polyphenylensulfid (PPS), Polyethylennaphthalat (PEN), Polyethylenterephthalat (PET), Polybutylenterephthalat (PBT), Polyarylat (PAR), Polyimid (PI), Polyetherimid (PEI), Polyphenylsulfon (PPSU), Polyethersulfon (PES), Polysulfon (PSU) oder Thermoplastischem Polyurethan (TPU) Suitable films for use as a second cover layer are, for example, films of polyetheretherketone (PEEK), commercial polyphenylene sulphide (PPS), polyethylene naphthalate (PEN), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyarylate (PAR), polyimide (PI), polyetherimide ( PEI), Polyphenylsulfone (PPSU), Polyethersulfone (PES), Polysulfone (PSU) or Thermoplastic Polyurethane (TPU)
In besonderer Weise erfindungsgemäß vorteilhaft ist es aber, auch die zweite Deckschicht aus halogenarmen PPS herzustellen, so dass beide Deckschichten des Mehrschicht-Verbundes aus Polyphenylensulfid-Kunststoff bestehen, deren Halogengehalt jeweils 550 ppm nicht übersteigt. In günstiger Weise weist auch die zweite Deckschicht eine Dicke von 1 bis 50 μηη, bevorzugt von 1 bis 5 μηι auf. However, it is particularly advantageous according to the invention to also produce the second cover layer from low-halogen PPS, so that both cover layers of the multi-layer composite consist of polyphenylene sulfide plastic whose halogen content does not exceed 550 ppm in each case. Conveniently, the second cover layer has a thickness of 1 to 50 μηη, preferably from 1 to 5 μηι on.
In einer besonders vorteilhaften Ausführungsform sind beide Deckschichten aus dem identischen halogenarmen PPS-Kunststoff hergestellt, und/oder die Dicken beider Deckschichten sind gleich, so dass insbesondere ein symmetrischer - oder zumindest bezüglich der äußeren Deckschichten symmetrischer - Mehrschicht-Verbund vorliegt. In a particularly advantageous embodiment, both cover layers are made of the identical low-halogen PPS plastic, and / or the thicknesses of both cover layers are the same, so that in particular a symmetrical - or at least symmetrical with respect to the outer cover layers - multi-layer composite is present.
In einer Ausführungsvariante besteht der erfindungsgemäße Mehrschicht-Verbund aus zwei zusammenlaminierten Kunststofffolien, von denen zumindest eine der Folien - gegebenenfalls auch beide Folien - aus Polyphenylensulfid-Kunststoff besteht, deren Halogengehalt 550 ppm nicht übersteigt. Solche Zweifolien-systeme lassen sich dann besonders gut für Membranen einsetzen, wenn der Zweischicht-Verbund auch ohne zusätzliche Dämpfungsschicht hinreichend dämpfende Eigenschaften aufweist und/oder die Anforderungen an die Dämpfung in der Anwendung gering sind. In one embodiment, the multilayer composite of the invention consists of two laminated plastic films, of which at least one of the films - optionally also both films - consists of polyphenylene sulfide plastic whose halogen content does not exceed 550 ppm. Such two-sheet systems can be used particularly well for membranes when the two-layer composite has sufficient damping properties without additional damping layer and / or the requirements for the damping in the application are low.
Insbesondere ist es vorteilhaft, wenn bei der Herstellung des Zweischicht-Verbundes eine der Folien erweicht und/oder angeschmolzen werden kann, um die Haftung an die andere Folie zu verbessern. Dafür eignet sich insbesondere vorteilhaft eine Folie aus thermoplastischem Polyurethan. Eine besonders vorteilhafte Ausgestaltung eines Zweischicht-Verbundes ist daher eine solche umfassend eine TPU-Folie und eine Folie aus Halogengehalt-reduziertem PPS. In particular, it is advantageous if, in the production of the two-layer composite, one of the films can be softened and / or melted in order to improve the adhesion to the other film. For this purpose, a film of thermoplastic polyurethane is particularly advantageous. A particularly advantageous embodiment of a two-layer composite is therefore one comprising a TPU film and a film of halogen-reduced PPS.
Wie eingangs ausgeführt sollte die Membran gut gedämpft sein, um einen möglichst glatten Frequenzgang zu zeigen. Zwischen den beiden Deckschichten des Mehrschicht-Verbundes befindet sich daher bevorzugt eine Dämpfungsschicht, die einschichtig oder ihrerseits mehrschichtig aufgebaut sein kann. Ein Maß für die Dämpfung des mehrschichtigen Membran-Gesamtaufbaues ist der mechanische Verlustfaktor (Tangens delta; tan δ) der durch das Verhältnis von Verlustmodul E" und Speichermodul E' definiert ist: tan δ = E7E'. As mentioned at the beginning, the membrane should be well damped to show the smoothest possible frequency response. Between the two cover layers of the multi-layer composite is therefore preferably a damping layer, which may be constructed in one layer or in turn multi-layered. A measure of the attenuation of the multilayer membrane overall structure is the mechanical loss factor (tangent delta; tan δ) which is defined by the ratio of loss modulus E "and storage modulus E ': tan δ = E7E'.
Es ist bekannt, dass Klebemassen, insbesondere Haftklebemassen, die Anforderungen an die Dämpfungsschicht erfüllen können und für eine hohe Dämpfung im Mehrschicht-Verbund sorgen können. In einer bevorzugten Vorgehensweise umfasst die Dämpfungsschicht daher ein einschichtiges oder mehrschichtiges doppelseitig klebendes Klebeband, insbesondere Haftklebeband; insbesondere wird die Dämpfungsschicht durch ein einschichtiges oder mehrschichtiges doppelseitig klebendes Klebeband, insbesondere Haftklebeband, gebildet. Ein solches Haftklebeband ist zusätzlich zu seiner dämpfenden Wirkung in der Lage, aufgrund seiner (selbst-)klebenden Eigenschaften den Zusammenhalt der Schichten im Verbund zu bewirken. It is known that adhesives, in particular pressure-sensitive adhesives, can meet the requirements of the damping layer and can provide high damping in the multilayer composite. In a preferred procedure, the damping layer therefore comprises a single-layer or multi-layer double-sided adhesive tape, in particular pressure-sensitive adhesive tape; In particular, the damping layer is formed by a single-layer or multilayer double-sided adhesive tape, in particular pressure-sensitive adhesive tape. Such Pressure-sensitive adhesive tape, in addition to its damping effect, is able to cause the cohesion of the layers in the composite due to its (self) adhesive properties.
In einer bevorzugten Ausführungsvariante ist die Dämpfungsschicht selbst einschichtig, so dass es sich bei dem Mehrschicht-Verbund um einen Dreischicht- Verbund handelt. Bevorzugt ist die Dämpfungsschicht dann eine Schicht einer Haftklebemasse. In sehr bevorzugter Weise hat der Mehrschicht-Verbund einen symmetrischen Dreischichtaufbau der Art Deckschicht-Haftklebemasse-Deckschicht, bei dem die äußeren Deckschichten identisch in ihrer chemischen Zusammensetzung und Dicke sind.  In a preferred embodiment variant, the damping layer itself is single-layered, so that the multi-layer composite is a three-layer composite. The damping layer is then preferably a layer of a pressure-sensitive adhesive. Most preferably, the multi-layer composite has a symmetrical three-layer structure of the kind of topcoat pressure-sensitive adhesive topcoat in which the outer cover layers are identical in chemical composition and thickness.
Die Schichtdicke der (Haft-)Klebemassenschicht in Dreischicht-Verbunden beträgt vorteilhaft 2 μηη bis 100 μηη, bevorzugt 5 μηη bis 50 μηη, besonders bevorzugt 10 μηη bis 30 μηι.  The layer thickness of the (adhesive) adhesive layer in three-layer composites is advantageously 2 μm to 100 μm, preferably 5 μm to 50 μm, particularly preferably 10 μm to 30 μm.
Eine weitere Variante der Erfindung wird durch einen - symmetrischen oder unsymmetrischen - Fünfschichtaufbau wiedergegeben, wobei die Deckschicht eine innere Träger- oder Stabilisierungsschicht aufweist, die zum Beispiel aus einer Folie aus Polyetheretherketon (PEEK), handelsüblichem Polyphenylensulfid (PPS), Polyethylennaphthalat (PEN), Polyethylenterephthalat (PET), Polybutylenterephthalat (PBT), Polyarylat (PAR), Polyimid (PI), Polyetherimid (PEI), Polyphenylsulfon (PPSU), Polyethersulfon (PES), Polysulfon (PSU) oder Thermoplastischem Polyurethan (TPU) besteht oder die insbesondere bevorzugt ebenfalls aus einer Folie aus einem halogenarmen Polyphenylensulfid (PPS) mit einem Halogengehalt von weniger als 550 ppm gebildet wird. Zwischen dieser inneren Träger- bzw. Stabilisierungsschicht und jeder äußeren Deckschicht ist jeweils eine (Haft-)Klebemassenschicht vorgesehen. Bevorzugt sind beide (Haft-)Klebemassenschichten chemisch identisch und/oder gleich dick. Die (Haft-)Klebemassenschichten können aber auch in Bezug auf ihre chemische Natur und/oder auf ihre Dicke unterschiedlich ausgewählt sein. A further variant of the invention is represented by a - five-layer structure - symmetrical or asymmetrical, wherein the cover layer has an inner support or stabilization layer, for example of a film of polyetheretherketone (PEEK), commercial polyphenylene sulfide (PPS), polyethylene naphthalate (PEN), Polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyarylate (PAR), polyimide (PI), polyetherimide (PEI), polyphenylsulfone (PPSU), polyethersulfone (PES), polysulfone (PSU) or thermoplastic polyurethane (TPU), or which are particularly preferred also formed from a film of a low halogenated polyphenylene sulfide (PPS) having a halogen content of less than 550 ppm. Between each of these inner backing or stabilization layer and each outer cover layer is provided a (adhesive) adhesive layer. Preferably, both adhesive (adhesive) layers are chemically identical and / or the same thickness. However, the (adhesive) adhesive layers can also be selected differently with regard to their chemical nature and / or their thickness.
Bevorzugt beträgt die Dicke der inneren Träger- oder Stabilisierungsschicht 1 -50 μηη, bevorzugt 1 -30 μηη, besonders bevorzugt 1 -5 μηη. The thickness of the inner carrier or stabilizing layer is preferably 1 to 50 μm, preferably 1 to 30 μm, particularly preferably 1 to 5 μm.
Bevorzugt betragen die Dicken der (Haft-)Klebmassenschichten unabhängig voneinander 1 -100 μηη, bevorzugt 1 -50 μηη, besonders bevorzugt 2-40 μηη.  The thicknesses of the (adhesive) adhesive layer layers are preferably 1 to 100 μηη, preferably 1 to 50 μηη, particularly preferably 2 to 40 μηη.
Sehr bevorzugt ist hier der völlig symmetrische fünfschichtige Verbundaufbau mit in Bezug auf ihre jeweilige chemische Zusammensetzung und ihre jeweilige Dicke identischen Deckschichten und mit in Bezug auf ihre jeweilige chemische Zusammensetzung und ihre jeweilige Dicke identischen (Haft-)Klebemassen- schichten. Most preferred here is the fully symmetrical five-layered composite structure having cover layers identical with respect to their respective chemical composition and their respective thickness, and with respect to their respective chemical Composition and their respective thickness identical (adhesive) adhesive layers.
Als Haftklebemassen, (auch bezeichnet als Selbstklebemassen oder PSA von englisch: „pressure sensitive adhesives") werden insbesondere solche polymeren Massen bezeichnet, die - gegebenenfalls durch geeignete Additivierung mit weiteren Komponenten, wie beispielsweise Klebharzen - bei der Anwendungstemperatur (sofern nicht anders definiert, bei Raumtemperatur) dauerhaft klebrig und permanent klebfähig sind und an einer Vielzahl von Oberflächen bei Kontakt anhaften, insbesondere sofort anhaften (einen sogenannten „Tack" [Klebrigkeit oder Anfassklebrigkeit] aufweisen). Sie sind in der Lage, bereits bei der Anwendungstemperatur ohne eine Aktivierung durch Lösemittel oder durch Wärme - üblicherweise aber durch den Einfluss eines mehr oder weniger hohen Druckes - ein zu verklebendes Substrat hinreichend zu benetzen, damit sich zwischen der Masse und dem Substrat für die Haftung hinreichende Wechselwirkungen ausbilden können. Diesen Vorgang beeinflussende Einflussparameter sind unter anderem der Druck sowie die Kontaktzeit. Die besonderen Eigenschaften der Haftklebemassen gehen unter anderem insbesondere auf deren viskoelastische Eigenschaften zurück. As pressure-sensitive adhesives, (also referred to as self-adhesives or PSA from English: "pressure sensitive adhesives"), in particular those polymeric compositions are referred to - optionally by suitable addition with other components, such as adhesive resins - at the application temperature (unless otherwise defined, in Room temperature) are permanently tacky and permanently tacky and adhere to a variety of surfaces on contact, in particular adhere immediately (a so-called "tack" [stickiness or Anfassklebrigkeit] have). They are able, even at the application temperature without activation by solvents or by heat - but usually by the influence of a more or less high pressure - sufficient to wet a substrate to be bonded so that between the mass and the substrate for the adhesion can form sufficient interactions. Factors influencing this process include pressure and contact time. The special properties of the PSAs are due in particular to their viscoelastic properties.
In vorteilhafter Weise werden für die Klebemassenschichten Acrylat-Haftklebemassen eingesetzt. Dies sind Klebemassen, deren Polymerbasis Polymere aus Acrylmonomeren sind - hierunter werden insbesondere Acryl- und Methacrylsäure, die Ester der vorgenannten Säuren sowie die copolymerisierbaren weiteren Derivate der vorgenannten Säuren verstanden -, wobei die Acrylmonomere - ggf. zusammen mit weiteren Comonomeren - bei der Polymerisation zumindest in einer Menge eingesetzt werden, dass die Eigenschaften der Klebemasse hierdurch maßgeblich bestimmt werden. So können beispielsweise Haftklebemassen mit einen Acrylmonomeranteil bei der Polymerisation von mindestens 50 Gew.-%, von mindestens 80 Gew.-% oder von 100 Gew.-% (Reinacrylatsysteme) eingesetzt werden. Advantageously, acrylate PSAs are used for the adhesive layers. These are adhesives whose polymer base are polymers of acrylic monomers - these are in particular acrylic and methacrylic acid, the esters of the aforementioned acids and the copolymerizable further derivatives of the aforementioned acids understood -, the acrylic monomers - optionally together with other comonomers - in the polymerization at least be used in an amount that the properties of the adhesive are thereby determined significantly. Thus, for example, pressure-sensitive adhesives having an acrylic monomer content in the polymerization of at least 50% by weight, of at least 80% by weight or of 100% by weight (pure acrylate systems) can be used.
Andere dem Fachmann geläufige Klebmassen, insbesondere Haftklebemassen, sind ebenfalls möglich und können im Sinne der Erfindung eingesetzt werden, wobei insbesondere diejenigen ausgewählt werden, die eine gute Haftung auf PPS bewirken und außerdem gute Dämfungseigenschaften besitzen. So lassen sich beispielsweise insbesondere auch Silikonklebemassen und/oder Polyurethanklebemassen und/oder Kautschukklebemassen, insbesondere Silikonhaftklebemassen, Polyurethanhaftklebemassen bzw. Kautschukhaftklebemassen, einsetzen. Zur Herstellung des Mehrschichtaufbaus wird die Haftklebemasse entweder direkt auf eine der beiden Deckschichten in der gewünschten Schichtstärke mit den dem Fachmann geläufigen Auftragsverfahren aufgetragen oder indirekt durch Beschichtung eines temporären Transferträgers wie silikonisiertem Papier oder silikonisierter Folie, Kaschieren mit der ersten der beiden Folienschichten und Ausdecken des temporären Transferträgers. Die zweite der beiden Folienschichten kann direkt zur haftklebrigen Seite des einseitig kaschierten Verbundes zugeführt werden. Zur Erzielung einer sicheren Verbund haftung und zum Vermeiden von Lufteinschlüssen eignen sich Kaschiereinrichtungen, die die Materialbahnen zwischen Gummizylindern bzw. einem Stahl und einem Gummizylinder mit variabel einstellbarem Anpressdruck kontinuierlich verbinden. Other adhesives which are familiar to the person skilled in the art, in particular pressure-sensitive adhesives, are likewise possible and can be used in the context of the invention, with particular preference being given to those which have good adhesion to PPS and, moreover, have good damping properties. For example, silicone adhesives and / or polyurethane adhesives and / or rubber adhesives, in particular silicone pressure-sensitive adhesives, polyurethane pressure-sensitive adhesives or rubber pressure-sensitive adhesives, can also be used in particular. To produce the multilayer structure, the PSA is applied either directly to one of the two outer layers in the desired layer thickness using the application method familiar to those skilled in the art, or indirectly by coating a temporary transfer support such as siliconized paper or siliconized film, laminating with the first of the two film layers and masking the temporary transfer support. The second of the two film layers can be fed directly to the pressure-sensitive adhesive side of the one-sided laminated composite. To achieve a secure bond adhesion and to avoid air pockets are laminating devices that connect the webs of material between rubber cylinders or a steel and a rubber cylinder with variably adjustable contact pressure continuously.
Die Herstellung von Membranen für elektroakustische Wandler, insbesondere Lautsprechermembranen, erfolgt beispielsweise durch Prägen oder Tiefziehen eines erfindungsgemäßen Mehrschicht-Verbundes, wodurch dieser Verbund in eine spezifische dreidimensionale Form gebracht wird. Hierzu wird der Mehrschicht- Verbund beispielsweise in einer Thermoform erwärmt und durch Anlegen von Druck und/oder Vakuum in die Form der fertigen Membran gepresst. The production of membranes for electroacoustic transducers, in particular loudspeaker membranes, takes place, for example, by embossing or thermoforming of a multilayer composite according to the invention, whereby this composite is brought into a specific three-dimensional form. For this purpose, the multi-layer composite is heated, for example in a thermoform and pressed by applying pressure and / or vacuum in the form of the finished membrane.
Die erfindungsgemäßen Mehrschicht-Verbunde lassen sich hervorragend in einem Verfahren zur Herstellung von Membranen für elektroakustische Wandler einsetzen, wobei sie dem Prozess des Multicavity-Thermoformens unterzogen werden. Bei diesem Verfahren wird das Mehrschicht-Laminat auf die beheizbare Thermoform gelegt, die Vertiefungen mit dem Negativ-Abdruck der zu formenden Membran enthält. Anschließend wird das Mehrschicht-Laminat z.B. durch IR-Strahlung aufgeheizt und dadurch erweicht und dann von oben mit Druckluft in die Vertiefungen gepresst. Alternativ kann das erweichte Mehrschicht-Laminat auch mit einem Stempel aus Silikon oder geschäumtem Silikon in die Formen gepresst werden. The multilayer composites according to the invention can be used excellently in a process for the production of membranes for electroacoustic transducers, wherein they are subjected to the process of multicavity thermoforming. In this method, the multilayer laminate is placed on the heatable thermoforming, which contains recesses with the negative impression of the membrane to be formed. Subsequently, the multi-layer laminate is e.g. heated by IR radiation and thereby softened and then pressed from above with compressed air into the recesses. Alternatively, the softened multi-layer laminate can also be pressed into the molds with a stamp made of silicone or foamed silicone.
Für die erfindungsgemäß hergestellten mehrschichtigen Verbünde können Gesamthalogengehalte von weniger als 400 ppm realisiert werden. Ein weiterer Vorteil neben der Verbesserung der akustischen Eigenschaften ist somit auch, dass die daraus erhältliche Lautsprechermembran in ihrem Einsatzgebiet wegen des niedrigeren Gesamt-Halogengehalts unter die in der Elektronik-Industrie üblicherweise geforderten Grenzwerte fällt. Beispiele, Vergleichsbeispiele For the multilayer composites produced according to the invention, total halogen contents of less than 400 ppm can be achieved. Another advantage in addition to the improvement of the acoustic properties is thus that the available speaker membrane falls in their field of application because of the lower total halogen content below the limits usually required in the electronics industry. Examples, Comparative Examples
Der Erfindungsgedanke soll im Folgenden an mehreren Beispielen und Gegenbeispielen erläutert werden, ohne die Erfindung damit einschränken zu wollen. The idea of the invention will be explained below with reference to several examples and counterexamples, without wishing to restrict the invention.
Zunächst wurde von kommerziell erhältlichen Standard-PPS-Folien der Halogengehalt durch ein externes Labor analysiert. Dabei wurde jeweils Chlor als enthaltenes Halogen festgestellt, andere Halogene waren nicht in signifikanten Mengen detektierbar. Die gemessenen Proben wiesen durchgängig einen Chlorgehalt von mehr als 1000 ppm (1000 mg/kg) auf. First, commercially available standard PPS films were used to analyze the halogen content of an external laboratory. In each case chlorine was detected as contained halogen, other halogens were not detectable in significant amounts. The measured samples consistently had a chlorine content of more than 1000 ppm (1000 mg / kg).
Der Halogengehalt einer halogen-reduzierten PPS-Folie betrug 532 ppm.  The halogen content of a halogen-reduced PPS film was 532 ppm.
Für die THD-Bestimmung wurden Dreischicht-Verbunde aus je einer 4 μηη dicken PPS- Folie, je einer 10 μηη Acrylat- bzw. Silikon-Dämpfungsschicht (jeweils Standard- Haftklebemasse; jeweils identisch in Beispiel 1 und Vergleichsbeispiel 1 sowie in Beispiel 2 und Vergleichsbeispiel 2) und je einer 4 μηη dicken PPS-Folie hergestellt, wobei für die erfindungsgemäßen Beispiele halogen-reduzierte PPS-Folien und für Vergleichsversuche Standard-PPS-Folien eingesetzt wurden (siehe Tabelle 1 ). For the determination of THD, three-layer composites each consisted of a 4 μm thick PPS film, each of a 10 μm acrylate or silicone damping layer (each standard pressure-sensitive adhesive, identical in each case in Example 1 and Comparative Example 1 and in Example 2 and Comparative Example) 2) and 4 μηη thick PPS film produced, wherein for the inventive examples, halogen-reduced PPS films and for comparative experiments standard PPS films were used (see Table 1).
Aus diesen Dreischicht-Verbunden wurden durch Thermoformen rechteckige Membranen der Länge 15 mm und Breite 1 1 mm geformt und diese in ansonsten baugleiche Mikrolautsprecher eingebaut. Die Aufzeichnung der THD-Kurven erfolgte mit dem R&S® UPV Audio Analyzer (Rohde & Schwarz) in jeweils identischer Vorgehensweise, so dass die Werte direkt miteinander vergleichbar sind. Auf den exakten jeweils bestimmten Wert bei der THD-Messung kommt es bei dem relativen Vergleich nicht an. From these three-layer composites were molded by thermoforming rectangular membranes of length 15 mm and width 1 1 mm and installed in otherwise identical microspeakers. The recording of the THD curves was carried out with the R & S ® UPV Audio Analyzer (Rohde & Schwarz) in identical procedures, so that the values can be directly compared with each other. The exact respective determined value in the THD measurement does not matter in the relative comparison.
Die Resonanzfrequenz beider Lautsprecher liegt bei 450 Hz. Die THD-Kurven der Lautsprecher mit den aus halogenreduzierter PPS-Folie heregstellten Mehrschichtverbund-Membranen lag im gesamten Frequenzbereich sowohl für die Verbünde mit Acrylat-Dämpfungsschicht als auch für die Verbünde mit Silikon- Dämpfungsschicht zwischen 0,1 und 10 kHz unterhalb der THD-Kurven der Lautsprecher mit den aus handelsüblicher PPS-Folie gefertigten Membranen. In Tabelle 1 sind beispielhaft THD-Werte bei Frequenzen unterhalb der Resonanzfrequenz angegeben. Tabelle 1 . Ergebnisse der THD-Bestimmung. The resonant frequency of both loudspeakers is 450 Hz. The THD curves of the loudspeakers with the multi-layer composite diaphragms made of halogen-reduced PPS foil was between 0 and 0 for the composites with acrylate damping layer as well as for the composites with silicone damping layer. 1 and 10 kHz below the THD curves of the speakers with the membranes made of commercially available PPS film. Table 1 shows examples of THD values at frequencies below the resonant frequency. Table 1 . Results of the THD determination.
Durch die Experimente wurde gezeigt, dass die erfindungsgemäße Aufgabe erfindungsgemäß gelöst werden konnte, indem in einer akustischen Membran Standard-PPS-Folien durch PPS-Folien mit reduziertem Halogengehalt (< 550 ppm) ersetzt wurde. Ein Effekt des Halogengehaltes der eingesetzten PPS-Folien auf die Klangqualität von mit solchen Folien hergestellten Lautsprechermembranen war vom Fachmann nicht zu erwarten. The experiments showed that the object according to the invention could be achieved according to the invention by replacing standard PPS films in an acoustic membrane with PPS films having a reduced halogen content (<550 ppm). An effect of the halogen content of the PPS films used on the sound quality of loudspeaker membranes produced with such films was not to be expected by the skilled person.
Es hat sich gezeigt, dass die unterhalb der Resonanzfrequenz bestimmten THD-Werte einer Membran, die unter Verwendung einer PPS-Folie mit reduziertem Halogengehalt hergestellt wurde, durchgängig niedriger liegen als diejenigen einer Vergleichsmembran (gleiche Dicke und Form, gleicher Lautsprecher), die unter Verwendung handelsüblicher Standard-PPS-Folie hergestellt wurde.  It has been found that the THD values of a membrane made below the resonant frequency and made using a reduced halogen PPS film are consistently lower than those of a comparative membrane (same thickness and shape, same loudspeaker) using commercial standard PPS film was made.

Claims

Patentansprüche claims
1 . Mehrschicht-Verbund zur Verwendung als Membran für elektroakustische Wandler, umfassend zumindest eine erste und eine zweite außenliegende Schicht (Deckschicht), wobei 1 . A multilayer composite for use as a membrane for electroacoustic transducers, comprising at least a first and a second outer layer (cover layer), wherein
zumindest eine der Deckschichten („erste Deckschicht") aus einem Polyphenylensulfid-Kunststoff besteht,  at least one of the cover layers ("first cover layer") consists of a polyphenylene sulfide plastic,
dadurch gekennzeichnet, dass der Halogengehalt des Polyphenylensulfid- Kunststoffs („PPS-Kunststoff") 550 ppm nicht übersteigt.  characterized in that the halogen content of the polyphenylene sulfide plastic ("PPS plastic") does not exceed 550 ppm.
2. Mehrschicht-Verbund nach Anspruch 1 , dadurch gekennzeichnet, dass 2. multilayer composite according to claim 1, characterized in that
die erste Deckschicht eine Dicke von 1 bis 50 μηη hat.  the first cover layer has a thickness of 1 to 50 μm.
3. Mehrschicht-Verbund nach Anspruch 1 , dadurch gekennzeichnet, dass 3. multilayer composite according to claim 1, characterized in that
die erste Deckschicht eine Dicke von 1 bis 5 μηη hat.  the first cover layer has a thickness of 1 to 5 μηη.
4. Mehrschicht-Verbund nach Anspruch 1 , dadurch gekennzeichnet, dass 4. multilayer composite according to claim 1, characterized in that
beide Deckschichten aus Polyphenylensulfid-Kunststoff bestehen, deren Halogengehalt jeweils 500 ppm nicht übersteigt.  both outer layers consist of polyphenylene sulfide plastic whose halogen content does not exceed 500 ppm.
5. Mehrschicht-Verbund nach Anspruch 4, dadurch gekennzeichnet, dass 5. Multi-layer composite according to claim 4, characterized in that
beide Deckschichten jeweils eine Dicke von 1 bis 50 μηη haben.  both cover layers each have a thickness of 1 to 50 μηη.
6. Mehrschicht-Verbund nach Anspruch 4, dadurch gekennzeichnet, dass 6. multilayer composite according to claim 4, characterized in that
beide Deckschichten jeweils eine Dicke von 1 bis 5 μηη haben.  both outer layers each have a thickness of 1 to 5 μηη.
7. Mehrschicht-Verbund nach einem der vorangehenden Ansprüche, dadurch gekennzeichnet, dass 7. Multilayer composite according to one of the preceding claims, characterized in that
beide Deckschichten aus dem identischen PPS-Kunststoff hergestellt sind.  Both cover layers are made of the same PPS plastic.
8. Mehrschicht-Verbund nach einem der vorangehenden Ansprüche, dadurch gekennzeichnet, dass 8. multilayer composite according to one of the preceding claims, characterized in that
zwischen den beiden Deckschichten eine Dämpfungsschicht angeordnet ist.  a damping layer is arranged between the two cover layers.
9. Mehrschicht-Verbund nach Anspruch 8, dadurch gekennzeichnet, dass die Dämpfungsschicht durch ein doppelseitig klebendes Haftklebeband gebildet wird oder ein solches umfasst. 9. multilayer composite according to claim 8, characterized in that the damping layer is formed by or comprises a double-sided adhesive pressure-sensitive adhesive tape.
10. Mehrschicht-Verbund nach einem der vorangehenden Ansprüche, dadurch gekennzeichnet, dass 10. Multilayer composite according to one of the preceding claims, characterized in that
die Dämpfungsschicht eine Schicht einer Haftklebemasse ist.  the cushioning layer is a layer of a pressure-sensitive adhesive.
1 1 . Mehrschicht-Verbund nach einem der vorangehenden Ansprüche, gekennzeichnet durch 1 1. Multilayer composite according to one of the preceding claims, characterized by
einen Dreischichtaufbau Deckschicht-Haftklebemasse-Deckschicht.  a three-layer construction overcoat pressure-sensitive adhesive topcoat.
12. Lautsprechermembran, erhältlich durch Thermoformen aus einem Mehrschicht- Verbund nach einem der vorangehenden Ansprüche, insbesondere durch Prägen und/oder Tiefziehen. 12. Loudspeaker membrane, obtainable by thermoforming from a multilayer composite according to one of the preceding claims, in particular by embossing and / or deep drawing.
EP15804082.4A 2014-12-11 2015-11-17 Multi-layer composite for acoustic membranes Pending EP3231193A1 (en)

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Families Citing this family (5)

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Publication number Priority date Publication date Assignee Title
CN109417670B (en) * 2016-07-06 2021-09-17 奥地利依索沃尔塔股份公司 Composite material for producing acoustic membranes
DE102017202622A1 (en) * 2017-02-17 2018-08-23 Tesa Se Membrane for microspeakers
CN109218924A (en) * 2018-08-20 2019-01-15 歌尔股份有限公司 Vibrating diaphragm, sounding device and its assemble method for sounding device
TWI683583B (en) * 2018-09-03 2020-01-21 輔仁大學學校財團法人輔仁大學 Sound membrane structure
CN111849103B (en) * 2019-04-24 2021-11-02 歌尔股份有限公司 Vibrating diaphragm for miniature sound generating device and miniature sound generating device

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3862617D1 (en) * 1987-07-03 1991-06-06 Electronic Werke Deutschland MEMBRANE FOR A SPEAKER.
US4910294A (en) 1988-06-20 1990-03-20 Idemitsu Petrochemical Company Limited Two-stage process for production of polyarylene sulfides with lithium compound
DE19513479A1 (en) 1995-04-13 1996-10-17 Hoechst Ag Process for the preparation of polyarylene sulfide
JP2006295245A (en) 2005-04-05 2006-10-26 Sony Corp Acoustic diaphragm
US7750111B2 (en) * 2005-09-22 2010-07-06 Toray Industries, Inc. Polyarylene sulfide and its production method
JP2010070656A (en) 2008-09-19 2010-04-02 Toray Ind Inc Poly(phenylene sulfide) resin composition and molded article of the same
US8189851B2 (en) 2009-03-06 2012-05-29 Emo Labs, Inc. Optically clear diaphragm for an acoustic transducer and method for making same
JP5918855B2 (en) * 2011-09-20 2016-05-18 ティコナ・エルエルシー Polyarylene sulfide / liquid crystal polymer alloy and composition containing the same
WO2013047875A1 (en) * 2011-09-30 2013-04-04 富士フイルム株式会社 Electroacoustic converter film, flexible display, vocal cord microphone, and musical instrument sensor
DE102012208477A1 (en) 2012-05-21 2013-11-21 Tesa Se Asymmetric multilayer membrane for electroacoustic transducers
US20140178662A1 (en) * 2012-12-20 2014-06-26 Ticona Llc Multilayer Polyarylene Sulfide Composite
DE102013206812A1 (en) 2013-04-16 2014-11-06 Tesa Se Composite for the production of an acoustic membrane and acoustic membrane
CN203883985U (en) * 2014-05-26 2014-10-15 歌尔声学股份有限公司 Loudspeaker diaphragm

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
None *
See also references of WO2016091542A1 *

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