Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
  • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
  • C08G63/16—Dicarboxylic acids and dihydroxy compounds
  • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
  • C08G63/181—Acids containing aromatic rings
  • C08G63/183—Terephthalic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/18—Manufacture of films or sheets
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
  • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
  • C08G63/16—Dicarboxylic acids and dihydroxy compounds
  • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
  • C08G63/19—Hydroxy compounds containing aromatic rings
  • C08G63/193—Hydroxy compounds containing aromatic rings containing two or more aromatic rings
  • C08G63/195—Bisphenol A
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/64—Polyesters containing both carboxylic ester groups and carbonate groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
  • C08G64/04—Aromatic polycarbonates
  • C08G64/06—Aromatic polycarbonates not containing aliphatic unsaturation
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
• • H—ELECTRICITY
  • H04—ELECTRIC COMMUNICATION TECHNIQUE
  • H04R—LOUDSPEAKERS, MICROPHONES, GRAMOPHONE PICK-UPS OR LIKE ACOUSTIC ELECTROMECHANICAL TRANSDUCERS; DEAF-AID SETS; PUBLIC ADDRESS SYSTEMS
  • H04R31/00—Apparatus or processes specially adapted for the manufacture of transducers or diaphragms therefor
  • H04R31/003—Apparatus or processes specially adapted for the manufacture of transducers or diaphragms therefor for diaphragms or their outer suspension
• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
  • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
  • C08J2367/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the hydroxy and the carboxyl groups directly linked to aromatic rings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
• • 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
  • H04R2307/029—Diaphragms comprising fibres

Definitions

• the invention relates to films and membranes produced therefrom for acoustic signal converters of a polyester containing the structural unit of the formula (I):
• R 1 and R 2 independently of one another are halogen, C 1 -C 8 -alkyl, C 5 -C 6 -cycloalkyl, C 6 -
• R is either the following formula (A) or preferably a carbonyl group.
• the film according to the invention may be produced by thermoplastic processes or preferably as a solvent casting film. It is preferably deep-drawn into a membrane for acoustic signal transducers such as a microphone or loudspeaker.
• a membrane for acoustic signal transducers such as a microphone or loudspeaker.
• acoustic signal converters for use in mobile devices such as microphones, Mobile telephones, laptops, personal digital assistants (PDAs), headphones or as signal generators, for example in automobiles, are currently using stretched polyester films (PET, PEN) and, for high-quality applications, films made from bisphenol A polycarbonate (PC).
• PET stretched polyester films
• PC bisphenol A polycarbonate
• the membranes In order to reduce the oscillating mass of the membranes, to ensure an exact formation of embossed structures during deep drawing and to allow further miniaturization, the membranes should be as thin as possible. Films made of the plastics mentioned are mechanically very resistant, but have the disadvantage that when used as loudspeaker membranes they produce a "metallic" sound or can not sufficiently deform for the formation of more complicated embossed structures, because the orientation leads to anisotropic shrinkage through the extrusion process , As a result, acoustic signals, in particular music and / or speech signals, are adversely altered in the conversion to electrical signals and vice versa. The production of small microphone and speaker membranes for the aforementioned applications is usually done by deep drawing.
• the film is heated to soften before deep drawing, for example, by irradiation with infrared light.
• Uniform heating and the resulting uniform softening of particularly thin films before the deep-drawing process is technically all the more difficult to control because of anisotropic shrinkage the more anisotropic the film is.
• Foils of extruded bisphenol A polycarbonate, stretched polyethylene naphthalate (PEN) or polyethylene terephthalate (PET) tend to anisotropic deformations and especially the hidden films to strong shrinkage.
• the production of cast films is not possible because of the lack of solubility of polyesters.
• the membranes of the invention may be prepared by thermoplastic processes such as extrusion or calendering. In one embodiment as a calendering film, the membrane according to the invention is less anisotropic than in an embodiment as an extrusion film.
• the calendering is the Extrusion process preferred.
• Particularly preferred is the cast film process in which the polymer is dissolved in a solvent, then spread on a web of metal, a coated paper or film, and then dried.
• This method not only advantageously produces an isotropic membrane, but also succeeds in producing it much thinner than is possible with a thermoplastic process, ie, for example, in the thickness range of 5 to 20 ⁇ m, which is advantageous as stated above.
• the object was to find a polymer for such a membrane, which is soluble in a less harmful solvent than a halogen-containing solvent.
• Other important requirements for membranes for acoustic applications are deep drawability, high modulus of elasticity, good water resistance and high temperature resistance.
• the latter can be characterized by the glass transition temperature, Vicat softening temperature (ISO 306 at 50 N and 120 K / h) or heat distortion temperature HDT Af (ISO 75-1, -2 at 1.8 MPa).
• the thickness of the film for the membrane is determined according to DIN 53370.
• the object of the invention was to provide films for the production of membranes for acoustic applications, which have a high modulus of elasticity and a high temperature resistance and if possible also consist of a polymer which is soluble in a halogen-free solvent. These membranes should also allow good speech intelligibility and the reproduction of music in good quality and sufficient volume and have a high mechanical stability at high temperature.
• membranes made of special films have significantly better acoustic properties than membranes made of extruded bisphenol A polycarbonate or polyester films.
• Such special films are those, in particular from the cast film process, of a polyester containing the structural unit of the formula (I)
• R 1 and R 2 independently of one another are halogen, C 1 -C 8 -alkyl, C 5 -C 6 -cycloalkyl, C 6 -C 10 -aryl, C 7 -C 12 -aralkyl or preferably hydrogen and R 3 either corresponds to or is of the following formula (A) is a carbonyl group.
• the polyester preferably contains the structural unit (I) and the structural unit of the formula (II):
• the polyesters according to the invention are, for example, soluble in acetone, toluene and tetrahydrofuran, provided that the proportion of the structural unit (I) based on the structural units (I) and (II) is at least 60% by weight.
• the membrane preferably contains a polyester having 60 to 90% by weight, particularly preferably 65 to 85% by weight of the structural unit (I) and 10 to 40% by weight, particularly preferably 15 to 35% by weight, of the structural unit (II ).
• the good solubility in halogen-free solvents therefore makes it possible to produce shrink-free and isotropic films for deep-drawn membranes and at the same time to produce particularly thin membranes. Both advantages have a positive effect on the acoustic properties.
• the polyester according to the invention which is contained in the film or membrane according to the invention preferably has a flexural modulus of at least 2350 MPa and / or preferably a yield stress of at least 75 MPa.
• the heat deflection temperature HDT Af of the polyester is preferably at least 173 ° C., more preferably at least 180 ° C., and / or the Vicat softening temperature is preferably at least 203 ° C.
• the improved temperature resistance to polycarbonate from bisphenol A (PC) or aromatic polyesters (AP) from terephthalic and isophthalic acid and bisphenol A also leads to a higher temperature resistance of the membranes.
• PC bisphenol A
• AP aromatic polyesters
• the acoustic signal converter is less prone to warp (re-deformation of the deep-drawn structure).
• the life is increased under normal conditions.
• the membranes of the present invention are less prone to "bleed” which degrades sound quality, possibly due to better mechanical properties such as flexural modulus or yield stress.
• Thinner membranes have lower strength and resistance to deformation than thicker ones, which is higher in the membranes of the present invention
• Aromatic polyesters of terephthalic and isophthalic acid and bisphenol-A show tendency to crystallize, which is why aggregates are formed in solutions which lead to ever-increasing viscosities and hence deviations in the coating process, which leads to unstable film quality If the problem can be narrowed down, disadvantages include poorer bondability and moisture sensitivity stable polyester according to the invention.
• the polyester according to the invention combines the advantages of PC (viscosity stability) and AP (modulus and temperature resistance).
• Polymers as contained in the membranes according to the invention are distinguished by high transparency, temperature resistance, refractive index and toughness and have hitherto been used exclusively for optical applications such as automotive lamp housings or luminaire covers in household appliances and in medical technology such as syringe attachments or sterilizable transparent vessels.
• these products have been produced exclusively by thermoplastic processing and not by a solvent process such as cast film technology.
• the membranes according to the invention have a high attenuation factor and largely linear acoustic properties over a large attenuation factor
• the membranes of the invention are particularly suitable for the production of deep-drawn
• Membranes as sound transducers for acoustic applications, preferably as microphone and / or loudspeaker membranes. They have less "metallic" sound than known membranes made of other polymers and are particularly suitable for high demands on speech intelligibility, such as when used as a microphone. and speaker diaphragms in microphone capsules, mobile phones, hands-free kits, radios, hearing aids, headphones, micro radios, computers and PDAs, or as signal heads.
• the film preferably contains a dye, a pigment or an IR absorber.
• these are organic dyes such as CAS no. 4702-90-3, carbon black such as toner or IR absorber such as SDA 7257 (HW Sands Corp.), vanadyl-5,14,23,32-tetraphenyl-2,3-naphthalocyanine, copper (II) -1,4, 8, 11, 15, 18, 22, 25-octabutoxy-29H, 31H-phthalocyanine and ITO (indium tin oxide, eg ITO with more than 94% indium oxide from Nanogate).
• the film preferably contains an additive which has an absorption in the range from 0.75 to 4.0 ⁇ m, more preferably in the range from 1.0 to 2.0 ⁇ m.
• the finished-shaped membranes can then be cut out of the film by means of a mechanical method, for example with a knife or a punch, or without contact, for example with the aid of a water jet or a laser.
• the shaped membranes are punched out or cut with a laser.
• the membranes can be connected at the outer periphery with a support ring made of plastic or metal and with a coil with terminals and installed as a microphone or speaker membrane together with a permanent magnet in corresponding devices for converting or generating acoustic signals.
• the film also contains an antistatic agent such as glycerol monostearate, cetyltrimethylammonium bromide or a nonionic or anionic surfactant.
• an antistatic agent such as glycerol monostearate, cetyltrimethylammonium bromide or a nonionic or anionic surfactant.
• Further additives are those which are usually used for the production of films, for example antioxidants, lubricants, sunscreens or hydrolysis stabilizers.
• the solutions which preferably have a solids content of 10 to 40%, more preferably 15 to 25%, for example, with a casting head, a nozzle, a doctor blade, a gravure cylinder applied to a support and on or dried in several stages.
• the foil according to the invention can subsequently be removed.
• other layers such as paint, laminating adhesive or adhesive tape are applied before peeling.
• Suitable supports are, for example, rolls and endless metal strips, siliconized papers or films and preferably non-siliconized biaxially stretched polypropylene and polyester films, more preferably polyethylene terephthalate.
• the use of such a biaxially stretched polypropylene or polyester film results in a trouble-free coating image and the adhesion of the film according to the invention on this carrier material is high enough that the film according to the invention is reinforced for further operations or transport / storage.
• the adhesion is not too high, so that the film can be easily removed at the desired time.
• the film also protects the film of the invention from contamination and mechanical damage.
• the film is preferably at least one side matt so that they can be easier to unwind and unwind.
• the matting can be achieved by a matte surface of the support or the addition of a matting agent (eg balls of polyolefin) to the casting solution.
• Thicker films can be made easier by extrusion as in the flat film process or calendering process.
• the film is deshrunk on a number of annealing rolls to eliminate stresses and anisotropy of the properties. Shrinkage can also be achieved by storing the film in an oven. In this case, the film should first be covered with a release paper, a release film or another film to prevent blocking.
• a polyester with 69% by weight of structural element (I) and 31% by weight is used.
• Vicat softening temperature 203 ° C (ISO 306, 50 N, 120 K / min), flexural modulus 2400 MPa (ISO 178, 2 mm / min), yield stress 76 MPa (ISO 527-1 and -2, 50 mm / min), Yield strain 6.9% (ISO 527-1 and -2, 50 mm / min), melt mass flow rate 8 g / 10 min (MVR, ISO 1 133, 330 ° C, 2.16 kg), heat distortion temperature HDT, Af 173 ° C (ISO 75-1 and -2, 1, 8 MPa).
• Polyester film according to the invention 10 ⁇ m
• the 23 ⁇ m thick polyester film is laminated.
• a polyester with 83% by weight of structural element (I) and 17% by weight is used.
• the polymer is mixed with 0.05% by weight of a color batches (carbon black in standard polycarbonate) and on a flat film system to a film with a thickness of 25 ⁇ m processed (nozzle temperature 280 ° C, chill roll temperature 150 ° C). The film is then shrunk at 150 ° C.
• a color batches carbon black in standard polycarbonate
• nozzle temperature 280 ° C, chill roll temperature 150 ° C The film is then shrunk at 150 ° C.
• a polycarbonate with the following properties is used:
• Example 2 It is dissolved in methylene chloride and processed without the addition of further additives as in Example 1 to a 10 micron thick film and then to the composite with tape.
• the polycarbonate from Comparative Example 1 is processed without the addition of a color batch on a flat film system to a film having a thickness of 25 microns (nozzle temperature 260 ° C, chill roll temperature 130 ° C) and not de-shrunk.
• a polyester of bisphenol A is used with equal proportions of isophthalic and terephthalic acid having the following properties:
• Example 2 It is dissolved in methylene chloride and processed as in Example 1 to a 10 micron thick film and then to the composite with tape.
• the film thickness does not remain constant during production because of increasing solution viscosity. Assessment of the produced films
• the films except those of Example 1 are rapidly contaminated with dust on the surface.
• the films are heated by an infrared heater.
• the films of Examples 1 and 2 heat up quickly and in those of the comparative examples had to be helped with hot air to achieve a sufficiently high temperature for deep drawing.
• the finished shaped membranes are cut with a punch to 13 mm diameter and connected at the outer periphery with the support ring and with a coil with connection contacts.
• Loudspeakers are produced together with permanent magnets. These are subjected to a life test in accordance with DIN ETS 300019.
• the loudspeakers are subjected to various tests under load, such as multiple cycles (-40 ° C to 85 ° C) at high humidity or continuous load at 85 ° C.
• Each loudspeaker is subjected to an electrical load of "Pink Noise" at the rated power of the loudspeaker for over 500 hours.At the beginning and end of the 500 hours, the sound quality is assessed subjectively: 1 very good, 2 with limitations, 3 failed.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Manufacturing & Machinery (AREA)
• Signal Processing (AREA)
• Physics & Mathematics (AREA)
• Acoustics & Sound (AREA)
• Materials Engineering (AREA)
• Multimedia (AREA)
• Manufacture Of Macromolecular Shaped Articles (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Polyesters Or Polycarbonates (AREA)
• Diaphragms For Electromechanical Transducers (AREA)

Applications Claiming Priority (2)

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• 2009
  • 2009-02-10 DE DE102009008323A patent/DE102009008323A1/de not_active Withdrawn
• 2010
  • 2010-01-28 KR KR1020117021066A patent/KR20110128854A/ko not_active Withdrawn
  • 2010-01-28 WO PCT/EP2010/050984 patent/WO2010091960A1/de active Application Filing
  • 2010-01-28 JP JP2011548644A patent/JP2012517490A/ja active Pending
  • 2010-01-28 US US13/143,982 patent/US8695752B2/en not_active Expired - Fee Related
  • 2010-01-28 CN CN2010800071670A patent/CN102317346A/zh active Pending
  • 2010-01-28 EP EP10702280A patent/EP2396362A1/de not_active Withdrawn
  • 2010-02-09 TW TW099103880A patent/TW201033285A/zh unknown

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