CN110708636B - Sound generating device's vibrating diaphragm and sound generating device - Google Patents

Sound generating device's vibrating diaphragm and sound generating device Download PDF

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CN110708636B
CN110708636B CN201911059136.9A CN201911059136A CN110708636B CN 110708636 B CN110708636 B CN 110708636B CN 201911059136 A CN201911059136 A CN 201911059136A CN 110708636 B CN110708636 B CN 110708636B
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butadiene rubber
diaphragm
agent
plasticizer
cis
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CN110708636A (en
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彭威锋
凌风光
李春
刘春发
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Goertek Inc
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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
    • H04R7/00—Diaphragms for electromechanical transducers; Cones
    • H04R7/02—Diaphragms for electromechanical transducers; Cones characterised by the construction
    • H04R7/04—Plane diaphragms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/04—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • H—ELECTRICITY
    • H04—ELECTRIC COMMUNICATION TECHNIQUE
    • H04R—LOUDSPEAKERS, MICROPHONES, GRAMOPHONE PICK-UPS OR LIKE ACOUSTIC ELECTROMECHANICAL TRANSDUCERS; DEAF-AID SETS; PUBLIC ADDRESS SYSTEMS
    • H04R7/00—Diaphragms for electromechanical transducers; Cones
    • H04R7/02—Diaphragms for electromechanical transducers; Cones characterised by the construction
    • H04R7/04—Plane diaphragms
    • H04R7/06—Plane diaphragms comprising a plurality of sections or layers
    • H04R7/10—Plane diaphragms comprising a plurality of sections or layers comprising superposed layers in contact
    • H—ELECTRICITY
    • H04—ELECTRIC COMMUNICATION TECHNIQUE
    • H04R—LOUDSPEAKERS, MICROPHONES, GRAMOPHONE PICK-UPS OR LIKE ACOUSTIC ELECTROMECHANICAL TRANSDUCERS; DEAF-AID SETS; PUBLIC ADDRESS SYSTEMS
    • H04R7/00—Diaphragms for electromechanical transducers; Cones
    • H04R7/02—Diaphragms for electromechanical transducers; Cones characterised by the construction
    • H04R7/12—Non-planar diaphragms or cones
    • 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
    • H04R9/06—Loudspeakers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/56—Damping, energy absorption
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2309/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
    • H—ELECTRICITY
    • H04—ELECTRIC COMMUNICATION TECHNIQUE
    • H04R—LOUDSPEAKERS, MICROPHONES, GRAMOPHONE PICK-UPS OR LIKE ACOUSTIC ELECTROMECHANICAL TRANSDUCERS; DEAF-AID SETS; PUBLIC ADDRESS SYSTEMS
    • H04R2307/00—Details of diaphragms or cones for electromechanical transducers, their suspension or their manufacture covered by H04R7/00 or H04R31/003, not provided for in any of its subgroups
    • H04R2307/025—Diaphragms comprising polymeric materials

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  • Acoustics & Sound (AREA)
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  • Chemical & Material Sciences (AREA)
  • Multimedia (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Laminated Bodies (AREA)

Abstract

The invention discloses a vibrating diaphragm of a sound generating device and the sound generating device. The diaphragm comprises at least one elastic body layer, wherein the elastic body layer is made of butadiene rubber; the cis-butadiene rubber is any one of nickel series cis-butadiene rubber, rare earth cis-butadiene rubber and cobalt series cis-butadiene rubber, and the cis content is more than 80-100%. The diaphragm provided by the invention can still keep good acoustic performance under the extreme condition of low temperature.

Description

Sound generating device's vibrating diaphragm and sound generating device
Technical Field
The invention relates to the technical field of acoustic devices, in particular to a vibrating diaphragm of a sound generating device and the sound generating device.
Background
With the rapid development of science and technology, various intelligent devices are driven to continuously update and iterate. In recent years, electronic products such as smart wearing and earphones have been developed rapidly, and higher requirements are made on acoustic performance of these electronic products.
The diaphragm is a very critical acoustic component in the sound-generating device, and therefore, higher requirements are also put on the manufacturing material of the diaphragm. One of them is to operate normally under extreme conditions of high and low temperature, and to maintain the original acoustic performance.
At present, for example, the materials commonly used in Driver and Watch for making diaphragms are mostly polyether ketone, polyetherimide, silica gel, polyurethane, etc. However, it is difficult for these existing materials to satisfy the necessary acoustic performance under extreme conditions of high and low temperatures.
Therefore, it is necessary to provide a new technology to solve the problems in the prior art.
Disclosure of Invention
The invention aims to provide a vibrating diaphragm of a sound generating device and a new technical scheme of the sound generating device.
According to one aspect of the invention, a diaphragm of a sound production device is provided, the diaphragm comprises at least one elastomer layer, and the elastomer layer is made of butadiene rubber;
the cis-butadiene rubber is any one of nickel series cis-butadiene rubber, rare earth cis-butadiene rubber and cobalt series cis-butadiene rubber, wherein the cis content is more than 80-100%.
Optionally, the butadiene rubber is mixed with an inorganic filler reinforcing agent, and the inorganic filler reinforcing agent is at least one of carbon black, white carbon black, nano titanium dioxide, talcum powder, precipitated calcium carbonate and barium sulfate.
Optionally, the butadiene rubber is mixed with an inorganic filler reinforcing agent, and the inorganic filler reinforcing agent is at least one of carbon black, white carbon black, nano titanium dioxide, talcum powder, precipitated calcium carbonate and barium sulfate.
Optionally, the content of the inorganic filler reinforcing agent is 15% -90% of the total amount of the butadiene rubber.
Optionally, a vulcanizing agent is mixed in the butadiene rubber, and the vulcanizing agent is at least one of a sulfur type vulcanizing agent, an organic peroxide vulcanizing agent and a thiuram vulcanizing agent.
Optionally, the content of the sulfur-type vulcanizing agent is 0.3% -1.5% of the total amount of the butadiene rubber.
Optionally, the thiuram based vulcanizing agent comprises at least one of tetramethylthiuram monosulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, diisobutylfuram disulfide, bis (1, 5-pentylene) thiuram tetrasulfide.
Optionally, the organic peroxide vulcanizing agent is at least one of 1, 3-1, 4-di (tert-butylperoxyisopropyl) benzene, dicumyl peroxide, 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane, tert-butylcumyl peroxide, 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) -3-hexyne, n-butyl 4, 4 '-bis (tert-butylperoxy) valerate, 1' -bis (tert-butylperoxy) -3, 3, 5 trimethylcyclohexane and 2, 4-dichlorobenzoyl peroxide, and the content of the organic peroxide vulcanizing agent is 2% -8% of the total amount of the butadiene rubber.
Optionally, the butadiene rubber is mixed with an anti-aging agent, the anti-aging agent is at least one of anti-aging agent N-445, anti-aging agent 246, anti-aging agent 4010, anti-aging agent SP, anti-aging agent RD, anti-aging agent ODA, anti-aging agent OD and anti-aging agent WH-02, and the content of the anti-aging agent is 0.5-10% of the total amount of the butadiene rubber.
Optionally, the content of the anti-aging agent is 1% -5% of the total amount of the butadiene rubber.
Optionally, the butadiene rubber is mixed with a plasticizer, the plasticizer is at least one of an aliphatic dibasic acid ester plasticizer, a phthalate plasticizer, a benzene polyacid ester plasticizer, a benzoate plasticizer, a polyol ester plasticizer, a chlorinated hydrocarbon plasticizer, an epoxy plasticizer, a citrate plasticizer and a polyester plasticizer, and the content of the plasticizer is 1% -10% of the total amount of the butadiene rubber.
Optionally, the plasticizer is present in an amount of 3% to 7% of the total amount of the butadiene rubber.
Optionally, the butadiene rubber is mixed with an internal release agent, the internal release agent is at least one of stearic acid, stearate, octadecyl amine, alkyl phosphate and alpha-octadecyl-omega-hydroxy polyoxyethylene phosphate, and the content of the internal release agent is 0.5-5% of the total amount of the butadiene rubber.
Optionally, the content of the internal mold release agent is 1% -3% of the total amount of the butadiene rubber.
Optionally, the diaphragm is a single-layer diaphragm, and the single-layer diaphragm is formed by a butadiene rubber film layer; or is
The vibrating diaphragm is a composite vibrating diaphragm, the composite vibrating diaphragm comprises two layers, three layers, four layers or five layers of film layers, and the composite vibrating diaphragm at least comprises a layer of butadiene rubber film layer.
Optionally, the thickness of the butadiene rubber film layer is 10 μm to 200 μm.
Optionally, the thickness of the butadiene rubber film layer is 30 μm to 120 μm.
Optionally, the butadiene rubber has a hardness of 30-95A.
Optionally, the butadiene rubber has a glass transition temperature of-120 to 0 ℃.
Optionally, the butadiene rubber has a loss factor greater than 0.06 at room temperature.
Optionally, the elongation at break of the butadiene rubber is greater than 100%.
According to another aspect of the present invention, a sound generating device is provided. This sound generating mechanism includes sound generating mechanism main part and foretell vibrating diaphragm, the vibrating diaphragm sets up in the sound generating mechanism main part, the vibrating diaphragm is configured to can vibrate the sound production.
The inventor of the present invention found that in the prior art, it is difficult for a diaphragm made of a commonly used material to satisfy the necessary acoustic performance under extreme conditions of low temperature. Therefore, the technical task to be achieved or the technical problems to be solved by the present invention are never thought or anticipated by those skilled in the art, and therefore the present invention is a new technical solution.
The invention has the beneficial effects that: the invention discloses a vibrating diaphragm made of butadiene rubber, which has good comprehensive performance, can still keep excellent elasticity, rigidity and damping performance at very low temperature, and can be normally used at extremely low temperature. Therefore, the sound generating apparatus can be applied to an extremely severe environment while its acoustic performance can be kept in a good state.
Other features of the present invention and advantages thereof will become apparent from the following detailed description of exemplary embodiments thereof, which proceeds with reference to the accompanying drawings.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description, serve to explain the principles of the invention.
Fig. 1 is a total harmonic distortion test curve of a diaphragm provided by an embodiment of the present invention and a conventional diaphragm in the prior art.
Fig. 2 is a test curve of vibration displacement of different parts of a diaphragm of a sound generating device under different frequencies according to an embodiment of the present invention.
Fig. 3 is a test curve of vibration displacement of different parts of a conventional diaphragm under different frequencies.
FIG. 4 is a graph of the impedance of diaphragms of the same thickness but different stiffness.
Fig. 5 is a test plot of loudness at different frequencies for a diaphragm provided in accordance with an embodiment of the present invention and a conventional diaphragm of the prior art.
Detailed Description
Various exemplary embodiments of the present invention will now be described in detail with reference to the accompanying drawings. It should be noted that: the relative arrangement of the components and steps, the numerical expressions and numerical values set forth in these embodiments do not limit the scope of the present invention unless specifically stated otherwise.
The following description of at least one exemplary embodiment is merely illustrative in nature and is in no way intended to limit the invention, its application, or uses.
Techniques, methods, and apparatus known to those of ordinary skill in the relevant art may not be discussed in detail but are intended to be part of the specification where appropriate.
In all examples shown and discussed herein, any particular value should be construed as merely illustrative, and not limiting. Thus, other examples of the exemplary embodiments may have different values.
It should be noted that: like reference numbers and letters refer to like items in the following figures, and thus, once an item is defined in one figure, further discussion thereof is not required in subsequent figures.
According to one embodiment of the present invention, a diaphragm of a sound generating apparatus is provided. The diaphragm comprises at least one elastic body layer, wherein the elastic body layer is made of butadiene rubber. The vibrating diaphragm can be applied to various sound production devices, particularly to a miniature sound production device, and is wide in application.
The butadiene rubber can be any one of nickel series butadiene rubber, rare earth butadiene rubber and cobalt series butadiene rubber. Wherein, the cis content is more than 80 percent to 100 percent. For example, the cis content is preferably 95% to 99% of the three. The performances of the three types of butadiene rubber can be shown in Table 1, and the butadiene rubber has good comprehensive performances such as rigidity, rebound resilience and the like.
Table 1 a table comparing the properties of three cis-butadiene rubbers of the present invention.
Figure BDA0002256428720000051
The molecular structural formula of the butadiene rubber can be shown as follows:
Figure BDA0002256428720000052
in the above molecular structural formula, n is a natural number.
The higher the cis content in the butadiene rubber, the more regular the molecular arrangement, the higher the orientation entropy in the stretching process, the higher the tensile strength is needed, and the higher the strength of the product. In addition, when the cis content is increased, a large number of carbon-carbon single bonds in the molecule are easier to rotate, especially the single bonds at two sides of the double bond are easier to rotate, the flexibility of the bonds is better, and the product can show very excellent resilience and cold resistance. (glass transition temperature Tg of-110 ℃ C.)
The vibrating diaphragm provided by the invention is made of the butadiene rubber material. The vibrating diaphragm has good comprehensive performance. In particular, excellent elasticity, stiffness and damping properties are maintained at very low temperatures, i.e. normal use at extremely low temperatures. Thus, the sound emitting device can be applied to extremely severe environments while its acoustic performance is kept in a good state.
Optionally, an inorganic filler reinforcing agent may be mixed in the butadiene rubber. The inorganic filler reinforcing agent comprises at least one of carbon black, white carbon black, nano titanium dioxide, talcum powder, precipitated calcium carbonate and barium sulfate. Preferably, the inorganic filler reinforcing agent comprises at least one of carbon black, white carbon black and nano titanium dioxide.
Under the condition that the mass fraction of the butadiene rubber is 100 parts, the mass fraction of the inorganic filler reinforcing agent is 15-90 parts, namely the content of the inorganic filler reinforcing agent is 15-90% of the total mass of the butadiene rubber.
Compared with natural rubber, styrene butadiene rubber and other rubbers, the butadiene rubber adopted in the invention has better structural regularity and flexibility, so that the butadiene rubber has more excellent wetting capacity, and more inorganic filler reinforcing agents can be mixed into the butadiene rubber, thereby reducing the production cost of rubber materials.
The surface of the inorganic filler reinforcing agent has a group such as hydrogen, carboxyl, lactone, radical, quinone, etc. capable of undergoing substitution, reduction, oxidation, etc. After the inorganic filler reinforcing agent is mixed into the butadiene rubber, due to the strong interaction between the interface of the inorganic filler reinforcing agent and the molecular chain segment of the butadiene rubber, when the material is stressed, the molecular chain is easy to slide on the surface of the inorganic filler reinforcing agent particle, but is not easy to be separated from the inorganic filler reinforcing agent particle, the butadiene rubber and the inorganic filler reinforcing agent particle form a strong bond capable of sliding, and the mechanical strength is increased.
In addition, the particle size, structure and surface activity of the inorganic filler reinforcing agent are the primary factors for the investigation of the rubber filler. These three main factors are generally interdependent, and the smaller the particle size of the inorganic filler reinforcing agent, the larger the corresponding specific surface area of the filler. The larger the specific surface area of the inorganic filler reinforcement, the stronger the corresponding surface activity.
Taking carbon black as an example, the carbon black mainly comprises carbon elements, the proportion of which reaches 95% -99%, and belongs to the graphite crystal type. Carbon black is an amorphous structure, and particles form aggregates by physicochemical bonding to each other. The primary structure of the carbon black is composed of aggregates, and van der waals force or hydrogen bonds exist among the aggregates, so that the aggregates can be aggregated into a spatial network structure, namely the secondary structure of the carbon black. The surface of the carbon black is provided with groups such as hydrogen, carboxyl, lactone group, free radical, quinone group and the like which can generate substitution, reduction, oxidation reaction and the like, when the carbon black is added into an elastomer, due to strong interaction between the surface of the carbon black and the molecular interface of the poly 1,4 butadiene, molecular chains can slide on the surface of the carbon black easily but are not easy to be separated from the carbon black when the material is stressed, and the butadiene rubber and the carbon black can form a strong slidable bond, so that the mechanical strength of the butadiene rubber is increased.
In an embodiment, in the case that the mass part of the butadiene rubber is 100, optionally, the mass part of the inorganic filler reinforcing agent is 15 to 85 parts, that is, the content of the inorganic filler reinforcing agent is 15 to 85% of the total mass of the butadiene rubber. Taking the example of selecting carbon black as the inorganic filler reinforcing agent, when the mass portion of the carbon black is 10, the mechanical strength and the elongation at break of the butadiene rubber material are both relatively small, because the amount of the carbon black is small, the carbon black is unevenly dispersed in the matrix, and the reinforcing effect is difficult to achieve. With the increase of the addition amount of carbon black, the mechanical strength of the butadiene rubber material can be increased, and the elongation at break can be gradually reduced. In this case, the resulting diaphragm may be at risk of rupture during prolonged use. Therefore, preferably, the inorganic filler reinforcing agent per se has a mass part of 15-80 parts, that is, when the content of the inorganic filler reinforcing agent is 15% -80% of the total amount of the butadiene rubber, the requirements of the invention on the performance of the diaphragm can be better met. More preferably, the inorganic filler reinforcing agent is 30 to 70 parts by mass per se, that is, the content of the inorganic filler reinforcing agent is 30 to 70% of the total amount of the butadiene rubber. Of course, those skilled in the art can flexibly adjust the method according to specific needs, and the method is not limited thereto.
Optionally, an antioxidant may be mixed in the butadiene rubber. The antioxidant may be at least one of antioxidant N-445, antioxidant 246, antioxidant 4010, antioxidant SP, antioxidant RD, antioxidant ODA, antioxidant OD and antioxidant WH-02, for example. And when the mass fraction of the butadiene rubber is 100 parts, the mass fraction of the anti-aging agent is 0.5-10 parts, namely the content of the anti-aging agent is 0.5-10% of the total mass of the butadiene rubber.
In the use process of the butadiene rubber, as the butadiene rubber is influenced by factors such as oxygen, ultraviolet lamps and the like for a long time along with the use time, molecular chains of the butadiene rubber are gradually broken to generate free radicals, so that the self-aging is accelerated, and the phenomenon is the natural aging phenomenon of the butadiene rubber. In the present invention, the incorporation of an antioxidant into the butadiene rubber can prevent or stop or slow down the generation of autocatalytically active radicals in the butadiene rubber. If the amount of the antioxidant is too small, the effect of extending the service life of the butadiene rubber may not be obtained. On the other hand, if the amount of the antioxidant is too large, the antioxidant is difficult to be sufficiently dissolved in butadiene rubber and difficult to be uniformly dispersed, which may cause a decrease in the mechanical properties of butadiene rubber. Therefore, when the mass part of the butadiene rubber is 100 parts, the mass part of the antioxidant itself may be selected within the range of 0.5 to 10 parts. Preferably, the mass part of the anti-aging agent is 1-5 parts, namely the content of the anti-aging agent is 1-5% of the total amount of the butadiene rubber. Of course, those skilled in the art can flexibly adjust the method according to specific needs, and the method is not limited thereto.
Optionally, a plasticizer may be mixed in the butadiene rubber. The plasticizer is at least one of aliphatic dibasic acid ester plasticizer, phthalate plasticizer (including phthalate and terephthalate, for example), benzene polyacid ester plasticizer, benzoate plasticizer, polyol ester plasticizer, chlorinated hydrocarbon plasticizer, epoxy plasticizer, citric acid ester plasticizer and polyester plasticizer.
The molecules of the plasticizer are much smaller than those of a butadiene rubber molecular chain, and the plasticizer molecules can move in poly (1, 4-butadiene) molecules after being introduced, so that the space required by chain segment movement can be conveniently provided, the glass transition temperature of the material is reduced, the cold resistance of the material is improved, and the processability of the material is improved. However, excessive plasticizer may be precipitated from the interior of the material, which may adversely degrade the mechanical properties of the material.
In an embodiment, in the case that the mass part of the butadiene rubber is 100 parts, optionally, the mass part of the plasticizer is 1 to 10 parts, that is, the content of the plasticizer is 1 to 10% of the total amount of the butadiene rubber. In fact, as the amount of plasticizer is increased, the glass transition temperature of the butadiene rubber material is decreased, but accordingly, the tensile strength of the butadiene rubber material is also decreased. For example, when the plasticizer content exceeds 10, the tensile strength of the butadiene rubber material is greatly reduced. In addition, excessive plasticizer may be precipitated from the inside of the butadiene rubber material, reducing the mechanical properties of the butadiene rubber material. When the mass portion of the plasticizer per se meets the range, the performance of the butadiene rubber can be ensured to meet the performance requirement of the vibrating diaphragm. Preferably, the mass part of the plasticizer is 3-7 parts, namely, the content of the plasticizer is 3% -7% of the total amount of the butadiene rubber. Of course, those skilled in the art can flexibly adjust the method according to specific needs, and the method is not limited thereto.
Optionally, an internal mold release agent may be mixed in the butadiene rubber. The internal mold release agent adopts at least one of stearic acid, stearate, octadecyl amine, alkyl phosphate and alpha-octadecyl-omega-hydroxyl polyoxyethylene phosphate.
In the embodiment of the invention, when the mass part of the butadiene rubber is 100 parts, the mass part of the internal mold release agent can be selected to be 0.5-5 parts, namely, the content of the internal mold release agent is 0.5-5% of the total mass of the butadiene rubber.
The demolding capacity of the butadiene rubber is related to the mass portion of the internal demolding agent. Specifically, the method comprises the following steps: when the mass fraction of the release agent is small, the molding state of the butadiene rubber is good, but the release capability is poor. When the mass portion of the release agent is large, the release performance of the butadiene rubber is obviously improved, but the release agent is easy to separate out of the formed butadiene rubber, is accumulated on the surface of a mold, and pollutes the mold. The inventor of the present invention has found that when the internal mold release agent is 1 to 3 parts by mass per se, that is, the content of the internal mold release agent is 1 to 3% of the total amount of the butadiene rubber, the formed butadiene rubber has a good molding state and little residue after molding. Of course, those skilled in the art can flexibly adjust the method according to specific needs, and the method is not limited thereto.
Optionally, a vulcanizing agent is mixed in the butadiene rubber. The vulcanizing agent is at least one of a sulfur vulcanizing agent, an organic peroxide vulcanizing agent and a thiuram vulcanizing agent.
When the vulcanizing agent is a sulfur type vulcanizing agent, the content of the sulfur type vulcanizing agent is more suitable when the content of the sulfur type vulcanizing agent is 0.3-1.5 percent of the total amount of the butadiene rubber. Compared with other rubbers, cis-butadiene rubber has lower double bond activity, so that less sulfur can achieve the vulcanization effect.
The thiuram vulcanizing agent includes at least one of tetramethylthiuram monosulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, diisobutylfuram disulfide, and bis (1, 5-pentamethylene) thiuram tetrasulfide.
Thiurams are sulfur-free vulcanizing agents and can be used alone to directly vulcanize rubber. After the temperature is raised to the vulcanization temperature, the sulfur-containing compound is cleaved to active sulfur, and the amount of sulfur contained varies depending on the structure of the sulfide. During vulcanization, the sulfur-containing compound is thermally cracked to form free radicals, which then react with the alpha-methine groups in the butadiene rubber to complete the vulcanization. The decomposition of the rubber into dimethylamine and carbon disulfide occurs in the absence of zinc oxide, the decomposed products have the effect of promoting the oxidation of rubber, and the aging performance is seriously reduced. In the presence of zinc oxide, the zinc dimethyldithiocarbamate can be generated by reaction, and the zinc dimethyldithiocarbamate has a positive effect on the anti-aging performance of the rubber.
The organic peroxide vulcanizing agent is at least one of 1, 3-1, 4-di (tert-butylperoxyisopropyl) benzene, dicumyl peroxide, 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane, tert-butylcumyl peroxide, 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) -3-hexyne, n-butyl 4, 4 '-bis (tert-butylperoxy) valerate, 1' -bis (tert-butylperoxy) -3, 3, 5 trimethylcyclohexane and 2, 4-dichlorobenzoyl peroxide. The content of the organic peroxide vulcanizing agent is 2 to 8 percent of the total amount of the butadiene rubber. The organic peroxide should be reasonably controlled, and if the content is too large, the tensile strength of the butadiene rubber is easily affected.
Optionally, the glass transition temperature of the diaphragm is in the range of-120 to 0 ℃. The butadiene rubber has higher molecular weight and more flexible molecular chains, so the butadiene rubber has better low-temperature resistance. When the vibrating diaphragm meets the range of the glass transition temperature, the vibrating diaphragm of the sound generating device can keep a high elastic state at normal temperature, and the rebound resilience is good. Within a certain range, the lower the glass transition temperature is, the lower the temperature at which the diaphragm can normally operate. The lower the glass transition temperature, the lower the resonant frequency F0 of the assembled sound generating device, with the thickness of the diaphragm unchanged. The glass transition temperature of the material can be adjusted by changing the content of the inorganic filler reinforcing agent and the content of the plasticizer mixed in the butadiene rubber.
In one embodiment, the glass transition temperature of the diaphragm provided by the present invention is preferably-60 to-20 ℃. The vibrating diaphragm can keep a high elastic state at normal temperature and has good rebound resilience. More importantly, even under the temperature below 0 ℃ and even under the lower extreme temperature, the diaphragm of the sound generating device can still keep better rubber elasticity when working, thereby leading the sound generating device to show higher sound quality. Meanwhile, the risk of damage of the vibrating diaphragm of the sound production device in a low-temperature environment is reduced, and the reliability is higher.
The elongation at break of the diaphragm is more than 100%. Preferably, the elongation at break of the diaphragm is greater than 150%. The vibrating diaphragm provided by the invention has higher elongation at break, so that the vibrating diaphragm is not easy to have the reliability problems of film breaking and the like when being used in a sound generating device.
Under the same stress, the strain of the diaphragm provided by the embodiment of the invention is obviously larger than that of the PEEK diaphragm in the prior art. This in turn indicates that: the Young modulus of the diaphragm provided by the embodiment of the invention is obviously smaller than that of a PEEK diaphragm in the prior art.
In addition, the PEEK diaphragms of the prior art form a significant yield point, on the order of 0.4-0.5% strain. The loudspeaker diaphragm provided by the invention has no yield point. This indicates that: the diaphragm provided by the invention has a wider elastic area and excellent resilience.
The diaphragm made of the butadiene rubber material has good flexibility. For example, the elongation at break is 100% or more. Among them, the molecular chain of butadiene rubber has very important influence on the elongation at break, and those skilled in the art can select the molecular chain according to actual needs. This makes the vibration displacement of sound generating mechanism vibrating diaphragm bigger, and the loudness is bigger. And has good reliability and durability. The better the flexibility of the butadiene rubber material, the greater the elongation at break, the stronger the ability of the diaphragm to resist damage. When the vibrating diaphragm vibrates in a large-amplitude state, the butadiene rubber material generates large strain, and the risk of membrane folding, membrane cracking or membrane breaking can occur during long-time vibration. The diaphragm of the invention which takes the butadiene rubber as the base material has good flexibility, and the risk of the diaphragm damage is reduced. The higher the elongation at break, the lower the membrane rupture rate of the diaphragm in long-term use.
Compared with engineering plastics, the butadiene rubber provided by the invention has a wider elastic area, and when the strain of the diaphragm occurs in the area, the diaphragm has excellent resilience after an external force is removed. Correspondingly, the vibrating diaphragm has less swing vibration and better tone quality and listening stability in the vibration process. Further, the diaphragm provided by the invention can be continuously used at high temperature and has higher damping performance compared with the existing material. The sound production device has better transient response and lower distortion due to the good rebound resilience of the diaphragm.
As shown in fig. 1, the diaphragm provided by the present invention has a lower THD (total harmonic distortion) than the PEEK diaphragm of the prior art. This indicates that: the diaphragm provided by the invention has more excellent anti-polarization capability and better tone quality.
The vibrating diaphragm provided by the invention is in a high-elastic state at room temperature, the molecular chain is easy to move, the intermolecular friction is large, and the vibrating diaphragm has better damping performance. Optionally, the loss factor of the diaphragm is greater than 0.06 at room temperature. The diaphragm has excellent damping performance and can have lower impedance. The damping of the vibrating diaphragm is improved, the ability of a vibration system of the sound generating device for inhibiting the polarization phenomenon in the vibration process is enhanced, and the vibration consistency is good. The existing diaphragm made of engineering plastics has low damping, the loss factor of the diaphragm is usually less than 0.01, and the damping property is small.
Preferably, the loss factor of the diaphragm provided by the invention is greater than 0.1.
Fig. 2 is a test curve of vibration displacement of different parts of a diaphragm of a sound generating device under different frequencies according to an embodiment of the present invention. Fig. 3 is a test curve of vibration displacement of different parts of a conventional diaphragm under different frequencies.
Wherein, the vibrating diaphragm is a rectangular corrugated rim vibrating diaphragm. The abscissa is frequency (Hz) and the ordinate is loudness displacement (mm). And (4) taking points at the edge position and the center position of the center part of the diaphragm for testing.
It can be seen that the curves in fig. 2 are more concentrated, while the curves in fig. 3 are more dispersed. This indicates that: the vibrating diaphragm provided by the embodiment of the invention has the advantages that the vibration consistency of all parts is better, the swinging vibration of the vibrating diaphragm is less in the vibration process, and the tone quality and the listening stability are better.
The Shore hardness of the diaphragm provided by the invention ranges from 30A to 95A. The resonant frequency F0 of the sound generator is proportional to the modulus, stiffness and thickness of the diaphragm, and for a butadiene rubber material, the modulus is proportional to the stiffness. Therefore, the modulus of the diaphragm can be expressed in terms of stiffness.
In one aspect, the strength and hardness of the butadiene rubber material may be adjusted by the reinforcing agent. On the other hand, the increase in the molecular chain amount increases intermolecular hydrogen bonds, and further increases the strength and hardness of the butadiene rubber material, and increases crosslinking points. The higher the strength and hardness of the butadiene rubber material are, the higher the F0 of the prepared diaphragm is, and accordingly, the loudness of the sound generating device is reduced and the bass performance is poor. FIG. 4 is a graph of the impedance of diaphragms of the same thickness but different stiffness. As can be seen from fig. 4, as the stiffness increases, the resonance frequency F0 of the sound emitting device increases sharply.
The diaphragm of the sound production device provided by the invention can be a corrugated diaphragm or a flat diaphragm, for example. The resonant frequency F0 of the sound generating device is proportional to the Young modulus and the thickness of the vibrating diaphragm, the change of F0 can be realized by changing the thickness and the Young modulus of the vibrating diaphragm of the sound generating device, and the specific regulation principle is as follows:
Figure BDA0002256428720000121
wherein, Mms is the equivalent vibration quality of sound generating mechanism, and Cms is the equivalent compliance of sound generating mechanism:
Figure BDA0002256428720000122
wherein, Cm1For compliance with the elastic wave, Cm2The diaphragm compliance is achieved. When there is no elastic wave design, the equivalent compliance of the sounding device is the compliance of the vibrating diaphragm:
Figure BDA0002256428720000123
wherein W is the total width of the bending ring part of the diaphragm, and t is the thickness of the diaphragm; dvc is the joint outer diameter of the vibrating diaphragm and the voice coil; e is the Young modulus of the vibrating diaphragm material; u is the Poisson's ratio of the vibrating diaphragm material.
It can be seen that the resonant frequency F0 of the sound generating device is proportional to the modulus and thickness of the diaphragm. The modulus of the diaphragm is proportional to its stiffness. Therefore, hardness may be used instead of its modulus. To obtain a full bass and comfortable hearing, the diaphragm should have sufficient stiffness and damping while the sound generator has a low resonance frequency F0. The size of F0 can be adjusted by one skilled in the art by adjusting the stiffness and thickness of the loudspeaker diaphragm.
The Shore hardness of the diaphragm is preferably 30-80A, and the thickness of the diaphragm is 30-120 μm. Within the above preferred range, the resonance frequency F0 of the sound generating device can be made to reach 150-1500 Hz. The low-frequency performance of the sound generating device is excellent.
Optionally, the diaphragm provided by the invention may be a single-layer structure, and may also be a multi-layer composite diaphragm. The single-layer diaphragm is a diaphragm formed by a butadiene rubber film layer. The composite diaphragm is formed by sequentially laminating a plurality of butadiene rubber film layers. Or, the composite diaphragm may include at least one layer of butadiene rubber film, and the butadiene rubber film is bonded and compounded with films made of other materials to form a composite diaphragm made of multiple materials. In addition, the multiple film layers can be compounded in a hot pressing mode and the like, and the composite diaphragm is further formed. The composite diaphragm may be a two-layer, three-layer, four-layer or five-layer composite diaphragm, which is not limited in the present invention. At least one film layer in the composite diaphragm is a butadiene rubber film layer made of the butadiene rubber provided by the invention.
For the butadiene rubber film layer, the thickness thereof may be selected from 10 to 200. mu.m, preferably 30 to 120. mu.m. When the thickness of the butadiene rubber film layer is within the range, the performance requirement and the assembly space requirement of the sound generating device can be better met.
The thickness of the diaphragm affects its acoustic performance. Generally, a lower thickness affects the reliability of the diaphragm, while a greater thickness affects the sensitivity of the diaphragm. Therefore, the thickness of the diaphragm provided by the invention can be controlled to be 30-120 μm. When the thickness range of the single-layer butadiene rubber diaphragm is 30-120 microns, the thickness range can enable the sensitivity of the sound production device diaphragm to be higher, and the elastic performance and the rigidity performance of the diaphragm can meet the manufacturing requirements of the sound production device. In particular, it can be applied in miniature sound-generating devices. And, the vibrating diaphragm is as the weakest original paper among the sound generating mechanism, vibrations the in-process repeatedly, can guarantee long-time normal use, and then extension sound generating mechanism's life.
The invention also provides a comparison curve chart of a specific implementation mode of the diaphragm provided by the invention and the conventional diaphragm, as shown in fig. 5. Fig. 5 shows the loudness test curves (SPL curves) for two diaphragms at different frequencies. Wherein, the vibrating diaphragm is a corrugated rim vibrating diaphragm. The abscissa is frequency (Hz) and the ordinate is loudness.
In fig. 5, a broken line is a test curve of the diaphragm provided by the present invention. The solid line is the test curve for a conventional diaphragm. From the SPL curve, it can be seen that the intermediate frequency performance of the two diaphragms is similar. And F0 of the sound generating device adopting the diaphragm provided by the invention is 856 Hz. The F0 of the sound generating device using the conventional diaphragm was 926Hz, which shows that the diaphragm provided by the present invention has a higher low frequency sensitivity than the existing PEEK diaphragm. In other words, the vibrating diaphragm provided by the invention can enable the sound generating device to have higher loudness and comfort.
The invention provides a vibrating diaphragm which is prepared by mixing a butadiene rubber material and an auxiliary agent and then integrally forming in a hot pressing mode. The diaphragm provided by the invention is simple in preparation method, can be normally used under an extreme low temperature condition, and simultaneously gives consideration to the rigidity, resilience and damping property required by the vibration of the diaphragm.
On the other hand, the invention also provides a sound production device.
The sound generating device comprises a sound generating device main body and the vibrating diaphragm made of butadiene rubber. The butadiene rubber may be any one of nickel-based butadiene rubber, rare earth butadiene rubber, and cobalt-based butadiene rubber, which is not limited in the present invention. The vibrating diaphragm is arranged on the sound-generating device main body and is configured to be driven to vibrate so as to generate sound through vibration. The sound generating device body can be provided with a coil, a magnetic circuit system and other components, and the vibrating diaphragm is driven to vibrate through electromagnetic induction. The sound production device provided by the invention can be an earphone, a smart watch and the like, and can be normally used under a low-temperature condition.
Although some specific embodiments of the present invention have been described in detail by way of examples, it should be understood by those skilled in the art that the above examples are for illustrative purposes only and are not intended to limit the scope of the present invention. It will be appreciated by those skilled in the art that modifications may be made to the above embodiments without departing from the scope and spirit of the invention. The scope of the invention is defined by the appended claims.

Claims (21)

1. The utility model provides a sound generating mechanism's vibrating diaphragm which characterized in that: the diaphragm comprises at least one elastic body layer, wherein the elastic body layer is made of butadiene rubber;
the cis-butadiene rubber is any one of nickel series cis-butadiene rubber, rare earth cis-butadiene rubber and cobalt series cis-butadiene rubber, and the cis content is more than 80-100%;
the molecular structural formula of the butadiene rubber is as follows:
Figure FDA0002256428710000011
2. the diaphragm of claim 1, wherein: the butadiene rubber is mixed with an inorganic filler reinforcing agent, and the inorganic filler reinforcing agent is at least one of carbon black, white carbon black, nano titanium dioxide, talcum powder, precipitated calcium carbonate and barium sulfate.
3. The diaphragm of claim 2, wherein: the content of the inorganic filler reinforcing agent is 15-90% of the total amount of the butadiene rubber.
4. The diaphragm of claim 1, wherein: the butadiene rubber is mixed with a vulcanizing agent, and the vulcanizing agent is at least one of a sulfur type vulcanizing agent, an organic peroxide vulcanizing agent and a thiuram vulcanizing agent.
5. The diaphragm of claim 4, wherein: the content of the sulfur type vulcanizing agent is 0.3 to 1.5 percent of the total amount of the butadiene rubber.
6. The diaphragm of claim 4, wherein: the thiuram vulcanizing agent comprises at least one of tetramethylthiuram monosulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, diisobutylfuram disulfide, and bis (1, 5-pentamethylene) thiuram tetrasulfide.
7. The diaphragm of claim 4, wherein: the organic peroxide vulcanizing agent is at least one of 1, 3-1, 4-di (tert-butylperoxyisopropyl) benzene, dicumyl peroxide, 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane, tert-butylcumyl peroxide, 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) -3-hexyne, 4 '-n-butyl bis (tert-butylperoxy) valerate, 1' -bis (tert-butylperoxy) -3, 3, 5 trimethylcyclohexane and 2, 4-dichlorobenzoyl peroxide, and the content of the organic peroxide vulcanizing agent is 2% -8% of the total amount of the butadiene rubber.
8. The diaphragm of claim 1, wherein: the butadiene rubber is mixed with an anti-aging agent, the anti-aging agent is at least one of anti-aging agent N-445, anti-aging agent 246, anti-aging agent 4010, anti-aging agent SP, anti-aging agent RD, anti-aging agent ODA, anti-aging agent OD and anti-aging agent WH-02, and the content of the anti-aging agent is 0.5-10% of the total amount of the butadiene rubber.
9. The diaphragm of claim 8, wherein: the content of the anti-aging agent is 1% -5% of the total amount of the butadiene rubber.
10. The diaphragm of claim 1, wherein: the cis-butadiene rubber is mixed with a plasticizer, the plasticizer is at least one of aliphatic dibasic acid ester plasticizer, phthalate plasticizer, benzene polyacid ester plasticizer, benzoate plasticizer, polyol ester plasticizer, chlorinated hydrocarbon plasticizer, epoxy plasticizer, citrate plasticizer and polyester plasticizer, and the content of the plasticizer is 1% -10% of the total amount of the cis-butadiene rubber.
11. The diaphragm of claim 10, wherein: the content of the plasticizer is 3% -7% of the total amount of the butadiene rubber.
12. The diaphragm of claim 1, wherein: the cis-butadiene rubber is mixed with an internal release agent, the internal release agent is at least one of stearic acid, stearate, octadecyl amine, alkyl phosphate and alpha-octadecyl-omega-hydroxy polyoxyethylene phosphate, and the content of the internal release agent is 0.5-5% of the total amount of the cis-butadiene rubber.
13. The diaphragm of claim 12, wherein: the content of the internal release agent is 1% -3% of the total amount of the butadiene rubber.
14. The diaphragm of claim 1, wherein: the vibrating diaphragm is a single-layer vibrating diaphragm which is formed by a butadiene rubber film layer; or is
The vibrating diaphragm is a composite vibrating diaphragm, the composite vibrating diaphragm comprises two layers, three layers, four layers or five layers of film layers, and the composite vibrating diaphragm at least comprises a layer of butadiene rubber film layer.
15. The diaphragm of claim 14, wherein: the thickness of the butadiene rubber film layer is 10-200 μm.
16. The diaphragm of claim 15, wherein: the thickness of the cis-butadiene rubber film layer is 30-120 mu m.
17. The diaphragm of claim 1, wherein: the hardness of the butadiene rubber is 30-95A.
18. The diaphragm of claim 1, wherein: the glass transition temperature of the butadiene rubber is-120-0 ℃.
19. The diaphragm of claim 1, wherein: the loss factor of the butadiene rubber is more than 0.06 at room temperature.
20. The diaphragm of claim 1, wherein: the elongation at break of the butadiene rubber is more than 100%.
21. A sound-generating device comprising a sound-generating device body and the diaphragm of any one of claims 1 to 20, wherein the diaphragm is disposed on the sound-generating device body, and the diaphragm is configured to vibrate and generate sound.
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