WO2022247911A1 - Diaphragm that may be used in sound generating device and preparation method therefor, and sound generating device - Google Patents
Diaphragm that may be used in sound generating device and preparation method therefor, and sound generating device Download PDFInfo
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- WO2022247911A1 WO2022247911A1 PCT/CN2022/095296 CN2022095296W WO2022247911A1 WO 2022247911 A1 WO2022247911 A1 WO 2022247911A1 CN 2022095296 W CN2022095296 W CN 2022095296W WO 2022247911 A1 WO2022247911 A1 WO 2022247911A1
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- diaphragm
- thermoplastic polyester
- polyester elastomer
- elastomer film
- film
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Images
Classifications
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- H—ELECTRICITY
- H04—ELECTRIC COMMUNICATION TECHNIQUE
- H04R—LOUDSPEAKERS, MICROPHONES, GRAMOPHONE PICK-UPS OR LIKE ACOUSTIC ELECTROMECHANICAL TRANSDUCERS; DEAF-AID SETS; PUBLIC ADDRESS SYSTEMS
- H04R31/00—Apparatus or processes specially adapted for the manufacture of transducers or diaphragms therefor
- H04R31/003—Apparatus or processes specially adapted for the manufacture of transducers or diaphragms therefor for diaphragms or their outer suspension
-
- H—ELECTRICITY
- H04—ELECTRIC COMMUNICATION TECHNIQUE
- H04R—LOUDSPEAKERS, MICROPHONES, GRAMOPHONE PICK-UPS OR LIKE ACOUSTIC ELECTROMECHANICAL TRANSDUCERS; DEAF-AID SETS; PUBLIC ADDRESS SYSTEMS
- H04R9/00—Transducers of moving-coil, moving-strip, or moving-wire type
- H04R9/02—Details
-
- H—ELECTRICITY
- H04—ELECTRIC COMMUNICATION TECHNIQUE
- H04R—LOUDSPEAKERS, MICROPHONES, GRAMOPHONE PICK-UPS OR LIKE ACOUSTIC ELECTROMECHANICAL TRANSDUCERS; DEAF-AID SETS; PUBLIC ADDRESS SYSTEMS
- H04R9/00—Transducers of moving-coil, moving-strip, or moving-wire type
- H04R9/02—Details
- H04R9/025—Magnetic circuit
-
- H—ELECTRICITY
- H04—ELECTRIC COMMUNICATION TECHNIQUE
- H04R—LOUDSPEAKERS, MICROPHONES, GRAMOPHONE PICK-UPS OR LIKE ACOUSTIC ELECTROMECHANICAL TRANSDUCERS; DEAF-AID SETS; PUBLIC ADDRESS SYSTEMS
- H04R9/00—Transducers of moving-coil, moving-strip, or moving-wire type
- H04R9/02—Details
- H04R9/04—Construction, mounting, or centering of coil
-
- H—ELECTRICITY
- H04—ELECTRIC COMMUNICATION TECHNIQUE
- H04R—LOUDSPEAKERS, MICROPHONES, GRAMOPHONE PICK-UPS OR LIKE ACOUSTIC ELECTROMECHANICAL TRANSDUCERS; DEAF-AID SETS; PUBLIC ADDRESS SYSTEMS
- H04R9/00—Transducers of moving-coil, moving-strip, or moving-wire type
- H04R9/02—Details
- H04R9/04—Construction, mounting, or centering of coil
- H04R9/045—Mounting
-
- H—ELECTRICITY
- H04—ELECTRIC COMMUNICATION TECHNIQUE
- H04R—LOUDSPEAKERS, MICROPHONES, GRAMOPHONE PICK-UPS OR LIKE ACOUSTIC ELECTROMECHANICAL TRANSDUCERS; DEAF-AID SETS; PUBLIC ADDRESS SYSTEMS
- H04R9/00—Transducers of moving-coil, moving-strip, or moving-wire type
- H04R9/06—Loudspeakers
Definitions
- the invention relates to the technical field of electroacoustics, in particular to a vibrating membrane that can be used for a sounding device, a preparation method thereof, and a sounding device.
- Existing loudspeaker diaphragms mostly use composite structural materials, which include: engineering plastics (such as PEEK, PAR, PET, PI, PEI, etc.) as the base layer, acrylic glue, silica gel layer, etc. , as a rebound layer.
- engineering plastics such as PEEK, PAR, PET, PI, PEI, etc.
- acrylic glue such as silica gel layer, etc.
- thermoplastic polyester elastomer can effectively improve the resilience of the diaphragm, reduce the folding of the diaphragm, and reduce the distortion caused by the sudden vibration of the diaphragm, more and more products use this material as the speaker diaphragm , to meet the high-quality needs of products such as sound quality and waterproof.
- the polyether-polyester thermoplastic polyester elastomer commonly used in the industry still has certain deficiencies in terms of high temperature resistance and chemical resistance.
- thermoplastic polyester elastomer commonly used in the loudspeaker industry is polyether-polyester type, which still has certain deficiencies in high temperature resistance and chemical resistance.
- thermoplastic polyester elastomers synthesized from polybutylene terephthalate hard segments and aliphatic polycarbonate soft segments, due to their It is used as insulating material, shell material and other materials that are different from sound-generating purposes, so it pays more attention to the optimization of properties such as insulation and tensile strength, while ignoring the acoustic properties such as chemical resistance, damping, and the lowest resonance frequency, which makes it impossible to be used in diaphragm.
- the main purpose of the present invention is to provide a diaphragm that can be used for sounding devices, wherein the thermoplastic polyester elastomer is composed of a polyester hard segment and an aliphatic polycarbonate soft segment.
- This material not only solves the problem of the existing thermoplastic elastomer The problem of poor high temperature resistance and chemical resistance is improved, and the sensitivity is improved.
- the basic properties such as stiffness, resilience, and damping required for Gu Gu membrane vibration are well combined.
- Another object of the present invention is to provide a method for preparing the above-mentioned diaphragm, which only involves conventional procedures, has a simple process, and does not have harsh process conditions.
- the third aspect of the present invention aims to provide a sound generating device composed of the above diaphragm.
- the present invention provides the following technical solutions.
- the diaphragm for a sound emitting device according to the embodiment of the first aspect of the present invention, is a multi-layer composite structure, and at least one surface layer is a thermoplastic polyester elastomer film;
- thermoplastic polyester elastomer is formed by copolymerizing polyester hard segments obtained by reacting aromatic dicarboxylic acids with diols and soft segments containing aliphatic polycarbonate;
- the thickness of the diaphragm is 10-200 ⁇ m
- the loss factor of the thermoplastic polyester elastomer film is 0.1-0.3 at 23°C.
- the aliphatic polycarbonate includes polyhexamethylene polycarbonate diol, which accounts for more than 70% by weight of the soft segment.
- the soft segment further includes one or more of polycaprolactone, polybutylene adipate, polytetrahydrofuran ether, and polyethylene oxide.
- the soft segment accounts for 20%-80% by weight of the thermoplastic polyester elastomer.
- the soft segment accounts for 30%-60% by weight of the thermoplastic polyester elastomer.
- the hard segment comprises polybutylene terephthalate.
- the loss factor of the diaphragm is 0.1-0.2 in an environment of 23°C.
- the tensile modulus of the thermoplastic polyester elastomer film is 20-100Mpa;
- the tensile modulus of the thermoplastic polyester elastomer film is 50-400 MPa.
- the ratio between the storage moduli in the MD and TD directions of the diaphragm is 80-120:100.
- the vibrating membrane is a structure in which the thermoplastic polyester elastomer film and glue layers are alternately stacked, and the two surface layers are the thermoplastic polyester elastomer film layers.
- the thickness of the thermoplastic polyester elastomer film is 5-50 ⁇ m
- the adhesive layer is one or more of a silicone layer and an acrylic adhesive layer with a thickness of 2-50 ⁇ m.
- the glass transition temperature of the adhesive layer is ⁇ -10°C.
- the prepolymer of the hard segment and the prepolymer of the soft segment are subjected to a copolymerization reaction, the temperature of the copolymerization reaction is preferably 230-265° C., and the reaction time is preferably 0.5-2 h; after that, pelletize and extrude the film material.
- the molecular weight of the prepolymer of the hard segment is 15000-30000; the molecular weight of the prepolymer of the soft segment is 10000-50000.
- the sound generating device includes a vibration system and a magnetic circuit system matched with the vibration system, the vibration system includes a diaphragm and a voice coil combined on one side of the diaphragm, the The magnetic circuit system drives the voice coil to vibrate to drive the diaphragm to produce sound, and the diaphragm is the diaphragm according to the above-mentioned embodiment of the present invention.
- the sound generating device includes a housing, a magnetic circuit system and a vibration system disposed in the housing, the vibration system includes a voice coil, a first diaphragm and a second diaphragm, the The top of the voice coil is connected to the first diaphragm, the magnetic circuit system drives the voice coil to vibrate to drive the first diaphragm to produce sound, and the two ends of the second diaphragm are respectively connected to the housing Connected to the bottom of the voice coil, the second diaphragm is the diaphragm according to the above embodiment of the present invention.
- the present invention utilizes the respective advantages of the polyaromatic dicarboxylic acid glycol ester hard segment and the soft segment containing polyhexamethylene polycarbonate diol, and increases the polyhexamethylene polycarbonate in the soft segment.
- the film formed after copolymerization is more suitable for the diaphragm, which can significantly improve high temperature resistance, chemical resistance and sensitivity, and can improve the product's long-term high temperature and/or Reliability under high humidity environment; at the same time, the diaphragm in the present invention can also take into account various acoustic performances such as stiffness, resilience, damping, distortion, etc., and can solve the polarization and distortion problems that occur during the vibration process of the product.
- Fig. 1 is the infrared spectrogram of the resin material of embodiment and comparative example
- Figure 2 is a graph showing the displacement change curve of the material at different temperatures under a 1MPa force
- Fig. 3 is the structural representation of the loudspeaker provided by the present invention.
- Fig. 4 is a structural schematic diagram of the sounding vibration unit in Fig. 3;
- Fig. 5 is the structural representation of diaphragm in the present invention.
- Fig. 6 is the total harmonic distortion curve of the embodiment and the comparative example.
- the invention provides a vibrating membrane that can be used for a sounding device, the vibrating membrane is a multi-layer composite structure, and at least one surface layer is a thermoplastic polyester elastomer film;
- thermoplastic polyester elastomer is formed by the copolymerization of polyester hard segment obtained by reaction of aromatic dicarboxylic acid and glycol and soft segment containing aliphatic polycarbonate; wherein, the thickness of the diaphragm is 10-200 ⁇ m , the loss factor of the thermoplastic polyester elastomer film is 0.1-0.3 under the environment of 23°C.
- the present invention utilizes the respective advantages of the hard segment of polyaromatic dicarboxylic acid diol ester and the soft segment of aliphatic polycarbonate to exert synergistic effect, enhance strengths and avoid weaknesses, and the film material formed after copolymerization is more suitable for diaphragm, and can significantly improve the resistance to vibration.
- High temperature resistance, chemical resistance and sensitivity can improve the working reliability of products in long-term high temperature and/or high humidity environments; at the same time, the diaphragm in the present invention can also take into account stiffness and resilience, damping, distortion, etc. In terms of performance, it can solve the polarization and distortion problems that occur during the vibration process of the product.
- Diaphragms made with the thermoplastic polyester elastomer film layer of the present invention have been tested to have significant advantages over diaphragms without aliphatic polycarbonate esters, especially in terms of high temperature resistance, chemical resistance and sensitivity etc.
- the aromatic dicarboxylic acid described in the present invention can be terephthalic acid, diphenyl dicarboxylic acid, naphthalene dicarboxylic acid, isophthalic acid or the above substituted aromatic dicarboxylic acid, preferably terephthalic acid .
- the dihydric alcohol described in the present invention can be ethylene glycol, butanediol, propylene glycol, cyclopentanediol, cyclohexanediol, etc., and can be optionally one of the above alcohols or a combination of multiple alcohols.
- the above-mentioned aromatic dicarboxylic acid and dihydric alcohol are polymerized to form a hard segment, which can be a kind of aromatic dicarboxylic acid and a kind of dibasic alcohol polymerized, or a kind of aromatic dicarboxylic acid and a variety of dibasic alcohols
- the polymerization may also be the polymerization of multiple aromatic dicarboxylic acids and one diol, or the polymerization of multiple aromatic dicarboxylic acids and multiple diols.
- polycaprolactone polybutylene adipate, polytetrahydrofuran ether, and polyethylene oxide may also be added to the soft segment of the present invention.
- Adding a small amount of the above polymers can help improve the blockiness of the polycarbonate soft segment and the polymerizability with the hard segment while maintaining the good strength, stiffness and resilience of the material. However, if the amount exceeds 30%, it will It affects the block structure characteristics of the entire material, resulting in the loss of the overall rigidity and resilience of the material.
- the weight percentage of the aliphatic polycarbonate in the soft segment is preferably above 70%, such as 70%, 75%, 80%, 85%, 90%, 95%, 100%, etc.
- Polycaprolactone is preferred as the polymer that is compatible with aliphatic polycarbonate to form the soft segment.
- the proportion of hard segment and soft segment in the thermoplastic polyester elastomer of the present invention has a significant impact on properties such as temperature resistance and damping.
- the weight percentage of soft segment is preferably 20% to 80%, such as 20%, 30%, 40%, 50%, 60%, 70%, 80%, etc.
- the soft segment content is not higher than 80%.
- the soft segment content is less than 25%.
- the soft segment content is more preferably 25% to 60%, such as 25%, 30%, 35%, 40%, 45%, 50%, 55% %, 60%, etc.
- the loss factor of the thermoplastic polyester elastomer film layer of the present invention is 0.1 to 0.3 (using DMA temperature scanning mode, 1Hz vibration frequency, 3°C/min heating rate, the loss factor is 23°C data), it will have good damping properties and can meet the needs of products for high performance and low performance.
- polycarbonate segments Due to the presence of polycarbonate segments in the thermoplastic polyester elastomer of the present invention, relative to polyester segments or polyether segments, polycarbonate segments have higher polarity, and the steric hindrance of segment movement is larger , when subjected to an external force, it can consume more energy, so it has better damping properties than other types of thermoplastic elastomer materials, which can easily reach 0.1-0.3.
- the loss factor is lower than 0.1, there is no advantage in distortion compared to polyether-polyester thermoplastic polyester elastomer; when the loss factor is higher than 0.2, the increase in damping of the material will lose the transient response of the material, and the diaphragm cannot be perfect To realize the feedback of the input signal, the sound quality will be sacrificed.
- it is more preferably 0.1 to 0.2, such as 0.12, 0.14, 0.15, 0.16, 0.17, 0.18, 0.19, 0.2 and the like.
- the tensile modulus of the thermoplastic polyester elastomer film layer is 20-500Mpa (using DMA temperature scanning mode, 1Hz vibration frequency, 3°C/min heating rate, data at 23°C).
- the stiffness of the diaphragm is insufficient.
- the F0 (minimum resonance frequency) required by the product it can only be achieved by increasing the thickness, but the increase in thickness will increase the quality of the diaphragm and lose its vibration space and reduces the sensitivity of the quality control zone.
- the modulus is high, the flexibility and resilience of the material become poor. In order to obtain high loudness, the product requires a large displacement of the diaphragm.
- the recommendation is as follows: when the minimum resonance frequency F0 of the sound generating device is ⁇ 500 Hz, the tensile modulus of the thermoplastic polyester elastomer film is 20-100 Mpa; the minimum resonance frequency F0 of the sound generating device When >500 Hz, the tensile modulus of the thermoplastic polyester elastomer film is 50-400 MPa. For example, when the lowest resonance frequency F0 of the sound generating device is 400 Hz, the tensile modulus of the thermoplastic polyester elastomer film may be 70 MPa. For example, when the lowest resonance frequency F0 of the sound generating device is 800 Hz, the tensile modulus of the thermoplastic polyester elastomer film may be 350 MPa.
- the ratio between the storage modulus in the MD and TD directions of the thermoplastic polyester elastomer film layer is 80 ⁇ 120:100.
- the storage modulus difference between the MD and TD directions of the thermoplastic polyester elastomer film layer is controlled within ⁇ 20%, preferably within ⁇ 10%.
- the vibrating membrane of the present invention is a multi-layer composite structure, which at least includes a thermoplastic polyester elastomer film, preferably a structure in which it is alternately stacked with adhesive film layers, and the thermoplastic polyester elastomer film is the surface layer. If a composite structure is adopted, due to the strong rigidity of the thermoplastic polyester elastomer film, it can meet the use requirements when it is set very thin, thereby avoiding the loss of sensitivity and vibration space caused by excessive material thickness.
- the thickness of the thermoplastic polyester elastomer film layer is preferably 5 to 50 ⁇ m.
- the diaphragm can include a three-layer structure, wherein the middle layer is an adhesive film layer, and the two surface layers are thermoplastic polyester elastomer film layers, and the thermoplastic polyester elastomer film layers are made of aromatic dicarboxylic acid.
- the polyester hard segment obtained by reacting with glycol and the soft segment containing aliphatic polycarbonate are copolymerized, and the middle layer is arranged between the two surface layers.
- the vibrating membrane may include a five-layer structure, the five-layer structure is alternately superimposed and distributed with thermoplastic polyester elastomer film layers and adhesive film layers, and its two surface layers are thermoplastic polyester elastomer film layers,
- the thermoplastic polyester elastomer film layer is formed by the copolymerization of the polyester hard segment obtained by the reaction of aromatic dicarboxylic acid and diol and the soft segment containing aliphatic polycarbonate.
- the adhesive layer in the composite film may be a typical adhesive in the field, such as one or more of a silicone layer and an acrylic adhesive layer with a thickness of 2-50 ⁇ m, preferably a pressure-sensitive adhesive film.
- the pressure-sensitive adhesive film is easy to use, and the lamination between layers can be realized through a simple lamination process.
- the 180° peeling force after lamination must meet: not less than 150g/25mm.
- the glass transition temperature of the adhesive layer should not be higher than -10°C.
- the modulus of the adhesive film layer will increase rapidly, resulting in excessive rigidity of the material, a significant increase in the F0 of the product, and a decrease in the toughness of the diaphragm, which is prone to the risk of film cracking.
- thermoplastic polyester elastomer film layer in the present invention only involves conventional procedures, including copolymerization reaction, making granular resin, and then using extrusion equipment to form a film material, and finally bonding it with other films to form the diaphragm .
- the process conditions of the copolymerization reaction have a certain influence on the performance of the thermoplastic polyester elastomer.
- the raw materials are guaranteed to be in a molten state, and the hard segment and the soft segment are both selected as prepolymers.
- the polyester hard segment prepolymer obtained by reacting aromatic dicarboxylic acid and diol is selected to have a molecular weight of 15,000-30,000, such as 15,000, 20,000, 25,000, 30,000, etc.
- the prepolymer of the aliphatic polycarbonate soft segment preferably has a molecular weight of 10,000-50,000, such as 10,000, 15,000, 20,000, 25,000, 30,000, 35,000, 40,000, 45,000, 50,000, etc.
- the temperature of the copolymerization reaction is preferably 230-265° C., and the reaction time is preferably 0.5-2 h.
- the type that both selects can be typical auxiliary agent, for example described stabilizing agent is preferably polycarbodiimide, and described catalyst is preferably n-butyl titanate, the consumption of both It can be adjusted according to the actual situation.
- the end point of the copolymerization reaction is usually when the resin becomes uniform and transparent.
- Granulation is usually carried out in a slicer or pelletizer.
- processing aids such as plasticizers, slip agents, lubricants, etc.
- an auxiliary material of a certain thickness such as a release film or release paper, etc.
- the types and amounts of processing aids are typical in the art.
- the vibrating membrane provided by the present invention can form a sounding device of any structure, such as the following typical sounding device: comprising a vibrating system and a magnetic circuit system matched with the vibrating system, the vibrating system includes a vibrating membrane and a magnetic circuit system combined with the vibrating Voice coil on one side of the membrane.
- the voice coil can vibrate up and down under the action of the magnetic field force of the magnetic circuit system after the voice coil is energized to drive the vibration of the diaphragm, and the sound can be produced when the diaphragm vibrates.
- the sound generating device may include a housing and a magnetic circuit system and a vibration system disposed in the housing.
- the vibration system may include a voice coil, a first diaphragm and a second diaphragm, and the top of the voice coil Connected with the first diaphragm, the magnetic circuit system drives the voice coil to vibrate to drive the first diaphragm to produce sound, and the two ends of the second diaphragm are respectively connected with the shell and the bottom of the voice coil.
- the second diaphragm may be the diaphragm according to the foregoing embodiments of the present invention.
- the first diaphragm can be used to vibrate and produce sound
- the second diaphragm can be used to balance the vibration of the voice coil.
- the voice coil can vibrate up and down under the action of the magnetic field force of the magnetic circuit system after the voice coil is energized to drive the first diaphragm to vibrate, and the first diaphragm can vibrate to produce sound.
- the second diaphragm can also vibrate up and down with the voice coil. Since the two ends of the second diaphragm are respectively connected to the bottom of the shell and the voice coil, the second diaphragm can balance the vibration of the voice coil and prevent the polarization of the voice coil. Therefore, the sounding effect of the sounding device can be improved.
- first diaphragm and the second diaphragm can use the diaphragm of the above-mentioned embodiment of the present invention at the same time, or one of the first diaphragm and the second diaphragm can adopt the diaphragm of the above-mentioned embodiment of the present invention.
- the diaphragm which is not specifically limited in the present invention. The following is a specific description in conjunction with the examples.
- the first step is to make resin particles
- the second step is to make the membrane
- the method of melt extrusion casting is adopted. Before film making, the particles are first dried and dehydrated, then added to the screw to melt, dispersed and mixed by the screw, and then output to the T-die. In order to reduce the orientation of the film, after the melt flows out of the T-die, it can be added before the cooling roll A certain thickness of auxiliary material (such as release film or release paper, etc.) is applied to one surface of the film, and after being flattened and shaped, it is rolled together. By controlling the speed of the vehicle and the pressure between the cooling rollers, etc., it is ensured that the difference of the storage modulus of the obtained thermoplastic polyester elastomer film in the MD and TD directions is within ⁇ 10%.
- auxiliary material such as release film or release paper, etc.
- the first step is to make resin particles
- the second step is to make the membrane
- the method of melt extrusion casting is adopted. Before film making, the particles are first dried and dehydrated, then added to the screw to melt, dispersed and mixed by the screw, and then output to the T-die. In order to reduce the orientation of the film, after the melt flows out of the T-die, it can be added before the cooling roll A certain thickness of auxiliary material (such as release film or release paper, etc.) is applied to one surface of the film, and after being flattened and shaped, it is rolled together. By controlling the speed of the vehicle and the pressure between the cooling rollers, etc., it is ensured that the difference of the storage modulus of the obtained thermoplastic polyester elastomer film in the MD and TD directions is within ⁇ 10%.
- auxiliary material such as release film or release paper, etc.
- the first step is to make resin particles
- the second step is to make the membrane
- the method of melt extrusion casting is adopted. Before film making, the particles are first dried and dehydrated, then added to the screw to melt, dispersed and mixed by the screw, and then output to the T-die. In order to reduce the orientation of the film, after the melt flows out of the T-die, it can be added before the cooling roll A certain thickness of auxiliary material (such as release film or release paper, etc.) is applied to one surface of the film, and after being flattened and shaped, it is rolled together. By controlling the speed of the vehicle and the pressure between the cooling rollers, etc., it is ensured that the difference of the storage modulus of the obtained thermoplastic polyester elastomer film in the MD and TD directions is within ⁇ 10%.
- auxiliary material such as release film or release paper, etc.
- Test method adopt TMA equipment, select the film (thermoplastic polyester elastomer film) material with a thickness of 20 ⁇ m as the comparative example, embodiment 1 and embodiment 2, adopt the tensile mode, maintain the tensile stress at 1MPa, and follow the 3°C/
- the heating rate of min increases from room temperature to 200°C, and the instrument will record and output the length change curve of the material at different temperatures during the test.
- Example 2 is better than Example 1, and better than Comparative Example.
- Test method Cut out materials with similar quality and weigh them with an analytical balance to record the mass M 1 , soak in oleic acid for 24 hours, take out the oleic acid on the surface with a dust-free cloth and weigh M 2 , and compare the materials before and after oleic acid absorption Changes in quality, so that the advantages and disadvantages of chemical resistance can be drawn.
- Test method Use a cutting knife or a utility blade to take a flat rectangular sample with a width of 5-10mm from the film, and use the ASTM D412-2016 standard for testing.
- the vibration frequency of the test is 1Hz and the temperature is 23°C.
- thermoplastic polyester elastomer films in Example 2 and Comparative Example were respectively selected to make diaphragms.
- the diaphragms in Example 2 and Comparative Example all adopt a three-layer composite structure, including a middle layer and two surface layers, the middle layer is an acrylic adhesive layer, and the two surface layers are respectively corresponding thermoplastic polyester elastomer layers, and the middle layer The thickness of both surface layers is 20 ⁇ m. That is to say, the difference between the diaphragm in Example 2 and the comparative example is only that the materials of the thermoplastic polyester elastomer film layers of the two surface layers are different.
- the manufacturing method of the diaphragm in Embodiment 2 and the comparative example is the same, as follows:
- thermoplastic polyester elastomer film layer and acrylic adhesive layer are laminated alternately to form a composite structure of thermoplastic polyester elastomer film layer + acrylic adhesive layer + thermoplastic polyester elastomer film layer, thus making Composite tape required.
- microspeakers SPK
- the micro-speaker adopts the structure shown in Fig. 3, which includes a vibration system and a magnetic circuit system matched with the vibration system, and the vibration system includes a diaphragm and a voice coil combined on one side of the diaphragm.
- the loudspeaker vibration unit is shown in FIG. 4 , and those skilled in the art can make corresponding adjustments according to actual product requirements.
- the vibrating membrane 1 is composed of a ring portion 11 and a ball top 12, and the thermoplastic polyester elastomer layer can be located at the ring portion 11 of the diaphragm, or at the ring portion 11 and the ball top. 12.
- Surround portion 11 protrudes toward the side away from voice coil 2; ball top 12 is connected to surround portion 11; a centering strut is provided in the vibration system, which can improve the anti-polarization ability of the vibration system, etc.
- the vibrating film 3 is composed of the thermoplastic polyester elastomers of Example 2 and Comparative Example respectively, and both adopt a three-layer structure of "thermoplastic polyester elastomer film layer 31-adhesive layer 32-thermoplastic polyester elastomer film layer 31", as Figure 5 shows.
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Abstract
The present invention relates to a diaphragm that may be used in a sound generating device and a preparation method therefor, and a sound generating device. A diaphragm that may be used in a sound generating device has a multi-layer composite structure, and at least one surface layer is a thermoplastic polyester elastomer film; the thermoplastic polyester elastomer is formed by the copolymerization of a polyester hard segment obtained by reacting an aromatic dicarboxylic acid with a diol and a soft segment containing an aliphatic polycarbonate; and the thickness of the diaphragm is 10-200 μm, and the loss factor of the thermoplastic polyester elastomer film in a 23°C environment is 0.1-0.3. The thermoplastic polyester elastomer of the present invention is composed of a polyester hard segment and an aliphatic polycarbonate soft segment. Said material not only solves the problems in existing thermoplastic elastomers of poor high temperature resistance and chemical resistance, but also improves sensitivity; meanwhile, said material also balances very well basic properties such as stiffness, resilience, and damping which are required for the vibration of a diaphragm.
Description
本发明涉及电声技术领域,特别涉及一种可用于发声装置的振膜及其制备方法、发声装置。The invention relates to the technical field of electroacoustics, in particular to a vibrating membrane that can be used for a sounding device, a preparation method thereof, and a sounding device.
随着行业内对扬声器性能要求的提高,越来越多的产品追求更高的响度、高品质的音质以及高等级的防水等。现有扬声器振膜多采用复合结构材料,其包括:工程塑料(如PEEK、PAR、PET、PI、PEI等)作为基层,丙烯酸胶、硅胶层等作为阻尼层,热塑性弹性材料兼顾模量与阻尼,作为回弹层。这种复合薄膜用作扬声器振膜时,并不能完全匹配更高的响度、高品质的音质以及高等级的防水等要求。近年来,因热塑性聚酯弹性体可以有效提高振膜回弹性,减少振膜膜折,降低振膜突变振动过程中产生的失真问题等,越来越多的产品采用该材料用作扬声器振膜,满足产品对音质和防水等高品质的需求。但是,目前行业内常用的聚醚-聚酯型的热塑性聚酯弹性体,其在耐高温性、耐化学品性等方面仍存在一定的不足。With the improvement of speaker performance requirements in the industry, more and more products are pursuing higher loudness, high-quality sound quality and high-level waterproof. Existing loudspeaker diaphragms mostly use composite structural materials, which include: engineering plastics (such as PEEK, PAR, PET, PI, PEI, etc.) as the base layer, acrylic glue, silica gel layer, etc. , as a rebound layer. When this composite film is used as a speaker diaphragm, it cannot fully match the requirements of higher loudness, high-quality sound quality, and high-level waterproofing. In recent years, because thermoplastic polyester elastomer can effectively improve the resilience of the diaphragm, reduce the folding of the diaphragm, and reduce the distortion caused by the sudden vibration of the diaphragm, more and more products use this material as the speaker diaphragm , to meet the high-quality needs of products such as sound quality and waterproof. However, the polyether-polyester thermoplastic polyester elastomer commonly used in the industry still has certain deficiencies in terms of high temperature resistance and chemical resistance.
目前,扬声器行业内常用的热塑性聚酯弹性体是聚醚-聚酯型的,其在耐高温性、耐化学品性等方面仍存在一定的不足。虽然在其他行业已报道过更多类型的热塑性聚酯弹性体,例如以聚对苯二甲酸丁二醇酯硬段和脂肪族聚碳酸酯软段合成的热塑性聚酯弹性体,但由于其被用作绝缘材料、外壳材料等不同于发声用途的材料,因此更注重绝缘性、抗拉强度等性能的优化,忽略了耐化学品性、阻尼性、最低共振频率等声学性能,导致无法用于振膜。At present, the thermoplastic polyester elastomer commonly used in the loudspeaker industry is polyether-polyester type, which still has certain deficiencies in high temperature resistance and chemical resistance. Although more types of thermoplastic polyester elastomers have been reported in other industries, such as thermoplastic polyester elastomers synthesized from polybutylene terephthalate hard segments and aliphatic polycarbonate soft segments, due to their It is used as insulating material, shell material and other materials that are different from sound-generating purposes, so it pays more attention to the optimization of properties such as insulation and tensile strength, while ignoring the acoustic properties such as chemical resistance, damping, and the lowest resonance frequency, which makes it impossible to be used in diaphragm.
为此,提出本发明。For this reason, the present invention is proposed.
发明内容Contents of the invention
本发明的主要目的在于提供一种可用于发声装置的振膜,其中的热塑性聚酯弹性体由聚酯硬段与脂肪族聚碳酸酯软段构成,该材料不仅解决了现有的热塑性弹性体耐高温性和耐化学品性差的问题,而且提高了灵敏度,同时很好地兼顾振膜振动所需的刚度和回弹性、阻尼性等基本性能。The main purpose of the present invention is to provide a diaphragm that can be used for sounding devices, wherein the thermoplastic polyester elastomer is composed of a polyester hard segment and an aliphatic polycarbonate soft segment. This material not only solves the problem of the existing thermoplastic elastomer The problem of poor high temperature resistance and chemical resistance is improved, and the sensitivity is improved. At the same time, the basic properties such as stiffness, resilience, and damping required for Gu Gu membrane vibration are well combined.
本发明的另一目的在于提供上述振膜的制备方法,该方法仅涉及常规工序,流程简单,无苛刻工艺条件。Another object of the present invention is to provide a method for preparing the above-mentioned diaphragm, which only involves conventional procedures, has a simple process, and does not have harsh process conditions.
本发明的第三方面目的在于提供上述振膜组成的发声装置。The third aspect of the present invention aims to provide a sound generating device composed of the above diaphragm.
为了实现以上目的,本发明提供了以下技术方案。In order to achieve the above objectives, the present invention provides the following technical solutions.
根据本发明第一方面实施例的用于发声装置的振膜,所述振膜为多层复合结构,并且至少一个表层为热塑性聚酯弹性体膜;According to the diaphragm for a sound emitting device according to the embodiment of the first aspect of the present invention, the diaphragm is a multi-layer composite structure, and at least one surface layer is a thermoplastic polyester elastomer film;
所述热塑性聚酯弹性体由芳香族二羧酸与二元醇反应得到的聚酯硬段和含有脂肪族聚碳酸酯的软段共聚而成;The thermoplastic polyester elastomer is formed by copolymerizing polyester hard segments obtained by reacting aromatic dicarboxylic acids with diols and soft segments containing aliphatic polycarbonate;
其中,所述振膜的厚度为10~200μm,所述热塑性聚酯弹性体膜在23℃环境下的损耗因子为0.1~0.3。Wherein, the thickness of the diaphragm is 10-200 μm, and the loss factor of the thermoplastic polyester elastomer film is 0.1-0.3 at 23°C.
根据本发明的一些实施例,所述脂肪族聚碳酸酯包括聚六亚甲基聚碳酸酯二醇,其占所述软段重量的70%以上。According to some embodiments of the present invention, the aliphatic polycarbonate includes polyhexamethylene polycarbonate diol, which accounts for more than 70% by weight of the soft segment.
根据本发明的一些实施例,所述软段还包括聚己内酯、聚已二酸丁二醇酯、聚四氢呋喃醚、聚环氧乙烷中的一种或多种。According to some embodiments of the present invention, the soft segment further includes one or more of polycaprolactone, polybutylene adipate, polytetrahydrofuran ether, and polyethylene oxide.
根据本发明的一些实施例,所述软段占所述热塑性聚酯弹性体重量的20%~80%。According to some embodiments of the present invention, the soft segment accounts for 20%-80% by weight of the thermoplastic polyester elastomer.
根据本发明的一些实施例,所述软段占所述热塑性聚酯弹性体重量的30%~60%。According to some embodiments of the present invention, the soft segment accounts for 30%-60% by weight of the thermoplastic polyester elastomer.
根据本发明的一些实施例,所述硬段包括聚对苯二甲酸丁二醇酯。According to some embodiments of the present invention, the hard segment comprises polybutylene terephthalate.
根据本发明的一些实施例,所述振膜在23℃环境下的损耗因子为0.1~0.2。According to some embodiments of the present invention, the loss factor of the diaphragm is 0.1-0.2 in an environment of 23°C.
根据本发明的一些实施例,在23℃环境下,According to some embodiments of the present invention, in an environment of 23°C,
所述发声装置的最低共振频率F0≤500Hz时,所述热塑性聚酯弹性体膜的拉伸模量为20~100Mpa;When the lowest resonance frequency F0 of the sound generating device is ≤ 500Hz, the tensile modulus of the thermoplastic polyester elastomer film is 20-100Mpa;
所述发声装置的最低共振频率F0>500Hz时,所述热塑性聚酯弹性体膜的拉伸模量为50~400MPa。When the lowest resonance frequency F0 of the sound generating device is >500 Hz, the tensile modulus of the thermoplastic polyester elastomer film is 50-400 MPa.
根据本发明的一些实施例,所述振膜的MD与TD两方向的储能模量之间比例为80~120:100。According to some embodiments of the present invention, the ratio between the storage moduli in the MD and TD directions of the diaphragm is 80-120:100.
根据本发明的一些实施例,所述振膜为所述热塑性聚酯弹性体膜与胶层交替叠加的结构,并且两个表层为所述热塑性聚酯弹性体膜层。According to some embodiments of the present invention, the vibrating membrane is a structure in which the thermoplastic polyester elastomer film and glue layers are alternately stacked, and the two surface layers are the thermoplastic polyester elastomer film layers.
根据本发明的一些实施例,所述热塑性聚酯弹性体膜的厚度为5~50μm,所述胶层为2~50μm厚度的硅胶层、丙烯酸胶层中的一种或多种。According to some embodiments of the present invention, the thickness of the thermoplastic polyester elastomer film is 5-50 μm, and the adhesive layer is one or more of a silicone layer and an acrylic adhesive layer with a thickness of 2-50 μm.
根据本发明的一些实施例,所述胶层的玻璃化转变温度≤-10℃。According to some embodiments of the present invention, the glass transition temperature of the adhesive layer is ≤ -10°C.
根据本发明第二方面实施例的振膜的制备方法,其包括:The method for preparing a diaphragm according to the embodiment of the second aspect of the present invention includes:
将硬段的预聚物和软段的预聚物进行共聚反应,所述共聚反应的温度优选为230~265℃,反应时间优选为0.5~2h;之后造粒、挤出膜材。The prepolymer of the hard segment and the prepolymer of the soft segment are subjected to a copolymerization reaction, the temperature of the copolymerization reaction is preferably 230-265° C., and the reaction time is preferably 0.5-2 h; after that, pelletize and extrude the film material.
根据本发明的一些实施例,所述硬段的预聚物的分子量为15000~30000;所述软段的预聚物的分子量为10000~50000。According to some embodiments of the present invention, the molecular weight of the prepolymer of the hard segment is 15000-30000; the molecular weight of the prepolymer of the soft segment is 10000-50000.
根据本发明第三方面实施例的发声装置,包括振动系统和与所述振动系统相配合的磁路系统,所述振动系统包括振膜和结合在所述振膜一侧的音圈,所述磁路系统系统驱动所述音圈振动以带动所述振膜发声,所述振膜为根据本发明上述实施例的所述振膜。The sound generating device according to the embodiment of the third aspect of the present invention includes a vibration system and a magnetic circuit system matched with the vibration system, the vibration system includes a diaphragm and a voice coil combined on one side of the diaphragm, the The magnetic circuit system drives the voice coil to vibrate to drive the diaphragm to produce sound, and the diaphragm is the diaphragm according to the above-mentioned embodiment of the present invention.
根据本发明第四方面实施例的发声装置,包括壳体以及设在所述壳体内的磁路系统和振动系统,所述振动系统包括音圈、第一振膜和第二振膜,所述音圈的顶部与所述第一振膜相连,所述磁路系统系统驱动所述音圈振动以带动所述第一振膜发声,所述第二振膜的两端分别与所述壳体和所述音圈的底部相连,所述第二振膜为根据本发明上述实施例的所述振膜。According to the fourth aspect of the present invention, the sound generating device includes a housing, a magnetic circuit system and a vibration system disposed in the housing, the vibration system includes a voice coil, a first diaphragm and a second diaphragm, the The top of the voice coil is connected to the first diaphragm, the magnetic circuit system drives the voice coil to vibrate to drive the first diaphragm to produce sound, and the two ends of the second diaphragm are respectively connected to the housing Connected to the bottom of the voice coil, the second diaphragm is the diaphragm according to the above embodiment of the present invention.
与现有技术相比,本发明利用聚芳香族二羧酸二元醇酯硬段与含聚六亚甲基聚碳酸酯二醇的软段各自的优点,并且增加软段中聚六亚甲基聚碳酸酯二醇的比例,从而发挥协同作用,扬长避短,经共聚后形成的膜材更适于振膜,能显著提高耐高温性、耐化学品性和灵敏度,可以提升产品在长期高温和/或高湿度环境下的工作可靠性;同时,本发明中的振膜还可以兼顾刚度和回弹性、阻尼性、失真等多方面声学性能,可以解决产品在振动过程中出现的偏振和失真问题。Compared with the prior art, the present invention utilizes the respective advantages of the polyaromatic dicarboxylic acid glycol ester hard segment and the soft segment containing polyhexamethylene polycarbonate diol, and increases the polyhexamethylene polycarbonate in the soft segment. The ratio of carbonate diols, so as to play a synergistic effect, maximize strengths and avoid weaknesses. The film formed after copolymerization is more suitable for the diaphragm, which can significantly improve high temperature resistance, chemical resistance and sensitivity, and can improve the product's long-term high temperature and/or Reliability under high humidity environment; at the same time, the diaphragm in the present invention can also take into account various acoustic performances such as stiffness, resilience, damping, distortion, etc., and can solve the polarization and distortion problems that occur during the vibration process of the product.
通过阅读下文优选实施方式的详细描述,各种其他的优点和益处对于本领域普通技术人员将变得清楚明了。附图仅用于示出优选实施方式的目的,而并不认为是对本发明的限制。Various other advantages and benefits will become apparent to those of ordinary skill in the art upon reading the following detailed description of the preferred embodiment. The drawings are only for the purpose of illustrating a preferred embodiment and are not to be considered as limiting the invention.
图1为实施例和对比例的树脂材料的红外谱图;Fig. 1 is the infrared spectrogram of the resin material of embodiment and comparative example;
图2为1MPa作用力下材料在不同温度下的位移变化曲线图;Figure 2 is a graph showing the displacement change curve of the material at different temperatures under a 1MPa force;
图3为本发明提供的扬声器的结构示意图;Fig. 3 is the structural representation of the loudspeaker provided by the present invention;
图4为图3中发声振动单元的结构示意图;Fig. 4 is a structural schematic diagram of the sounding vibration unit in Fig. 3;
图5为本发明中振膜的结构示意图;Fig. 5 is the structural representation of diaphragm in the present invention;
图6为实施例和对比例的总谐波失真曲线。Fig. 6 is the total harmonic distortion curve of the embodiment and the comparative example.
下面将结合实施例对本发明的实施方案进行详细描述,但是本领域技术人员将会理解,下列实施例仅用于说明本发明,而不应视为限制本发明的范围。实施例中未注明具体条件者,按照常规条件或制造商建议的条件进行。所用原药、试剂或仪器未注明生产厂商者,均为可以通过市售购买获得的常规产品或者可以根据现有技术制备得到。Embodiments of the present invention will be described in detail below in conjunction with examples, but those skilled in the art will understand that the following examples are only for illustrating the present invention, and should not be considered as limiting the scope of the present invention. Those who do not indicate the specific conditions in the examples are carried out according to the conventional conditions or the conditions suggested by the manufacturer. The original drugs, reagents or instruments used are not indicated by the manufacturer, and they are all conventional products that can be purchased from the market or can be prepared according to the existing technology.
本发明提供了一种可用于发声装置的振膜,所述振膜为多层复合结构,并且至少一个表层为热塑性聚酯弹性体膜;The invention provides a vibrating membrane that can be used for a sounding device, the vibrating membrane is a multi-layer composite structure, and at least one surface layer is a thermoplastic polyester elastomer film;
所述热塑性聚酯弹性体由芳香族二羧酸与二元醇反应得到的聚酯硬段和含有脂肪族聚碳酸酯的软段共聚而成;其中,所述振膜的厚度为10~200μm,所述热塑性聚酯弹性体膜在23℃环境下的损耗因子为0.1~0.3。The thermoplastic polyester elastomer is formed by the copolymerization of polyester hard segment obtained by reaction of aromatic dicarboxylic acid and glycol and soft segment containing aliphatic polycarbonate; wherein, the thickness of the diaphragm is 10-200 μm , the loss factor of the thermoplastic polyester elastomer film is 0.1-0.3 under the environment of 23°C.
本发明利用聚芳香族二羧酸二元醇酯硬段与脂肪族聚碳酸酯软段各自的优点,发挥协同作用,扬长避短,经共聚后形成的膜材更适于振膜,能显著提高耐高温性、耐化学品性和灵敏度,可以提升产品在长期高温和/或高湿度环境下的工作可靠性;同时,本发明中的振膜还可以兼顾刚度和回弹性、阻尼性、失真等多方面性能,可以解决产品在振动过程中出现的偏振和失真问题。经测试,利用本发明的热塑性聚酯弹性体膜层制成的振膜相比不含脂肪族聚碳酸酯酯的振膜具有显著的优势,尤其是在耐高温性、耐化学品性和灵敏度等方面。The present invention utilizes the respective advantages of the hard segment of polyaromatic dicarboxylic acid diol ester and the soft segment of aliphatic polycarbonate to exert synergistic effect, enhance strengths and avoid weaknesses, and the film material formed after copolymerization is more suitable for diaphragm, and can significantly improve the resistance to vibration. High temperature resistance, chemical resistance and sensitivity can improve the working reliability of products in long-term high temperature and/or high humidity environments; at the same time, the diaphragm in the present invention can also take into account stiffness and resilience, damping, distortion, etc. In terms of performance, it can solve the polarization and distortion problems that occur during the vibration process of the product. Diaphragms made with the thermoplastic polyester elastomer film layer of the present invention have been tested to have significant advantages over diaphragms without aliphatic polycarbonate esters, especially in terms of high temperature resistance, chemical resistance and sensitivity etc.
本发明所述的芳香族二羧酸可以是对苯二甲酸、二苯基二羧酸、萘二羧酸、间苯二羧酸或者以上被取代的芳香族二羧酸,优选对苯二甲酸。The aromatic dicarboxylic acid described in the present invention can be terephthalic acid, diphenyl dicarboxylic acid, naphthalene dicarboxylic acid, isophthalic acid or the above substituted aromatic dicarboxylic acid, preferably terephthalic acid .
本发明所述的二元醇可以是乙二醇、丁二醇、丙二醇、环戊二醇、环己二醇等,可以是任选以上一种醇或者多种醇组合。The dihydric alcohol described in the present invention can be ethylene glycol, butanediol, propylene glycol, cyclopentanediol, cyclohexanediol, etc., and can be optionally one of the above alcohols or a combination of multiple alcohols.
上述芳香族二羧酸与二元醇聚合反应后形成硬段,可以是一种芳香族二羧酸 与一种二元醇聚合,也可以是一种芳香族二羧酸与多种二元醇聚合,还可以是多种芳香族二羧酸与一种二元醇聚合,还可以是多种芳香族二羧酸与多种二元醇聚合。The above-mentioned aromatic dicarboxylic acid and dihydric alcohol are polymerized to form a hard segment, which can be a kind of aromatic dicarboxylic acid and a kind of dibasic alcohol polymerized, or a kind of aromatic dicarboxylic acid and a variety of dibasic alcohols The polymerization may also be the polymerization of multiple aromatic dicarboxylic acids and one diol, or the polymerization of multiple aromatic dicarboxylic acids and multiple diols.
本发明所述的软段中还可以添加聚己内酯、聚已二酸丁二醇酯、聚四氢呋喃醚、聚环氧乙烷中的一种或多种。添加少量的以上聚合物可以在保持材料良好强度、刚度和回弹性的前提下,利于提高聚碳酸酯软段的嵌段性和与硬段的聚合性,但若添加量超过30%,又会影响整个材料的嵌段结构特性,导致材料整体的刚性及回弹性损失。因脂肪族聚碳酸酯具有更强的极性,耐湿热、化学品性等方面会优于聚酯或聚醚嵌段,所以软段中脂肪族聚碳酸酯嵌段的含量占主导,材料的整体性能应更优。相应地,软段中所述脂肪族聚碳酸酯的重量百分比优选在70%以上,例如可以是70%、75%、80%、85%、90%、95%、100%等。与脂肪族聚碳酸酯配伍组成软段的聚合物优选聚己内酯。One or more of polycaprolactone, polybutylene adipate, polytetrahydrofuran ether, and polyethylene oxide may also be added to the soft segment of the present invention. Adding a small amount of the above polymers can help improve the blockiness of the polycarbonate soft segment and the polymerizability with the hard segment while maintaining the good strength, stiffness and resilience of the material. However, if the amount exceeds 30%, it will It affects the block structure characteristics of the entire material, resulting in the loss of the overall rigidity and resilience of the material. Because aliphatic polycarbonate has stronger polarity, it is better than polyester or polyether block in terms of moisture resistance and chemical resistance, so the content of aliphatic polycarbonate block in the soft segment is dominant, and the material's Overall performance should be better. Correspondingly, the weight percentage of the aliphatic polycarbonate in the soft segment is preferably above 70%, such as 70%, 75%, 80%, 85%, 90%, 95%, 100%, etc. Polycaprolactone is preferred as the polymer that is compatible with aliphatic polycarbonate to form the soft segment.
同时,本发明的热塑性聚酯弹性体中硬段和软段的比例对耐温性、阻尼性等性能都有显著影响,通常软段的重量百分比优选为20%~80%,例如20%、30%、40%、50%、60%、70%、80%等。软段含量越多,材料的刚性及强度降低,而振膜需要振动发生,良好的刚性及强度是必要特性,根据该材料的结构特性,软段含量不高于80%。软段含量较低时,整个材料硬段特性占主导,材料虽然刚度和强度明显提升,但柔韧性降低,为了保证扬声器实现大位移、大响度以及良好的防水回弹性等,所述软段含量不低于25%。根据扬声器振膜振动所需的模量、强度及回弹性的要求,软段含量更优选为25%~60%,例如25%、30%、35%、40%、45%、50%、55%、60%等。At the same time, the proportion of hard segment and soft segment in the thermoplastic polyester elastomer of the present invention has a significant impact on properties such as temperature resistance and damping. Usually, the weight percentage of soft segment is preferably 20% to 80%, such as 20%, 30%, 40%, 50%, 60%, 70%, 80%, etc. The more the soft segment content, the lower the rigidity and strength of the material, and the diaphragm needs to vibrate. Good rigidity and strength are necessary characteristics. According to the structural characteristics of the material, the soft segment content is not higher than 80%. When the soft segment content is low, the hard segment characteristics of the entire material are dominant. Although the stiffness and strength of the material are significantly improved, the flexibility is reduced. Not less than 25%. According to the requirements of modulus, strength and resilience required for speaker diaphragm vibration, the soft segment content is more preferably 25% to 60%, such as 25%, 30%, 35%, 40%, 45%, 50%, 55% %, 60%, etc.
此外,由于聚合物化学组成的复杂性,需要结合到实际用途中限定其性能。In addition, due to the complexity of the chemical composition of polymers, their properties need to be limited in combination with practical applications.
就其用于振膜而言,本发明的所述热塑性聚酯弹性体膜层的损耗因子为0.1~0.3时(采用DMA温度扫描模式,1Hz振动频率,3℃/min升温速率,损耗因子为23℃的数据),将具有良好的阻尼性,能够满足产品对高性能、低性能的需求。本发明的热塑性聚酯弹性体中由于存在聚碳酸酯链段,相对于聚酯链段或聚醚链段,聚碳酸酯链段具有更高的极性,链段运动的空间位阻更大,当受外力作用时,可以消耗更多的能量,因此相对于其他类型的热塑性弹性体材料,其具有更好的阻尼性,可以很容易达到0.1~0.3。当损耗因子低于0.1,相对于聚醚-聚 酯型热塑性聚酯弹性体在失真方面无优势;损耗因子高于0.2,材料的阻尼提升会损失材料的瞬态响应性,振膜不能完美的实现输入信号的反馈,音质会有所牺牲。在此基础上更优选0.1~0.2,例如0.12、0.14、0.15、0.16、0.17、0.18、0.19、0.2等。As far as it is used for a diaphragm, when the loss factor of the thermoplastic polyester elastomer film layer of the present invention is 0.1 to 0.3 (using DMA temperature scanning mode, 1Hz vibration frequency, 3°C/min heating rate, the loss factor is 23°C data), it will have good damping properties and can meet the needs of products for high performance and low performance. Due to the presence of polycarbonate segments in the thermoplastic polyester elastomer of the present invention, relative to polyester segments or polyether segments, polycarbonate segments have higher polarity, and the steric hindrance of segment movement is larger , when subjected to an external force, it can consume more energy, so it has better damping properties than other types of thermoplastic elastomer materials, which can easily reach 0.1-0.3. When the loss factor is lower than 0.1, there is no advantage in distortion compared to polyether-polyester thermoplastic polyester elastomer; when the loss factor is higher than 0.2, the increase in damping of the material will lose the transient response of the material, and the diaphragm cannot be perfect To realize the feedback of the input signal, the sound quality will be sacrificed. On this basis, it is more preferably 0.1 to 0.2, such as 0.12, 0.14, 0.15, 0.16, 0.17, 0.18, 0.19, 0.2 and the like.
在一些实施方式中,所述热塑性聚酯弹性体膜层的拉伸模量为20~500Mpa(采用DMA温度扫描模式,1Hz振动频率,3℃/min升温速率,为23℃时的数据)。模量太低时,振膜的刚度不足,如果达到产品所需的F0(最低共振频率),只能通过增加厚度实现,但厚度的增加会带来振膜质量的升高,会损失其振动空间并且降低了质量控制区的灵敏度。模量较高时,材料的柔韧性及回弹性变差,为了得到高响度时,产品需要振膜具有较大的位移,此时模量的增加势必带来不利的影响。根据产品设计及性能需求,推荐如下:所述发声装置的最低共振频率F0≤500Hz时,所述热塑性聚酯弹性体膜的拉伸模量为20~100Mpa;所述发声装置的最低共振频率F0>500Hz时,所述热塑性聚酯弹性体膜的拉伸模量为50~400MPa。例如,发声装置的最低共振频率F0为400Hz时,热塑性聚酯弹性体膜的拉伸模量可以为70Mpa。例如,发声装置的最低共振频率F0为800Hz时,热塑性聚酯弹性体膜的拉伸模量可以为350Mpa。In some embodiments, the tensile modulus of the thermoplastic polyester elastomer film layer is 20-500Mpa (using DMA temperature scanning mode, 1Hz vibration frequency, 3°C/min heating rate, data at 23°C). When the modulus is too low, the stiffness of the diaphragm is insufficient. If the F0 (minimum resonance frequency) required by the product is achieved, it can only be achieved by increasing the thickness, but the increase in thickness will increase the quality of the diaphragm and lose its vibration space and reduces the sensitivity of the quality control zone. When the modulus is high, the flexibility and resilience of the material become poor. In order to obtain high loudness, the product requires a large displacement of the diaphragm. At this time, the increase of the modulus will inevitably bring adverse effects. According to product design and performance requirements, the recommendation is as follows: when the minimum resonance frequency F0 of the sound generating device is ≤ 500 Hz, the tensile modulus of the thermoplastic polyester elastomer film is 20-100 Mpa; the minimum resonance frequency F0 of the sound generating device When >500 Hz, the tensile modulus of the thermoplastic polyester elastomer film is 50-400 MPa. For example, when the lowest resonance frequency F0 of the sound generating device is 400 Hz, the tensile modulus of the thermoplastic polyester elastomer film may be 70 MPa. For example, when the lowest resonance frequency F0 of the sound generating device is 800 Hz, the tensile modulus of the thermoplastic polyester elastomer film may be 350 MPa.
在一些实施方式中,为了保证扬声器振膜振动的一致性,减少产品偏振,选用的膜材,所述热塑性聚酯弹性体膜层的MD与TD两方向的储能模量之间比例为80~120:100。换言之,所述热塑性聚酯弹性体膜层的MD与TD两方向的储能模量差异控制在±20%以内,优选±10%以内。In some embodiments, in order to ensure the consistency of the vibration of the loudspeaker diaphragm and reduce the polarization of the product, the selected film material, the ratio between the storage modulus in the MD and TD directions of the thermoplastic polyester elastomer film layer is 80 ~120:100. In other words, the storage modulus difference between the MD and TD directions of the thermoplastic polyester elastomer film layer is controlled within ±20%, preferably within ±10%.
本发明的振膜为多层复合结构,其至少包括热塑性聚酯弹性体膜,优选其与胶膜层交替叠加的结构,所述热塑性聚酯弹性体膜为表层。若采用复合结构,由于热塑性聚酯弹性体膜具有较强的刚性,可以在设置很薄的情况下就可以满足使用需求,由此可以避免因材料厚度过高带来的灵敏度及振动空间损失,热塑性聚酯弹性体膜层的厚度优选为5~50μm。The vibrating membrane of the present invention is a multi-layer composite structure, which at least includes a thermoplastic polyester elastomer film, preferably a structure in which it is alternately stacked with adhesive film layers, and the thermoplastic polyester elastomer film is the surface layer. If a composite structure is adopted, due to the strong rigidity of the thermoplastic polyester elastomer film, it can meet the use requirements when it is set very thin, thereby avoiding the loss of sensitivity and vibration space caused by excessive material thickness. The thickness of the thermoplastic polyester elastomer film layer is preferably 5 to 50 μm.
在本发明的一个具体实施例中,振膜可以包括三层结构,其中中间层为胶膜层,两表层为热塑性聚酯弹性体膜层,热塑性聚酯弹性体膜层由芳香族二羧酸与二元醇反应得到的聚酯硬段和含有脂肪族聚碳酸酯的软段共聚而成,中间层设在两表层之间。In a specific embodiment of the present invention, the diaphragm can include a three-layer structure, wherein the middle layer is an adhesive film layer, and the two surface layers are thermoplastic polyester elastomer film layers, and the thermoplastic polyester elastomer film layers are made of aromatic dicarboxylic acid. The polyester hard segment obtained by reacting with glycol and the soft segment containing aliphatic polycarbonate are copolymerized, and the middle layer is arranged between the two surface layers.
在本发明的另一个具体实施例中,振膜可以包括五层结构,五层结构为热塑性聚酯弹性体膜层与胶膜层交替叠加分布,其两表层为热塑性聚酯弹性体膜层,热塑性聚酯弹性体膜层由芳香族二羧酸与二元醇反应得到的聚酯硬段和含有脂肪族聚碳酸酯的软段共聚而成。In another specific embodiment of the present invention, the vibrating membrane may include a five-layer structure, the five-layer structure is alternately superimposed and distributed with thermoplastic polyester elastomer film layers and adhesive film layers, and its two surface layers are thermoplastic polyester elastomer film layers, The thermoplastic polyester elastomer film layer is formed by the copolymerization of the polyester hard segment obtained by the reaction of aromatic dicarboxylic acid and diol and the soft segment containing aliphatic polycarbonate.
对于复合膜中的胶层,其可以是本领域典型的胶,例如厚度为2~50μm的硅胶层、丙烯酸胶层中的一种或多种,优选为压敏胶膜。压敏胶膜使用方便,通过简单的复合工艺就可实现多层间的贴合,贴合后的180°剥离力需满足:不低于150g/25mm。为使扬声器振膜满足在低温下仍能保持良好的音质,胶层的玻璃化转变温度不高于-10℃。高于-10℃后,胶膜层模量会迅速上升,导致材料刚性过高,产品F0升高明显,且振膜韧性降低,易出现膜裂风险。The adhesive layer in the composite film may be a typical adhesive in the field, such as one or more of a silicone layer and an acrylic adhesive layer with a thickness of 2-50 μm, preferably a pressure-sensitive adhesive film. The pressure-sensitive adhesive film is easy to use, and the lamination between layers can be realized through a simple lamination process. The 180° peeling force after lamination must meet: not less than 150g/25mm. In order to ensure that the speaker diaphragm can still maintain good sound quality at low temperatures, the glass transition temperature of the adhesive layer should not be higher than -10°C. When the temperature is higher than -10°C, the modulus of the adhesive film layer will increase rapidly, resulting in excessive rigidity of the material, a significant increase in the F0 of the product, and a decrease in the toughness of the diaphragm, which is prone to the risk of film cracking.
对于本发明中热塑性聚酯弹性体膜层的制备方法,其仅涉及常规工序,包括共聚反应、制成颗粒状树脂,之后利用挤出设备形成膜材,最后与其他膜贴合成所述振膜。For the preparation method of the thermoplastic polyester elastomer film layer in the present invention, it only involves conventional procedures, including copolymerization reaction, making granular resin, and then using extrusion equipment to form a film material, and finally bonding it with other films to form the diaphragm .
其中,共聚反应的工艺条件对热塑性聚酯弹性体的性能有一定影响,通常在保证原料在熔融状态下进行,硬段和软段都选用预聚物。Among them, the process conditions of the copolymerization reaction have a certain influence on the performance of the thermoplastic polyester elastomer. Usually, the raw materials are guaranteed to be in a molten state, and the hard segment and the soft segment are both selected as prepolymers.
在一些优选的实施方式中,由芳香族二羧酸与二元醇反应得到的聚酯硬段预聚物选用分子量为15000~30000的,例如15000、20000、25000、30000等。脂肪族聚碳酸酯软段的预聚物优选分子量为10000~50000,例如10000、15000、20000、25000、30000、35000、40000、45000、50000等。共聚反应的温度优选为230~265℃,反应时间优选为0.5~2h。In some preferred embodiments, the polyester hard segment prepolymer obtained by reacting aromatic dicarboxylic acid and diol is selected to have a molecular weight of 15,000-30,000, such as 15,000, 20,000, 25,000, 30,000, etc. The prepolymer of the aliphatic polycarbonate soft segment preferably has a molecular weight of 10,000-50,000, such as 10,000, 15,000, 20,000, 25,000, 30,000, 35,000, 40,000, 45,000, 50,000, etc. The temperature of the copolymerization reaction is preferably 230-265° C., and the reaction time is preferably 0.5-2 h.
共聚反应中通常还加入催化剂和交联剂,二者选用的类型可以是典型助剂,例如所述稳定剂优选为聚碳化二亚胺,所述催化剂优选钛酸正丁酯,二者的用量根据实际情况可调整。共聚反应的终点通常以树脂变成均一的透明状为准。Usually also add catalyst and crosslinking agent in the copolymerization reaction, the type that both selects can be typical auxiliary agent, for example described stabilizing agent is preferably polycarbodiimide, and described catalyst is preferably n-butyl titanate, the consumption of both It can be adjusted according to the actual situation. The end point of the copolymerization reaction is usually when the resin becomes uniform and transparent.
造粒通常在切片机或造粒机中进行。Granulation is usually carried out in a slicer or pelletizer.
对于挤出成膜工序,通常在挤出机中进行,还可以加入适量的加工助剂(如增塑剂、爽滑剂、润滑剂等)一起加入至螺杆中熔融,经螺杆分散混合后输出至T模头,为了降低薄膜的取向,熔体从T模头流出后,可在过冷却辊前添加一定厚度的辅材(如离型膜或离型纸等)至薄膜的一表面,展平定型后,一起收卷。 加工助剂的类型和用量都是现有典型的。For the extrusion film forming process, it is usually carried out in an extruder, and an appropriate amount of processing aids (such as plasticizers, slip agents, lubricants, etc.) can also be added to the screw to melt, and then output after being dispersed and mixed by the screw. To the T die head, in order to reduce the orientation of the film, after the melt flows out from the T die head, an auxiliary material of a certain thickness (such as a release film or release paper, etc.) can be added to one surface of the film before the supercooling roll to spread After flattening, roll together. The types and amounts of processing aids are typical in the art.
本发明提供的振膜可组成任意构造的发声装置,例如如下典型的发声装置:包括振动系统和与所述振动系统相配合的磁路系统,所述振动系统包括振膜和结合在所述振膜一侧的音圈。当发声装置工作时,音圈通电后在磁路系统的磁场力的作用下,音圈可以上下振动以带动振膜振动,振膜振动时可以进行发声。The vibrating membrane provided by the present invention can form a sounding device of any structure, such as the following typical sounding device: comprising a vibrating system and a magnetic circuit system matched with the vibrating system, the vibrating system includes a vibrating membrane and a magnetic circuit system combined with the vibrating Voice coil on one side of the membrane. When the sound generating device is working, the voice coil can vibrate up and down under the action of the magnetic field force of the magnetic circuit system after the voice coil is energized to drive the vibration of the diaphragm, and the sound can be produced when the diaphragm vibrates.
根据本发明另一方面的实施例,发声装置可以包括壳体以及设在壳体内的磁路系统和振动系统,振动系统可以包括音圈、第一振膜和第二振膜,音圈的顶部与第一振膜相连,磁路系统系统驱音圈振动以带动第一振膜发声,第二振膜的两端分别与壳体和音圈的底部相连。其中,第二振膜可以为根据本发明上述实施例中的振膜。According to another embodiment of the present invention, the sound generating device may include a housing and a magnetic circuit system and a vibration system disposed in the housing. The vibration system may include a voice coil, a first diaphragm and a second diaphragm, and the top of the voice coil Connected with the first diaphragm, the magnetic circuit system drives the voice coil to vibrate to drive the first diaphragm to produce sound, and the two ends of the second diaphragm are respectively connected with the shell and the bottom of the voice coil. Wherein, the second diaphragm may be the diaphragm according to the foregoing embodiments of the present invention.
也就是说,第一振膜可以用于振动发声,第二振膜可以用于平衡音圈的振动。具体而言,当发声装置工作时,音圈通电后在磁路系统的磁场力的作用下,音圈可以上下振动以带动第一振膜振动,第一振膜振动时可以进行发声。第二振膜也可以跟随音圈上下振动,由于第二振膜的两端分别与壳体和音圈的底部相连,第二振膜可以平衡音圈的振动,可以防止音圈出现偏振的现象,从而可以提升发声装置的发声效果。That is to say, the first diaphragm can be used to vibrate and produce sound, and the second diaphragm can be used to balance the vibration of the voice coil. Specifically, when the sound generating device is working, the voice coil can vibrate up and down under the action of the magnetic field force of the magnetic circuit system after the voice coil is energized to drive the first diaphragm to vibrate, and the first diaphragm can vibrate to produce sound. The second diaphragm can also vibrate up and down with the voice coil. Since the two ends of the second diaphragm are respectively connected to the bottom of the shell and the voice coil, the second diaphragm can balance the vibration of the voice coil and prevent the polarization of the voice coil. Therefore, the sounding effect of the sounding device can be improved.
需要进行说明的是,可以将第一振膜和第二振膜同时采用本发明上述实施例的振膜,也可以是第一振膜和第二振膜中的一个采用本发明上述实施例的振膜,本发明对此不作具体限制。下文结合实施例具体展开说明。It should be noted that the first diaphragm and the second diaphragm can use the diaphragm of the above-mentioned embodiment of the present invention at the same time, or one of the first diaphragm and the second diaphragm can adopt the diaphragm of the above-mentioned embodiment of the present invention. The diaphragm, which is not specifically limited in the present invention. The following is a specific description in conjunction with the examples.
实施例1Example 1
第一步,制作树脂颗粒The first step is to make resin particles
向惰性气体氛围的反应罐中加入70质量份的数据分子量为25000聚对苯二甲酸丁二醇酯预聚物、25质量份数均分子量为15000的聚六亚甲基聚碳酸酯二醇及5质量份的聚己内酯,以及0.15质量份的钛酸正丁酯为催化剂、加入0.5质量份聚碳化二亚胺,缓慢升温至熔融状态(230~265℃)后,继续反应1h左右,直至树脂变成均一的透明状,冷却后用切片机或造粒机裁切成颗粒状,用于薄膜的制作。该树脂的红外谱图如图1所示,显示在1743cm
-1附近有明显的软段聚碳酸酯的C=O的特征吸收峰。
In the reaction tank of inert gas atmosphere, add the polyhexamethylene polycarbonate diol that the data molecular weight of 70 mass parts is 25000 polybutylene terephthalate prepolymers, 25 mass parts number average molecular weights and 5 parts by mass of polycaprolactone and 0.15 parts by mass of n-butyl titanate are used as catalysts, 0.5 parts by mass of polycarbodiimide is added, and the temperature is slowly raised to a molten state (230-265°C), and the reaction is continued for about 1 hour. Until the resin becomes uniform and transparent, after cooling, cut it into granules with a slicer or granulator for film production. The infrared spectrum of the resin is shown in Figure 1, which shows that there is an obvious characteristic absorption peak of C=O of soft segment polycarbonate near 1743cm -1 .
第二步,制作膜材The second step is to make the membrane
采用熔融挤出流延的方式。制膜前首先将粒子干燥除水,然后加入至螺杆中熔融,经螺杆分散混合后输出至T模头,为了降低薄膜的取向,熔体从T模头流出后,可在过冷却辊前添加一定厚度的辅材(如离型膜或离型纸等)至薄膜的一表面,展平定型后,一起收卷。通过控制车速和冷却辊间的压力等,保证所得热塑性聚酯弹性体膜在MD及TD两方向的储能模量差异在±10%以内。The method of melt extrusion casting is adopted. Before film making, the particles are first dried and dehydrated, then added to the screw to melt, dispersed and mixed by the screw, and then output to the T-die. In order to reduce the orientation of the film, after the melt flows out of the T-die, it can be added before the cooling roll A certain thickness of auxiliary material (such as release film or release paper, etc.) is applied to one surface of the film, and after being flattened and shaped, it is rolled together. By controlling the speed of the vehicle and the pressure between the cooling rollers, etc., it is ensured that the difference of the storage modulus of the obtained thermoplastic polyester elastomer film in the MD and TD directions is within ±10%.
实施例2Example 2
第一步,制作树脂颗粒The first step is to make resin particles
向惰性气体氛围的反应罐中加入70质量份的数据分子量为25000聚对苯二甲酸丁二醇酯预聚物、30质量份数均分子量为15000的聚六亚甲基聚碳酸酯二醇,以及0.15质量份的钛酸正丁酯为催化剂、加入0.5质量份聚碳化二亚胺,缓慢升温至熔融状态(230~265℃)后,继续反应1h左右,直至树脂变成均一的透明状,冷却后用切片机或造粒机裁切成颗粒状,用于薄膜的制作。该树脂的红外谱图如图1所示,显示在1743cm
-1附近有明显的软段聚碳酸酯的C=O的特征吸收峰。
In the reaction tank of inert gas atmosphere, add the polyhexamethylene polycarbonate diol that the data molecular weight of 70 mass parts is 25000 polybutylene terephthalate prepolymers, 30 mass parts number average molecular weights, and 0.15 parts by mass of n-butyl titanate as a catalyst, adding 0.5 parts by mass of polycarbodiimide, slowly heating up to a molten state (230-265°C), and continuing to react for about 1 hour until the resin becomes uniform and transparent. After cooling, use a slicer or granulator to cut into granules for film production. The infrared spectrum of the resin is shown in Figure 1, which shows that there is an obvious characteristic absorption peak of C=O of soft segment polycarbonate near 1743cm -1 .
第二步,制作膜材The second step is to make the membrane
采用熔融挤出流延的方式。制膜前首先将粒子干燥除水,然后加入至螺杆中熔融,经螺杆分散混合后输出至T模头,为了降低薄膜的取向,熔体从T模头流出后,可在过冷却辊前添加一定厚度的辅材(如离型膜或离型纸等)至薄膜的一表面,展平定型后,一起收卷。通过控制车速和冷却辊间的压力等,保证所得热塑性聚酯弹性体膜在MD及TD两方向的储能模量差异在±10%以内。The method of melt extrusion casting is adopted. Before film making, the particles are first dried and dehydrated, then added to the screw to melt, dispersed and mixed by the screw, and then output to the T-die. In order to reduce the orientation of the film, after the melt flows out of the T-die, it can be added before the cooling roll A certain thickness of auxiliary material (such as release film or release paper, etc.) is applied to one surface of the film, and after being flattened and shaped, it is rolled together. By controlling the speed of the vehicle and the pressure between the cooling rollers, etc., it is ensured that the difference of the storage modulus of the obtained thermoplastic polyester elastomer film in the MD and TD directions is within ±10%.
对比例comparative example
第一步,制作树脂颗粒The first step is to make resin particles
向惰性气体氛围的反应罐中加入70质量份的数均分子质量为25000的聚对苯二甲酸丁二醇酯预聚物和30质量份的数据分子量为2000的聚四氢呋喃醚嵌段,以及0.15质量份的钛酸正丁酯为催化剂、加入0.5质量份聚碳化二亚胺,缓慢升温至熔融状态(230~265℃)后,继续反应1h左右,直至树脂变成均一的透明状,冷却后用切片机或造粒机裁切成颗粒状,用于薄膜的制作。该树脂的红 外谱图如图1所示。Add 70 mass parts of polybutylene terephthalate prepolymers with a number average molecular weight of 25000 and 30 mass parts of polytetrahydrofuran ether blocks with a data molecular weight of 2000 in the reaction tank of an inert gas atmosphere, and 0.15 Parts by mass of n-butyl titanate as a catalyst, add 0.5 parts by mass of polycarbodiimide, slowly heat up to a molten state (230-265°C), and continue to react for about 1 hour until the resin becomes uniform and transparent. After cooling, Cut into granules with a slicer or a granulator for film production. The infrared spectrum of the resin is shown in Figure 1.
第二步,制作膜材The second step is to make the membrane
采用熔融挤出流延的方式。制膜前首先将粒子干燥除水,然后加入至螺杆中熔融,经螺杆分散混合后输出至T模头,为了降低薄膜的取向,熔体从T模头流出后,可在过冷却辊前添加一定厚度的辅材(如离型膜或离型纸等)至薄膜的一表面,展平定型后,一起收卷。通过控制车速和冷却辊间的压力等,保证所得热塑性聚酯弹性体膜在MD及TD两方向的储能模量差异在±10%以内。The method of melt extrusion casting is adopted. Before film making, the particles are first dried and dehydrated, then added to the screw to melt, dispersed and mixed by the screw, and then output to the T-die. In order to reduce the orientation of the film, after the melt flows out of the T-die, it can be added before the cooling roll A certain thickness of auxiliary material (such as release film or release paper, etc.) is applied to one surface of the film, and after being flattened and shaped, it is rolled together. By controlling the speed of the vehicle and the pressure between the cooling rollers, etc., it is ensured that the difference of the storage modulus of the obtained thermoplastic polyester elastomer film in the MD and TD directions is within ±10%.
检测不同热塑性弹性体膜的性能Examining the properties of different thermoplastic elastomer films
1、耐热性评价1. Evaluation of heat resistance
测试方法:采用TMA设备,选取厚度为20μm的对比例、实施例1和实施例2的薄膜(热塑性聚酯弹性体膜)材料,采用拉伸模式,维持拉伸应力为1MPa,按照3℃/min的升温速率由室温升高至200℃,仪器会记录并输出测试过程中材料在不同温度下的长度变化曲线。Test method: adopt TMA equipment, select the film (thermoplastic polyester elastomer film) material with a thickness of 20 μm as the comparative example, embodiment 1 and embodiment 2, adopt the tensile mode, maintain the tensile stress at 1MPa, and follow the 3°C/ The heating rate of min increases from room temperature to 200°C, and the instrument will record and output the length change curve of the material at different temperatures during the test.
结果显示:如图2所示,材料在受力状态下,随着温度的升高,长度会增加。不难理解,长度随温度的变化越大,材料的耐高温下越差。由此可知耐热性方面,实施例2优于实施例1,优于对比例。The results show that as shown in Figure 2, the length of the material will increase as the temperature increases under the stress state. It is not difficult to understand that the greater the change in length with temperature, the worse the material's high temperature resistance. It can be seen that in terms of heat resistance, Example 2 is better than Example 1, and better than Comparative Example.
2、吸油率测试2. Oil absorption test
测试方法:裁取质量相近的物料并用分析天平进行称量记录质量M
1,置于油酸中浸泡24h后取出用无尘布擦拭表面的油酸后称重M
2,通过对比吸油酸前后材料质量的变化,从而可以得出耐化学品的优劣。
Test method: Cut out materials with similar quality and weigh them with an analytical balance to record the mass M 1 , soak in oleic acid for 24 hours, take out the oleic acid on the surface with a dust-free cloth and weigh M 2 , and compare the materials before and after oleic acid absorption Changes in quality, so that the advantages and disadvantages of chemical resistance can be drawn.
结果显示:如表1所示,对比例的吸油率最高,实施例2的吸油率最低。由此可以推测,聚碳酸酯软段的存在有利于阻隔有机小分子的浸入,提升整个材料的耐化学品性。The result shows: as shown in Table 1, the oil absorption rate of the comparative example is the highest, and the oil absorption rate of the embodiment 2 is the lowest. It can be speculated that the presence of polycarbonate soft segments is beneficial to block the immersion of small organic molecules and improve the chemical resistance of the entire material.
表1吸油率对比Table 1 Comparison of oil absorption
样品sample | M 1/g M 1 /g | M 2/g M 2 /g | 吸油率Oil absorption |
对比例comparative example | 0.10910.1091 | 0.12330.1233 | 13.02%13.02% |
实施例1Example 1 | 0.11150.1115 | 0.12090.1209 | 8.43%8.43% |
实施例2Example 2 | 0.15070.1507 | 0.15790.1579 | 4.78%4.78% |
3、测试热塑性聚酯弹性体膜的拉伸模量和损耗因子3. Test the tensile modulus and loss factor of thermoplastic polyester elastomer film
测试方法:使用裁刀或美工刀片从薄膜上采取宽度为5~10mm的平整矩形样条,采用ASTM D412-2016标准进行测试,采测试振动频率为1Hz,温度23℃。Test method: Use a cutting knife or a utility blade to take a flat rectangular sample with a width of 5-10mm from the film, and use the ASTM D412-2016 standard for testing. The vibration frequency of the test is 1Hz and the temperature is 23°C.
结果显示:如表2所示,对比例与实施例2在室温下具有相近的储能模量,但实施例2高温下的模量高于对比例,说明本发明在高温下具有更稳定的结构强度。损耗模量的峰值温度为材料的玻璃化转变温度,代表热塑性聚酯弹性体材料具有高弹态特性的开始温度。由损耗模量随温度的曲线可知,本发明具有更低的玻璃化转变温度。综上可知,本发明的热塑性聚酯弹性体具有更宽的使用温度范围。另外,由图2可知,实施例2具有更高的阻尼性(材料的损耗因子=损耗模量与储能模量的比值)。The result shows: as shown in table 2, comparative example and embodiment 2 have close storage modulus at room temperature, but the modulus at high temperature of embodiment 2 is higher than comparative example, illustrates that the present invention has more stable at high temperature Structural strength. The peak temperature of the loss modulus is the glass transition temperature of the material, which represents the onset temperature at which the thermoplastic polyester elastomer material has high elastic properties. From the curve of loss modulus with temperature, it can be seen that the present invention has a lower glass transition temperature. It can be seen from the above that the thermoplastic polyester elastomer of the present invention has a wider service temperature range. In addition, it can be seen from FIG. 2 that Example 2 has higher damping properties (loss factor of the material=ratio of loss modulus to storage modulus).
表2Table 2
测试不同热塑性聚酯弹性体制成的振膜的F0、灵敏度和总谐波失真曲线Test F0, Sensitivity and Total Harmonic Distortion Curves of Diaphragms Made of Different Thermoplastic Polyester Elastomers
1、制作振膜1. Make the diaphragm
分别选取实施例2和对比例中的热塑性聚酯弹性体膜分别制作振膜。其中,实施例2和对比例中的振膜均采用三层复合结构,均包括中间层和两表层,中间层为丙烯酸胶层,两表层均为分别对应的热塑性聚酯弹性体层,中间层和两表层的厚度均为20μm。也就是说,实施例2与对比例中的振膜的区别仅在于两表层的热塑性聚酯弹性体膜层的材料不同。实施例2和对比例中的振膜的制作方法相同,具体如下:The thermoplastic polyester elastomer films in Example 2 and Comparative Example were respectively selected to make diaphragms. Wherein, the diaphragms in Example 2 and Comparative Example all adopt a three-layer composite structure, including a middle layer and two surface layers, the middle layer is an acrylic adhesive layer, and the two surface layers are respectively corresponding thermoplastic polyester elastomer layers, and the middle layer The thickness of both surface layers is 20 μm. That is to say, the difference between the diaphragm in Example 2 and the comparative example is only that the materials of the thermoplastic polyester elastomer film layers of the two surface layers are different. The manufacturing method of the diaphragm in Embodiment 2 and the comparative example is the same, as follows:
采用复合设备,将制备的热塑性聚酯弹性体膜层与丙烯酸胶层交替叠加压合形成热塑性聚酯弹性体膜层+丙烯酸胶层+热塑性聚酯弹性体膜层的复合结构,由此制得所需搭配的复合料带。将上述复合料带置于热压成型机上进行二次成型,制备得到所需的振膜形状,裁切至产品尺寸后与音圈、磁路系统等部件一起装配 至微型扬声器单元中(如图3和图4所示)。Using composite equipment, the prepared thermoplastic polyester elastomer film layer and acrylic adhesive layer are laminated alternately to form a composite structure of thermoplastic polyester elastomer film layer + acrylic adhesive layer + thermoplastic polyester elastomer film layer, thus making Composite tape required. Place the above-mentioned composite strip on a thermocompression molding machine for secondary molding to prepare the required diaphragm shape, cut it to the product size and assemble it into the micro speaker unit together with the voice coil, magnetic circuit system and other components (as shown in the figure 3 and Figure 4).
2、测试方法:2. Test method:
分别对装配有上述实施例2和对比例中的振膜的微型扬声器(SPK)进行产品性能测试。微型扬声器采用如图3所示的结构,其包括振动系统和与所述振动系统相配合的磁路系统,所述振动系统包括振膜和结合在所述振膜一侧的音圈。扬声器振动单元如图4所示,本领域技术人员可根据实际产品需求做相应的调整。例如,如图3和4所示,振膜1由折环部11和球顶部12组成,热塑性聚酯弹性体层可位于振膜的折环部11,也可位于折环部11及球顶部12。折环部11向远离音圈2的一侧凸起;球顶部12与折环部11相连;振动系统中设有定心支片,可提高振动系统的抗偏振能力等。振膜3分别采用实施例2和对比例的热塑性聚酯弹性体组成,均采用“热塑性聚酯弹性体膜层31-胶层32-热塑性聚酯弹性体膜层31”的三层结构,如图5所示。Product performance tests were performed on the microspeakers (SPK) equipped with the diaphragms in the above-mentioned embodiment 2 and the comparative example, respectively. The micro-speaker adopts the structure shown in Fig. 3, which includes a vibration system and a magnetic circuit system matched with the vibration system, and the vibration system includes a diaphragm and a voice coil combined on one side of the diaphragm. The loudspeaker vibration unit is shown in FIG. 4 , and those skilled in the art can make corresponding adjustments according to actual product requirements. For example, as shown in Figures 3 and 4, the vibrating membrane 1 is composed of a ring portion 11 and a ball top 12, and the thermoplastic polyester elastomer layer can be located at the ring portion 11 of the diaphragm, or at the ring portion 11 and the ball top. 12. Surround portion 11 protrudes toward the side away from voice coil 2; ball top 12 is connected to surround portion 11; a centering strut is provided in the vibration system, which can improve the anti-polarization ability of the vibration system, etc. The vibrating film 3 is composed of the thermoplastic polyester elastomers of Example 2 and Comparative Example respectively, and both adopt a three-layer structure of "thermoplastic polyester elastomer film layer 31-adhesive layer 32-thermoplastic polyester elastomer film layer 31", as Figure 5 shows.
结果显示:如表3和图6所示,相对于对比例SPK产品(即应用对比例中的热塑性聚酯弹性体膜层的SPK产品),实施例SPK产品(即应用实施例2中的热塑性聚酯弹性体膜层的SPK产品)F0低8Hz,产品在500Hz的灵敏度(SPL@500Hz)高1dB。实施例2的SPK在产品F0稍低于对比例的前提下,较对比例SPK产品具有更低的失真。The result shows: as shown in table 3 and Fig. 6, with respect to comparative example SPK product (being the SPK product of the thermoplastic polyester elastomer film layer in application comparative example), embodiment SPK product (being the thermoplastic polyester elastomer film layer in application example 2) SPK product with polyester elastomer film) F0 is 8Hz lower, and the sensitivity of the product at 500Hz (SPL@500Hz) is 1dB higher. On the premise that the product F0 of the SPK of Example 2 is slightly lower than that of the Comparative Example, it has lower distortion than the SPK product of the Comparative Example.
表3table 3
以上所述,仅为本发明较佳的具体实施方式,但本发明的保护范围并不局限于此,任何熟悉本技术领域的技术人员在本发明揭露的技术范围内,可轻易想到的变化或替换,都应涵盖在本发明的保护范围之内。因此,本发明的保护范围应以所述权利要求的保护范围为准。The above is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any person skilled in the art within the technical scope disclosed in the present invention can easily think of changes or Replacement should be covered within the protection scope of the present invention. Therefore, the protection scope of the present invention should be determined by the protection scope of the claims.
Claims (16)
- 一种可用于发声装置的振膜,其特征在于,所述振膜为多层复合结构,并且至少一个表层为热塑性聚酯弹性体膜;A diaphragm that can be used in a sounding device, characterized in that the diaphragm is a multi-layer composite structure, and at least one surface layer is a thermoplastic polyester elastomer film;所述热塑性聚酯弹性体膜由芳香族二羧酸与二元醇反应得到的聚酯硬段和含有脂肪族聚碳酸酯的软段共聚而成;The thermoplastic polyester elastomer film is formed by copolymerizing polyester hard segments obtained from the reaction of aromatic dicarboxylic acids and glycols and soft segments containing aliphatic polycarbonate;其中,所述振膜的厚度为10~200μm,所述热塑性聚酯弹性体膜在23℃环境下的损耗因子为0.1~0.3。Wherein, the thickness of the diaphragm is 10-200 μm, and the loss factor of the thermoplastic polyester elastomer film is 0.1-0.3 at 23°C.
- 根据权利要求1所述的振膜,其特征在于,所述脂肪族聚碳酸酯包括聚六亚甲基聚碳酸酯二醇,并且占所述软段重量的70%以上。The diaphragm according to claim 1, wherein the aliphatic polycarbonate comprises polyhexamethylene polycarbonate diol and accounts for more than 70% by weight of the soft segment.
- 根据权利要求1所述的振膜,其特征在于,所述软段还包括聚己内酯、聚已二酸丁二醇酯、聚四氢呋喃醚、聚环氧乙烷中的一种或多种。The diaphragm according to claim 1, wherein the soft segment further comprises one or more of polycaprolactone, polybutylene adipate, polytetrahydrofuran ether, and polyethylene oxide .
- 根据权利要求1-3任一项所述的振膜,其特征在于,所述软段占所述热塑性聚酯弹性体重量的20%~80%。The diaphragm according to any one of claims 1-3, characterized in that, the soft segment accounts for 20%-80% of the weight of the thermoplastic polyester elastomer.
- 根据权利要求4所述的振膜,其特征在于,所述软段占所述热塑性聚酯弹性体重量的30%~60%。The diaphragm according to claim 4, wherein the soft segment accounts for 30%-60% of the weight of the thermoplastic polyester elastomer.
- 根据权利要求1所述的振膜,其特征在于,所述硬段包括聚对苯二甲酸丁二醇酯。The diaphragm of claim 1, wherein the hard segment comprises polybutylene terephthalate.
- 根据权利要求1所述的振膜,其特征在于,所述振膜在23℃环境下的损耗因子为0.1~0.2。The diaphragm according to claim 1, characterized in that, the loss factor of the diaphragm in an environment of 23° C. is 0.1˜0.2.
- 根据权利要求1-3任一项或6或7所述的振膜,其特征在于,在23℃环境下,The diaphragm according to any one of claims 1-3 or 6 or 7, characterized in that, in an environment of 23°C,所述发声装置的最低共振频率F0≤500Hz,所述热塑性聚酯弹性体膜的拉伸模量为20~100Mpa;The lowest resonance frequency F0 of the sound generating device is ≤500Hz, and the tensile modulus of the thermoplastic polyester elastomer film is 20-100Mpa;或者,or,所述发声装置的最低共振频率F0>500Hz,所述热塑性聚酯弹性体膜的拉伸模量为50~400MPa。The lowest resonance frequency F0 of the sound generating device is >500 Hz, and the tensile modulus of the thermoplastic polyester elastomer film is 50-400 MPa.
- 根据权利要求1-3任一项或6或7所述的振膜,其特征在于,所述振膜的MD与TD两方向的储能模量之间比例为80~120:100。The diaphragm according to any one of claims 1-3 or 6 or 7, characterized in that the ratio between the storage moduli in the MD and TD directions of the diaphragm is 80-120:100.
- 根据权利要求1-3任一项或6或7所述的振膜,其特征在于,所述振膜为所述热塑性聚酯弹性体膜与胶层交替叠加的结构,并且两个表层为所述热塑性 聚酯弹性体膜。According to any one of claims 1-3 or 6 or 7, the diaphragm is characterized in that, the diaphragm is a structure in which the thermoplastic polyester elastomer film and the glue layer are alternately stacked, and the two surface layers are the The thermoplastic polyester elastomer film.
- 根据权利要求10所述的振膜,其特征在于,所述热塑性聚酯弹性体膜的厚度为5~50μm,所述胶层为2~50μm厚度的硅胶层、丙烯酸胶层中的一种或多种。The diaphragm according to claim 10, characterized in that, the thickness of the thermoplastic polyester elastomer film is 5-50 μm, and the adhesive layer is one of a silica gel layer and an acrylic adhesive layer with a thickness of 2-50 μm or Various.
- 根据权利要求10所述的振膜,其特征在于,所述胶层的玻璃化转变温度≤-10℃。The diaphragm according to claim 10, characterized in that, the glass transition temperature of the adhesive layer is ≤ -10°C.
- 权利要求1-12任一项所述的振膜的制备方法,其特征在于,采用如下方法制备所述热塑性聚酯弹性体膜:The preparation method of the diaphragm according to any one of claims 1-12, characterized in that the thermoplastic polyester elastomer film is prepared by the following method:将硬段的预聚物和软段的预聚物进行共聚反应,所述共聚反应的温度为230~265℃,反应时间为0.5~2h;之后造粒、挤出膜材;Copolymerize the prepolymer of the hard segment and the prepolymer of the soft segment, the temperature of the copolymerization reaction is 230-265°C, and the reaction time is 0.5-2h; after that, granulate and extrude the film material;之后将所述热塑性聚酯弹性体膜与其他层贴合成所述振膜。After that, the thermoplastic polyester elastomer film and other layers are laminated to form the diaphragm.
- 根据权利要求13所述的振膜的制备方法,其特征在于,所述硬段的预聚物的分子量为15000~30000,所述软段的预聚物的分子量为10000~50000。The method for preparing a diaphragm according to claim 13, wherein the molecular weight of the prepolymer of the hard segment is 15000-30000, and the molecular weight of the prepolymer of the soft segment is 10000-50000.
- 一种发声装置,其特征在于,包括振动系统和与所述振动系统相配合的磁路系统,所述振动系统包括振膜和结合在所述振膜一侧的音圈,所述磁路系统系统驱动所述音圈振动以带动所述振膜发声,所述振膜采用权利要求1-12任一项所述的振膜。A sounding device, characterized in that it includes a vibration system and a magnetic circuit system matched with the vibration system, the vibration system includes a diaphragm and a voice coil combined on one side of the diaphragm, the magnetic circuit system The system drives the voice coil to vibrate to drive the diaphragm to produce sound, and the diaphragm adopts the diaphragm described in any one of claims 1-12.
- 一种发声装置,其特征在于,包括壳体以及设在所述壳体内的磁路系统和振动系统,所述振动系统包括音圈、第一振膜和第二振膜,所述音圈的顶部与所述第一振膜相连,所述磁路系统系统驱动所述音圈振动以带动所述第一振膜发声,所述第二振膜的两端分别与所述壳体和所述音圈的底部相连,所述第二振膜为根据权利要求1-12中任一项所述的振膜。A sounding device, characterized in that it includes a housing and a magnetic circuit system and a vibration system arranged in the housing, the vibration system includes a voice coil, a first diaphragm and a second diaphragm, the voice coil The top is connected with the first diaphragm, the magnetic circuit system drives the voice coil to vibrate to drive the first diaphragm to produce sound, and the two ends of the second diaphragm are respectively connected to the housing and the The bottom of the voice coil is connected, and the second diaphragm is the diaphragm according to any one of claims 1-12.
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