WO2022160683A1 - Diaphragm and sound generating device - Google Patents

Diaphragm and sound generating device Download PDF

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Publication number
WO2022160683A1
WO2022160683A1 PCT/CN2021/114294 CN2021114294W WO2022160683A1 WO 2022160683 A1 WO2022160683 A1 WO 2022160683A1 CN 2021114294 W CN2021114294 W CN 2021114294W WO 2022160683 A1 WO2022160683 A1 WO 2022160683A1
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WO
WIPO (PCT)
Prior art keywords
diaphragm
diisocyanate
polyol
isocyanate
polyurethane
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PCT/CN2021/114294
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French (fr)
Chinese (zh)
Inventor
闫付臻
王伟超
李春
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歌尔股份有限公司
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Publication of WO2022160683A1 publication Critical patent/WO2022160683A1/en

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    • HELECTRICITY
    • H04ELECTRIC COMMUNICATION TECHNIQUE
    • H04RLOUDSPEAKERS, MICROPHONES, GRAMOPHONE PICK-UPS OR LIKE ACOUSTIC ELECTROMECHANICAL TRANSDUCERS; DEAF-AID SETS; PUBLIC ADDRESS SYSTEMS
    • H04R31/00Apparatus or processes specially adapted for the manufacture of transducers or diaphragms therefor
    • H04R31/003Apparatus or processes specially adapted for the manufacture of transducers or diaphragms therefor for diaphragms or their outer suspension
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08Processes
    • C08G18/10Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18Manufacture of films or sheets
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04Polyurethanes
    • HELECTRICITY
    • H04ELECTRIC COMMUNICATION TECHNIQUE
    • H04RLOUDSPEAKERS, MICROPHONES, GRAMOPHONE PICK-UPS OR LIKE ACOUSTIC ELECTROMECHANICAL TRANSDUCERS; DEAF-AID SETS; PUBLIC ADDRESS SYSTEMS
    • H04R31/00Apparatus or processes specially adapted for the manufacture of transducers or diaphragms therefor
    • HELECTRICITY
    • H04ELECTRIC COMMUNICATION TECHNIQUE
    • H04RLOUDSPEAKERS, MICROPHONES, GRAMOPHONE PICK-UPS OR LIKE ACOUSTIC ELECTROMECHANICAL TRANSDUCERS; DEAF-AID SETS; PUBLIC ADDRESS SYSTEMS
    • H04R7/00Diaphragms for electromechanical transducers; Cones
    • HELECTRICITY
    • H04ELECTRIC COMMUNICATION TECHNIQUE
    • H04RLOUDSPEAKERS, MICROPHONES, GRAMOPHONE PICK-UPS OR LIKE ACOUSTIC ELECTROMECHANICAL TRANSDUCERS; DEAF-AID SETS; PUBLIC ADDRESS SYSTEMS
    • H04R7/00Diaphragms for electromechanical transducers; Cones
    • H04R7/16Mounting or tensioning of diaphragms or cones
    • H04R7/18Mounting or tensioning of diaphragms or cones at the periphery
    • HELECTRICITY
    • H04ELECTRIC COMMUNICATION TECHNIQUE
    • H04RLOUDSPEAKERS, MICROPHONES, GRAMOPHONE PICK-UPS OR LIKE ACOUSTIC ELECTROMECHANICAL TRANSDUCERS; DEAF-AID SETS; PUBLIC ADDRESS SYSTEMS
    • H04R9/00Transducers of moving-coil, moving-strip, or moving-wire type
    • H04R9/02Details
    • HELECTRICITY
    • H04ELECTRIC COMMUNICATION TECHNIQUE
    • H04RLOUDSPEAKERS, MICROPHONES, GRAMOPHONE PICK-UPS OR LIKE ACOUSTIC ELECTROMECHANICAL TRANSDUCERS; DEAF-AID SETS; PUBLIC ADDRESS SYSTEMS
    • H04R9/00Transducers of moving-coil, moving-strip, or moving-wire type
    • H04R9/02Details
    • H04R9/025Magnetic circuit
    • HELECTRICITY
    • H04ELECTRIC COMMUNICATION TECHNIQUE
    • H04RLOUDSPEAKERS, MICROPHONES, GRAMOPHONE PICK-UPS OR LIKE ACOUSTIC ELECTROMECHANICAL TRANSDUCERS; DEAF-AID SETS; PUBLIC ADDRESS SYSTEMS
    • H04R9/00Transducers of moving-coil, moving-strip, or moving-wire type
    • H04R9/06Loudspeakers
    • HELECTRICITY
    • H04ELECTRIC COMMUNICATION TECHNIQUE
    • H04RLOUDSPEAKERS, MICROPHONES, GRAMOPHONE PICK-UPS OR LIKE ACOUSTIC ELECTROMECHANICAL TRANSDUCERS; DEAF-AID SETS; PUBLIC ADDRESS SYSTEMS
    • H04R2231/00Details of apparatus or processes specially adapted for the manufacture of transducers or diaphragms therefor covered by H04R31/00, not provided for in its subgroups
    • H04R2231/001Moulding aspects of diaphragm or surround
    • HELECTRICITY
    • H04ELECTRIC COMMUNICATION TECHNIQUE
    • H04RLOUDSPEAKERS, MICROPHONES, GRAMOPHONE PICK-UPS OR LIKE ACOUSTIC ELECTROMECHANICAL TRANSDUCERS; DEAF-AID SETS; PUBLIC ADDRESS SYSTEMS
    • H04R2307/00Details 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
    • H04R2307/023Diaphragms comprising ceramic-like materials, e.g. pure ceramic, glass, boride, nitride, carbide, mica and carbon materials
    • HELECTRICITY
    • H04ELECTRIC COMMUNICATION TECHNIQUE
    • H04RLOUDSPEAKERS, MICROPHONES, GRAMOPHONE PICK-UPS OR LIKE ACOUSTIC ELECTROMECHANICAL TRANSDUCERS; DEAF-AID SETS; PUBLIC ADDRESS SYSTEMS
    • H04R2307/00Details 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
    • H04R2307/025Diaphragms comprising polymeric materials

Definitions

  • the invention relates to the technical field of electro-acoustic conversion, in particular to a vibrating membrane and a sound-generating device.
  • the diaphragm in the sound generating device usually adopts a thermoplastic elastomer diaphragm, such as a thermoplastic polyurethane elastomer and a thermoplastic polyester elastomer diaphragm.
  • thermoplastic polyurethane elastomer and thermoplastic polyester elastomer diaphragm have good plasticity, damping and temperature resistance, with the high demand for high power and high sound quality of speakers, thermoplastic elastomer diaphragm has been widely used in the field of speakers. Promote the application.
  • thermoplastic elastomer diaphragm is often formed by air pressure, and the stretching is uneven during the molding process, resulting in uneven thickness of the diaphragm after molding and uneven molding, resulting in a decrease in the yield of the diaphragm and an impact on the acoustic performance;
  • thermoplastic elastomer diaphragm has a linear structure.
  • under large strain the intermolecular slip is easy to occur, the viscous part increases, and the loss increases.
  • the acoustic performance of the loudspeaker using this diaphragm becomes poor after large displacement vibration and high-demand waterproof test; moreover, in the long-term high-temperature stress test, the molecular chain is stretched at high temperature for a long time, and the molecular chain moves at high temperature The ability is enhanced, and slippage is more likely to occur. After the external force is removed, the recovery rate becomes poor, which makes the diaphragm deformed after the reliability of the loudspeaker using the diaphragm, resulting in poor performance and even the risk of membrane rupture.
  • the main purpose of the present invention is to provide a vibrating membrane and a sounding device, which aims to overcome the deformation and membrane rupture of the thermoplastic elastomer vibrating membrane after large displacement vibration, high-demand waterproof test or long-term high-temperature reliability, and can overcome the The defects of the thermoplastic elastomer diaphragm during the air pressure forming process make the diaphragm thickness uniform and the forming flat, thereby ensuring its good acoustic performance.
  • the diaphragm proposed by the present invention is prepared by using cast-type polyurethane, and the cast-type polyurethane is prepared by vulcanization of a polyurethane prepolymer and a compounding agent, and the polyurethane prepolymer is a block polymer, so
  • the block polymer is formed by alternately arranging hard segments and soft segments, the hard segments are isocyanates, the soft segments are polyol flexible long chains, the end groups of the block polymers are all isocyanate hard segments, and the The elastic recovery rate of the diaphragm after 20% strain is greater than 70%.
  • the compression set ratio of the diaphragm is less than 50%.
  • the compounding agent includes a chain extender and a catalyst
  • the diaphragm is formed by reacting a polyol and a polyisocyanate to generate a polyurethane prepolymer, then adding a chain extender and a catalyst, and injecting it into the diaphragm after mixing. In the processing mold, it is formed by cross-linking reaction.
  • the amount of the chain extender is 10%-30% of the polyurethane prepolymer.
  • the chain extender is a multifunctional low molecular alcohol or amine compound that can react with isocyanate.
  • the chain extender is 3,3'-dichloro-4,4'-diaminodiphenylmethane, 2,5-diethyltoluenediamine, 1,2-bis( 2-Aminophenylthio)ethane, propylene glycol-bis(p-aminobenzoate), 3,5-diamino-4-chloro-benzoic acid isobutyl ester, 4,4-methylene-bis- (3-chloro-2,6-diethylaniline), 3,5-dimethylthiotoluenediamine, 1,4-butanediol, trimethylolpropane, triisopropanolamine, hydroquinone At least one in bis-hydroxyethyl ether, resorcinol-bis(P-hydroxyethyl) ether, triethanolamine; and/or, described catalyst selects butyltin dilaurate, stannous octoate, phosphoric acid, oleic
  • the amount of isocyanate used ranges from 2% to 50%; and/or, the isocyanate is selected from toluene diisocyanate, diphenylmethane diisocyanate, and hexamethylene diisocyanate.
  • naphthalene 1.5-diisocyanate isophorone diisocyanate, m-dimethylene diisocyanate, p-phenylene diisocyanate, 3,3.-dimethyl-4,4.-biphenyl diisocyanate, 4,4' -at least one of dicyclohexylmethane diisocyanate, hydrogenated toluene diisocyanate, trimethylhexamethylene diisocyanate; and/or, described polyol is selected from polyester polyol, polyether polyol, polybutadiene type polyol At least one of alcohol, castor oil polyol, tetrahydrofuran-propylene oxide copolymer polyol, and epoxy resin modified polyol.
  • the compounding agent further includes a filler, and the filler is at least one of carbon black, silica, clay, calcium carbonate, kaolin, talc, and glass microbeads; and/or,
  • the compounding agent also includes an auxiliary agent, which is at least one of an antioxidant, an ultraviolet absorber, an anti-hydrolysis stabilizer, a plasticizer, a colorant, and an anti-aging agent.
  • the hardness range of the diaphragm is 10A-95A.
  • the hardness range of the diaphragm is 30A-85A.
  • the thickness of the diaphragm ranges from 10 ⁇ m to 300 ⁇ m;
  • the thickness of the diaphragm ranges from 10 ⁇ m to 200 ⁇ m;
  • the present invention also provides a sound-generating device.
  • the sound-generating device includes a diaphragm, and the diaphragm is made of cast-type polyurethane.
  • the cast-type polyurethane is made of polyurethane prepolymer and compounding agent through vulcanization.
  • the polyurethane prepolymer is a block polymer, the block polymer is formed by alternating hard segments and soft segments, the hard segment is isocyanate, the soft segment is a long flexible polyol chain, and the block polymer is The end groups are all isocyanate hard segments, and the elastic recovery rate of the diaphragm after 20% strain is greater than 70%.
  • the vibrating membrane is prepared from cast-type polyurethane
  • the cast-type polyurethane is prepared by vulcanizing a polyurethane prepolymer and a compounding agent to obtain a cast-type polyurethane with a cross-linked structure. Since the cast polyurethane has a cross-linked structure, the molecules are networked, and there are chemical bonds between the molecules, it still has a relatively high recovery rate after a certain strain. The recovery rate of the diaphragm after 20% strain is greater than 70%, and the loudspeaker using the diaphragm still maintains good acoustic performance after large-displacement vibration and high-demand waterproof tests.
  • the diaphragm of the present invention adopts a casting molding process. Compared with the thermoplastic elastomer diaphragm formed by air pressure, the diaphragm of the present invention has a uniform thickness, small residual stress after molding, and a flat diaphragm, thereby obtaining better acoustic performance.
  • FIG. 1 is a schematic cross-sectional structural diagram of a sound producing device-acoustic speaker of the present invention.
  • the invention provides a vibrating membrane, which is applied to a sound generating device.
  • the vibrating film of the present invention is prepared by using cast polyurethane, the cast polyurethane is a polyurethane prepolymer and a compounding agent is added through vulcanization, and the polyurethane prepolymer is a block polymer, and the block polymer is composed of hard segments and The soft segments are alternately arranged, the hard segment is isocyanate, the soft segment is a flexible long chain of polyol, the end groups of the block polymer are all isocyanate hard segments, and the strain recovery rate of the diaphragm is >70% after 20% strain.
  • the molecular structure of the polyurethane prepolymer of the present invention is as follows, wherein n is a natural number:
  • the polyurethane prepolymer is a block polymer.
  • the soft segment is composed of the flexible long chain of oligomer polyol
  • the hard segment, the hard segment and the soft segment are composed of isocyanate.
  • the isocyanate group (-NCO) is located at the end of the block polymer, that is, the isocyanate group (-NCO) is terminated.
  • the structure of the hard segment composed of isocyanate is as follows:
  • the structure of the soft segment composed of polyols is as follows:
  • the role of the hard segment here is to provide hardness and modulus, while the soft segment provides toughness.
  • the hardness, modulus and resilience of the diaphragm can be adjusted by adjusting the type and proportion of the hard segment and the type of the soft segment. Therefore, when preparing the diaphragm, the type and proportion of the hard segment, the type of the soft segment, and the weight and dosage of the compounding agent in the cast polyurethane can be adjusted to ensure that the prepared diaphragm has a good elastic recovery rate, which can be Optionally, it is ensured that the elastic recovery rate of the prepared diaphragm after 20% strain is greater than 70%.
  • a compounding agent is added during the preparation of the diaphragm, and the compounding agent and the main material polyurethane prepolymer can undergo a vulcanization reaction under certain conditions to obtain a cross-linked structure.
  • Molecular parts are connected by chemical bonds, so they still have a relatively high recovery rate after a certain strain.
  • thermoplastic elastomer diaphragm has a linear structure.
  • intermolecular slip easily occurs, the viscous part increases, and the loss increases.
  • the irrecoverable part increases, and the resilience is relatively high. Poor, the acoustic performance of the loudspeaker using this diaphragm deteriorates after large displacement vibration and high-demand waterproof test; The movement ability is enhanced, and slippage is more likely to occur.
  • the recovery rate becomes poor, which makes the diaphragm deformed after the reliability of the loudspeaker using the diaphragm, resulting in poor performance and even the risk of membrane rupture.
  • the diaphragm is made of cast polyurethane, and the cast polyurethane is a polyurethane prepolymer and a compounding agent is vulcanized to obtain a cast polyurethane with a cross-linked structure. Since the cast polyurethane has a cross-linked structure, the molecules are networked, and there are chemical bonds between the molecules, it still has a relatively high recovery rate after a certain strain. The recovery rate of the diaphragm after 20% strain is greater than 70%, and the loudspeaker using the diaphragm still maintains good acoustic performance after large-displacement vibration and high-demand waterproof tests.
  • the diaphragm of the present invention adopts a casting molding process. Compared with the thermoplastic elastomer diaphragm formed by air pressure, the diaphragm of the present invention has a uniform thickness, small residual stress after molding, and a flat diaphragm, thereby obtaining better acoustic performance.
  • the cast polyurethane is a cross-linked structure
  • the temperature resistance of the diaphragm will be improved, and permanent deformation will not easily occur during long-term high-temperature stretching at high temperature. Therefore, the preparation process of the diaphragm is adjusted reasonably.
  • the types of raw materials and their added amounts can ensure that the compression permanent deformation rate of the diaphragm is less than 50%.
  • the loudspeaker using this diaphragm can still maintain the original shape and performance after long-term high temperature reliability, and will not be deformed or broken. Membrane and other risks.
  • the compounding agent includes a chain extender and a catalyst.
  • the diaphragm is formed by reacting polyol and polyisocyanate to form a polyurethane prepolymer, and then adding a chain extender and a catalyst. After mixing, it is injected into the diaphragm processing mold. Cross-linking reaction molding is obtained.
  • the polyol and polyisocyanate are first reacted to form a liquid polyurethane prepolymer, and then a chain extender and a catalyst are added to mix evenly, and then injected into the diaphragm processing mold, and formed through a cross-linking reaction.
  • the reaction temperature of the cross-linking reaction is 20°C-230°C, and the reaction time is 3s-120min.
  • the amount of the chain extender should be reasonably controlled to ensure that the prepared diaphragm has suitable hardness and resilience, so that it has suitable acoustic performance and reliability after being applied to a sound-emitting device.
  • the amount of chain extender is 10%-30% of the polyurethane prepolymer. If the dosage is less than 10%, the cross-linking is too low, the hardness of the diaphragm is small, and a thicker thickness is required to achieve the appropriate F0 (resonant frequency).
  • the molecular chain After large strain or long-term high temperature stress, the molecular chain is prone to slip, resulting in the deformation of the diaphragm, which in turn affects the acoustic performance and reliability; if the dosage is more than 30%, the hardness of the diaphragm is too large and the elongation at break decreases. , the diaphragm becomes brittle, and the speaker using this diaphragm is prone to membrane cracking or even rupture after reliability. Therefore, the amount of the chain extender is controlled to be 10% to 30% of the prepolymer, and the diaphragm has a relatively suitable hardness, elongation at break and resilience to ensure that the sound device still maintains excellent performance before and after large strain or long-term stress.
  • the chain extender is 10 parts, 15 parts, 20 parts, 25 parts or 30 parts. It is not easy to produce film rupture and deformation when vibrating at high temperature for a long time.
  • the rebound performance of the diaphragm is optimized by adjusting the amount of the chain extender, so that it has a higher rebound elasticity, that is, when preparing the diaphragm, the amount of the chain extender is 10wt%. -30wt%, it can be ensured that the elastic recovery rate of the vibrating membrane prepared in this way is greater than 70% after 20% strain.
  • the chain extender is a multifunctional low molecular alcohol, amine or alcoholamine compound that can react with isocyanate.
  • the chain extender acts to cross-link with the isocyanate to adjust the hardness and resilience of the final diaphragm.
  • the chain extender is usually 3,3'-dichloro-4,4'-diaminodiphenylmethane (MOCA), 2,5-diethyltoluenediamine, 1,2-bis(2-amino) Phenylthio)ethane, Propylene glycol-bis(p-aminobenzoate), 3,5-diamino-4-chloro-benzoic acid isobutyl ester, 4,4-methylene-bis-(3- chloro-2,6-diethylaniline), 3,5-dimethylthiotoluenediamine, 1,4-butanediol, trimethylolpropane, triisopropanolamine, hydroquinone bishydroxyethyl At least one of base ether, resorcinol-bis(P-hydroxyethyl) ether (HER), and triethanolamine
  • the type of the chain extender is adjusted to ensure that the prepared diaphragm has high resilience, that is, when the diaphragm is prepared, the chain extender is selected and mixed with one or more of the above. , then it can be guaranteed that the elastic recovery rate of the vibrating membrane thus prepared is greater than 70% after 20% strain.
  • the catalyst selects at least one of butyltin dilaurate, stannous octoate, phosphoric acid, oleic acid, adipic acid, azelaic acid, phenylmercuric acetate, phenylmercuric propionate, and iron acetylacetonate.
  • the role of the catalyst here is to speed up the cross-linking reaction, thereby speeding up the film-forming speed of the cast polyurethane and improving the preparation efficiency of the diaphragm.
  • the catalyst can be selected from one or more mixtures of the above substances.
  • the amount of isocyanate used ranges from 2% to 50%.
  • the amount of hardness isocyanate is 2%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45% or 50%, so that better resilience performance can be obtained , more suitable F0 and low frequency performance.
  • the prepared diaphragm has high resilience by adjusting the amount of hard-segment isocyanate, that is, when preparing the diaphragm, the amount of isocyanate in the range of 2% to 50% can be used. It is ensured that the elastic recovery rate of the vibrating membrane thus prepared after 20% strain is greater than 70%.
  • isocyanate selects toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), naphthalene 1.5-diisocyanate (NDI), isophorone diisocyanate (IPDI) for use.
  • TDI toluene diisocyanate
  • MDI diphenylmethane diisocyanate
  • HDI hexamethylene diisocyanate
  • NDI naphthalene 1.5-diisocyanate
  • IPDI isophorone diisocyanate
  • XDI m-dimethylene diisocyanate
  • PPDI p-phenylene diisocyanate
  • TODI 3,3.-dimethyl-4,4.-biphenyl diisocyanate
  • HMDI hexylmethane diisocyanate
  • HTDI hydrogenated toluene diisocyanate
  • TMDI trimethyl hexamethylene diisocyanate
  • the polyol is selected from at least one of polyester polyol, polyether polyol, polybutadiene polyol, castor oil polyol, tetrahydrofuran-propylene oxide copolymer polyol, and epoxy resin modified polyol. .
  • the technical scheme of the present invention can adjust the rebound performance of the diaphragm by reasonably adjusting the amount and type of chain extender, the type and amount of hard-segment isocyanate, and the type of soft-segment polyol at the same time, so that the preparation The elastic recovery rate of the diaphragm after 20% strain is >70%.
  • the diaphragm provided by the present invention is made of cast polyurethane (CPU), which is different from thermoplastic polyurethane (TPU), which has a linear or branched structure and can be processed twice. After extending or coating to make a film, it is then made into a diaphragm by air pressure or molding, while the cast polyurethane of the present invention is a cross-linked structure and cannot be processed twice.
  • CPU cast polyurethane
  • TPU thermoplastic polyurethane
  • Conventional urethane rubber conventional urethane rubber is solid rubber, generally after plasticizing and kneading with compounding agents, it is calendered into a sheet or coated to form a film, and then compressed into a diaphragm by air pressure or molding, vulcanizing agent
  • sulfur, peroxides and isocyanates the resulting diaphragm hardness can be adjusted in a narrow range, and the need for subsequent bonding of components such as casings leads to poor air tightness of the sounding device.
  • the casting type polyurethane described in the present invention is a liquid rubber, which is cast and formed, and a chain extender is added for chain extension and cross-linking.
  • the chain extender is usually alcohols, amines or alcoholamines.
  • the adjustable range is wide, and because it is integrally formed with the casing, the sound-emitting device using the diaphragm has better air tightness.
  • the diaphragm when the diaphragm is prepared, its hardness should be reasonably designed to ensure that the loudspeaker using the diaphragm has excellent acoustic performance.
  • the hardness of the diaphragm is 10A-95A. 85A, 90A or 95A. If the hardness of the diaphragm is lower than 10A, the rigidity of the diaphragm is poor, and it is easy to generate polarization, resulting in poor THD (Total Harmonic Distortion). It is easy to break the film and cause product failure, and too much filler in the formula leads to defects.
  • the hardness of the diaphragm when the hardness of the diaphragm is in the range of 30A-85A, the loudspeaker using the diaphragm has more excellent acoustic performance.
  • the thickness of the diaphragm is in the range of 10 ⁇ m-300 ⁇ m.
  • the thickness of the diaphragm should be reasonably controlled to ensure that the sound-generating device using the diaphragm has excellent acoustic performance. If the thickness of the diaphragm is less than 10 ⁇ m. The damping of the diaphragm is small, and the listening performance is poor; if the thickness of the diaphragm is greater than 300 ⁇ m, the weight of the diaphragm is too large, and the sensitivity becomes poor.
  • the thickness of the diaphragm is 10 ⁇ m, 50 ⁇ m, 100 ⁇ m, 150 ⁇ m, 200 ⁇ m, 250 ⁇ m or 300 ⁇ m. More preferably, when the thickness of the diaphragm is 10-200 ⁇ m, the sound generating device using the diaphragm has more excellent acoustic performance.
  • the rebound performance of the diaphragm is adjusted by reasonably adjusting the amount and type of chain extender, the type of catalyst, the type and amount of hard-segment isocyanate, and the type of soft-segment polyol.
  • the hardness and thickness of the diaphragm are adjusted to make the hardness and thickness design more reasonable, so as to ensure that the sound-emitting device using the diaphragm has better acoustic performance.
  • the compounding agent also includes a filler, and the filler is selected from at least one of carbon black, silica, clay, calcium carbonate, kaolin, talc, unsaturated carboxylic acid metal salt, and glass microbeads .
  • the filler is selected from at least one of carbon black, silica, clay, calcium carbonate, kaolin, talc, unsaturated carboxylic acid metal salt, and glass microbeads .
  • fillers are added to enhance the strength of the diaphragm and further ensure that the diaphragm is not prone to rupture in a high temperature environment.
  • the compounding agent also includes an auxiliary agent
  • the auxiliary agent is selected from at least one of an antioxidant, an ultraviolet absorber, an anti-hydrolysis stabilizer, a plasticizer, a color paste, and an anti-aging agent.
  • the addition of antioxidants can improve its antioxidant performance.
  • the antioxidants can be antioxidants 1010, antioxidants 2, antioxidants 6, antioxidants 4, antioxidants 1076, antioxidants 168, etc. At least one of them is used in an amount of 0.5 to 5 parts by mass.
  • Anti-hydrolysis stabilizer can improve the anti-hydrolysis stability of cast polyurethane
  • plasticizer can increase the processing performance of cast polyurethane
  • color paste can give a certain color
  • antioxidant can improve its anti-aging performance.
  • the addition of the above additives can further improve the comprehensive performance of the cast polyurethane, thereby improving the comprehensive performance of the diaphragm.
  • Users can choose the above additives according to operational requirements and product requirements. one or more of the agents.
  • the castable polyurethane of the present invention is obtained by mixing the liquid polyurethane with a chain extender, a catalyst, a filler and other auxiliaries uniformly, and then injecting it into a corresponding mold and then cross-linking.
  • the cast polyurethane diaphragm of the present invention does not contain a foaming agent, because the addition of the foaming agent will cause the temperature resistance of the diaphragm to deteriorate, and problems such as deformation and even film rupture are likely to occur after reliability testing. , resulting in poor performance and affecting user experience.
  • the use of cast polyurethane in the present invention aims to improve the resilience performance of the diaphragm, and ensures that the loudspeaker using the diaphragm can still maintain the original shape and performance after long-term high temperature reliability, and there will be no risks such as deformation and rupture of the diaphragm. , if the foaming agent is added, it will go against the concept of the present invention.
  • the preparation materials of the vibrating film of the present invention are relatively simple, the preparation process is relatively simple, the operation is relatively simple, and the preparation cost is relatively low.
  • the present invention also proposes a sound-generating device, including a sound-generating device main body and a vibrating membrane.
  • a sound-generating device main body and a vibrating membrane.
  • the specific structure of the vibrating membrane can refer to the above-mentioned embodiments. All the beneficial effects brought by the technical solution will not be repeated here.
  • 1 is an example sectional view of an acoustic speaker, wherein 10 is a speaker casing; 20 is the diaphragm according to the present invention; 30 is a voice coil; and 40 is a magnet.
  • the electrical signal is input to the voice coil 30 of the product, and the voice coil 30 is subjected to the force of the magnetic field, and moves in different amplitudes and directions with the alternating change of the signal size and the positive and negative directions, thereby driving the diaphragm 20 to vibrate and emit sound , complete the electricity-electricity-sound energy conversion process.
  • the vibrating membrane of the present invention can be a ring-shaped vibrating membrane or a flat vibrating membrane, the vibrating membrane is arranged on the main body of the sound generating device, and the vibrating membrane is configured to be able to be driven to vibrate, thereby generating sound through vibration.
  • a coil, a magnetic circuit system and other components may be arranged in the main body of the sounding device to drive the diaphragm to vibrate through electromagnetic induction.
  • the sound producing device provided by the present invention has better sound producing effect and good durability.
  • the Shore hardness of the diaphragm is 10-95A, and the thickness is in the range of 10-300 ⁇ m.
  • the resonant frequency F0 of the micro-sounding device reaches 100-1500 Hz, and the low-frequency performance of the micro-sounding device is excellent. .
  • the CPU Since the diaphragm of the speaker needs to vibrate back and forth, it needs to have high resilience.
  • the CPU has a cross-linked structure, the molecules are networked, and there are chemical bonds between the molecules, so the resilience is better.
  • the inventor further adjusted the ratio of the chain extender. When the mass of the chain extender was in the range of 10%-30%, the recovery rate of the CPU was >70% after a certain strain. It is required to maintain good acoustic performance after the waterproof test; in addition, the cross-linked structure itself improves the temperature resistance, and it is not easy to produce permanent deformation when stretched at high temperature for a long time, and the compression set rate is less than 50%.
  • the speaker of the diaphragm can maintain the original shape and performance after long-term high-temperature reliability, and there will be no risks such as deformation and film rupture; on the other hand, conventional thermoplastic elastomer diaphragms are often formed by air pressure, and the molding process The uneven stretching in the middle leads to the uneven thickness of the diaphragm after molding and the defects such as uneven molding, which leads to a decrease in the yield of the diaphragm and affects the acoustic performance.
  • the cast polyurethane diaphragm of the present invention adopts injection molding, The thickness of the diaphragm is uniform, the residual stress after molding is small, the diaphragm is flat, and better acoustic performance is obtained.
  • the diaphragm of the present invention will be described in detail below through specific examples, wherein the diaphragms shown in the embodiment and the comparative example have basically the same F0 at room temperature, and the difference of F0 is within 20 Hz. It is to be understood that the following description is exemplary only, rather than a specific limitation of the present invention.
  • Example 1 This example is a diaphragm prepared by using cast-type polyurethane.
  • the main raw materials of the diaphragm and its dosage are as follows: 100 parts of polyurethane prepolymer, 5 parts of white carbon black, trimethylolpropane 2 parts, 8 parts of 1,4-butanediol, wherein, trimethylolpropane and 1,4-butanediol are chain extenders, and the proportion of chain extenders is 10% of the polyurethane prepolymer.
  • the diaphragm can be prepared.
  • the thickness of the prepared diaphragm is 110 ⁇ m and the hardness is 40A.
  • Example 2 This example is a diaphragm prepared by using cast polyurethane.
  • the main raw materials of the diaphragm and its dosage are as follows: 100 parts of polyurethane prepolymer, 10 parts of white carbon black, trimethylolpropane 5 parts, 25 parts of 1,4-butanediol, wherein, trimethylolpropane and 1,4-butanediol are chain extenders, and the amount of chain extenders is 30% of the polyurethane prepolymer.
  • the above-mentioned raw materials are mixed uniformly, they are injected into the diaphragm mold, and the diaphragm is formed after vulcanization at 100° C.
  • the prepared diaphragm has a thickness of 70 ⁇ m and a hardness of 75A.
  • Comparative Example 1 is a thermoplastic polyurethane elastomer (TPU) diaphragm with a thickness of 80 ⁇ m and a hardness of 60A.
  • TPU thermoplastic polyurethane elastomer
  • Comparative Example 2 is a thermoplastic polyester elastomer (TPEE) composite diaphragm, the diaphragm is a 3-layer structure, two of which are TPEE layers with a thickness of 15 ⁇ m, and the middle layer is a polyacrylate pressure-sensitive adhesive film with a thickness of 15 ⁇ m. 20 ⁇ m.
  • TPEE thermoplastic polyester elastomer
  • Example 1 The vibrating membranes in Example 1, Example 2, Comparative Example 1 and Comparative Example 2 were tested as follows:
  • Example 1-2 and Comparative Example 1-2 the warpage degree of the diaphragm in Example 1-2 and Comparative Example 1-2 was tested, and the specific test method was: test the product with a tester at room temperature, and the tester includes three parts: Test probes, monitors, and granite platforms, where the test probes are non-contact displacement sensors; during testing, place the product on the three fulcrums of the granite platform, and the upper and lower test probes scan the product synchronously according to the same trajectory, and record the test probe to The distance between the nearest surface of the product, and the difference between the two test probes at each test point is calculated, and half of the difference is the test value of the warpage of the test point, and the test with the largest warpage in each test point is taken The value is defined as the warpage of the product.
  • 100 parallel products were made in each example, the warpage of each parallel product was tested respectively, and the distribution of warpage of each parallel product was counted. For the test the preparation methods of Example 1-2 and Comparative Example 1-2, 100 parallel products were
  • the strain recovery test method is as follows: the stress relaxation is tested in the dynamic thermodynamic analyzer (DMA) tensile mode, the strain is set to 20%, the relaxation is 10 min, the recovery is 10 min, and the final recovery rate is recorded.
  • DMA dynamic thermodynamic analyzer
  • the large-strain (20%) recovery rate of the cast polyurethane diaphragm of the present invention is higher, and it can still be used after the 60m waterproof test. return to its original shape, thus maintaining the same acoustic performance. Therefore, the cast polyurethane diaphragm of the present invention has higher resilience and better waterproof performance.
  • Example 1 In order to verify the performance of the product of the present invention, the compression set of the diaphragm raw materials in Example 1 and Comparative Example 1 was tested.
  • the test standard refers to GB1683-81. Table 3.

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Abstract

A diaphragm and a sound generating device. The diaphragm (20) is prepared by using a casting polyurethane, which is prepared from a polyurethane prepolymer and a compounding agent by means of vulcanization. The polyurethane prepolymer is a block polymer formed by the alternate arrangement of hard and soft segments, wherein the hard segments are isocyanates, and the soft segments are polyol flexible long chains, and each end group of the block polymer is an isocyanate hard segment. The elastic recovery rate of the diaphragm (20) at 20% strain is greater than 70%, which can allow the diaphragm (20) to have a uniform thickness and the diaphragm is formed to be flat during the process of gas pressure forming, so as to ensure that same has good acoustic performance.

Description

振膜和发声装置Diaphragm and sound-generating device 技术领域technical field
本发明涉及电声转换技术领域,特别涉及一种振膜和发声装置。The invention relates to the technical field of electro-acoustic conversion, in particular to a vibrating membrane and a sound-generating device.
背景技术Background technique
目前发声装置中的振膜通常采用热塑性弹性体振膜,比如热塑性聚氨酯弹性体和热塑性聚酯类弹性体振膜。因热塑性聚氨酯弹性体和热塑性聚酯类弹性体振膜具有良好的可塑性、阻尼性和耐温性,随着对扬声器高功率化及高音质的高需求,热塑性弹性体振膜在扬声器领域得到了推广应用。但是,热塑性弹性体振膜常采用气压成型,成型过程中拉伸不均匀,导致成型后振膜厚度不均且出现成型不平整等不良,导致振膜良率降低,声学性能也会受到影响;另一方面,热塑性弹性体振膜由于热塑性弹性体为线形结构,一方面,在大应变下,分子间容易出现滑移,粘性部分增加,损耗增加,撤去外力后,不可恢复部分增加,回弹性较差,使用该振膜的扬声器在大位移振动和高要求防水试验后声学性能变差;而且,长时间高温受力实验时,分子链被长时间在高温下拉伸,高温下分子链运动能力增强,更容易出现滑移,撤去外力后,回复率变差,使得使用该振膜的扬声器可靠性后振膜变形导致性能不良,甚至有破膜的风险。At present, the diaphragm in the sound generating device usually adopts a thermoplastic elastomer diaphragm, such as a thermoplastic polyurethane elastomer and a thermoplastic polyester elastomer diaphragm. Because thermoplastic polyurethane elastomer and thermoplastic polyester elastomer diaphragm have good plasticity, damping and temperature resistance, with the high demand for high power and high sound quality of speakers, thermoplastic elastomer diaphragm has been widely used in the field of speakers. Promote the application. However, the thermoplastic elastomer diaphragm is often formed by air pressure, and the stretching is uneven during the molding process, resulting in uneven thickness of the diaphragm after molding and uneven molding, resulting in a decrease in the yield of the diaphragm and an impact on the acoustic performance; On the other hand, the thermoplastic elastomer diaphragm has a linear structure. On the one hand, under large strain, the intermolecular slip is easy to occur, the viscous part increases, and the loss increases. After the external force is removed, the irrecoverable part increases, and the resilience Poor, the acoustic performance of the loudspeaker using this diaphragm becomes poor after large displacement vibration and high-demand waterproof test; moreover, in the long-term high-temperature stress test, the molecular chain is stretched at high temperature for a long time, and the molecular chain moves at high temperature The ability is enhanced, and slippage is more likely to occur. After the external force is removed, the recovery rate becomes poor, which makes the diaphragm deformed after the reliability of the loudspeaker using the diaphragm, resulting in poor performance and even the risk of membrane rupture.
发明内容SUMMARY OF THE INVENTION
本发明的主要目的是提供一种振膜和发声装置,旨在克服热塑性弹性体振膜在大位移振动、高要求防水试验或长时间高温可靠性后出现变形、破膜等现象,且能够克服热塑性弹性体振膜在气压成型过程中出现的缺陷,使得振膜厚度均匀,成型平整,从而保证其具有较好的声学性能。The main purpose of the present invention is to provide a vibrating membrane and a sounding device, which aims to overcome the deformation and membrane rupture of the thermoplastic elastomer vibrating membrane after large displacement vibration, high-demand waterproof test or long-term high-temperature reliability, and can overcome the The defects of the thermoplastic elastomer diaphragm during the air pressure forming process make the diaphragm thickness uniform and the forming flat, thereby ensuring its good acoustic performance.
为实现上述目的,本发明提出的振膜采用浇注型聚氨酯制备而成,所述浇注型聚氨酯为聚氨酯预聚物外加配合剂经硫化制成,所述聚氨酯预聚物为嵌段聚合物,所述嵌段聚合物由硬段和软段交替排列形成,所述硬段为异氰 酸酯,所述软段为多元醇柔性长链,所述嵌段聚合物的端基均为异氰酸酯硬段,所述振膜于20%应变后的弹性回复率>70%。In order to achieve the above purpose, the diaphragm proposed by the present invention is prepared by using cast-type polyurethane, and the cast-type polyurethane is prepared by vulcanization of a polyurethane prepolymer and a compounding agent, and the polyurethane prepolymer is a block polymer, so The block polymer is formed by alternately arranging hard segments and soft segments, the hard segments are isocyanates, the soft segments are polyol flexible long chains, the end groups of the block polymers are all isocyanate hard segments, and the The elastic recovery rate of the diaphragm after 20% strain is greater than 70%.
可选的实施例中,所述振膜的压缩永久形变率小于50%。In an optional embodiment, the compression set ratio of the diaphragm is less than 50%.
可选的实施例中,所述配合剂包括扩链剂和催化剂,所述振膜是将多元醇与多异氰酸酯反应生成聚氨酯预聚物,之后加入扩链剂和催化剂,混合后注入至振膜加工模具内,通过交联反应成型得到。In an optional embodiment, the compounding agent includes a chain extender and a catalyst, and the diaphragm is formed by reacting a polyol and a polyisocyanate to generate a polyurethane prepolymer, then adding a chain extender and a catalyst, and injecting it into the diaphragm after mixing. In the processing mold, it is formed by cross-linking reaction.
可选的实施例中,按质量百分比计,所述扩链剂的用量为所述聚氨酯预聚物的10%-30%。In an optional embodiment, in terms of mass percentage, the amount of the chain extender is 10%-30% of the polyurethane prepolymer.
可选的实施例中,所述扩链剂为可与异氰酸酯反应的多官能度的低分子醇类或胺类化合物。In an optional embodiment, the chain extender is a multifunctional low molecular alcohol or amine compound that can react with isocyanate.
可选的实施例中,所述扩链剂为3,3’-二氯-4,4’-二氨基二苯基甲烷、2,5-二乙基甲苯二胺、1,2-双(2-氨基苯基硫代)乙烷、丙二醇-双(对氨基苯甲酸酯)、3,5-二氨基-4-氯-苯甲酸异丁酯、4,4-亚甲基-双-(3-氯-2,6-二乙基苯胺)、3,5-二甲基硫基甲苯二胺、1,4-丁二醇、三羟甲基丙烷、三异丙醇胺、氢醌双羟乙基醚、间苯二酚-双(P-羟乙基)醚、三乙醇胺中的至少一种;和/或,所述催化剂选用二月桂酸丁基锡、辛酸亚锡、磷酸、油酸、己二酸、壬二酸、乙酸苯汞、丙酸苯汞、乙酰丙酮铁中的至少一种。In an optional embodiment, the chain extender is 3,3'-dichloro-4,4'-diaminodiphenylmethane, 2,5-diethyltoluenediamine, 1,2-bis( 2-Aminophenylthio)ethane, propylene glycol-bis(p-aminobenzoate), 3,5-diamino-4-chloro-benzoic acid isobutyl ester, 4,4-methylene-bis- (3-chloro-2,6-diethylaniline), 3,5-dimethylthiotoluenediamine, 1,4-butanediol, trimethylolpropane, triisopropanolamine, hydroquinone At least one in bis-hydroxyethyl ether, resorcinol-bis(P-hydroxyethyl) ether, triethanolamine; and/or, described catalyst selects butyltin dilaurate, stannous octoate, phosphoric acid, oleic acid for use , at least one of adipic acid, azelaic acid, phenylmercuric acetate, phenylmercuric propionate, and iron acetylacetonate.
可选的实施例中,按质量百分比计,所述异氰酸酯的用量范围为2%-50%;和/或,所述异氰酸酯选用甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、六亚甲基二异氰酸酯、萘1.5-二异氰酸酯、异佛尔酮二异氰酸酯、间二亚甲基二异氰酸酯、对苯二异氰酸酯、3,3.-二甲基-4,4.-联苯二异氰酸酯、4,4'-二环己基甲烷二异氰酸酯、氢化甲苯二异氰酸酯、三甲基己二异氰酸酯中的至少一种;和/或,所述多元醇选用聚酯多元醇、聚醚多元醇、聚丁二烯型多元醇、蓖麻油多元醇、四氢呋喃-氧化丙烯共聚多元醇、环氧树脂改性多元醇中的至少一种。In an optional embodiment, in terms of mass percentage, the amount of isocyanate used ranges from 2% to 50%; and/or, the isocyanate is selected from toluene diisocyanate, diphenylmethane diisocyanate, and hexamethylene diisocyanate. , naphthalene 1.5-diisocyanate, isophorone diisocyanate, m-dimethylene diisocyanate, p-phenylene diisocyanate, 3,3.-dimethyl-4,4.-biphenyl diisocyanate, 4,4' -at least one of dicyclohexylmethane diisocyanate, hydrogenated toluene diisocyanate, trimethylhexamethylene diisocyanate; and/or, described polyol is selected from polyester polyol, polyether polyol, polybutadiene type polyol At least one of alcohol, castor oil polyol, tetrahydrofuran-propylene oxide copolymer polyol, and epoxy resin modified polyol.
可选的实施例中,所述配合剂还包括填料,所述填料为炭黑、二氧化硅、粘土、碳酸钙、高岭土、滑石粉、玻璃微珠中的至少一种;和/或,所述配合剂还包括助剂,所述助剂为抗氧剂、紫外线吸收剂、抗水解稳定剂、增塑剂、色浆、防老剂中的至少一种。In an optional embodiment, the compounding agent further includes a filler, and the filler is at least one of carbon black, silica, clay, calcium carbonate, kaolin, talc, and glass microbeads; and/or, The compounding agent also includes an auxiliary agent, which is at least one of an antioxidant, an ultraviolet absorber, an anti-hydrolysis stabilizer, a plasticizer, a colorant, and an anti-aging agent.
可选的实施例中,所述振膜的硬度范围为10A-95A。In an optional embodiment, the hardness range of the diaphragm is 10A-95A.
可选的实施例中,所述振膜的硬度范围为30A-85A。In an optional embodiment, the hardness range of the diaphragm is 30A-85A.
可选的实施例中,所述振膜的厚度范围为10μm-300μm;In an optional embodiment, the thickness of the diaphragm ranges from 10 μm to 300 μm;
可选的实施例中,所述振膜的厚度范围为10μm-200μm;In an optional embodiment, the thickness of the diaphragm ranges from 10 μm to 200 μm;
本发明还提出了一种发声装置,所述发声装置包括振膜,所述振膜采用浇注型聚氨酯制备而成,所述浇注型聚氨酯为聚氨酯预聚物外加配合剂经硫化制成,所述聚氨酯预聚物为嵌段聚合物,所述嵌段聚合物由硬段和软段交替排列形成,所述硬段为异氰酸酯,所述软段为多元醇柔性长链,所述嵌段聚合物的端基均为异氰酸酯硬段,所述振膜于20%应变后的弹性回复率>70%。The present invention also provides a sound-generating device. The sound-generating device includes a diaphragm, and the diaphragm is made of cast-type polyurethane. The cast-type polyurethane is made of polyurethane prepolymer and compounding agent through vulcanization. The polyurethane prepolymer is a block polymer, the block polymer is formed by alternating hard segments and soft segments, the hard segment is isocyanate, the soft segment is a long flexible polyol chain, and the block polymer is The end groups are all isocyanate hard segments, and the elastic recovery rate of the diaphragm after 20% strain is greater than 70%.
本发明的技术方案,振膜采用浇注型聚氨酯制备而成,浇注型聚氨酯为聚氨酯预聚物外加配合剂经硫化制成,得到交联结构的浇注型聚氨酯。由于浇注型聚氨酯为交联结构,分子为网状、分子间有化学键连接,在一定应变后仍具有比较高的回复率,并通过合理调节振膜制备过程中的原料种类及其加入量,使得振膜在20%应变后的回复率大于70%,使用该振膜的扬声器在大位移振动和高要求防水试验后依然保持良好的声学性能。并且,本发明振膜采用浇注成型工艺,相较于气压成型的热塑性弹性体振膜,本发明振膜厚度均匀,成型后残余应力小,振膜平整,获得更好的声学性能。In the technical scheme of the present invention, the vibrating membrane is prepared from cast-type polyurethane, and the cast-type polyurethane is prepared by vulcanizing a polyurethane prepolymer and a compounding agent to obtain a cast-type polyurethane with a cross-linked structure. Since the cast polyurethane has a cross-linked structure, the molecules are networked, and there are chemical bonds between the molecules, it still has a relatively high recovery rate after a certain strain. The recovery rate of the diaphragm after 20% strain is greater than 70%, and the loudspeaker using the diaphragm still maintains good acoustic performance after large-displacement vibration and high-demand waterproof tests. In addition, the diaphragm of the present invention adopts a casting molding process. Compared with the thermoplastic elastomer diaphragm formed by air pressure, the diaphragm of the present invention has a uniform thickness, small residual stress after molding, and a flat diaphragm, thereby obtaining better acoustic performance.
附图说明Description of drawings
为了更清楚地说明本发明实施例或现有技术中的技术方案,下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍,显而易见地,下面描述中的附图仅仅是本发明的一些实施例,对于本领域普通技术人员来讲,在不付出创造性劳动的前提下,还可以根据这些附图示出的结构获得其他的附图。In order to explain the embodiments of the present invention or the technical solutions in the prior art more clearly, the following briefly introduces the accompanying drawings that need to be used in the description of the embodiments or the prior art. Obviously, the accompanying drawings in the following description are only These are some embodiments of the present invention, and for those of ordinary skill in the art, other drawings can also be obtained according to the structures shown in these drawings without creative efforts.
图1为本发明发声装置-声学扬声器的剖视结构示意图。FIG. 1 is a schematic cross-sectional structural diagram of a sound producing device-acoustic speaker of the present invention.
附图标号说明:Description of reference numbers:
标号label 名称 name 标号label 名称name
100100 扬声器speaker 3030 音圈voice coil
1010 外壳 shell 4040 磁路系统 Magnetic circuit system
2020 振膜Diaphragm      
本发明目的的实现、功能特点及优点将结合实施例,参照附图做进一步说明。The realization, functional characteristics and advantages of the present invention will be further described with reference to the accompanying drawings in conjunction with the embodiments.
具体实施方式Detailed ways
下面将对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明的一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.
另外,各个实施例之间的技术方案可以相互结合,但是必须是以本领域普通技术人员能够实现为基础,当技术方案的结合出现相互矛盾或无法实现时应当认为这种技术方案的结合不存在,也不在本发明要求的保护范围之内。In addition, the technical solutions between the various embodiments can be combined with each other, but must be based on the realization by those of ordinary skill in the art. When the combination of technical solutions is contradictory or cannot be realized, it should be considered that the combination of such technical solutions does not exist. , is not within the scope of protection required by the present invention.
本发明提出一种振膜,应用于发声装置。The invention provides a vibrating membrane, which is applied to a sound generating device.
本发明振膜采用浇注型聚氨酯制备而成,浇注型聚氨酯为聚氨酯预聚物外加配合剂经硫化制成,所述聚氨酯预聚物为嵌段聚合物,所述嵌段聚合物由硬段和软段交替排列形成,硬段为异氰酸酯,软段为多元醇柔性长链,嵌段聚合物的端基均为异氰酸酯硬段,于20%应变后振膜的应变回复率>70%。The vibrating film of the present invention is prepared by using cast polyurethane, the cast polyurethane is a polyurethane prepolymer and a compounding agent is added through vulcanization, and the polyurethane prepolymer is a block polymer, and the block polymer is composed of hard segments and The soft segments are alternately arranged, the hard segment is isocyanate, the soft segment is a flexible long chain of polyol, the end groups of the block polymer are all isocyanate hard segments, and the strain recovery rate of the diaphragm is >70% after 20% strain.
本发明聚氨酯预聚物的分子结构如下所示,其中n为自然数:The molecular structure of the polyurethane prepolymer of the present invention is as follows, wherein n is a natural number:
Figure PCTCN2021114294-appb-000001
Figure PCTCN2021114294-appb-000001
从上述分子结构中可以看出,聚氨酯预聚物是一种嵌段聚合物,一般由低聚物多元醇柔性长链构成软段部分,以异氰酸酯构成硬段部分,硬段部分和软段部分交替排列,形成重复结构单元,异氰酸酯基(-NCO)位于嵌段聚合物的端部,即异氰酸酯基(-NCO)封端。其中异氰酸酯构成的硬段部分结构如下:It can be seen from the above molecular structure that the polyurethane prepolymer is a block polymer. Generally, the soft segment is composed of the flexible long chain of oligomer polyol, and the hard segment, the hard segment and the soft segment are composed of isocyanate. Alternately arranged to form repeating structural units, the isocyanate group (-NCO) is located at the end of the block polymer, that is, the isocyanate group (-NCO) is terminated. The structure of the hard segment composed of isocyanate is as follows:
Figure PCTCN2021114294-appb-000002
Figure PCTCN2021114294-appb-000002
多元醇组成的软段部分结构如下:The structure of the soft segment composed of polyols is as follows:
-O-R 1-O- -OR 1 -O-
这里硬段部分所起的作用是提供硬度和模量,软段部分提供韧性,通过调整硬段部分的种类和比例及软段部分的种类来调节振膜的硬度、模量及回弹性能。故在制备振膜时,可以通过调整浇注型聚氨酯中硬段部分的种类和比例、软段部分的种类及配合剂的重量及用量来保证制备得到的振膜具有较好的弹性回复率,可选地,保证制备得到的振膜于20%应变后的弹性回复率大于70%。并且,在制备振膜时加入了配合剂,配合剂与主体材料聚氨酯预聚物在一定条件下可以发生硫化反应,以得到交联结构的浇注型聚氨酯,浇注型聚氨酯分子为网状结构,且分子件有化学键连接,则在一定应变后仍具有比较高的回复率。The role of the hard segment here is to provide hardness and modulus, while the soft segment provides toughness. The hardness, modulus and resilience of the diaphragm can be adjusted by adjusting the type and proportion of the hard segment and the type of the soft segment. Therefore, when preparing the diaphragm, the type and proportion of the hard segment, the type of the soft segment, and the weight and dosage of the compounding agent in the cast polyurethane can be adjusted to ensure that the prepared diaphragm has a good elastic recovery rate, which can be Optionally, it is ensured that the elastic recovery rate of the prepared diaphragm after 20% strain is greater than 70%. In addition, a compounding agent is added during the preparation of the diaphragm, and the compounding agent and the main material polyurethane prepolymer can undergo a vulcanization reaction under certain conditions to obtain a cross-linked structure. Molecular parts are connected by chemical bonds, so they still have a relatively high recovery rate after a certain strain.
而目前的热塑性弹性体振膜由于热塑性弹性体为线形结构,一方面,在大应变下,分子间容易出现滑移,粘性部分增加,损耗增加,撤去外力后,不可恢复部分增加,回弹性较差,使用该振膜的扬声器在大位移振动和高要求防水试验后声学性能变差;另一方面,长时间高温受力实验时,分子链被长时间在高温下拉伸,高温下分子链运动能力增强,更容易出现滑移,撤去外力后,回复率变差,使得使用该振膜的扬声器可靠性后振膜变形导致性能不良,甚至有破膜的风险。However, the current thermoplastic elastomer diaphragm has a linear structure. On the one hand, under large strain, intermolecular slip easily occurs, the viscous part increases, and the loss increases. After the external force is removed, the irrecoverable part increases, and the resilience is relatively high. Poor, the acoustic performance of the loudspeaker using this diaphragm deteriorates after large displacement vibration and high-demand waterproof test; The movement ability is enhanced, and slippage is more likely to occur. After the external force is removed, the recovery rate becomes poor, which makes the diaphragm deformed after the reliability of the loudspeaker using the diaphragm, resulting in poor performance and even the risk of membrane rupture.
可以理解的,本发明的技术方案,振膜采用浇注型聚氨酯制备而成,浇注型聚氨酯为聚氨酯预聚物外加配合剂经硫化制成,得到交联结构的浇注型聚氨酯。由于浇注型聚氨酯为交联结构,分子为网状、分子间有化学键连接,在一定应变后仍具有比较高的回复率,并通过合理调节振膜制备过程中的原料种类及其加入量,使得振膜在20%应变后的回复率大于70%,使用该振膜的扬声器在大位移振动和高要求防水试验后依然保持良好的声学性能。并且,本发明振膜采用浇注成型工艺,相较于气压成型的热塑性弹性体振膜,本发明振膜厚度均匀,成型后残余应力小,振膜平整,获得更好的声学性能。It can be understood that in the technical solution of the present invention, the diaphragm is made of cast polyurethane, and the cast polyurethane is a polyurethane prepolymer and a compounding agent is vulcanized to obtain a cast polyurethane with a cross-linked structure. Since the cast polyurethane has a cross-linked structure, the molecules are networked, and there are chemical bonds between the molecules, it still has a relatively high recovery rate after a certain strain. The recovery rate of the diaphragm after 20% strain is greater than 70%, and the loudspeaker using the diaphragm still maintains good acoustic performance after large-displacement vibration and high-demand waterproof tests. In addition, the diaphragm of the present invention adopts a casting molding process. Compared with the thermoplastic elastomer diaphragm formed by air pressure, the diaphragm of the present invention has a uniform thickness, small residual stress after molding, and a flat diaphragm, thereby obtaining better acoustic performance.
本发明实施例中,由于浇注型聚氨酯为交联结构,则会使得振膜的耐温 性提高,在高温下在长时间高温拉伸时也不易产生永久变形,故通过合理调节振膜制备过程中的原料种类及其加入量,可以保证振膜压缩永久形变率小于50%,使用该振膜的扬声器满足在长时间高温可靠性后仍能保持原来的形状和性能,不会出现变形、破膜等风险。In the embodiment of the present invention, since the cast polyurethane is a cross-linked structure, the temperature resistance of the diaphragm will be improved, and permanent deformation will not easily occur during long-term high-temperature stretching at high temperature. Therefore, the preparation process of the diaphragm is adjusted reasonably. The types of raw materials and their added amounts can ensure that the compression permanent deformation rate of the diaphragm is less than 50%. The loudspeaker using this diaphragm can still maintain the original shape and performance after long-term high temperature reliability, and will not be deformed or broken. Membrane and other risks.
本发明实施例中,配合剂包括扩链剂和催化剂,振膜是将多元醇与多异氰酸酯反应生成聚氨酯预聚物,之后加入扩链剂和催化剂,混合后注入至振膜加工模具内,通过交联反应成型得到。In the embodiment of the present invention, the compounding agent includes a chain extender and a catalyst. The diaphragm is formed by reacting polyol and polyisocyanate to form a polyurethane prepolymer, and then adding a chain extender and a catalyst. After mixing, it is injected into the diaphragm processing mold. Cross-linking reaction molding is obtained.
具体操作时,先将多元醇与多异氰酸酯反应生成液体聚氨酯预聚物,然后外加扩链剂和催化剂混合均匀后,经注射进入振膜加工模具内,通过交联反应成型得到。其中,交联反应反应温度为20℃-230℃,反应时间3s-120min。In the specific operation, the polyol and polyisocyanate are first reacted to form a liquid polyurethane prepolymer, and then a chain extender and a catalyst are added to mix evenly, and then injected into the diaphragm processing mold, and formed through a cross-linking reaction. Wherein, the reaction temperature of the cross-linking reaction is 20°C-230°C, and the reaction time is 3s-120min.
在加入扩链剂时,要合理控制扩链剂的用量,以保证制备的振膜有合适的硬度和回弹性,从而在应用于发声装置后具有比较合适的声学性能和可靠性。可选地,按质量百分比计,扩链剂的用量为聚氨酯预聚物的10%-30%。用量<10%,交联度过低,振膜硬度小,需要较厚的厚度才能达到合适的F0(谐振频率),而厚度过大会导致重量过重使得灵敏度降低,且交联度过低,在大应变或者长时间高温受力后,分子链容易产生滑移,导致振膜发生形变,进而使得声学性能和可靠性受到影响;用量>30%,振膜硬度过大导致断裂伸长率降低,振膜变脆,使用该振膜的扬声器在可靠性后容易产生膜裂甚至破膜。因此控制扩链剂的用量为预聚物的10%~30%,振膜有较为合适的硬度、断裂伸长率和回弹性,保证发声装置在大应变或长时间受力前后依然保持优异的声学性能。比如,按质量份计,浇注型聚氨酯为100份,则扩链剂为10份、15份、20份、25份或30份,由此制得的振膜具有更高的回弹性,在防水和高温长时间振动时不易产生破膜和变形的现象。When adding a chain extender, the amount of the chain extender should be reasonably controlled to ensure that the prepared diaphragm has suitable hardness and resilience, so that it has suitable acoustic performance and reliability after being applied to a sound-emitting device. Optionally, in terms of mass percentage, the amount of chain extender is 10%-30% of the polyurethane prepolymer. If the dosage is less than 10%, the cross-linking is too low, the hardness of the diaphragm is small, and a thicker thickness is required to achieve the appropriate F0 (resonant frequency). After large strain or long-term high temperature stress, the molecular chain is prone to slip, resulting in the deformation of the diaphragm, which in turn affects the acoustic performance and reliability; if the dosage is more than 30%, the hardness of the diaphragm is too large and the elongation at break decreases. , the diaphragm becomes brittle, and the speaker using this diaphragm is prone to membrane cracking or even rupture after reliability. Therefore, the amount of the chain extender is controlled to be 10% to 30% of the prepolymer, and the diaphragm has a relatively suitable hardness, elongation at break and resilience to ensure that the sound device still maintains excellent performance before and after large strain or long-term stress. acoustic performance. For example, if the casting polyurethane is 100 parts by mass, the chain extender is 10 parts, 15 parts, 20 parts, 25 parts or 30 parts. It is not easy to produce film rupture and deformation when vibrating at high temperature for a long time.
可以理解的,本实施例中是通过调节扩链剂的用量来优化振膜的回弹性能,使其具有更高的回弹性,即在制备振膜时,扩链剂的用量范围为10wt%-30wt%,则可以保证由此制备得到的振膜在20%应变后的弹性回复率大于70%。It can be understood that in this example, the rebound performance of the diaphragm is optimized by adjusting the amount of the chain extender, so that it has a higher rebound elasticity, that is, when preparing the diaphragm, the amount of the chain extender is 10wt%. -30wt%, it can be ensured that the elastic recovery rate of the vibrating membrane prepared in this way is greater than 70% after 20% strain.
本发明实施例中,扩链剂为可与异氰酸酯反应的多官能度的低分子醇类、胺类或醇胺类化合物。In the embodiment of the present invention, the chain extender is a multifunctional low molecular alcohol, amine or alcoholamine compound that can react with isocyanate.
这里扩链剂起到与异氰酸酯交联的作用,以调节最终振膜的硬度和回弹性。所述扩链剂通常为3,3’-二氯-4,4’-二氨基二苯基甲烷(MOCA)、2,5-二乙基甲苯二胺、1,2-双(2-氨基苯基硫代)乙烷、丙二醇-双(对氨基苯甲酸酯)、3,5-二氨基-4-氯-苯甲酸异丁酯、4,4-亚甲基-双-(3-氯-2,6-二乙基苯胺)、3,5-二甲基硫基甲苯二胺、1,4-丁二醇、三羟甲基丙烷、三异丙醇胺、氢醌双羟乙基醚、间苯二酚-双(P-羟乙基)醚(HER)、三乙醇胺中的至少一种。可以理解的,本实施例中,通过调节扩链剂的种类来保证制备的振膜具有较高的回弹性,即,在制备振膜时,扩链剂选用上述中的一种或多种混合,则可以保证由此制备得到的振膜在20%应变后的弹性回复率大于70%。Here the chain extender acts to cross-link with the isocyanate to adjust the hardness and resilience of the final diaphragm. The chain extender is usually 3,3'-dichloro-4,4'-diaminodiphenylmethane (MOCA), 2,5-diethyltoluenediamine, 1,2-bis(2-amino) Phenylthio)ethane, Propylene glycol-bis(p-aminobenzoate), 3,5-diamino-4-chloro-benzoic acid isobutyl ester, 4,4-methylene-bis-(3- chloro-2,6-diethylaniline), 3,5-dimethylthiotoluenediamine, 1,4-butanediol, trimethylolpropane, triisopropanolamine, hydroquinone bishydroxyethyl At least one of base ether, resorcinol-bis(P-hydroxyethyl) ether (HER), and triethanolamine. It can be understood that in this embodiment, the type of the chain extender is adjusted to ensure that the prepared diaphragm has high resilience, that is, when the diaphragm is prepared, the chain extender is selected and mixed with one or more of the above. , then it can be guaranteed that the elastic recovery rate of the vibrating membrane thus prepared is greater than 70% after 20% strain.
本发明的实施例中,催化剂选用二月桂酸丁基锡、辛酸亚锡、磷酸、油酸、己二酸、壬二酸、乙酸苯汞、丙酸苯汞、乙酰丙酮铁中的至少一种。In the embodiment of the present invention, the catalyst selects at least one of butyltin dilaurate, stannous octoate, phosphoric acid, oleic acid, adipic acid, azelaic acid, phenylmercuric acetate, phenylmercuric propionate, and iron acetylacetonate.
这里催化剂的作用是加快交联反应,从而加快浇注型聚氨酯的成膜速度,提高振膜的制备效率。在制备振膜时,催化剂可选用上述物质的其中一种或多种混合物。The role of the catalyst here is to speed up the cross-linking reaction, thereby speeding up the film-forming speed of the cast polyurethane and improving the preparation efficiency of the diaphragm. When preparing the diaphragm, the catalyst can be selected from one or more mixtures of the above substances.
本发明实施例中,按质量百分比计,异氰酸酯的用量范围为2%-50%。In the embodiment of the present invention, in terms of mass percentage, the amount of isocyanate used ranges from 2% to 50%.
硬段部分含量太低,橡胶的硬度和模量太低,回弹性太差,并且F0(谐振频率)太低;含量太高,硬度和模量过高,响度变低,低频性能较差,故要合理控制硬度异氰酸酯的用量。可选地,异氰酸酯的用量为2%、5%、10%、15%、20%、25%、30%、35%、40%、45%或50%,如此可以获得较好的回弹性能、较为合适的F0和低频性能。If the content of the hard segment is too low, the hardness and modulus of the rubber are too low, the resilience is too poor, and the F0 (resonant frequency) is too low; if the content is too high, the hardness and modulus are too high, the loudness becomes low, and the low-frequency performance is poor. Therefore, it is necessary to reasonably control the amount of hardness isocyanate. Optionally, the amount of isocyanate is 2%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45% or 50%, so that better resilience performance can be obtained , more suitable F0 and low frequency performance.
可以理解的,本实施例中,通过调节硬段异氰酸酯的用量来保证制备的振膜具有较高的回弹性,即,在制备振膜时,异氰酸酯的用量范围为2%-50%,则可以保证由此制备得到的振膜在20%应变后的弹性回复率大于70%。It can be understood that in this embodiment, the prepared diaphragm has high resilience by adjusting the amount of hard-segment isocyanate, that is, when preparing the diaphragm, the amount of isocyanate in the range of 2% to 50% can be used. It is ensured that the elastic recovery rate of the vibrating membrane thus prepared after 20% strain is greater than 70%.
进一步地,通过调节硬段异氰酸酯和软段多元醇的种类来保证制备的振膜具有较高的回弹性。Further, by adjusting the types of hard-segment isocyanate and soft-segment polyol, it is ensured that the prepared diaphragm has high resilience.
可选地,异氰酸酯选用甲苯二异氰酸酯(TDI)、二苯基甲烷二异氰酸酯(MDI)、六亚甲基二异氰酸酯(HDI)、萘1.5—二异氰酸酯(NDI)、异佛尔酮二异氰酸酯(IPDI)、间二亚甲基二异氰酸酯(XDI)、对苯二异氰酸酯(PPDI)、3,3.-二甲基-4,4.-联苯二异氰酸酯(TODI)、4,4'-二环己基甲 烷二异氰酸酯(HMDI)、氢化甲苯二异氰酸酯(HTDI)、三甲基己二异氰酸酯(TMDI)中的至少一种。Optionally, isocyanate selects toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), naphthalene 1.5-diisocyanate (NDI), isophorone diisocyanate (IPDI) for use. ), m-dimethylene diisocyanate (XDI), p-phenylene diisocyanate (PPDI), 3,3.-dimethyl-4,4.-biphenyl diisocyanate (TODI), 4,4'-bicyclo At least one of hexylmethane diisocyanate (HMDI), hydrogenated toluene diisocyanate (HTDI), and trimethyl hexamethylene diisocyanate (TMDI).
可选地,多元醇选用聚酯多元醇、聚醚多元醇、聚丁二烯型多元醇、蓖麻油多元醇、四氢呋喃-氧化丙烯共聚多元醇、环氧树脂改性多元醇中的至少一种。Optionally, the polyol is selected from at least one of polyester polyol, polyether polyol, polybutadiene polyol, castor oil polyol, tetrahydrofuran-propylene oxide copolymer polyol, and epoxy resin modified polyol. .
可以理解的,本发明的技术方案,可以通过同时合理调节扩链剂的用量及其种类,硬段异氰酸酯的种类及其用量、软段多元醇的种类来调节振膜的回弹性能,使得制备的振膜在20%应变后的弹性回复率>70%。It can be understood that the technical scheme of the present invention can adjust the rebound performance of the diaphragm by reasonably adjusting the amount and type of chain extender, the type and amount of hard-segment isocyanate, and the type of soft-segment polyol at the same time, so that the preparation The elastic recovery rate of the diaphragm after 20% strain is >70%.
需要说明的是,本发明提供的振膜,采用浇注型聚氨酯(CPU)制成,区别于热塑性聚氨酯(TPU),热塑性聚氨酯(TPU)是线形或支化结构,可二次加工,一般经流延或涂布制成薄膜后,再通过气压或模压制成振膜,而本发明所述浇注型聚氨酯为交联结构,不可二次加工,经注入模具一体成型制备成振膜;也区别于常规的聚氨酯橡胶,常规的聚氨酯橡胶为固体橡胶,一般与配合剂经过塑炼、混炼加工后,通过压延制成片状或涂布成膜,再经气压或模压制成振膜,硫化剂常为硫黄、过氧化物和异氰酸酯,由此制得的振膜硬度可调范围较窄,且因需后续粘接外壳等部件,导致发声装置气密性差。而本发明所述的浇注型聚氨酯为液态橡胶,浇注成型,外加扩链剂进行扩链和交联,扩链剂通常为醇类、胺类或醇胺类,由此制得的振膜硬度可调范围宽,且因为是与外壳一体成型,故应用该振膜的发声装置具有较好的气密性。It should be noted that the diaphragm provided by the present invention is made of cast polyurethane (CPU), which is different from thermoplastic polyurethane (TPU), which has a linear or branched structure and can be processed twice. After extending or coating to make a film, it is then made into a diaphragm by air pressure or molding, while the cast polyurethane of the present invention is a cross-linked structure and cannot be processed twice. Conventional urethane rubber, conventional urethane rubber is solid rubber, generally after plasticizing and kneading with compounding agents, it is calendered into a sheet or coated to form a film, and then compressed into a diaphragm by air pressure or molding, vulcanizing agent Usually sulfur, peroxides and isocyanates, the resulting diaphragm hardness can be adjusted in a narrow range, and the need for subsequent bonding of components such as casings leads to poor air tightness of the sounding device. The casting type polyurethane described in the present invention is a liquid rubber, which is cast and formed, and a chain extender is added for chain extension and cross-linking. The chain extender is usually alcohols, amines or alcoholamines. The adjustable range is wide, and because it is integrally formed with the casing, the sound-emitting device using the diaphragm has better air tightness.
本发明实施例中,振膜制备时,其硬度要设计合理,以保证使用该振膜的扬声器具有优异的声学性能。可选地,振膜的硬度范围为10A-95A,比如振膜的硬度为10A、15A、20A、25A、30A、35A、40A、45A、50A、55A、60A、65A、70A、75A、80A、85A、90A或95A。若振膜的硬度低于10A,振膜刚性差,易产生偏振,造成THD(总谐波失真,Total Harmonic Distortion)不良;若硬度高于95A,橡胶断裂伸长率变小,低温可靠性验证中易破膜造成产品失效,且配方中填料过多导致缺陷。优选地,振膜的硬度范围为30A-85A时,使用该振膜的扬声器具有更优异的声学性能。In the embodiment of the present invention, when the diaphragm is prepared, its hardness should be reasonably designed to ensure that the loudspeaker using the diaphragm has excellent acoustic performance. Optionally, the hardness of the diaphragm is 10A-95A. 85A, 90A or 95A. If the hardness of the diaphragm is lower than 10A, the rigidity of the diaphragm is poor, and it is easy to generate polarization, resulting in poor THD (Total Harmonic Distortion). It is easy to break the film and cause product failure, and too much filler in the formula leads to defects. Preferably, when the hardness of the diaphragm is in the range of 30A-85A, the loudspeaker using the diaphragm has more excellent acoustic performance.
本发明实施例中,振膜的厚度范围为10μm-300μm。在采用浇注型聚氨酯制备振膜时,要合理控制振膜的厚度,以保证应用该振膜的发声装置具 有优异的声学性能。若振膜的厚度小于10μm。振膜的阻尼小,听音性能差;若振膜的厚度大于300μm,振膜重量过大,灵敏度变差。可选地,振膜的厚度为10μm、50μm、100μm、150μm、200μm、250μm或300μm。更优选地,振膜的厚度为10-200μm时,使用该振膜的发声装置具有更优异的声学性能。In the embodiment of the present invention, the thickness of the diaphragm is in the range of 10 μm-300 μm. When using cast polyurethane to prepare the diaphragm, the thickness of the diaphragm should be reasonably controlled to ensure that the sound-generating device using the diaphragm has excellent acoustic performance. If the thickness of the diaphragm is less than 10μm. The damping of the diaphragm is small, and the listening performance is poor; if the thickness of the diaphragm is greater than 300 μm, the weight of the diaphragm is too large, and the sensitivity becomes poor. Optionally, the thickness of the diaphragm is 10 μm, 50 μm, 100 μm, 150 μm, 200 μm, 250 μm or 300 μm. More preferably, when the thickness of the diaphragm is 10-200 μm, the sound generating device using the diaphragm has more excellent acoustic performance.
需要说明的是,在制备振膜时,通过合理调节扩链剂的用量及其种类,催化剂的种类、硬段异氰酸酯的种类及其用量、软段多元醇的种类来调节振膜的回弹性能,同时也调节了振膜的硬度和厚度,使其硬度和厚度设计较为合理,从而保证使用该振膜的发声装置具有更优异的声学性能。It should be noted that when preparing the diaphragm, the rebound performance of the diaphragm is adjusted by reasonably adjusting the amount and type of chain extender, the type of catalyst, the type and amount of hard-segment isocyanate, and the type of soft-segment polyol. At the same time, the hardness and thickness of the diaphragm are adjusted to make the hardness and thickness design more reasonable, so as to ensure that the sound-emitting device using the diaphragm has better acoustic performance.
进一步地,本发明的实施例中,配合剂还包括填料,填料选用炭黑、二氧化硅、粘土、碳酸钙、高岭土、滑石粉、不饱和羧酸金属盐、玻璃微珠中的至少一种。在保证振膜具有较好的回弹性的基础上,加入了填料,可以增强振膜的强度,进一步保证振膜在高温环境下不易出现破膜的现象。Further, in the embodiment of the present invention, the compounding agent also includes a filler, and the filler is selected from at least one of carbon black, silica, clay, calcium carbonate, kaolin, talc, unsaturated carboxylic acid metal salt, and glass microbeads . On the basis of ensuring that the diaphragm has good resilience, fillers are added to enhance the strength of the diaphragm and further ensure that the diaphragm is not prone to rupture in a high temperature environment.
进一步地,本发明的实施例中,配合剂还包括助剂,助剂选用抗氧剂、紫外线吸收剂、抗水解稳定剂、增塑剂、色浆、防老剂中的至少一种。其中,抗氧剂的加入,可以提高其抗氧化性能,抗氧剂可以是抗氧剂1010、抗氧剂2、抗氧剂6,抗氧剂4,抗氧剂1076、抗氧剂168等中的至少一种,用量为0.5~5份(质量份)。抗水解稳定剂可以提高浇注型聚氨酯的抗水解稳定性,增塑剂可以增加浇注型聚氨酯的加工性能,色浆可以赋予一定的色彩,防老剂可以提高其防老化性能。在保证振膜具有较好的回弹性的基础上,加入了上述助剂,可以进一步提高浇注型聚氨酯的综合性能,从而提高振膜的综合性能,用户可以根据操作需求和产品需求来选用上述助剂的一种或多种。Further, in the embodiment of the present invention, the compounding agent also includes an auxiliary agent, and the auxiliary agent is selected from at least one of an antioxidant, an ultraviolet absorber, an anti-hydrolysis stabilizer, a plasticizer, a color paste, and an anti-aging agent. Among them, the addition of antioxidants can improve its antioxidant performance. The antioxidants can be antioxidants 1010, antioxidants 2, antioxidants 6, antioxidants 4, antioxidants 1076, antioxidants 168, etc. At least one of them is used in an amount of 0.5 to 5 parts by mass. Anti-hydrolysis stabilizer can improve the anti-hydrolysis stability of cast polyurethane, plasticizer can increase the processing performance of cast polyurethane, color paste can give a certain color, and antioxidant can improve its anti-aging performance. On the basis of ensuring the better resilience of the diaphragm, the addition of the above additives can further improve the comprehensive performance of the cast polyurethane, thereby improving the comprehensive performance of the diaphragm. Users can choose the above additives according to operational requirements and product requirements. one or more of the agents.
可以理解的,本发明浇注型聚氨酯是由液体聚氨酯外加扩链剂、催化剂、填料以及其他助剂混合均匀后,经注射进入相应模具后交联得到。It can be understood that the castable polyurethane of the present invention is obtained by mixing the liquid polyurethane with a chain extender, a catalyst, a filler and other auxiliaries uniformly, and then injecting it into a corresponding mold and then cross-linking.
需要说明的是,本发明所述浇注型聚氨酯振膜中不含有发泡剂,因为发泡剂的加入会导致振膜耐温性变差,经过可靠性测试后容易产生变形甚至破膜等问题,导致性能不良,影响用户的使用体验。本发明采用浇注型聚氨酯旨在提高振膜的回弹性能,且保证使用该振膜的扬声器满足在长时间高温可靠性后仍能保持原来的形状和性能,不会出现变形、破膜等风险,若加入发 泡剂则会与本发明的构思相违背。同时本发明振膜的制备原料较为简单,制备工艺较为简化,操作较为简单,制备成本相对较低。It should be noted that the cast polyurethane diaphragm of the present invention does not contain a foaming agent, because the addition of the foaming agent will cause the temperature resistance of the diaphragm to deteriorate, and problems such as deformation and even film rupture are likely to occur after reliability testing. , resulting in poor performance and affecting user experience. The use of cast polyurethane in the present invention aims to improve the resilience performance of the diaphragm, and ensures that the loudspeaker using the diaphragm can still maintain the original shape and performance after long-term high temperature reliability, and there will be no risks such as deformation and rupture of the diaphragm. , if the foaming agent is added, it will go against the concept of the present invention. At the same time, the preparation materials of the vibrating film of the present invention are relatively simple, the preparation process is relatively simple, the operation is relatively simple, and the preparation cost is relatively low.
本发明还提出了一种发声装置,包括发声装置主体和振膜,振膜的具体结构可参照上述实施例,由于发声装置采用了前述所有实施例的全部技术方案,因此至少具有前述实施例的技术方案所带来的所有有益效果,在此不再一一赘述。The present invention also proposes a sound-generating device, including a sound-generating device main body and a vibrating membrane. The specific structure of the vibrating membrane can refer to the above-mentioned embodiments. All the beneficial effects brought by the technical solution will not be repeated here.
如附图1是声学扬声器的示例剖视图,其中,10为扬声器外壳;20为本发明所述振膜;30为音圈;40为磁铁。当扬声器工作时,电信号输入产品音圈30,音圈30受到磁场的作用力,并随着信号大小、正负方向的交替变化做不同幅度和方向的运动,从而带动振膜20振动发出声音,完成电-力-声能量转化过程。1 is an example sectional view of an acoustic speaker, wherein 10 is a speaker casing; 20 is the diaphragm according to the present invention; 30 is a voice coil; and 40 is a magnet. When the speaker is working, the electrical signal is input to the voice coil 30 of the product, and the voice coil 30 is subjected to the force of the magnetic field, and moves in different amplitudes and directions with the alternating change of the signal size and the positive and negative directions, thereby driving the diaphragm 20 to vibrate and emit sound , complete the electricity-electricity-sound energy conversion process.
本发明的振膜可以为折环振膜或者平板振膜,振膜设置在发声装置主体上,振膜被配置为能够被驱动振动,通过振动进而产生声音。发声装置主体中可以配置有线圈、磁路系统等部件,通过电磁感应驱动振膜振动。本发明提供的发声装置具有较好的发声效果和良好的耐用性。The vibrating membrane of the present invention can be a ring-shaped vibrating membrane or a flat vibrating membrane, the vibrating membrane is arranged on the main body of the sound generating device, and the vibrating membrane is configured to be able to be driven to vibrate, thereby generating sound through vibration. A coil, a magnetic circuit system and other components may be arranged in the main body of the sounding device to drive the diaphragm to vibrate through electromagnetic induction. The sound producing device provided by the present invention has better sound producing effect and good durability.
在一个具体的实施例中,振膜的邵氏硬度在10-95A,厚度在10-300μm这一范围,此时微型发声装置的谐振频率F0达到100-1500Hz,则微型发声装置的低频性能优良。In a specific embodiment, the Shore hardness of the diaphragm is 10-95A, and the thickness is in the range of 10-300 μm. At this time, the resonant frequency F0 of the micro-sounding device reaches 100-1500 Hz, and the low-frequency performance of the micro-sounding device is excellent. .
扬声器的振膜由于需要往复振动,因此需要具有较高的回弹性。本申请实施例中,相比普通的热塑性弹性体振膜材料,CPU为交联结构,分子为网状、分子间有化学键连接,因此其回弹性较好。发明人进一步调整扩链剂的比例,当扩链剂的质量位于10%-30%的范围内时,CPU在一定应变后回复率>70%,使用该振膜的扬声器在大位移振动和高要求防水试验后依然保持良好的声学性能;另外,本身的交联结构使得耐温性也提高,在高温下在长时间高温拉伸时也不易产生永久变形,压缩永久变形率<50%,使用该振膜的扬声器满足在长时间高温可靠性后仍能保持原来的形状和性能,不会出现变形、破膜等风险;另一方面,常规的热塑性弹性体振膜常采用气压成型,成型过程中拉伸不均匀,导致成型后振膜厚度不均且出现成型不平整等不 良,导致振膜良率降低,声学性能也会受到影响,而本发明所述浇注型聚氨酯振膜采用注射成型,振膜厚度均匀,成型后残余应力小,振膜平整,获得更好的声学性能。Since the diaphragm of the speaker needs to vibrate back and forth, it needs to have high resilience. In the embodiment of the present application, compared with the common thermoplastic elastomer diaphragm material, the CPU has a cross-linked structure, the molecules are networked, and there are chemical bonds between the molecules, so the resilience is better. The inventor further adjusted the ratio of the chain extender. When the mass of the chain extender was in the range of 10%-30%, the recovery rate of the CPU was >70% after a certain strain. It is required to maintain good acoustic performance after the waterproof test; in addition, the cross-linked structure itself improves the temperature resistance, and it is not easy to produce permanent deformation when stretched at high temperature for a long time, and the compression set rate is less than 50%. The speaker of the diaphragm can maintain the original shape and performance after long-term high-temperature reliability, and there will be no risks such as deformation and film rupture; on the other hand, conventional thermoplastic elastomer diaphragms are often formed by air pressure, and the molding process The uneven stretching in the middle leads to the uneven thickness of the diaphragm after molding and the defects such as uneven molding, which leads to a decrease in the yield of the diaphragm and affects the acoustic performance. The cast polyurethane diaphragm of the present invention adopts injection molding, The thickness of the diaphragm is uniform, the residual stress after molding is small, the diaphragm is flat, and better acoustic performance is obtained.
下面通过具体实施例对本发明振膜进行详细说明,其中实施例和对比例所示振膜在室温条件下F0基本相同,F0的差值在20Hz以内。值得理解的是,下面描述仅是示例性的,而不是对本发明的具体限制。The diaphragm of the present invention will be described in detail below through specific examples, wherein the diaphragms shown in the embodiment and the comparative example have basically the same F0 at room temperature, and the difference of F0 is within 20 Hz. It is to be understood that the following description is exemplary only, rather than a specific limitation of the present invention.
实施例1:本实施例为采用浇注型聚氨酯制备的振膜,按重量份计,振膜的主要原料及其用量如下:聚氨酯预聚物100份,白炭黑5份,三羟甲基丙烷2份,1,4-丁二醇8份,其中,三羟甲基丙烷和1,4-丁二醇为扩链剂,扩链剂的比例为聚氨酯预聚物的10%。将上述原料混合均匀后,注入振膜模具,经100℃硫化后便可制备得到振膜,制备的振膜的厚度为110μm,硬度为40A。Example 1: This example is a diaphragm prepared by using cast-type polyurethane. In parts by weight, the main raw materials of the diaphragm and its dosage are as follows: 100 parts of polyurethane prepolymer, 5 parts of white carbon black, trimethylolpropane 2 parts, 8 parts of 1,4-butanediol, wherein, trimethylolpropane and 1,4-butanediol are chain extenders, and the proportion of chain extenders is 10% of the polyurethane prepolymer. After mixing the above-mentioned raw materials evenly, injecting into the diaphragm mold, and vulcanizing at 100°C, the diaphragm can be prepared. The thickness of the prepared diaphragm is 110 μm and the hardness is 40A.
实施例2:本实施例为采用浇注型聚氨酯制备的振膜,按重量份计,振膜的主要原料及其用量如下:聚氨酯预聚物100份,白炭黑10份,三羟甲基丙烷5份,1,4-丁二醇25份,其中,三羟甲基丙烷和1,4-丁二醇为扩链剂,扩链剂的用量为聚氨酯预聚物的30%。将上述原料混合均匀后,注入振膜模具,经100℃硫化后形成振膜,制备的振膜的厚度为70μm,硬度为75A。Example 2: This example is a diaphragm prepared by using cast polyurethane. In parts by weight, the main raw materials of the diaphragm and its dosage are as follows: 100 parts of polyurethane prepolymer, 10 parts of white carbon black, trimethylolpropane 5 parts, 25 parts of 1,4-butanediol, wherein, trimethylolpropane and 1,4-butanediol are chain extenders, and the amount of chain extenders is 30% of the polyurethane prepolymer. After the above-mentioned raw materials are mixed uniformly, they are injected into the diaphragm mold, and the diaphragm is formed after vulcanization at 100° C. The prepared diaphragm has a thickness of 70 μm and a hardness of 75A.
对比例1为热塑性聚氨酯弹性体(TPU)振膜,振膜厚度为80μm,硬度为60A。Comparative Example 1 is a thermoplastic polyurethane elastomer (TPU) diaphragm with a thickness of 80 μm and a hardness of 60A.
对比例2为热塑性聚酯类弹性体(TPEE)复合振膜,振膜为3层结构,其中两个表层均为TPEE层,厚度为15μm,中间层为聚丙烯酸酯压敏胶膜,厚度为20μm。Comparative Example 2 is a thermoplastic polyester elastomer (TPEE) composite diaphragm, the diaphragm is a 3-layer structure, two of which are TPEE layers with a thickness of 15 μm, and the middle layer is a polyacrylate pressure-sensitive adhesive film with a thickness of 15 μm. 20μm.
将实施例1、实施例2、对比例1及对比例2中的振膜进行如下性能测试:The vibrating membranes in Example 1, Example 2, Comparative Example 1 and Comparative Example 2 were tested as follows:
(1)振膜成型后翘曲程度测试:(1) Warpage degree test after the diaphragm is formed:
为验证本发明产品性能,测试实施例1-2和对比例1-2中振膜的翘曲程度,具体测试方法为:在室温条件下用测试仪对产品进行测试,测试仪包括三部分:测试探头、显示器、和花岗岩平台,其中测试探头为非接触式位移 传感器;测试时,将产品放置在花岗岩平台的三个支点上,上下两个测试探头按照相同轨迹同步扫描产品,记录测试探头到产品最近表面的距离,求出每个测试点两个测试探头的差值,其中差值的一半即是该测试点翘曲度的测试值,其中取各个测试点中最大的翘曲度的测试值定义为该产品的翘曲度。分别根据实施例1-2和对比例1-2的制备方法,每个实例制作100个平行产品,分别测试各平行产品的翘曲度,统计各平行产品翘曲度的分布情况,测试结果参见表3。In order to verify the performance of the product of the present invention, the warpage degree of the diaphragm in Example 1-2 and Comparative Example 1-2 was tested, and the specific test method was: test the product with a tester at room temperature, and the tester includes three parts: Test probes, monitors, and granite platforms, where the test probes are non-contact displacement sensors; during testing, place the product on the three fulcrums of the granite platform, and the upper and lower test probes scan the product synchronously according to the same trajectory, and record the test probe to The distance between the nearest surface of the product, and the difference between the two test probes at each test point is calculated, and half of the difference is the test value of the warpage of the test point, and the test with the largest warpage in each test point is taken The value is defined as the warpage of the product. According to the preparation methods of Example 1-2 and Comparative Example 1-2, 100 parallel products were made in each example, the warpage of each parallel product was tested respectively, and the distribution of warpage of each parallel product was counted. For the test results, see table 3.
表1实施例1-2和对比例1-2中振膜翘曲程度测试结果Table 1 The test results of the warpage degree of the diaphragm in Example 1-2 and Comparative Example 1-2
Figure PCTCN2021114294-appb-000003
Figure PCTCN2021114294-appb-000003
从表3的测试结果可知,对比例1-2振膜采用气压成型的方式制备而成,实施例1-2为本发明所述浇注型聚氨酯振膜,采用注塑方法制备,可明显看出,本发明浇注型聚氨酯振膜的翘曲程度明显优于传统的气压成型的热塑性弹性体振膜,平整度更好。It can be seen from the test results in Table 3 that the diaphragms of Comparative Examples 1-2 are prepared by air pressure molding, and Examples 1-2 are the cast polyurethane diaphragms of the present invention, which are prepared by injection molding. It can be clearly seen that, The warpage degree of the cast polyurethane vibrating film of the present invention is obviously better than that of the traditional air pressure forming thermoplastic elastomer vibrating film, and the flatness is better.
(2)应变回复率和防水测试(2) Strain recovery rate and waterproof test
为验证本发明产品性能,测试实施例1-2和对比例1-2中振膜原材料的应变回复以及对应使用该振膜的发声装置在60m防水试验后统计的振膜的膜折率,测试数据见表2。In order to verify the performance of the product of the present invention, the strain recovery of the raw materials of the diaphragm in Example 1-2 and Comparative Example 1-2 and the membrane refracting rate of the diaphragm after the 60m waterproof test of the sound-emitting device corresponding to the diaphragm were tested. The data are shown in Table 2.
应变回复测试方法如下:在动态热力学分析仪(DMA)拉伸模式下测试应力松弛,应变设置为20%,松弛10min,回复10min,记录最终的回复率。The strain recovery test method is as follows: the stress relaxation is tested in the dynamic thermodynamic analyzer (DMA) tensile mode, the strain is set to 20%, the relaxation is 10 min, the recovery is 10 min, and the final recovery rate is recorded.
表2实施例1-2和对比例1-2中振膜的应变回复率及防水试验数据Table 2 Strain recovery rate and waterproof test data of the diaphragm in Example 1-2 and Comparative Example 1-2
振膜原材料Diaphragm raw material 应变恢复率Strain recovery rate 60m防水试验后膜折率Refractive index of membrane after 60m waterproof test
对比例1(TPU振膜)Comparative example 1 (TPU diaphragm) 70%70% 90%90%
对比例2(TPEE复合振膜)Comparative example 2 (TPEE composite diaphragm) 60%60% 100%100%
实施例1Example 1 85%85% 00
实施例2Example 2 90%90% 00
从表2的测试数据中可以看出,相较于对比例1-2的振膜,本发明浇注型聚氨酯振膜的大应变(20%)回复率更高,且在60m防水试验后依然能够恢复到原来的形状,从而保持声学性能不变。因此,本发明浇注型聚氨酯振膜具有较高的回弹性能和较好的防水性能。It can be seen from the test data in Table 2 that, compared with the diaphragms of Comparative Examples 1-2, the large-strain (20%) recovery rate of the cast polyurethane diaphragm of the present invention is higher, and it can still be used after the 60m waterproof test. return to its original shape, thus maintaining the same acoustic performance. Therefore, the cast polyurethane diaphragm of the present invention has higher resilience and better waterproof performance.
(3)压缩永久变化率K的测试:(3) Test of compression permanent change rate K:
为验证本发明产品性能,测试实施例1和对比例1中的振膜原材料的压缩永久形变,试验标准参考GB1683-81,压缩率选择30%,温度85℃,时间48h,其测试结果记录于表3中。In order to verify the performance of the product of the present invention, the compression set of the diaphragm raw materials in Example 1 and Comparative Example 1 was tested. The test standard refers to GB1683-81. Table 3.
表3压缩永久变形率及高温长时间受力可靠性振膜形变率测试数据Table 3 Compression set rate and high temperature long-term stress reliability test data of diaphragm deformation rate
Figure PCTCN2021114294-appb-000004
Figure PCTCN2021114294-appb-000004
由表3的测试数据可以看出:相较对比例1,本发明浇注型聚氨酯振膜的压缩永久变形更小,表明回弹性更好。使用该振膜的发声装置在高温长时间受力类可靠性试验后仍能回复原来的形状,保持良好的声学性能。It can be seen from the test data in Table 3 that compared with Comparative Example 1, the compression set of the cast polyurethane diaphragm of the present invention is smaller, indicating better resilience. The sound-generating device using the diaphragm can still return to its original shape after a high-temperature and long-term stress-type reliability test, and maintains good acoustic performance.
以上所述仅为本发明的优选实施例,并非因此限制本发明的专利范围,凡是在本发明的发明构思下,利用本发明说明书内容所作的等效结构变换, 或直接/间接运用在其他相关的技术领域均包括在本发明的专利保护范围内。The above descriptions are only preferred embodiments of the present invention, and are not intended to limit the scope of the present invention. Under the inventive concept of the present invention, any equivalent structural transformations made by the contents of the present invention, or directly/indirectly applied to other related All technical fields are included in the scope of patent protection of the present invention.

Claims (13)

  1. 一种振膜,其特征在于,所述振膜采用浇注型聚氨酯制备而成,所述浇注型聚氨酯为聚氨酯预聚物外加配合剂经硫化制成,所述聚氨酯预聚物为嵌段聚合物,所述嵌段聚合物由硬段和软段交替排列形成,所述硬段为异氰酸酯,所述软段为多元醇柔性长链,所述嵌段聚合物的端基均为异氰酸酯硬段,所述振膜于20%应变后的弹性回复率>70%。A vibrating membrane is characterized in that, the vibrating membrane is made of cast polyurethane, the cast polyurethane is a polyurethane prepolymer and a compounding agent is added through vulcanization, and the polyurethane prepolymer is a block polymer , the block polymer is formed by alternating hard segments and soft segments, the hard segment is isocyanate, the soft segment is a polyol flexible long chain, and the end groups of the block polymer are all isocyanate hard segments, The elastic recovery rate of the diaphragm after 20% strain is greater than 70%.
  2. 如权利要求1所述的振膜,其特征在于,所述振膜的压缩永久形变率小于50%。The diaphragm of claim 1, wherein the compression set ratio of the diaphragm is less than 50%.
  3. 如权利要求1所述的振膜,其特征在于,所述配合剂包括扩链剂和催化剂,所述振膜是将多元醇与多异氰酸酯反应生成聚氨酯预聚物,之后加入扩链剂和催化剂,混合后注入至振膜加工模具内,通过交联反应成型得到。The diaphragm of claim 1, wherein the complexing agent comprises a chain extender and a catalyst, and the diaphragm is formed by reacting polyol and polyisocyanate to form a polyurethane prepolymer, and then adding the chain extender and the catalyst , mixed and injected into the diaphragm processing mold, and obtained by cross-linking reaction molding.
  4. 如权利要求3所述的振膜,其特征在于,按质量百分比计,所述扩链剂的用量为所述聚氨酯预聚物的10%-30%。The diaphragm according to claim 3, wherein the amount of the chain extender is 10%-30% of the polyurethane prepolymer in terms of mass percentage.
  5. 如权利要求3所述的振膜,其特征在于,所述扩链剂为可与异氰酸酯反应的多官能度的低分子醇类或胺类化合物。The diaphragm of claim 3, wherein the chain extender is a multifunctional low-molecular alcohol or amine compound that can react with isocyanate.
  6. 如权利要求3所述的振膜,其特征在于,所述扩链剂为3,3’-二氯-4,4’-二氨基二苯基甲烷、2,5-二乙基甲苯二胺、1,2-双(2-氨基苯基硫代)乙烷、丙二醇-双(对氨基苯甲酸酯)、3,5-二氨基-4-氯-苯甲酸异丁酯、4,4-亚甲基-双-(3-氯-2,6-二乙基苯胺)、3,5-二甲基硫基甲苯二胺、1,4-丁二醇、三羟甲基丙烷、三异丙醇胺、氢醌双羟乙基醚、间苯二酚-双(P-羟乙基)醚、三乙醇胺中的至少一种;The diaphragm according to claim 3, wherein the chain extender is 3,3'-dichloro-4,4'-diaminodiphenylmethane, 2,5-diethyltoluenediamine , 1,2-bis(2-aminophenylthio)ethane, propylene glycol-bis(p-aminobenzoate), 3,5-diamino-4-chloro-benzoic acid isobutyl ester, 4,4 -Methylene-bis-(3-chloro-2,6-diethylaniline), 3,5-dimethylthiotoluenediamine, 1,4-butanediol, trimethylolpropane, trimethylolpropane At least one of isopropanolamine, hydroquinone bis-hydroxyethyl ether, resorcinol-bis(P-hydroxyethyl) ether, and triethanolamine;
    和/或,所述催化剂选用二月桂酸丁基锡、辛酸亚锡、磷酸、油酸、己二酸、壬二酸、乙酸苯汞、丙酸苯汞、乙酰丙酮铁中的至少一种。And/or, the catalyst is selected from at least one of butyltin dilaurate, stannous octoate, phosphoric acid, oleic acid, adipic acid, azelaic acid, phenylmercuric acetate, phenylmercuric propionate, and iron acetylacetonate.
  7. 如权利要求3所述的振膜,其特征在于,按质量百分比计,所述异氰酸酯的用量范围为2%-50%;The diaphragm according to claim 3, characterized in that, in terms of mass percentage, the amount of the isocyanate used ranges from 2% to 50%;
    和/或,所述异氰酸酯选用甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、六亚甲基二异氰酸酯、萘1.5-二异氰酸酯、异佛尔酮二异氰酸酯、间二亚甲基二异氰酸酯、对苯二异氰酸酯、3,3.-二甲基-4,4.-联苯二异氰酸酯、4,4'-二环己基甲烷二异氰酸酯、氢化甲苯二异氰酸酯、三甲基己二异氰酸酯中的至少一种;And/or, described isocyanate selects toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, naphthalene 1.5-diisocyanate, isophorone diisocyanate, m-dimethylene diisocyanate, terephthalic diisocyanate for use At least one of isocyanate, 3,3.-dimethyl-4,4.-biphenyl diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, hydrogenated toluene diisocyanate, and trimethylhexamethylene diisocyanate;
    和/或,所述多元醇选用聚酯多元醇、聚醚多元醇、聚丁二烯型多元醇、蓖麻油多元醇、四氢呋喃-氧化丙烯共聚多元醇、环氧树脂改性多元醇中的至少一种。And/or, the polyol is selected from at least one of polyester polyol, polyether polyol, polybutadiene polyol, castor oil polyol, tetrahydrofuran-propylene oxide copolymer polyol, and epoxy resin modified polyol. A sort of.
  8. 如权利要求3所述的振膜,其特征在于,所述配合剂还包括填料,所述填料为炭黑、二氧化硅、粘土、碳酸钙、高岭土、滑石粉、玻璃微珠中的至少一种;The diaphragm according to claim 3, wherein the compounding agent further comprises a filler, and the filler is at least one of carbon black, silica, clay, calcium carbonate, kaolin, talc, and glass beads kind;
    和/或,所述配合剂还包括助剂,所述助剂为抗氧剂、紫外线吸收剂、抗水解稳定剂、增塑剂、色浆、防老剂中的至少一种。And/or, the compounding agent further includes an adjuvant, and the adjuvant is at least one of an antioxidant, an ultraviolet absorber, an anti-hydrolysis stabilizer, a plasticizer, a colorant, and an anti-aging agent.
  9. 如权利要求1至8中任一项所述的振膜,其特征在于,所述振膜的硬度范围为10A-95A。The diaphragm according to any one of claims 1 to 8, wherein the hardness of the diaphragm is in the range of 10A-95A.
  10. 如权利要求9所述的振膜,其特征在于,所述振膜的硬度范围为30A-85A。The diaphragm according to claim 9, wherein the hardness of the diaphragm is in the range of 30A-85A.
  11. 如权利要求1至8中任一项所述的振膜,其特征在于,所述振膜的厚度范围为10μm-300μm。The diaphragm according to any one of claims 1 to 8, wherein the thickness of the diaphragm is in the range of 10 μm-300 μm.
  12. 如权利要求11中任一项所述的振膜,其特征在于,所述振膜的厚度范围为10μm-200μm。The diaphragm according to any one of claims 11, wherein the thickness of the diaphragm is in the range of 10 μm-200 μm.
  13. 一种发声装置,其特征在于,包括如权利要求1至12中任一项所述的振膜。A sound producing device, characterized in that it comprises the diaphragm according to any one of claims 1 to 12.
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