CN117440298A - Vibrating diaphragm, sound generating device and electronic equipment - Google Patents
Vibrating diaphragm, sound generating device and electronic equipment Download PDFInfo
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- CN117440298A CN117440298A CN202311549568.4A CN202311549568A CN117440298A CN 117440298 A CN117440298 A CN 117440298A CN 202311549568 A CN202311549568 A CN 202311549568A CN 117440298 A CN117440298 A CN 117440298A
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- thermoplastic polyester
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- 239000000956 alloy Substances 0.000 claims abstract description 75
- 229920001971 elastomer Polymers 0.000 claims abstract description 69
- 239000000806 elastomer Substances 0.000 claims abstract description 67
- 229920000570 polyether Polymers 0.000 claims abstract description 66
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 65
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 56
- 239000004417 polycarbonate Substances 0.000 claims abstract description 56
- 230000009467 reduction Effects 0.000 claims abstract description 19
- 230000009477 glass transition Effects 0.000 claims abstract description 17
- 239000010410 layer Substances 0.000 claims description 93
- 239000003963 antioxidant agent Substances 0.000 claims description 28
- 230000003078 antioxidant effect Effects 0.000 claims description 27
- 229920005862 polyol Polymers 0.000 claims description 17
- 150000003077 polyols Chemical class 0.000 claims description 17
- 238000012360 testing method Methods 0.000 claims description 15
- 229920006341 elastomeric alloy Polymers 0.000 claims description 13
- -1 polybutylene terephthalate Polymers 0.000 claims description 13
- 239000002131 composite material Substances 0.000 claims description 11
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 10
- 239000000945 filler Substances 0.000 claims description 9
- 239000003086 colorant Substances 0.000 claims description 8
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- 238000005266 casting Methods 0.000 claims description 6
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- 229920002803 thermoplastic polyurethane Polymers 0.000 description 3
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
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- 229920001223 polyethylene glycol Polymers 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- OYLPGPHZZJCYLP-UHFFFAOYSA-N (2-diphenylphosphanylphenyl)methanol Chemical compound OCC1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 OYLPGPHZZJCYLP-UHFFFAOYSA-N 0.000 description 1
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 1
- VETPHHXZEJAYOB-UHFFFAOYSA-N 1-n,4-n-dinaphthalen-2-ylbenzene-1,4-diamine Chemical compound C1=CC=CC2=CC(NC=3C=CC(NC=4C=C5C=CC=CC5=CC=4)=CC=3)=CC=C21 VETPHHXZEJAYOB-UHFFFAOYSA-N 0.000 description 1
- ZRMMVODKVLXCBB-UHFFFAOYSA-N 1-n-cyclohexyl-4-n-phenylbenzene-1,4-diamine Chemical compound C1CCCCC1NC(C=C1)=CC=C1NC1=CC=CC=C1 ZRMMVODKVLXCBB-UHFFFAOYSA-N 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- UTGQNNCQYDRXCH-UHFFFAOYSA-N N,N'-diphenyl-1,4-phenylenediamine Chemical compound C=1C=C(NC=2C=CC=CC=2)C=CC=1NC1=CC=CC=C1 UTGQNNCQYDRXCH-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
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- 239000012298 atmosphere Substances 0.000 description 1
- 230000003190 augmentative effect Effects 0.000 description 1
- 150000001565 benzotriazoles Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
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- 125000000686 lactone group Chemical group 0.000 description 1
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- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
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- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
Classifications
-
- 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
-
- 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
- H04R2400/00—Loudspeakers
- H04R2400/11—Aspects regarding the frame of loudspeaker transducers
Landscapes
- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Acoustics & Sound (AREA)
- Signal Processing (AREA)
- Diaphragms For Electromechanical Transducers (AREA)
Abstract
The invention discloses a vibrating diaphragm, a sound generating device and electronic equipment, and relates to the field of acoustics, wherein the vibrating diaphragm comprises at least one elastomer alloy material layer; the elastomer alloy material layer comprises polyether type thermoplastic polyester elastomer and polycarbonate type thermoplastic polyester elastomer; the glass transition temperature of the elastomer alloy material layer is lower than-25 ℃, and the elongation at break reduction rate of the elastomer alloy material layer after being baked at 160 ℃ for 200 hours is less than or equal to 60%. The vibrating diaphragm provided by the invention has better high temperature resistance and better low temperature resistance, improves the reliability of the vibrating diaphragm, and can ensure that the sound generating device always maintains excellent acoustic performance in the use process.
Description
Technical Field
The invention relates to the field of acoustics, in particular to a vibrating diaphragm, a sound generating device and electronic equipment.
Background
With the development of society, products are iteratively upgraded, the products are diversified to develop, and the requirements on low temperature resistance and high temperature resistance of materials are also improved. For the sound generating device, the low temperature resistance of the vibrating diaphragm is insufficient, so that the acoustic performance of the vibrating diaphragm in a low-temperature environment is reduced, and even the vibrating diaphragm is damaged in the low-temperature environment, and the reliability of the sound generating device is low; insufficient high temperature resistance of the diaphragm can lead to the reduction of acoustic performance of the diaphragm in a high temperature environment, even lead to deformation of the diaphragm and generate irreversible damage.
The high and low temperature resistance of the current mass-produced vibrating diaphragm material is limited to a certain extent, the long-term low temperature resistance of TPU (Thermoplastic Urethane, thermoplastic polyurethane elastomer) can reach-60 ℃, but the long-term high temperature resistance is only 100 ℃; polyether type TPEE (Thermoplastic Polyester Elastomer ) has long-term low temperature resistance up to-60 ℃, but has long-term high temperature resistance only 140 ℃, while polycarbonate type TPEE has excellent high temperature resistance, and has long-term high temperature resistance up to 170 ℃, but has long-term low temperature resistance only up to-20 ℃. That is, it is difficult for the existing thermoplastic diaphragm to have both high temperature resistance and low temperature resistance.
Disclosure of Invention
The invention mainly aims to provide a vibrating diaphragm, a sound generating device and electronic equipment, and aims to solve the technical problem that the existing thermoplastic vibrating diaphragm is difficult to have better high temperature resistance and low temperature resistance at the same time.
To achieve the above object, the present invention provides a diaphragm including at least one elastomeric alloy material layer; the elastomer alloy material layer comprises polyether type thermoplastic polyester elastomer and polycarbonate type thermoplastic polyester elastomer; the glass transition temperature of the elastomer alloy material layer is lower than-25 ℃, and the elongation at break reduction rate of the elastomer alloy material layer after being baked at 160 ℃ for 200 hours is less than or equal to 60%.
Optionally, the soft segments of the polyether thermoplastic polyester elastomer comprise polyether polyols;
and/or, the glass transition temperature of the polyether thermoplastic polyester elastomer is lower than-40 ℃;
and/or the embrittlement temperature of the polyether thermoplastic polyester elastomer is below-60 ℃.
Optionally, the soft segments of the polycarbonate-type thermoplastic polyester elastomer comprise a polycarbonate polyol;
and/or, the polycarbonate-type thermoplastic polyester elastomer has an elongation at break reduction rate of 10% or less after baking at 160 ℃ for 200 hours;
and/or, the polycarbonate type thermoplastic polyester elastomer has a tensile strength reduction rate of 20% or less after baking at 160 ℃ for 200 hours.
Optionally, the hard segments of the polyether thermoplastic polyester elastomer comprise polybutylene terephthalate;
and/or the hard segments of the polycarbonate-type thermoplastic polyester elastomer comprise polybutylene terephthalate.
Optionally, the mass ratio of the polyether type thermoplastic polyester elastomer to the polycarbonate type thermoplastic polyester elastomer is 1 (0.4-2).
Optionally, the elastomeric alloy material layer further includes at least one of an antioxidant, a colorant, a filler, a plasticizer, an anti-uv additive, an antistatic agent, and a processing aid.
Optionally, the mass ratio of the antioxidant to the polyether thermoplastic polyester elastomer is (0.5-5): 100.
Optionally, the elastomer alloy material layer is made by a casting method;
and/or the elastomeric alloy material layer has a thickness of 10-100 μm.
Optionally, the diaphragm is formed into a single-layer structure, and the diaphragm comprises one layer of the elastomer alloy material layer;
or the vibrating diaphragm is formed into a composite layer structure, and the composite layer structure comprises at least one elastomer alloy material layer.
Optionally, the thickness of the diaphragm is 25-300 μm;
and/or the rupture rate of the elastomer alloy material layer after the reliability test is carried out at the temperature of minus 30 ℃ is less than or equal to 0.5%;
and/or, the tensile strength reduction rate of the elastomer alloy material layer after baking at 160 ℃ for 200 hours is less than or equal to 60%.
The invention also provides a sound generating device which comprises the vibrating diaphragm.
Optionally, the sound generating device comprises a magnetic circuit system and a vibration system; the vibration system comprises a voice coil, a first vibrating diaphragm and a second vibrating diaphragm; the first vibrating diaphragm and the second vibrating diaphragm are respectively arranged at two axial ends of the voice coil, one end of the voice coil drives the first vibrating diaphragm to vibrate and sound, the other end of the voice coil is connected with one end of the second vibrating diaphragm to balance the vibration of the voice coil, and the first vibrating diaphragm and/or the second vibrating diaphragm are the vibrating diaphragms according to any one of claims 1-10.
The invention also provides electronic equipment, which comprises the sounding device.
The invention provides a vibrating diaphragm, a sound generating device and electronic equipment, wherein the vibrating diaphragm comprises at least one elastomer alloy material layer; the elastomer alloy material layer comprises polyether type thermoplastic polyester elastomer and polycarbonate type thermoplastic polyester elastomer; the glass transition temperature of the elastomer alloy material layer is lower than-25 ℃, and the elongation at break reduction rate of the elastomer alloy material layer after being baked at 160 ℃ for 200 hours is less than or equal to 60%. By blending the polyether thermoplastic polyester elastomer and the polycarbonate thermoplastic polyester elastomer, the excellent low temperature resistance of the polyether thermoplastic polyester elastomer and the excellent high temperature resistance of the polycarbonate thermoplastic polyester elastomer can be effectively combined, so that the polyether thermoplastic polyester elastomer and the polycarbonate thermoplastic polyester elastomer complement each other, compared with the polyether thermoplastic polyester elastomer which can resist the high temperature of 150 ℃, the high temperature resistance of the elastomer alloy material layer can reach more than 160 ℃, the temperature resistance of the elastomer alloy material layer can be improved by 10 ℃, compared with the polycarbonate thermoplastic polyester elastomer which can resist the low temperature of minus 25 ℃, and the temperature resistance of the elastomer alloy material layer can be reduced by 15 ℃. Therefore, the technical problem that the existing thermoplastic diaphragm is difficult to have better high temperature resistance and low temperature resistance at the same time is solved. The vibrating diaphragm provided by the invention has better high temperature resistance and better low temperature resistance, improves the reliability of the vibrating diaphragm, and can ensure that the sound generating device always maintains excellent acoustic performance in the use process.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to the structures shown in these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a cross-sectional view of an embodiment of a sound emitting device in accordance with the present invention;
fig. 2 is a cross-sectional view of another embodiment of a sound emitting device according to the present invention.
Description of the embodiments reference numerals:
| 100 | sounding device | 110 | Outer casing |
| 120 | Vibrating diaphragm | 130 | Voice coil |
| 140 | Magnetic circuit system | 121 | First vibrating diaphragm |
| 122 | Second vibrating diaphragm |
The achievement of the objects, functional features and advantages of the present invention will be further described with reference to the accompanying drawings, in conjunction with the embodiments.
Detailed Description
In order to make the above objects, features and advantages of the present invention more comprehensible, the following description of the embodiments accompanied with the accompanying drawings will be given in detail. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The embodiment of the invention provides a vibrating diaphragm, which comprises at least one elastomer alloy material layer; the elastomer alloy material layer comprises polyether type thermoplastic polyester elastomer and polycarbonate type thermoplastic polyester elastomer; the glass transition temperature of the elastomer alloy material layer is lower than-25 ℃, and the elongation at break reduction rate of the elastomer alloy material layer after being baked at 160 ℃ for 200 hours is less than or equal to 60%.
In this embodiment, the elastomer alloy material layer refers to a composite material layer formed by combining multiple elastomers, and other components such as a filler, an auxiliary agent, and the like may be further added to the elastomer alloy material layer, which may be specifically determined according to actual needs, and this embodiment is not limited thereto. The elastomer is a high polymer material which is obviously deformed under weak stress and can quickly recover to be close to the original state and size after stress is relaxed. The thermoplastic elastomer shows rubber elasticity at normal temperature, can be plasticized and molded at high temperature, has high strength, good flexibility and dynamic mechanical property, can effectively improve the rebound resilience of the diaphragm, reduces diaphragm folding, has good processing property, is environment-friendly and recyclable, and can effectively reduce the production and processing cost.
The polyether type thermoplastic polyester elastomer is a linear block copolymer containing hard polyester segments, which may be high-crystallinity polyesters such as PBT (polybutylene terephthalat, polybutylene terephthalate) and PET (polyethylene glycol terephthalate, polyethylene terephthalate), and soft polyether segments, which may be amorphous polyethers. The polyether soft segment has good low-temperature flexibility, so that the long-term low-temperature resistance of the polyether type TPEE can reach-60 ℃, but the high-temperature resistance is poor, and the long-term high-temperature resistance of the polyether type TPEE is only 140 ℃.
As an example, the hard segments of the polyether thermoplastic polyester elastomer may be polybutylene terephthalate and the soft segments of the polyether thermoplastic polyester elastomer may be polyether polyols having the following structural formula:
wherein O in R-O-R represents ether bond group, R represents hydrocarbon chain or carbocycle chain, -OH is terminal hydroxyl, and the terminal hydroxyl has good activity and can be polymerized with the hard segment of TPEE. Polyether polyol is usually obtained by reacting epoxy compound, mercaptan or hydroxymethyl triphenylphosphine, and polyether polyol with different molecular weights and molecular structures can be obtained by regulating and controlling different reaction conditions, and the polyether polyol can be specifically designed and controlled according to actual needs, and the embodiment is not limited to the above. The polyether polyol has excellent flexibility, the TPEE prepared by using the polyether polyol in the soft section has excellent low-temperature flexibility, the glass transition temperature is extremely low and can reach below minus 40 ℃, the low-temperature resistance is excellent, the embrittlement temperature is lower than minus 60 ℃, the TPEE prepared by using the polyether polyol in the single-layer soft section is used as a vibrating diaphragm, and the phenomenon of membrane rupture hardly occurs in the process of low-temperature vibration reliability test.
The polycarbonate type thermoplastic polyester elastomer is a linear block copolymer containing a hard polyester segment and a soft polycarbonate segment, wherein the hard polyester segment may be a polyester with high crystallinity such as PBT (polybutylene terephthalat, polybutylene terephthalate) and PET (polyethylene glycol terephthalate, polyethylene terephthalate), and the soft polyester segment is polycarbonate. The carbonate group in the polycarbonate has extremely high chemical corrosion resistance and mechanical strength, can meet the application requirements in various severe environments, has high rigidity and high glass transition temperature, so that the polycarbonate type TPEE has better thermal stability and oxidation stability, the elongation at break reduction rate is less than or equal to 10 percent and the tensile strength reduction rate is less than or equal to 20 percent after being baked at 160 ℃ for 200 hours, but the low temperature resistance is poor, and the long-term low temperature resistance of the polycarbonate type TPEE is only-20 ℃.
As an example, the hard segment of the polycarbonate type thermoplastic polyester elastomer may be polybutylene terephthalate and the soft segment of the polycarbonate type thermoplastic polyester elastomer may be a polycarbonate polyol having the following structural formula:
wherein-O-C (=O) represents a carbonate group, R represents a hydrocarbon chain or a carbocycle chain, -OH is a terminal hydroxyl group, and the terminal hydroxyl group has good activity and can be polymerized with a hard segment of TPEE. The molecular main chain of the polycarbonate polyol consists of carbonate groups, and the groups have extremely high chemical corrosion resistance and mechanical strength and can meet the application requirements in various severe environments; the side chain of the molecule of the polycarbonate polyol consists of a hydrocarbon chain or a carbocycle chain, and the chain has higher rigidity and stability, so that the mechanical property and chemical stability of the material can be ensured. Therefore, the polycarbonate type TPEE has better thermal stability and oxidation stability, can be used at high temperature, is not easy to deform, age and the like, has better mechanical strength, can bear larger stress and strain, is suitable for manufacturing high-performance mechanical parts and structural parts, and can resist corrosion of various chemical substances including acid, alkali, salt, organic solvent and the like. However, the polycarbonate polyol has a high glass transition temperature of about-20 ℃, so that the low temperature resistance of the polycarbonate TPEE is poor, the glass transition temperature of the polycarbonate TPEE is about-10 ℃, the embrittlement temperature is about-40 ℃, and the TPEE prepared by using the polycarbonate polyol in a single-layer soft section is used as a diaphragm, so that the diaphragm breaking phenomenon occurs in the process of low-temperature vibration reliability test.
Therefore, the single thermoplastic elastomer has certain limitation on high and low temperature resistance, namely, the prior single thermoplastic elastomer has difficult to have better high temperature resistance and low temperature resistance. By blending the polyether thermoplastic polyester elastomer and the polycarbonate thermoplastic polyester elastomer, the excellent low temperature resistance of the polyether thermoplastic polyester elastomer and the excellent high temperature resistance of the polycarbonate thermoplastic polyester elastomer can be effectively combined, so that the two are mutually complemented, compared with the polyether thermoplastic polyester elastomer which is resistant to high temperature of 150 ℃, the high temperature resistance of an elastomer alloy material layer can reach more than 160 ℃, the temperature resistance is improved by at least 10 ℃, the elongation at break reduction rate is less than or equal to 60 percent, the tensile strength reduction rate is less than or equal to 60 percent and the high temperature resistance is obviously improved after the elastomer alloy material layer is baked at 160 ℃ for 200 hours; compared with the glass transition temperature of the polycarbonate type thermoplastic polyester elastomer at minus 10 ℃, the low temperature resistance of the elastomer alloy material layer can reach below minus 25 ℃, the temperature is reduced by at least 15 ℃, the film breaking rate of the elastomer alloy material layer after the reliability test is carried out at minus 30 ℃ is less than or equal to 0.5%, and the low temperature resistance is obviously improved.
It should be noted that, the content of the mixed polyether TPEE in the elastomer alloy material layer is too high, the high temperature resistance of the elastomer alloy material layer is insufficient, the content of the polycarbonate type TPEE is too high, and the low temperature resistance of the elastomer alloy material layer is insufficient, so that the mass ratio of the polyether type thermoplastic polyester elastomer to the polycarbonate type thermoplastic polyester elastomer may be 1 (0.4-2), for example, 1:0.4, 1:0.75, 1:1, 1:1.5, 1:2, etc.
Optionally, the elastomeric alloy material layer further includes at least one of an antioxidant, a colorant, a filler, a plasticizer, an anti-uv additive, an antistatic agent, and a processing aid.
In this embodiment, various properties of the elastomer alloy material layer can be improved by adding additives, fillers and the like, so that the diaphragm has more abundant functions.
The antioxidant can reduce molecular chain breakage in the modified thermoplastic polyester elastomer, so as to improve the strength of the vibrating membrane and achieve the effect of prolonging the service life. The antioxidant includes at least one of antioxidant 1010, antioxidant 2, antioxidant 6, antioxidant 4, antioxidant 1076, antioxidant 168, antioxidant RD, antioxidant AW, antioxidant DD, antioxidant BLE, antioxidant 4010, 4010NA, 4020, 4030, 4040, antioxidant DNP, antioxidant H, antioxidant A, antioxidant D, antioxidant SP, antioxidant 264, antioxidant 2246, antioxidants 2246-S, antioxidant NBC, antioxidant MB, etc.
Optionally, the mass ratio of the antioxidant to the polyether thermoplastic polyester elastomer is (0.5-5): 100.
In this embodiment, the addition amount of the antioxidant is too low to achieve the effect of prolonging the service life, while the addition amount is too large, because of poor intersolubility with the elastomer, the antioxidant is difficult to uniformly disperse, the mechanical property of the elastomer alloy material layer is reduced, and the antioxidant is easy to be precipitated to the surface along with the extension of time. Thus, the mass ratio of the antioxidant to the polyether thermoplastic polyester elastomer is determined to be (0.5-5): 100, e.g., 0.5:100, 1:100, 2:100, 3:100, 4:100, 5:100, etc.
The coloring agent can dye the elastomer alloy material layer, and vibrating diaphragms with different colors can be made by adding the coloring agent, so that the attractiveness is improved. The coloring agent may be selected according to actual needs, and this embodiment is not limited thereto.
The filler can be used for improving the strength of an elastomer alloy material layer, the molecular chain flexibility of polyether polyol in the polyether type thermoplastic polyester elastomer is higher, the manufactured vibrating diaphragm is high in compliance and poor in stiffness, polarization is easily generated in the vibrating diaphragm in a large-amplitude vibration process, the product is distorted, the hardness of the filler is high, the modulus is high, the temperature resistance is good, the hardness, the modulus, the tensile strength, the temperature resistance and the damping performance of rubber can be obviously improved, and the filler can be carbon materials, silicon dioxide, silicate, carbonate, metal oxide, metal hydroxide and the like.
The plasticizer is used for improving the processability of each raw material for preparing the elastomer alloy material layer, improving the wettability, the adhesiveness and the fluidity among the components, and facilitating the mixing processing of the components and the forming of the elastomer alloy material layer. The plasticizer comprises at least one of petroleum plasticizer, coal tar plasticizer, rosin oil plasticizer, fatty dibasic acid esters, fatty acids, phosphoric acid esters, polyesters, epoxy and the like.
The anti-ultraviolet auxiliary agent is used for improving the capability of the diaphragm for resisting ultraviolet rays, and the TPEE can be degraded under the irradiation of the ultraviolet rays, so that the TPEE has an ultraviolet ray absorption function by adding the ultraviolet ray absorber, and the ultraviolet rays can be effectively resisted. The anti-ultraviolet auxiliary agent comprises at least one of salicylates, phenones, benzotriazoles, triazines, hindered amines, substituted acrylonitriles and the like.
The antistatic agent and the processing aid can improve the process problem in the processing process, improve the stability of the casting film and reduce the viscosity of the surface after film formation.
In one embodiment, the elastomeric alloy material layer may include carbon black, which may act as both a colorant and a filler. Carbon black is an amorphous structure, particles form aggregates through mutual physical and chemical combination, the primary structure of the carbon black is formed by the aggregates, van der Waals force or hydrogen bonds exist between the aggregates, the aggregates can be aggregated into a space network structure, namely a secondary structure of the carbon black, the surface of the carbon black is provided with hydrogen, carboxyl, lactone groups, free radicals, quinone groups and the like which can be substituted, reduced, oxidized and the like, after the carbon black is added into TPEE, molecular chains slide on the surface of the carbon black relatively easily due to strong interaction between the surface of the carbon black and the TPEE interface, but are not easy to separate from the carbon black, and the elastomer and the carbon black form a strong bond capable of sliding, so that the mechanical strength is increased.
Optionally, the elastomer alloy material layer is made by a casting method;
and/or the elastomeric alloy material layer has a thickness of 10-100 μm.
In this embodiment, when different materials are blended and modified, poor moldability or poor film performance is often caused by compatibility or melting point difference. After the melt blending of various materials with poor compatibility, the materials are easy to delaminate, when the various materials with different melting points are melted, if the temperature is lower, part of the materials cannot be melted, if the temperature is too high, the fluidity of the materials with lower melting points and the fluidity of the materials with lower melting points are obviously different, the materials are difficult to simultaneously mold in molding, the situation of melt fracture easily occurs in the preparation process, the molding property is poor, and the film can only be applied to processing a film layer with thicker thickness, and a film with stable thickness of 10-100 mu m thickness even smaller thickness cannot be prepared. The polyether type TPEE and the polycarbonate type TPEE have similar hard segment structures, have good compatibility, can be mixed almost in any proportion, and can prepare a film with uniform thickness and smooth and stable surface without adding a compatilizer. That is, an elastomer alloy material layer having a thickness of 10 to 100 μm may be prepared by casting, and the thickness of the prepared elastomer alloy material layer may be 10 μm, 30 μm, 50 μm, 80 μm, 100 μm, or the like.
Optionally, the diaphragm is formed into a single-layer structure, and the diaphragm comprises one layer of the elastomer alloy material layer;
or the vibrating diaphragm is formed into a composite layer structure, and the composite layer structure comprises at least one elastomer alloy material layer.
The diaphragm may be of a single layer structure, in which case the diaphragm is a layer of the elastomeric alloy material. The diaphragm may also be a composite layer structure, in this case, the composite layer structure includes at least one layer of the elastomer alloy material layer, and the diaphragm may be formed by compounding a plurality of layers of the elastomer alloy material layer, or may be formed by compounding at least one layer of the elastomer alloy material layer and other material layers together, which may be specifically determined according to practical situations, and this embodiment is not limited thereto. Under the condition that the vibrating diaphragm is formed into a composite layer structure, the elastomer alloy material layer and the adhesive film layer can be sequentially laminated, wherein the adhesive film layer can increase damping of materials and improve the hearing volume rate. In the case where the diaphragm is formed in a composite layer structure, the thickness of the diaphragm may be 25 to 300 μm, for example 25 μm, 75 μm, 150 μm, 200 μm, 250 μm, 300 μm, or the like.
In this embodiment, the diaphragm includes at least one layer of elastomeric alloy material; the elastomer alloy material layer comprises polyether type thermoplastic polyester elastomer and polycarbonate type thermoplastic polyester elastomer; the glass transition temperature of the elastomer alloy material layer is lower than-25 ℃, and the elongation at break reduction rate of the elastomer alloy material layer after being baked at 160 ℃ for 200 hours is less than or equal to 60%. By blending the polyether thermoplastic polyester elastomer and the polycarbonate thermoplastic polyester elastomer, the excellent low temperature resistance of the polyether thermoplastic polyester elastomer and the excellent high temperature resistance of the polycarbonate thermoplastic polyester elastomer can be effectively combined, so that the polyether thermoplastic polyester elastomer and the polycarbonate thermoplastic polyester elastomer complement each other, compared with the polyether thermoplastic polyester elastomer which can resist the high temperature of 150 ℃, the high temperature resistance of the elastomer alloy material layer can reach more than 160 ℃, the temperature resistance of the elastomer alloy material layer can be improved by 10 ℃, compared with the polycarbonate thermoplastic polyester elastomer which can resist the low temperature of minus 25 ℃, and the temperature resistance of the elastomer alloy material layer can be reduced by 15 ℃. Therefore, the technical problem that the existing thermoplastic diaphragm is difficult to have better high temperature resistance and low temperature resistance at the same time is solved. The vibrating diaphragm provided by the invention has better high temperature resistance and better low temperature resistance, improves the reliability of the vibrating diaphragm, and can ensure that the sound generating device always maintains excellent acoustic performance in the use process.
Further, the invention also discloses a sound generating device, referring to fig. 1, the sound generating device 100 comprises the diaphragm 120 as described above.
In this embodiment, the sound generating device 100 may be a speaker, and referring to fig. 1, fig. 1 is an exemplary cross-sectional view of the sound generating device 100 in an embodiment of the invention, where the sound generating device 100 includes a housing 110, a vibration system disposed in the housing 110, and a magnetic circuit system 140 matched with the vibration system, the vibration system includes a diaphragm 120 and a voice coil 130 combined on one side of the diaphragm 120, and the magnetic circuit system 140 drives the voice coil 130 to vibrate to drive the diaphragm 120 to generate sound. When the sound generating device 100 works, an electrical signal is input into the voice coil 130, the voice coil 130 is driven by the magnetic force of the magnetic circuit system 140, and moves in different magnitudes and directions along with the alternating change of the signal magnitude and the positive and negative directions, so as to drive the vibrating diaphragm 120 to vibrate and generate sound, and the electric energy-mechanical energy-acoustic energy conversion process is completed.
Alternatively, referring to fig. 2, the diaphragm 120 may include a first diaphragm 121 and a second diaphragm 122. The sound generating device comprises a magnetic circuit system 140 and a vibration system; the vibration system includes a voice coil 130, a first diaphragm 121, and a second diaphragm 122; the first diaphragm 121 and the second diaphragm 122 are respectively disposed at two axial ends of the voice coil 130, one end of the voice coil 130 drives the first diaphragm 121 to vibrate and sound, the other end of the voice coil 130 is connected with one end of the second diaphragm 122 to balance the vibration of the voice coil 130, and the first diaphragm 121 and/or the second diaphragm 122 are diaphragms as described above.
The sounding device provided by the invention solves the technical problem that the existing thermoplastic vibrating diaphragm is difficult to have better high temperature resistance and low temperature resistance. Compared with the prior art, the sound generating device provided by the embodiment of the invention has the same beneficial effects as the vibrating diaphragm of the embodiment, and the description is omitted here.
Further, the invention also discloses electronic equipment, which comprises the sounding device.
In this embodiment, the electronic device includes a mobile phone, a notebook computer, a tablet computer, a VR (Virtual Reality) device, an AR (Augmented Reality ) device, a TWS (True Wireless Stereo, true wireless) earphone, an intelligent sound box, an intelligent wearable device, and the like.
The electronic equipment provided by the invention solves the technical problem that the thermoplastic vibrating diaphragm in the traditional electronic equipment is difficult to have better high temperature resistance and low temperature resistance. Compared with the prior art, the beneficial effects of the electronic equipment provided by the embodiment of the invention are the same as those of the sound generating device of the embodiment, and are not repeated here.
The diaphragms of the present invention are described in detail below with specific examples and comparative examples. It is to be understood that the following description is exemplary only and is not intended to limit the invention in any way.
Example 1
The elastomer alloy material layer of example 1, which was used as a diaphragm, includes 100 parts of a polyether type thermoplastic polyester elastomer, 40 parts of a polycarbonate type thermoplastic polyester elastomer, and 2 parts of an antioxidant.
Example 2
The elastomer alloy material layer of example 2, which was used as a diaphragm, includes 100 parts of a polyether type thermoplastic polyester elastomer, 100 parts of a polycarbonate type thermoplastic polyester elastomer, and 2 parts of an antioxidant.
Example 3
The elastomer alloy material layer of example 3, which was used as a diaphragm, includes 100 parts of a polyether type thermoplastic polyester elastomer, 180 parts of a polycarbonate type thermoplastic polyester elastomer, and 2 parts of an antioxidant.
Comparative example 1
A layer of polyether type thermoplastic polyester elastomer was used as the diaphragm, and the polyether type thermoplastic polyester elastomer of comparative example 1 includes 100 parts of polyether type thermoplastic polyester elastomer and 2 parts of antioxidant.
Comparative example 2
A layer of a polycarbonate type thermoplastic polyester elastomer was used as the diaphragm, and the polycarbonate type thermoplastic polyester elastomer of comparative example 2 comprises 100 parts of a polycarbonate type thermoplastic polyester elastomer and 2 parts of an antioxidant.
In the above examples and comparative examples, the same polyether type TPEE, the same polycarbonate type TPEE material, and the polyether type TPEE and the polycarbonate type TPEE materials each had a hardness of 50D, and were each cast films having a thickness of 50 μm by the casting method.
Further, the cast films of examples 1 to 3 and comparative examples 1 to 2 were subjected to tests for high temperature resistance including a glass transition temperature and a low temperature rupture rate, and low temperature resistance including a high temperature elongation at break rate, a high temperature tensile strength rate and a high temperature rupture rate, and the test results are shown in table 1.
The method for testing the low-temperature die breaking rate comprises the following steps: and (3) assembling the prepared vibrating diaphragm into a sound generating device of the same model, placing the vibrating diaphragm in an environment of minus 30 ℃, vibrating for 100 hours, and after the vibration is finished, recovering for 2 hours, and observing the die breaking rate of the product.
The method for testing the high-temperature membrane rupture rate comprises the following steps: and placing the prepared vibrating diaphragm in an atmosphere at 150 ℃, then carrying out an electrifying test, wherein the voltage is 2.4v, the time is 300h, and observing the die breaking rate of the product after taking out.
The glass transition temperature test method comprises the following steps: the test equipment is differential scanning calorimetric analysis, the test temperature is-100 ℃, and the heating rate is 20 ℃/min.
Elongation at break and strength test method: the universal material stretcher was subjected to a tensile test with a standard ASTM D882, gauge length of 30mm, and tensile speed of 300mm/min.
The method for testing the elongation at break reduction rate and the strength reduction rate comprises the following steps: the tensile property of the material is tested before high-temperature aging, and the elongation at break is recorded as L 0 Intensity is denoted as M 0 The method comprises the steps of carrying out a first treatment on the surface of the The tensile property of the material is tested after high-temperature aging, and the elongation at break is recorded as L 1 Intensity is denoted as M 1 ；
High-temperature aging mode: the film was placed in 160℃for 300h.
Elongation at break decrease rate= (L 0 -L 1 )/L 0 *100％；
Intensity decrease rate= (M 0 -M 1 )/M 0 *100％。
TABLE 1
According to the test result of low temperature resistance, the diaphragms of the comparative example 1 and the examples 1-3 comprise polyether type thermoplastic polyester elastomer, the glass transition temperature is below minus 25 ℃, the low temperature resistance is excellent, and the product still has good flexibility and toughness at low temperature, so the diaphragms of the comparative example 1 and the examples 1-3 are not easy to tear when vibrating in a low temperature environment, and the modulus breaking rate is 0%; the diaphragm of comparative example 2 is made of pure polycarbonate thermoplastic polyester elastic material, the glass transition temperature is higher than 5 ℃, the low temperature resistance is poor, and the toughness of the product is poor at low temperature, so that when the diaphragm of comparative example 2 vibrates in low temperature environment, the diaphragm is easy to tear due to the fact that the elongation at break is reduced greatly, the elasticity and toughness are insufficient, and the modulus breaking rate reaches 100%. The result shows that the polyether TPEE has obvious effect of improving the low temperature resistance of the polycarbonate TPEE.
According to the test result of the high temperature resistance, the diaphragms of the examples 1-3 and the comparative example 2 contain polycarbonate type thermoplastic polyester elastic, have excellent high temperature resistance, still have good mechanical properties at high temperature, the tensile strength decline rate and the breaking elongation decline rate are both less than or equal to 50% before and after high temperature aging treatment, and the toughness of the products is still good at high temperature, so the diaphragms of the comparative examples 2 and the examples 1-3 are not easy to tear when vibrating in a high temperature environment, and the breaking modulus is 0%; the diaphragm of comparative example 1 is made of pure polyether thermoplastic polyester elastomer, has poor high temperature resistance and obviously deteriorated mechanical properties, so that after high temperature aging treatment, the tensile strength and the elongation at break are seriously reduced to 81% and 70%, respectively, and the toughness of the product is deteriorated at high temperature, the product is easy to tear, and the modulus of rupture is 65%. The improvement effect of the polycarbonate type TPEE on the high temperature resistance of the polyether type TPEE is obvious.
The foregoing description of the preferred embodiments of the present invention should not be construed as limiting the scope of the invention, but rather utilizing equivalent structural changes made in the present invention description and drawings or directly/indirectly applied to other related technical fields are included in the scope of the present invention.
Claims (13)
1. A diaphragm, wherein the diaphragm comprises at least one layer of elastomeric alloy material; the elastomer alloy material layer comprises polyether type thermoplastic polyester elastomer and polycarbonate type thermoplastic polyester elastomer; the glass transition temperature of the elastomer alloy material layer is lower than-25 ℃, and the elongation at break reduction rate of the elastomer alloy material layer after being baked at 160 ℃ for 200 hours is less than or equal to 60%.
2. The diaphragm of claim 1, wherein the soft segments of polyether thermoplastic polyester elastomer comprise polyether polyol;
and/or, the glass transition temperature of the polyether thermoplastic polyester elastomer is lower than-40 ℃;
and/or the embrittlement temperature of the polyether thermoplastic polyester elastomer is below-60 ℃.
3. The diaphragm of claim 1, wherein the soft segments of polycarbonate thermoplastic polyester elastomer comprise a polycarbonate polyol;
and/or, the polycarbonate-type thermoplastic polyester elastomer has an elongation at break reduction rate of 10% or less after baking at 160 ℃ for 200 hours;
and/or, the polycarbonate type thermoplastic polyester elastomer has a tensile strength reduction rate of 20% or less after baking at 160 ℃ for 200 hours.
4. The diaphragm of claim 1, wherein the hard segments of polyether thermoplastic polyester elastomer comprise polybutylene terephthalate;
and/or the hard segments of the polycarbonate-type thermoplastic polyester elastomer comprise polybutylene terephthalate.
5. The diaphragm of claim 1, wherein the mass ratio of the polyether thermoplastic polyester elastomer to the polycarbonate thermoplastic polyester elastomer is 1 (0.4-2).
6. The diaphragm of claim 1, wherein the elastomeric alloy material layer further comprises at least one of an antioxidant, a colorant, a filler, a plasticizer, an anti-uv additive, an antistatic agent, and a processing aid.
7. The diaphragm of claim 6, wherein the mass ratio of said antioxidant to said polyether thermoplastic polyester elastomer is (0.5-5) 100.
8. The diaphragm of claim 1, wherein the elastomeric alloy material layer is formed by a casting process;
and/or the elastomeric alloy material layer has a thickness of 10-100 μm.
9. The diaphragm of claim 1, wherein the diaphragm is formed as a single layer structure, the diaphragm comprising a layer of the elastomeric alloy material;
or the vibrating diaphragm is formed into a composite layer structure, and the composite layer structure comprises at least one elastomer alloy material layer.
10. The diaphragm of any one of claims 1-9, wherein the diaphragm has a thickness of 25-300 μm;
and/or the rupture rate of the elastomer alloy material layer after the reliability test is carried out at the temperature of minus 30 ℃ is less than or equal to 0.5%;
and/or, the tensile strength reduction rate of the elastomer alloy material layer after baking at 160 ℃ for 200 hours is less than or equal to 60%.
11. A sound generating device comprising a diaphragm according to any one of claims 1-10.
12. The sound emitting apparatus of claim 11, wherein the sound emitting apparatus comprises a magnetic circuit system and a vibration system; the vibration system comprises a voice coil, a first vibrating diaphragm and a second vibrating diaphragm; the first vibrating diaphragm and the second vibrating diaphragm are respectively arranged at two axial ends of the voice coil, one end of the voice coil drives the first vibrating diaphragm to vibrate and sound, the other end of the voice coil is connected with one end of the second vibrating diaphragm to balance the vibration of the voice coil, and the first vibrating diaphragm and/or the second vibrating diaphragm are the vibrating diaphragms according to any one of claims 1-10.
13. An electronic device comprising the sound emitting apparatus according to claim 11 or 12.
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