CN111925586A - Vibrating diaphragm of sound production device, preparation method of vibrating diaphragm and sound production device - Google Patents

Vibrating diaphragm of sound production device, preparation method of vibrating diaphragm and sound production device Download PDF

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CN111925586A
CN111925586A CN202011010811.1A CN202011010811A CN111925586A CN 111925586 A CN111925586 A CN 111925586A CN 202011010811 A CN202011010811 A CN 202011010811A CN 111925586 A CN111925586 A CN 111925586A
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diaphragm
rubber
raw
layer
agent
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CN111925586B (en
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周厚强
李春
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Goertek Inc
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Goertek Inc
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    • C—CHEMISTRY; METALLURGY
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    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • B32B25/08—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 of synthetic resin
    • 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
    • B32B25/14—Layered products comprising a layer of natural or synthetic rubber comprising synthetic rubber copolymers
    • 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
    • B32B25/16—Layered products comprising a layer of natural or synthetic rubber comprising polydienes homopolymers or poly-halodienes homopolymers
    • 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
    • B32B25/20—Layered products comprising a layer of natural or synthetic rubber comprising silicone rubber
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/288—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyketones
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B32B27/365—Layered products comprising a layer of synthetic resin comprising polyesters comprising polycarbonates
    • 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
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • 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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • 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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/28—Treatment by wave energy or particle radiation
    • 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
    • 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
    • C08J2309/02—Copolymers with acrylonitrile
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    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/08—Copolymers of ethene
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    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/16—Ethene-propene or ethene-propene-diene copolymers
    • C—CHEMISTRY; METALLURGY
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    • C08J2381/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
    • C08J2381/04—Polysulfides
    • 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
    • C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2383/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/16—Ethene-propene or ethene-propene-diene copolymers
    • 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
    • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2483/04—Polysiloxanes

Abstract

The invention discloses a vibrating diaphragm of a sound generating device, a preparation method thereof and the sound generating device, wherein the vibrating diaphragm comprises at least one vulcanized rubber layer, the vulcanized rubber layer is prepared by adopting a rubber compound in a gas explosion forming mode, and ultraviolet irradiation crosslinking is carried out in the gas explosion forming; the raw materials of the rubber compound comprise raw rubber, a photoinitiator and a filler reinforcing agent. The invention combines the gas explosion forming and the ultraviolet irradiation crosslinking curing process to prepare the vulcanized rubber diaphragm, can realize crosslinking reaction at room temperature, reduces the requirements on temperature and pressure, has low energy consumption, saves the production cost and obviously improves the forming efficiency; the problem that the single-layer vulcanized rubber diaphragm is difficult to demould in the forming process is solved, and the warping deformation of the diaphragm product is reduced; according to the invention, a vulcanizing agent is not required to be added, the problem of nonuniform cross-linking bonds caused by nonuniform vulcanizing agent in the traditional vulcanizing process is avoided, the energy is saved, the environment is protected, no pollution is caused to the environment, and the comprehensive performance of vulcanized rubber is better.

Description

Vibrating diaphragm of sound production device, preparation method of vibrating diaphragm and sound production device
Technical Field
The invention relates to the technical field of acoustic devices, in particular to a vibrating diaphragm of a sound generating device, a preparation method of the vibrating diaphragm and the sound generating device.
Background
A loudspeaker for converting electrical energy into acoustic energy generally comprises a housing having a basin-like structure, and a vibration system and a magnetic circuit system accommodated in an inner cavity defined by the housing, the vibration system including a diaphragm and a voice coil connected together. The loudspeaker diaphragm is a main component of a loudspeaker, and electromagnetic force is converted to the diaphragm tightly connected with the loudspeaker diaphragm through a voice coil at the center of the diaphragm to form mechanical force so as to generate sound to complete electric-force-sound conversion. The diaphragm is the central mechanical part and the most important part in the electro-acoustic-electro-acoustic conversion process, and can affect the acoustic performance of the loudspeaker.
The diaphragm of the speaker needs to have proper mechanical properties, so that the diaphragm is not easy to tear in the working process under the conditions of light weight and thin thickness, and can generate excellent sound quality. The properties of the diaphragm of a loudspeaker depend primarily on the material of the diaphragm.
Compared with a multilayer composite structure diaphragm, a single-layer vulcanized rubber diaphragm (such as nitrile rubber, ethylene-vinyl acetate rubber, polysulfide rubber, silicon rubber, styrene butadiene rubber and polyurethane rubber) in the existing sound production device is a hotspot direction for diaphragm development due to the fact that the production process is simple, the diaphragm is excellent in damping performance, good in rebound resilience, good in heat resistance and good in ageing resistance.
In the prior art, in the preparation of the vulcanized rubber diaphragm, a vulcanizing agent needs to be added into raw rubber, and the raw rubber is molded by vulcanizing for a long time under the conditions of high temperature and high pressure. The molding temperature is usually 120-200 ℃, and the molding time is 30-200 seconds.
However, in the process of implementing the embodiments of the present application, the inventors of the present application found that the above-mentioned technology has at least the following technical problems: (1) the molding temperature is high, the energy consumption is large, the vulcanization period is long, and the production efficiency is low; (2) the vulcanizing agent is not easy to disperse uniformly in the crude rubber, so that the cross-linking bond is not uniform, and the vulcanizing agent is easy to generate small molecular gas in the vulcanizing process to cause environmental pollution and product surface flaws; (3) at high temperature in the forming process, the rubber is tightly attached to the mold, so that the vibration diaphragm is difficult to demold, and the vibration diaphragm causes product pulling deformation in the film taking process, so that the product yield is influenced.
Disclosure of Invention
The invention mainly aims to provide a vibrating diaphragm of a sound generating device, a preparation method thereof and the sound generating device, wherein the vibrating diaphragm can be molded at normal temperature, high-temperature pressure maintaining vulcanization is not needed in the molding process, the molding efficiency is obviously improved, the problem that a single-layer vulcanized rubber vibrating diaphragm is difficult to demold in the molding process is solved, and the warping deformation of a vibrating diaphragm product is reduced; the diaphragm is crosslinked by ultraviolet irradiation without adding a vulcanizing agent, so that the problems of nonuniform crosslinking bonds and environmental pollution caused by the vulcanizing agent in the traditional vulcanizing process are solved.
The technical problem to be solved by the invention is realized by the following technical scheme:
the invention provides a vibrating diaphragm of a sound generating device, which comprises at least one vulcanized rubber layer, wherein the vulcanized rubber layer is prepared by adopting rubber compound in a gas explosion forming mode, and ultraviolet irradiation crosslinking is carried out in the gas explosion forming; the raw materials of the rubber compound comprise raw rubber, a photoinitiator and a filler reinforcing agent.
Optionally, the molecular weight of the raw rubber is 10000-1000000.
Optionally, the raw rubber comprises at least one of raw ethylene-vinyl acetate rubber, raw ethylene-propylene rubber, raw silicone rubber, raw nitrile rubber, raw hydrogenated nitrile rubber, raw acrylate rubber and raw polysulfide rubber.
Optionally, the raw rubber content is 45-97.5% of the total amount of the rubber compound.
Optionally, the photoinitiator comprises at least one of benzoin dimethyl ether, 2-methyl-2 (4-sulfophenyl) -2-morpholinyl-1-propanone, α -hydroxyisobutyrophenone, an acylphosphide photoinitiator, dialkoxyacetophenone, 1-hydroxy-cyclohexyl-phenylaminoketone, 2-phenylbenzyl-2-dimethylamine-1- (4-morpholinylbenzyl) butanone, benzophenone, 2-chlorobenzophenone, 4-dichlorobenzophenone, dodecyl benzophenone, anthraquinone, fluorenone, xanthone.
Optionally, the content of the photoinitiator is 0.5-5% of the total amount of the rubber compound.
Optionally, the filler reinforcing agent includes at least one of a carbon-based material, silica, silicate, carbonate, metal oxide, metal hydroxide, mineral whisker.
Optionally, the content of the filler reinforcing agent is 1-40% of the total amount of the rubber compound.
Optionally, the raw materials of the rubber compound further comprise an auxiliary agent, wherein the auxiliary agent comprises at least one of an auxiliary crosslinking agent, an anti-aging agent, a softening agent, a surface modifier, a release agent and a colorant; the content of the auxiliary agent is 1-10% of the total amount of the rubber compound.
Optionally, the raw materials of the mix do not include vulcanizing agents.
Optionally, the Shore A hardness of the diaphragm is 30-85; the 100% modulus of elongation of the diaphragm is 0.1-30 MPa.
Optionally, the diaphragm is a single-layer diaphragm, and the single-layer diaphragm is formed by a vulcanized rubber layer; or, 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 one vulcanized rubber layer.
Optionally, the diaphragm is a composite diaphragm, and the composite diaphragm further includes at least one of a thermoplastic elastomer layer and an engineering plastic layer.
Optionally, the material of the thermoplastic elastomer layer is at least one selected from polyester thermoplastic elastomer, polyurethane thermoplastic elastomer, polyamide thermoplastic elastomer, polystyrene thermoplastic elastomer, polyolefin thermoplastic elastomer and silicone thermoplastic elastomer; the engineering plastic layer is made of at least one of polyamide, polycarbonate, polyformaldehyde, polyethylene terephthalate, polybutylene terephthalate, polyarylsulfone, polyethersulfone, polyimide, polyphenylene sulfide, polyarylate, polyphenyl ester, polyaryletherketone and polyetheretherketone.
According to another aspect of the present invention, there is provided a method for preparing a diaphragm of a sound generating apparatus, including the steps of:
providing a rubber compound; wherein the raw materials of the rubber compound comprise raw rubber, a photoinitiator and a filler reinforcing agent;
preparing the rubber compound into a film body through a film forming process;
and carrying out gas explosion forming on the membrane body to form a vibrating membrane, and carrying out ultraviolet irradiation crosslinking in the gas explosion forming.
Optionally, the pressure of the gas explosion forming is 0.05-2 MPa.
Optionally, the wavelength of the ultraviolet light for ultraviolet light irradiation crosslinking is 100-500 nm, the intensity of the ultraviolet light irradiation is 200-3000 mw/cm2, and the time of the ultraviolet light irradiation is 2-60 s.
According to another aspect of the present invention, a sound generating apparatus is provided, which includes the above-mentioned diaphragm.
The invention has the following beneficial effects:
in the traditional process, the vulcanized rubber diaphragm is prepared by adding a vulcanizing agent into raw rubber and molding the raw rubber through long-time vulcanization under the conditions of high temperature and high pressure. The invention changes the tradition, creatively combines the gas explosion forming and the ultraviolet irradiation crosslinking curing process to prepare the vulcanized rubber diaphragm, can realize crosslinking reaction at room temperature, does not need high-temperature and high-pressure vulcanization in the forming process, thereby reducing the temperature rise time, the temperature fall time and the pressure maintaining time in the forming process, reducing the requirements on temperature and pressure, having low energy consumption, saving the production cost and obviously improving the forming efficiency; the problem that the single-layer vulcanized rubber diaphragm is difficult to demould in the forming process is solved, and the warping deformation of the diaphragm product is reduced; the vulcanized rubber diaphragm is prepared without adding a vulcanizing agent, so that the problem of nonuniform cross-linking bonds caused by nonuniform vulcanizing agent in the traditional vulcanization process is solved, the diaphragm is energy-saving and environment-friendly, has no pollution to the environment, and has better comprehensive performance of vulcanized rubber.
Drawings
FIG. 1 is a graph showing the influence of the content of a photoinitiator on the gel fraction and modulus of a rubber;
FIG. 2 is a graph showing the effect of filler reinforcement content on rubber modulus and hardness;
fig. 3 is a frequency response curve corresponding to diaphragms with different hardnesses.
Detailed Description
The raw materials and equipment used in the invention are common raw materials and equipment in the field if not specified; the methods used in the present invention are conventional in the art unless otherwise specified.
Unless otherwise defined, terms used in the present specification have the same meaning as those generally understood by those skilled in the art, but in case of conflict, the definitions in the present specification shall control.
The use of "including," "comprising," "containing," "having," or other variations thereof herein, is meant to encompass the non-exclusive inclusion, as such terms are not to be construed. The term "comprising" means that other steps and ingredients can be added that do not affect the end result. The term "comprising" also includes the terms "consisting of …" and "consisting essentially of …". The compositions and methods/processes of the present invention comprise, consist of, and consist essentially of the essential elements and limitations described herein, as well as any of the additional or optional ingredients, components, steps, or limitations described herein.
All numbers or expressions referring to quantities of ingredients, process conditions, etc. used in the specification and claims are to be understood as modified in all instances by the term "about". All ranges directed to the same component or property are inclusive of the endpoints, and independently combinable. Because these ranges are continuous, they include every value between the minimum and maximum values. It should also be understood that any numerical range recited herein is intended to include all sub-ranges within that range.
As described in the background art, in the preparation of a vulcanized rubber diaphragm in the prior art, a vulcanizing agent needs to be added into raw rubber, and the diaphragm is molded by vulcanizing for a long time under high temperature and high pressure conditions, which has the following technical problems: (1) the molding temperature is high, the energy consumption is large, the vulcanization period is long, and the production efficiency is low; (2) the vulcanizing agent is not easy to disperse uniformly in the crude rubber, so that the cross-linking bond is not uniform, and the vulcanizing agent is easy to generate small molecular gas in the vulcanizing process to cause environmental pollution and product surface flaws; (3) at high temperature in the forming process, the rubber is tightly attached to the mold, so that the vibration diaphragm is difficult to demold, and the vibration diaphragm causes product pulling deformation in the film taking process, so that the product yield is influenced. In order to solve the technical problem, the invention provides a vibrating diaphragm of a sound generating device, a preparation method of the vibrating diaphragm and the sound generating device.
In a first aspect, the vibrating diaphragm of the sound production device comprises at least one vulcanized rubber layer, wherein the vulcanized rubber layer is prepared by adopting rubber compound in a gas explosion forming mode, and ultraviolet irradiation crosslinking is carried out in the gas explosion forming; the raw materials of the rubber compound comprise raw rubber, a photoinitiator and a filler reinforcing agent.
In the embodiment of the invention, the molecular weight of the raw rubber is 10000-1000000. If the molecular weight of the raw rubber is less than 10000, the raw rubber has high viscosity and is difficult to mix, and the self-adhesion of vulcanized rubber after vulcanization is high, so that the vibration diaphragm is difficult to transfer; if the molecular weight of the raw rubber is more than 1000000, the plasticity of the raw rubber is poor, and the mixing is difficult.
In the embodiment of the present invention, the kind of the raw rubber is not particularly limited, and may be a kind of a common raw rubber well known to those skilled in the art, and preferably, the raw rubber includes at least one of ethylene-vinyl acetate rubber raw rubber, ethylene-propylene rubber raw rubber, silicone rubber raw rubber, nitrile rubber raw rubber, hydrogenated nitrile rubber raw rubber, acrylate rubber raw rubber, and polysulfide rubber raw rubber. By adopting the raw rubber, the service temperature can reach more than 150 ℃ after crosslinking, and the use requirement of the vibrating diaphragm under high power can be met.
In the examples of the present invention, the raw rubber is present in an amount of 45% to 97.5% of the total amount of the rubber composition, for example, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 97.5% and any value therebetween. If the content of the raw rubber is less than 45 percent of the total amount of the rubber compound, the modulus of the vulcanized rubber is high, the resilience is poor, and the vibrating diaphragm is easy to generate unrecoverable deformation in the long-term vibration process, so that the vibrating diaphragm fails; if the content of the crude rubber is more than 97.5 percent of the total amount of the rubber compound, the molecular chain flexibility of the crude rubber is high, so that the modulus of the vulcanized rubber is small, the smoothness of a vibrating diaphragm is high, and the distortion is caused by easy polarization in the large-amplitude vibration process.
The photoinitiator is a compound which can absorb light waves in an ultraviolet region (250-420 nm) to generate free radicals, cations and the like so as to initiate rubber raw rubber chemical crosslinking. Active groups in the raw rubber generate chemical crosslinking and shaping under the irradiation of ultraviolet light, and the photoinitiator can obviously improve the crosslinking efficiency of the raw rubber.
In the examples of the present invention, the kind of the photoinitiator is not particularly limited, and a general photoinitiator known to those skilled in the art may be used, and preferably, the photoinitiator includes at least one of benzoin dimethyl ether, 2-methyl-2 (4-sulfophenyl) -2-morpholinyl-1-propanone, α -hydroxyisobutyrophenone, acylphosphide photoinitiators, dialkoxyacetophenone, 1-hydroxy-cyclohexyl-phenylketal, 2-phenylbenzyl-2-dimethylamine-1- (4-morpholinylbenzyl) butanone, benzophenone, 2-chlorobenzone, 4-dichlorobenzophenone, dodecylbenzophenone, anthraquinone, fluorenone, and xanthone.
In the examples of the present invention, the photoinitiator is present in an amount of 0.5% to 5% of the total amount of the rubber composition, for example, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5% and any value therebetween. As shown in fig. 1, in order to solve the influence of the content of the photoinitiator on the gel fraction and modulus of the rubber, the inventors found in the research that if the content of the photoinitiator is less than 0.5% of the total amount of the rubber compound, the absorption efficiency of the raw rubber to ultraviolet light is low, which results in low vulcanization efficiency of the rubber film and few chemical cross-linking points of molecules of the raw rubber, which results in low modulus and low temperature resistance of the vibrating diaphragm, and the vibrating diaphragm is easy to deform and fail during high-power vibration; if the content of the photoinitiator is more than 5% of the total amount of the rubber compound, the rubber crude rubber vulcanization efficiency is too high, so that the cross-linking point of the rubber film is not uniform, and the vibrating film is not effective in the reliability verification process.
The molecular chain flexibility of the rubber crude rubber is high, the glass transition temperature is generally lower than-30 ℃, if no filler reinforcing agent is added, the modulus of the vulcanized rubber crude rubber is generally between 0.5 and 3MPa, the manufactured vibrating diaphragm is high in smoothness and poor in stiffness, and the vibrating diaphragm is easy to generate polarization in a large-amplitude vibration process, so that the product distortion is caused. In the invention, by adding the filler reinforcing agent, the hardness, the modulus, the tensile strength, the temperature resistance and the damping performance of the rubber can be obviously improved due to the large hardness, the high modulus and the good temperature resistance of the filler reinforcing agent.
In the embodiment of the present invention, the type of the filler reinforcing agent is not particularly limited, and may be a common type of filler reinforcing agent known to those skilled in the art, and preferably, the filler reinforcing agent includes at least one of a carbon-based material, silica, silicate, carbonate, metal oxide, metal hydroxide, and mineral whisker. As the carbon-based material, carbon black, graphite, graphene, carbon nanotube, and the like can be exemplified, and the silica includes fumed silica, precipitated silica, and the like.
In the embodiment of the present invention, the shape of the filler reinforcing agent is not particularly limited, and those skilled in the art can select the reinforcing agent according to actual needs, and the shape of the filler reinforcing agent may be, for example, spherical, spheroidal, sheet, fibrous, whisker, etc., and more preferably, the shape of the filler reinforcing agent is sheet or fibrous, which is more preferable in the reinforcing effect.
In the examples of the present invention, the content of the filler as a reinforcing agent is 1% to 40% of the total amount of the rubber compound, for example, 1%, 5%, 8%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, and any value therebetween. As shown in fig. 2, in order to determine the effect of the content of the filler reinforcing agent on the modulus and hardness of the rubber, the inventors found in the research that if the content of the filler reinforcing agent is less than 1% of the total amount of the rubber compound, the reinforcing effect on the rubber is poor, the modulus of the vulcanized rubber is small, the temperature resistance is poor, and the diaphragm is prone to polarization distortion during large-amplitude vibration.
As mentioned above, in the invention, by adding the filler reinforcing agent, the hardness, modulus, tensile strength, temperature resistance and damping performance of the rubber can be remarkably improved due to the large hardness, high modulus and good temperature resistance of the filler reinforcing agent. However, the use of a large amount of filler reinforcing agent results in a low photocrosslinking efficiency in ultraviolet irradiation crosslinking so that a satisfactory degree of crosslinking cannot be obtained. In order to solve the technical problems, a large number of experimental screens are carried out on a formula system of a vulcanized rubber material, and researches show that the crosslinking depth and uniformity of a product are obviously improved by controlling the dosage and proportion of raw rubber, a photoinitiator and a filler reinforcing agent, the prepared vulcanized rubber vibrating diaphragm has good high-temperature resistance, can effectively inhibit the distortion of an acoustic product and has good sound production effect.
Furthermore, the raw materials of the rubber compound also comprise an auxiliary agent, wherein the auxiliary agent comprises at least one of an auxiliary cross-linking agent, an anti-aging agent, a softening agent, a surface modifier, a release agent and a coloring agent.
The assistant crosslinking agent is a material with multiple functionality, can reduce irradiation amount, and obviously improves the crosslinking efficiency and temperature resistance of rubber. In the embodiment of the present invention, there is no particular limitation on the kind of the auxiliary crosslinking agent, and the kind of the auxiliary crosslinking agent known to those skilled in the art may be used, and the auxiliary crosslinking agent includes, by way of example: triallyl cyanurate, triallyl isocyanurate, trimethylolpropane tri (meth) acrylate, trimethylolpropane triallyl ether, pentaerythritol tetraallyl ether, triethylene glycol methacrylate, propoxylated trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, triallyl isocyanurate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tripropylene glycol diacrylate, dipropylene glycol diacrylate, or combinations thereof.
The anti-aging agent can prevent or inhibit the formation of free radicals, avoid rubber molecule chain reaction, and the substances for delaying rubber aging obviously improve the service life of rubber in a use environment. In the embodiment of the present invention, the kind of the antioxidant is not particularly limited, and may be one known to those skilled in the art, and examples thereof include: at least one of age inhibitor N-445, age inhibitor 246, age inhibitor 4010, age inhibitor SP, age inhibitor RD, age inhibitor ODA, age inhibitor OD and age inhibitor WH-02.
In the embodiment of the present invention, there is no particular limitation on the type of the softener, and a common softener known to those skilled in the art may be used, for example, the softener is at least one of paraffin oil, naphthenic oil, and vegetable oil.
In the embodiment of the invention, the content of the auxiliary agent is 1-10% of the total amount of the rubber compound.
The raw materials of the rubber compound do not include a vulcanizing agent. The vulcanized rubber diaphragm is prepared without adding a vulcanizing agent, so that the problem of nonuniform cross-linking bonds caused by nonuniform vulcanizing agent in the traditional vulcanization process is solved, the diaphragm is energy-saving and environment-friendly, has no pollution to the environment, and has better comprehensive performance of vulcanized rubber.
In the embodiment of the invention, the Shore A hardness of the diaphragm is 30-85. As shown in fig. 3, for frequency response curves corresponding to diaphragms with different hardnesses, the inventors found in research that when the hardness of the diaphragm is reduced, the modulus of the rubber is reduced, the resonant frequency of the rubber diaphragm is reduced, the response performance of the low frequency is improved, but the intermediate frequency performance is reduced.
In the embodiment of the invention, the 100% modulus of the diaphragm is 0.1-30 MPa.
The diaphragm provided by the invention can be a single-layer diaphragm or a multi-layer composite diaphragm.
The single-layer diaphragm is a diaphragm formed by one vulcanized rubber layer.
The composite diaphragm is formed by sequentially laminating a plurality of vulcanized rubber layers. Alternatively, the composite diaphragm may include at least one vulcanized rubber layer and at least one film layer made of other materials. The vulcanized rubber layer is bonded and compounded with a film layer made of other materials to form the composite diaphragm made of various 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 the vulcanized rubber layer provided by the invention.
For the film layer made of other materials, at least one of a thermoplastic elastomer layer and an engineering plastic layer may be preferable.
In the embodiment of the present invention, the material of the thermoplastic elastomer layer is at least one selected from polyester thermoplastic elastomers, polyurethane thermoplastic elastomers, polyamide thermoplastic elastomers, polystyrene thermoplastic elastomers, polyolefin thermoplastic elastomers, and silicone thermoplastic elastomers, for example.
In the embodiment of the present invention, as an example, the engineering plastic layer is made of at least one of polyamide, polycarbonate, polyoxymethylene, polyethylene terephthalate, polybutylene terephthalate, polyarylsulfone, polyethersulfone, polyimide, polyphenylene sulfide, polyarylate, polyphenylene ester, polyaryletherketone, and polyetheretherketone.
In the embodiment of the present invention, the material of the adhesive film layer is not particularly limited, and a common adhesive film known to those skilled in the art may be used, for example, the material of the adhesive film layer includes at least one of an acrylic adhesive film and a silicone adhesive film. The engineering plastic layer and/or the thermoplastic elastomer layer can be fixedly combined through the adhesive film layer or not.
In a second aspect, a method for preparing a diaphragm of the sound generating apparatus in the first aspect is provided, which includes the following steps:
providing a rubber compound; wherein the raw materials of the rubber compound comprise raw rubber, a photoinitiator and a filler reinforcing agent;
preparing the rubber compound into a film body through a film forming process;
and carrying out gas explosion forming on the membrane body to form a vibrating membrane, and carrying out ultraviolet irradiation crosslinking in the gas explosion forming.
In the examples of the present invention, the film formation process is not particularly limited, and a film formation process known to those skilled in the art can be used. Preferably, the film forming process may employ a calendering process or a coating process or a casting process to form a film.
In the gas explosion forming process, after the film body is completely attached to the mold for shaping, ultraviolet light is adopted for irradiation to make the rubber film crosslinked and shaped.
In the embodiment of the invention, the pressure of the gas explosion forming is 0.05-2 MPa.
In the embodiment of the invention, the wavelength of the ultraviolet light for ultraviolet light irradiation crosslinking is 100-500 nm, and more preferably, the wavelength of the ultraviolet light is 200-400 nm; by adopting the ultraviolet wavelength, the vulcanized rubber has high absorption efficiency and high crosslinking speed.
In the embodiment of the invention, the illumination intensity of the ultraviolet light is 200-3000 mw/cm2If the ultraviolet light illumination intensity is less than 200mw/cm2The crosslinking speed of vulcanized rubber is slow, and the molding period is long; illumination by ultraviolet lightThe strength is more than 3000mw/cm2The problems of too high crosslinking speed and nonuniform local crosslinking are easily caused.
In the embodiment of the present invention, the ultraviolet irradiation time is 2s to 60s, and more preferably, the ultraviolet irradiation time is 10s to 30 s.
In the prior art, the existing vibrating diaphragm is cured by high-temperature and high-pressure vulcanization, and compared with the prior art, the invention adopts a gas explosion forming process and an ultraviolet irradiation crosslinking process, so that the temperature rise time, the temperature fall time and the pressure maintaining time in the forming process are reduced, the requirements on temperature and pressure are reduced, the energy consumption is low, the production cost is saved, and the forming efficiency is obviously improved; the problem that the single-layer vulcanized rubber diaphragm is difficult to demould in the forming process is solved, and the warping deformation of the diaphragm product is reduced; energy conservation and environmental protection, and no pollution to the environment; the damage of ultraviolet irradiation to the material is small, and the mechanical property and the electrical property of the product are excellent; the product cost is low.
In order to better understand the technical solutions, the technical solutions will be described in detail with reference to specific examples, which are only preferred embodiments of the present invention and are not intended to limit the present invention.
Example 1
A vibrating diaphragm of a sound production device is composed of a vulcanized rubber layer, wherein the preparation method of the vulcanized rubber layer comprises the following steps:
providing a rubber compound; wherein, the rubber compound comprises the following raw materials in percentage by weight: 65% of raw rubber, 3% of photoinitiator, 25% of filler reinforcing agent and 7% of auxiliary agent, wherein the sum of the weight of the raw materials is one hundred percent;
preparing the rubber compound into a film body through a coating process;
carrying out gas explosion molding on the membrane body to form a vibrating membrane, and carrying out ultraviolet irradiation crosslinking in the gas explosion molding; the pressure of the gas explosion forming is 1 MPa; the ultraviolet wavelength of the ultraviolet irradiation crosslinking is 200nm, and the ultraviolet irradiation intensity is 1000mw/cm2The ultraviolet irradiation time was 30 seconds.
Wherein the molecular weight of the raw rubber is 10000-1000000; the raw rubber comprises ethylene-vinyl acetate rubber raw rubber; the photoinitiator comprises benzoin dimethyl ether; the filler reinforcement comprises a silicate; the auxiliary agent comprises an auxiliary crosslinking agent, and the auxiliary crosslinking agent comprises triallyl cyanurate.
Example 2
A vibrating diaphragm of a sound production device comprises a vulcanized rubber layer and a thermoplastic elastomer layer, wherein the preparation method of the vulcanized rubber layer comprises the following steps:
providing a rubber compound; wherein, the rubber compound comprises the following raw materials in percentage by weight: 45% of raw rubber, 5% of photoinitiator, 40% of filler reinforcing agent and 10% of auxiliary agent, wherein the sum of the weight of the raw materials is one hundred percent;
preparing the rubber compound into a membrane body by a calendaring process;
carrying out gas explosion molding on the membrane body to form a vibrating membrane, and carrying out ultraviolet irradiation crosslinking in the gas explosion molding; the pressure of the gas explosion forming is 0.05 MPa; the wavelength of ultraviolet light for ultraviolet light irradiation crosslinking is 100nm, the irradiation intensity of the ultraviolet light is 200mw/cm2, and the irradiation time of the ultraviolet light is 60 s.
Wherein the molecular weight of the raw rubber is 10000-1000000; the raw rubber comprises ethylene propylene rubber raw rubber and silicon rubber raw rubber; the photoinitiator comprises 2-methyl-2 (4-sulfophenyl) -2-morpholinyl-1-acetone and alpha-hydroxyisobutyrophenone; the filler reinforcement comprises silica and carbonate; the auxiliary agent comprises an auxiliary crosslinking agent and an anti-aging agent; the auxiliary crosslinking agent comprises triallyl isocyanurate and pentaerythritol tetraallyl ether; the antioxidant may comprise antioxidant N-445.
The thermoplastic elastomer layer is made of polyester thermoplastic elastomer.
Example 3
A vibrating diaphragm of a sound production device comprises at least one vulcanized rubber layer and one engineering plastic layer, wherein the preparation method of the vulcanized rubber layer comprises the following steps:
providing a rubber compound; wherein, the rubber compound comprises the following raw materials in percentage by weight: 97.5 percent of raw rubber, 0.5 percent of photoinitiator, 1 percent of filler reinforcing agent and 1 percent of auxiliary agent, wherein the sum of the weight of the raw materials is one hundred percent;
preparing the rubber compound into a film body by a tape casting process;
carrying out gas explosion molding on the membrane body to form a vibrating membrane, and carrying out ultraviolet irradiation crosslinking in the gas explosion molding; the pressure of the gas explosion forming is 2 MPa; the ultraviolet wavelength of the ultraviolet irradiation crosslinking is 500nm, and the ultraviolet irradiation intensity is 3000mw/cm2The ultraviolet irradiation time was 2 seconds.
Wherein the molecular weight of the raw rubber is 10000-1000000; the raw rubber comprises nitrile rubber raw rubber; the photoinitiator comprises an acyl phosphide photoinitiator; the filler reinforcement comprises a metal oxide; the auxiliary agent comprises an anti-aging agent and a softening agent; the anti-aging agent comprises an anti-aging agent 246; the softening agent is paraffin oil.
The engineering plastic layer is made of polyether-ether-ketone.
Example 4
The vibrating diaphragm of the sound production device comprises a thermoplastic elastomer layer, a vulcanized rubber layer and an engineering plastic layer which are sequentially stacked, wherein the preparation method of the vulcanized rubber layer comprises the following steps:
providing a rubber compound; wherein, the rubber compound comprises the following raw materials in percentage by weight: 55% of raw rubber, 2% of photoinitiator, 37% of filler reinforcing agent and 6% of auxiliary agent, wherein the sum of the weight of the raw materials is one hundred percent;
preparing the rubber compound into a film body through a coating process;
carrying out gas explosion molding on the membrane body to form a vibrating membrane, and carrying out ultraviolet irradiation crosslinking in the gas explosion molding; the pressure of the gas explosion forming is 0.8 MPa; the ultraviolet wavelength of the ultraviolet irradiation crosslinking is 300nm, the ultraviolet irradiation intensity is 1000mw/cm2, and the ultraviolet irradiation time is 30 s.
Wherein the molecular weight of the raw rubber is 10000-1000000; the raw rubber comprises polysulfide rubber raw rubber; the photoinitiator comprises benzophenone and xanthone; the filler reinforcing agent comprises metal hydroxide; the auxiliary agent comprises a softening agent; the softener is naphthenic oil.
The thermoplastic elastomer layer is made of polystyrene thermoplastic elastomer; the engineering plastic layer is made of polycarbonate.
The above-mentioned embodiments only express the embodiments of the present invention, and the description is more specific and detailed, but not understood as the limitation of the patent scope of the present invention, but all the technical solutions obtained by using the equivalent substitution or the equivalent transformation should fall within the protection scope of the present invention.

Claims (13)

1. A vibrating diaphragm of a sound generating device comprises at least one vulcanized rubber layer, and is characterized in that the vulcanized rubber layer is prepared by adopting rubber compound in a gas explosion forming mode, and ultraviolet irradiation crosslinking is carried out in the gas explosion forming; the raw materials of the rubber compound comprise raw rubber, a photoinitiator and a filler reinforcing agent.
2. The diaphragm of claim 1, wherein the molecular weight of the raw rubber is 10000-1000000.
3. The diaphragm of the sound generating apparatus as claimed in claim 1, wherein the raw rubber includes at least one of raw ethylene-vinyl acetate rubber, raw ethylene-propylene rubber, raw silicone rubber, raw nitrile rubber, raw hydrogenated nitrile rubber, raw acrylate rubber, and raw polysulfide rubber; the content of the raw rubber is 45-97.5% of the total amount of the rubber compound.
4. The diaphragm of claim 1, wherein the photoinitiator comprises at least one of benzoin dimethyl ether, 2-methyl-2 (4-sulfophenyl) -2-morpholinyl-1-propanone, α -hydroxyisobutyrophenone, an acylphosphide photoinitiator, dialkoxyacetophenone, 1-hydroxy-cyclohexyl-phenylaminoketone, 2-phenylbenzyl-2-dimethylamine-1- (4-morpholinylbenzyl phenyl) butanone, benzophenone, 2-chlorobenzone, 4-dichlorobenzophenone, dodecylbenzophenone, anthraquinone, fluorenone, and xanthone; the content of the photoinitiator is 0.5-5% of the total amount of the rubber compound.
5. The diaphragm of claim 1, wherein the filler reinforcing agent comprises at least one of a carbon-based material, silica, a silicate, a carbonate, a metal oxide, a metal hydroxide, and a mineral whisker; the content of the filler reinforcing agent is 1-40% of the total amount of the rubber compound.
6. The diaphragm of the sound generating apparatus as claimed in claim 1, wherein the raw material of the rubber compound further includes an auxiliary agent, and the auxiliary agent includes at least one of an auxiliary crosslinking agent, an anti-aging agent, a softening agent, a surface modifier, a mold release agent, and a colorant; the content of the auxiliary agent is 1-10% of the total amount of the rubber compound.
7. The diaphragm of the sound generating apparatus according to claim 1, wherein the shore a hardness of the diaphragm is 30 to 85; the 100% modulus of elongation of the diaphragm is 0.1-30 MPa.
8. The diaphragm of the sound-generating apparatus according to claim 1, wherein the diaphragm is a single-layer diaphragm, and the single-layer diaphragm is formed by a vulcanized rubber layer; or, 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 one vulcanized rubber layer.
9. The diaphragm of claim 8, wherein the diaphragm is a composite diaphragm, and the composite diaphragm further comprises at least one of a thermoplastic elastomer layer and an engineering plastic layer.
10. The diaphragm of claim 9, wherein the thermoplastic elastomer layer is made of at least one of a polyester thermoplastic elastomer, a polyurethane thermoplastic elastomer, a polyamide thermoplastic elastomer, a polystyrene thermoplastic elastomer, a polyolefin thermoplastic elastomer, and a silicone thermoplastic elastomer; the engineering plastic layer is made of at least one of polyamide, polycarbonate, polyformaldehyde, polyethylene terephthalate, polybutylene terephthalate, polyarylsulfone, polyethersulfone, polyimide, polyphenylene sulfide, polyarylate, polyphenyl ester, polyaryletherketone and polyetheretherketone.
11. The method for preparing a diaphragm of a sound generating apparatus as claimed in any one of claims 1 to 10, comprising the steps of:
providing a rubber compound; wherein the raw materials of the rubber compound comprise raw rubber, a photoinitiator and a filler reinforcing agent;
preparing the rubber compound into a film body through a film forming process;
and carrying out gas explosion forming on the membrane body to form a vibrating membrane, and carrying out ultraviolet irradiation crosslinking in the gas explosion forming.
12. The method for preparing the diaphragm of the sound generating apparatus according to claim 11, wherein the pressure of the gas explosion molding is 0.05 to 2 MPa; the ultraviolet wavelength of the ultraviolet irradiation crosslinking is 100-500 nm, the ultraviolet irradiation intensity is 200-3000 mw/cm2, and the ultraviolet irradiation time is 2-60 s.
13. A sound-emitting device, characterized in that it comprises a diaphragm according to any one of claims 1 to 10.
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