WO2022253136A1 - 一种泡沫材料及其制备方法、振动板和扬声器 - Google Patents

一种泡沫材料及其制备方法、振动板和扬声器 Download PDF

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Publication number
WO2022253136A1
WO2022253136A1 PCT/CN2022/095614 CN2022095614W WO2022253136A1 WO 2022253136 A1 WO2022253136 A1 WO 2022253136A1 CN 2022095614 W CN2022095614 W CN 2022095614W WO 2022253136 A1 WO2022253136 A1 WO 2022253136A1
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Prior art keywords
foam material
foaming
stage
resin
heating
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English (en)
French (fr)
Inventor
谢保存
李美玲
凌风光
李春
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Goertek Inc
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Goertek Inc
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    • 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
    • C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
    • C08J9/102—Azo-compounds
    • 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0066—Use of inorganic compounding ingredients
    • H—ELECTRICITY
    • H04—ELECTRIC COMMUNICATION TECHNIQUE
    • H04R—LOUDSPEAKERS, MICROPHONES, GRAMOPHONE PICK-UPS OR LIKE ACOUSTIC ELECTROMECHANICAL TRANSDUCERS; ELECTRIC HEARING AIDS; PUBLIC ADDRESS SYSTEMS
    • H04R31/00—Apparatus or processes specially adapted for the manufacture of transducers or diaphragms therefor
    • 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
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
    • 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
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • 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
    • C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C08J2463/02—Polyglycidyl ethers of bis-phenols
    • 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
    • C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
    • C08J2479/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors

Definitions

  • the invention relates to the technical field of electroacoustic conversion equipment, in particular to a foam material and a preparation method thereof, a vibrating plate and a loudspeaker.
  • PMI foam material has a low density and is widely used as the core layer to prepare acoustic vibration plates, but it is very easy to absorb water. Under high temperature and high humidity conditions, a large amount of water vapor invades, resulting in The bonding between the adhesive layer and the surface layer or the bonding between the adhesive layer and the core layer fails, resulting in failure of the reliability test of the microspeaker. In addition, with the update and iteration of electronic products, the requirements for material strength and heat and humidity resistance are getting higher and higher, and traditional PMI foams are also difficult to meet the demand.
  • a kind of vibrating plate it comprises two layers of skin and middle core layer, and middle core layer is foam layer, and it comprises epoxy resin, hollow sphere and foaming microcapsule, and foaming microcapsule comprises shell and accommodates A volatile liquid blowing agent inside the shell.
  • the volatile substances in the foam microcapsules volatilize gas and are discharged through the shell, so that the foam layer enters a foamed state.
  • the volatile gases used in the microcapsules in the above scheme are low-boiling alkanes, chlorinated alkanes or olefins, etc., which are flammable, explosive, or toxic gases such as chlorine, which are harmful to the environment and operators. greater hazard.
  • the main purpose of the present invention is to provide a foam material, which has the characteristics of cohesiveness, porous light weight, high strength and low water absorption, and can be used as a binder in sound-generating devices or as a foam material .
  • Another object of the present invention is the preparation method of the above-mentioned foam material, which can simultaneously complete the foaming and bonding and curing processes, thereby simplifying the preparation process of the material.
  • Another object of the present invention is to provide a vibrating plate, which includes the above-mentioned foam material of the present invention.
  • Another object of the present invention is to provide a loudspeaker comprising the above-mentioned vibration plate of the present invention.
  • the present invention provides the following technical solutions:
  • the foam material of the embodiment of the first aspect of the present invention is mainly formed by foaming and solidifying raw materials, and the raw materials include:
  • the main resin includes at least one of cyanate resin and bismaleimide resin, and the chemical foaming agent reacts with heat to generate nitrogen and/or carbon dioxide to allow the raw material to enter the foaming bubble state.
  • the chemical blowing agent includes at least one of N-nitroso compounds, azo compounds, hydrazide compounds, and carbonate compounds.
  • the chemical blowing agent includes azobisisobutyronitrile.
  • the amount of the chemical foaming agent is 5%-40% of the total weight of the main resin and the curing agent.
  • the amount of the chemical foaming agent is 12%-20% of the total weight of the main resin and the curing agent.
  • the curing agent includes epoxy resin; and/or, the amount of the curing agent is 10%-35% by weight of the main resin.
  • the raw material of the foam material further includes: at least one of a catalyst, an accelerator and hollow glass microspheres.
  • the catalyst includes cobalt acetylacetonate.
  • the catalyst is used in an amount of 1%-10% by weight of the main resin.
  • the accelerator includes nonylphenol.
  • the amount of the accelerator is 1%-5% of the weight of the main resin.
  • the particle size of the hollow glass microspheres is 110 ⁇ m-150 ⁇ m, the density is 0.08 g/cm 3 -1.5 g/cm 3 , and the amount added is the total weight of the main resin and the curing agent. 15% to 40% of that.
  • the foam material has a density of 0.35 g/cm 3 to 0.8 g/cm 3 and a modulus of 8 GPa to 40 GPa.
  • the vibration plate according to the embodiment of the second aspect of the present invention includes a foam material layer, and the foam material layer adopts the foam material described in the first aspect of the present invention.
  • the present invention also includes: at least one substrate layer, and the substrate layer is arranged on the outer surface of the foam material layer.
  • the substrate layer is made of at least one of aluminum foil, engineering plastics, carbon fiber, and aramid fiber composite material.
  • the thickness of the vibrating plate is 0.04mm ⁇ 0.25mm.
  • the loudspeaker according to the embodiment of the third aspect of the present invention includes a sounding diaphragm, and a vibrating plate for connecting and supporting the sounding diaphragm, and the vibrating plate is the vibrating plate described in the second aspect of the present invention; the vibrating The plate and the sound-emitting diaphragm can be bonded by adhesive film or glue.
  • the first stage of temperature rise is carried out to carry out the foaming reaction
  • the end temperature of the first stage of heating is 140°C to 150°C
  • the end temperature of the second stage of heating is 150°C to 180°C
  • the end temperature of the third stage of heating is 180°C ⁇ 200°C.
  • the heating rate of the first stage is 0.8°C/min-1°C/min
  • the heating rate of the second stage is 2°C/min-3°C/min
  • the The holding time after the third stage of heating is 2h to 3h.
  • the foaming reaction is controlled so that the foaming ratio reaches 1.5-3.5.
  • the present invention selects cyanate ester resin, bismaleimide resin, etc. as the main resin, and then adds a chemical foaming agent, which reacts chemically to generate nitrogen and/or carbon dioxide, etc.
  • Environmentally friendly gas so that the main resin enters the foaming state to form a porous structure, not only retains the good adhesive performance of the above resins, but also retains the low water absorption and excellent performance of cyanate ester and bismaleimide resins.
  • Heat resistance and other characteristics, and the material has the characteristics of low density, high modulus and high strength after foaming.
  • Fig. 1 provides a structural schematic diagram of a vibrating plate for the present invention
  • Fig. 2 is a schematic structural view of another vibrating plate provided by the present invention.
  • Fig. 3 is the sectional view of the vibrating plate that embodiment makes
  • Fig. 4 is the sectional view of the vibrating plate that comparative example makes
  • Fig. 5 is the loudspeaker FR curve diagram of the vibrating plate
  • FIG. 6 is a structural diagram of a loudspeaker assembly provided by the present invention.
  • Fig. 7 is a structural diagram of another loudspeaker assembly provided by the present invention.
  • the foam material provided by the present invention is mainly formed by foaming and solidifying raw materials, and the raw materials include:
  • the main resin includes at least one of cyanate resin and bismaleimide resin; the chemical foaming agent undergoes a chemical reaction when heated to generate nitrogen and/or carbon dioxide so that the raw material enters the foam bubble state.
  • the material uses cyanate ester resin, bismaleimide resin and other main resins as the main resin, and then adds a chemical foaming agent to produce a porous structure, which not only retains the good bonding performance of this type of resin, but also retains It has the characteristics of low water absorption and excellent heat resistance of cyanate resin and bismaleimide resin, and the material has low density, high modulus and high strength after foaming.
  • the foam material obtained by the present invention has a density of 0.35g/cm 3 to 0.8g/cm 3 and a modulus of 8GPa to 40GPa.
  • the above-mentioned main resin can be cyanate resin or bismaleimide resin alone, or a combination of the two, or a combination of two or more cyanate resins, or two or more
  • the combination of bismaleimide resins, etc., the present invention is not specifically limited to this.
  • the foaming agent used in the present invention is a chemical foaming agent. Adding a chemical blowing agent can generate nitrogen and/or carbon dioxide at a certain temperature, and the gas expands to produce a cell structure. At the same time, the main resin undergoes a curing reaction to harden the structure, and finally the cell shape is fixed. It is usually a non-toxic and environmentally friendly gas such as nitrogen or carbon dioxide, which has good environmental protection.
  • Preferred chemical blowing agents include at least one of N-nitroso compounds, azo compounds, hydrazide compounds, and carbonate compounds.
  • N-nitroso compounds include but not limited to N,N-dinitrosopentamethylenetetramine, N,N-dimethyl-N,N-diterephthalamide, etc., azo compounds Including but not limited to azodicarbonamide, azobisisobutyronitrile, isopropyl azodicarboxylate, diethyl azodicarboxylate, diazaminobenzene, azodicarboxylate, etc.; hydrazides Compounds include but are not limited to 4,4-disulfonyl hydrazide diphenyl ether, p-benzenesulfonyl hydrazide, 3,3-disulfonyl hydrazide diphenyl sulfone, 4,4-diphenyl disulfonyl hydrazide, 1,3- Benzene disulfonyl hydrazide, etc., carbonate compounds include but not limited to sodium chloride carbonate
  • the amount of foaming agent can be adjusted according to the type of main resin and the performance of foam material.
  • the consumption of the chemical foaming agent is preferably 5% to 40% of the total weight of the main resin and the curing agent, for example, it can be 5%, 10%, 15%. %, 20%, 25%, 30%, 35%, 40%, etc., more preferably 12% to 20%, such as 12%, 13%, 14%, 15%, 16%, 17%, 18% , 19%, 20%, more preferably 15% to 20%.
  • curing agents suitable for the main resin including typical aliphatic amines (such as vinyltriamine DETA, ethylenediamine EDA, triethylenetetramine, dipropylenetriamine DPTA, etc.), aromatic amines Classes (such as m-phenylenediamine, diaminodiphenylmethane, benzidine, etc.), amidoamines, epoxy resins, etc.
  • typical aliphatic amines such as vinyltriamine DETA, ethylenediamine EDA, triethylenetetramine, dipropylenetriamine DPTA, etc.
  • aromatic amines Classes such as m-phenylenediamine, diaminodiphenylmethane, benzidine, etc.
  • amidoamines epoxy resins
  • the epoxy resin itself has both adhesiveness and can be combined with cyanate resin Cross-linking reaction with bismaleimide resin, etc., has a good curing effect, that is, the combination of epoxy resin and cyanate resin/bismaleimide resin can achieve synergistic effect .
  • the epoxy resin may include typical epoxy resin E51, epoxy resin E44, epoxy resin E128, etc., preferably, the epoxy resin may be epoxy resin E51.
  • the amount of curing agent is preferably 10% to 35% of the weight of the main resin, such as 10%, 15%, 17%, 20%, 22%, 25%, 27%, 29%, 30%, 33%, 35% % etc., preferably 25% to 30%, specifically 25%, 26%, 27%, 28%, 29%, 30%.
  • At least one of catalyst, accelerator and hollow glass microspheres can also be introduced into the foam material of the present invention. That is to say, any one of catalyst, promotor and hollow glass microspheres can be added in the foam material, and any two of catalyst, promotor and hollow glass microspheres can be added in the foam material.
  • the catalyst, accelerator and hollow glass microspheres are added at the same time, and the setting can be selected according to actual usage requirements, which is not limited in the present invention.
  • hollow glass microspheres have the functions of reducing density and maintaining material strength, and catalysts and accelerators can promote the resin curing reaction.
  • cobalt acetylacetonate as a catalyst to promote resin curing, and its consumption is preferably 1% to 10% of the weight of the main resin, such as 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, etc.
  • nonylphenol is used as an accelerator, which together with a curing agent can better promote resin curing, and is also conducive to improving the overall performance of the foam material. Its consumption is preferably 3% to 5% of the weight of the main resin, such as 3 %, 3.5%, 4%, 4.5%, 5%, etc.
  • Hollow glass microspheres preferably have a particle size of 110 ⁇ m to 150 ⁇ m, a density of 0.08 g/cm3-1.5 g/cm3, and an addition amount of 15% to 40% of the total weight of the main resin and the curing agent, such as 15%, 20%, 22%, 25%, 27%, 29%, 30%, 33%, 35%, 40%, etc.
  • the particle size of the hollow glass microspheres is 130 ⁇ m
  • the packing density is 1 g/cm 3
  • the amount of the hollow glass microspheres is 19% or more of the total weight of the main resin and the curing agent. 28%.
  • the foam material is mainly formed by foaming and curing the following raw materials:
  • main resin 100 parts of main resin, 20-30 parts of epoxy resin E51, 10-20 parts of azobisisobutyronitrile, 25-35 parts of hollow glass microspheres, 1-2 parts of cobalt acetylacetonate, nonylphenol 3 to 5 copies;
  • the host resin includes at least one of cyanate resin and bismaleimide resin, preferably at least one of bisphenol A cyanate resin and bisphenol E cyanate resin. kind.
  • Foam materials are mainly made of the following raw materials after foaming and curing:
  • main resin 100 parts of main resin, 30 parts of epoxy resin E51, 10 parts of azobisisobutyronitrile, 35 parts of hollow glass microspheres, 1 part of cobalt acetylacetonate, and 5 parts of nonylphenol.
  • main resin 100 parts of main resin, 20 parts of epoxy resin E51, 10 parts of azobisisobutyronitrile, 25 parts of hollow glass microspheres, 1 part of cobalt acetylacetonate, and 3 parts of nonylphenol.
  • main resin 100 parts of main resin, 30 parts of epoxy resin E51, 20 parts of azobisisobutyronitrile, 35 parts of hollow glass microspheres, 2 parts of cobalt acetylacetonate, and 5 parts of nonylphenol.
  • main resin 100 parts of main resin, 25 parts of epoxy resin E51, 15 parts of azobisisobutyronitrile, 30 parts of hollow glass microspheres, 1.5 parts of cobalt acetylacetonate, and 3.5 parts of nonylphenol.
  • main resin 100 parts of main resin, 25 parts of epoxy resin E51, 15 parts of azobisisobutyronitrile, 30 parts of hollow glass microspheres, 1.2 parts of cobalt acetylacetonate, and 4 parts of nonylphenol.
  • main resin 100 parts of main resin, 25 parts of epoxy resin E51, 15 parts of azobisisobutyronitrile, 30 parts of hollow glass microspheres, 1.7 parts of cobalt acetylacetonate, and 4.5 parts of nonylphenol.
  • the foaming ratio can also be adjusted by controlling the preparation process conditions or the amount of raw materials used.
  • the foaming ratio referred to in the present invention is: the ratio of the thickness of the material after foaming to the thickness of the material before foaming.
  • the present invention also provides the preparation method of above foam material, and this method makes foaming and solidification carry out synergistically through heating mode, and the finally gained composite vibrating plate has better reliability (humidity and heat resistance performance), rigidity and modulus, has Better acoustic performance.
  • the first stage of temperature rise is carried out to carry out the foaming reaction
  • the three-stage heating can ensure that the material is fully foamed and cured, and has more reliable moisture resistance, rigidity and modulus.
  • the first stage of heating is mainly to complete the foaming process;
  • the second stage of heating is mainly to complete the curing reaction, so that the structure formed by the first stage of foaming is fixed, and at the same time accompanied by a small amount of foaming reaction;
  • the third stage of heating The material is fully cured to ensure that the material obtained in the second stage is maximized in terms of heat resistance and mechanical properties.
  • the end temperature of the first stage of heating is 140°C-150°C; for example, the end temperature of the first stage of heating can be 140°C, 143°C, 145°C, 150°C, etc.
  • the end temperature of the second stage of heating is 150-180°C; for example, the end temperature of the second stage of heating can be 150°C, 155°C, 160°C, 165°C, 170°C, 175°C, 180°C, etc.;
  • the end temperature of the third stage of heating is 180°C to 200°C, for example, the end temperature of the third stage of heating can be 180°C, 185°C, 190°C, 195°C, 200°C, etc.
  • the heating rate of the first stage is 0.8°C/min ⁇ 1°C/min (for example, it can be 0.8°C/min, 0.9°C/min, 1.0°C/min, etc.), and the second stage The heating rate of heating is 2°C/min ⁇ 3°C/min (for example, it can be 2°C/min, 2.5°C/min, 3°C/min, etc.), and the holding time after the third stage of heating is 2h ⁇ 3h (For example, it could be 2h, 2.5h, 3h, etc.).
  • the foaming reaction is controlled so that the foaming ratio reaches 1.5-3.5 (for example, it can be 1.5, 1.7, 2.0, 2.3, 2.5, 3.0, 3.5, etc.).
  • the mixing order of the raw materials is staged, and the foaming agent and optional additives are added last, for example: the first stage: first mix one or more of cyanate ester, bismaleimide with curing agent, optional Hollow glass microsphere mixing; the second stage, on the basis of the first stage, add foaming agent and other optional additives to carry out the second stage mixing.
  • the foam material of the present invention when used to make the loudspeaker vibration plate, it is more suitable for foaming now, that is, the selected surface layer (can be at least one of aluminum foil, engineering plastics, carbon fiber, aramid fiber composite material) and Core layer material, the core layer adopts the foam material described above in the present invention, and then prepares: fix the lower surface layer, place the raw material of the core layer material on the lower surface layer, cover the upper surface layer, and then carry out hot pressing and bonding, hot pressing and pasting Combined with the "three-stage heating method" described above, the three layers of materials are firmly combined to obtain an acoustic vibration plate.
  • the selected surface layer can be at least one of aluminum foil, engineering plastics, carbon fiber, aramid fiber composite material
  • Core layer material the core layer adopts the foam material described above in the present invention, and then prepares: fix the lower surface layer, place the raw material of the core layer material on the lower surface layer, cover the upper surface layer, and then carry out hot pressing and bonding, hot pressing and past
  • a preferred vibrating plate provided by the present invention includes base material layers positioned on two surface layers, and a foam material layer positioned between the two base material layers; the foam material layer described above Foam material; the substrate layer is preferably at least one of aluminum foil, engineering plastics, carbon fiber, and aramid fiber composite materials; the thickness of the vibration plate is preferably 0.04-0.25mm.
  • each layer in the vibration plate can be adjusted flexibly.
  • engineering plastics can be PEN, PET, PEI, LCP, PI and other engineering plastics, with a thickness ⁇ 3 ⁇ m; carbon fiber composite materials can be unidirectional carbon fiber prepreg, carbon fiber woven cloth prepreg, chopped carbon fiber prepreg Carbon fiber materials such as impregnated materials and carbon fiber paper have a thickness of 20-400 ⁇ m; aramid fibers have a thickness of 20-400 ⁇ m; foil materials can be soft aluminum, duralumin, aluminum alloy, etc., and the thickness is between 7 ⁇ m and 40 ⁇ m.
  • the foam material of the present invention can also be made into a vibrating plate with only one substrate layer, that is, the substrate layer is arranged on one of the outer surfaces of the foam material layer.
  • the other surface of the foam material layer can be fixed on a releasable plate, and the releasable plate can be removed after the foaming is completed.
  • the foam of the present invention can be made into a vibrating plate without a substrate layer, ie, with only one foam layer.
  • both surfaces of the foam material layer are fixed on a releaseable sheet, and the release sheets on both sides can be removed after the foaming is completed.
  • Any vibration plate described above can be used to further form a loudspeaker assembly, which includes a sound diaphragm, and a vibration plate for connecting and supporting the sound diaphragm, and the vibration plate and the sound diaphragm can be separated. Bonded by film or glue.
  • the sounding diaphragm can be made of one or more of engineering plastics (such as PEEK, PAR, etc.), elastomeric materials (such as TPU, TPEE, silicone rubber, etc.), rubber films (such as acrylic glue, silicone glue, etc.) Composed of multiple materials, the thickness is between 20-500 ⁇ m.
  • the foam material also has excellent moisture resistance and low water absorption
  • the foam material also has higher rigidity and modulus, and high mechanical strength
  • the modulus, strength and other properties of the material can be further improved by adopting the three-stage heating method.
  • the foaming and curing process is as follows: first raise the temperature to 150°C with a heating rate of 0.8°C/min-1°C/min for foaming reaction; then raise the temperature to 180°C with a heating rate of 2°C/min-3°C/min; finally raise the temperature Keep warm at 200°C for 2h-3h.
  • the resulting expansion ratio was 1.5.
  • the structure of the vibrating plate obtained in this embodiment can be a special-shaped plate as shown in Figure 1 (shown as a convex hull structure in the figure), or a straight plate as shown in Figure 2, all including two upper and lower surfaces and a middle hair.
  • the cross-sectional view of the bubble layer is shown in FIG. 3 , and the surface layer is aluminum foil as an example, including aluminum foil 11 , foam layer 12 , and aluminum foil 11 .
  • the structure is aluminum foil/styrofoam resin/aluminum foil.
  • a vibrating plate is obtained, and the vibrating plate can also have the structures shown in FIGS. 1 to 3 .
  • the foaming and curing process is as follows: first raise the temperature to 150°C with a heating rate of 0.8°C/min-1°C/min for foaming reaction; then raise the temperature to 180°C with a heating rate of 2°C/min-3°C/min; finally raise the temperature Keep warm at 200°C for 2h-3h.
  • the resulting expansion ratio was 1.5.
  • the structure is a five-layer structure, namely aluminum foil/glue/PMI/glue/aluminum foil (glue is epoxy resin E51). Curing process (curing at 160°C for 2 hours), and then punching can produce an acoustic vibration plate.
  • the cross-sectional structure is shown in Figure 4, including aluminum foil 3, glue 4, PMI5, glue 4, and aluminum foil 3.
  • the foam material of the present invention has a higher modulus.
  • the modulus of Example 1 and Example 2 The volume density ratio E/ ⁇ has increased by 35.0% and 27.5% respectively, which has very obvious performance advantages.
  • the vibrating plate of the above-mentioned embodiment can be used for a sounding device, such as a common loudspeaker assembly, as shown in Figure 6 or 7, including a sounding diaphragm 2, and a vibrating plate 1 for connecting and supporting the sounding diaphragm 2;
  • the vibrating plate 1 and the sound-emitting diaphragm 2 can be bonded by adhesive film or glue.

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Abstract

本发明涉及一种泡沫材料及其制备方法、振动板和扬声器。本发明使用氰酸酯、双马来酰亚胺等为主体树脂，加入化学发泡剂，也可以加入一定量的中空玻璃微球，制备的发泡层仍然具有非常好的粘接性能，并且在发泡后材料具有低密度、高模量、低吸水率、和优良的耐热性能，可用于替代传统PMI发泡材料，制备的振动板具有更高的强度，更好的高频性能，优异的可靠性。

Description

一种泡沫材料及其制备方法、振动板和扬声器 技术领域
本发明涉及电声转换设备技术领域，特别涉及一种泡沫材料及其制备方法、振动板和扬声器。
背景技术
常规聚甲基丙烯酰亚胺(PMI)泡沫材料，具有较低的密度，被广泛用作芯层来制备声学振动板，但其极易吸水，在高温高湿条件下，大量水汽侵入，导致胶层与表层的粘接或胶层与芯层的粘接发生失效，导致微型扬声器可靠性测试失败。另外随着电子产品的更新迭代，对材料强度和耐湿热性能的要求越来越高，传统PMI发泡体也难以满足需求。
在相关技术中，提出一种振动板，其包括两层表层和中间芯层，中间芯层为泡沫层，其包括环氧树脂、空心球和发泡微胶囊，发泡微胶囊包括外壳以及收容在外壳内的挥发性液体发泡剂。对泡沫层进行加热时，发泡微胶囊内的挥发性物质挥发出气体并通过外壳排出，以使发泡层进入发泡状态。但是，上述方案中的微胶囊采用的挥发性气体为低沸点烷烃类、含氯的烷烃或烯烃类等，均为易燃、易爆、或含氯等有毒性气体，对环境、以及操作人员的危害较大。
发明内容
本发明的主要目的在于提供一种泡沫材料，该材料具有粘结性、多孔轻质、高强度和低吸水率等特性，既可以用作发声器件中的粘结剂，也可以用作泡沫材料。
本发明的另一目的在于上述泡沫材料的制备方法，该方法可同时完成发泡和粘结固化过程，简化了材料的制备流程。
本发明的又一目的在于提出一种振动板，所述振动板包括本发明上述的泡沫材料。
本发明的再一目的在于提出一种扬声器，所述扬声器包括本发明上述的振动板。
为了实现以上目的，本发明提供了以下技术方案：
本发明第一方面实施例的泡沫材料，其主要由原料经过发泡、固化而成，所 述原料包括：
主体树脂、化学发泡剂和固化剂；
其中，所述主体树脂包括氰酸酯类树脂和双马来酰亚胺类树脂中的至少一种，所述化学发泡剂受热发生化学反应生成氮气和/或二氧化碳以使所述原料进入发泡状态。
根据本发明的一些实施例，所述化学发泡剂包括N-亚硝化合物、偶氮化合物、酰肼类化合物、碳酸盐类化合物中的至少一种。
根据本发明的一些实施例，所述化学发泡剂包括偶氮二异丁腈。
根据本发明的一些实施例，所述化学发泡剂的用量为所述主体树脂和所述固化剂总重量的5％～40％。
根据本发明的一些实施例，所述化学发泡剂的用量为所述主体树脂和所述固化剂总重量的12％～20％。
根据本发明的一些实施例，所述固化剂包括环氧树脂；和/或，所述固化剂的用量为所述主体树脂重量的10％～35％。
根据本发明的一些实施例，所述泡沫材料的原料还包括：催化剂、促进剂和中空玻璃微球中的至少一种。
根据本发明的一些实施例，所述催化剂包括乙酰丙酮钴。
根据本发明的一些实施例，所述催化剂的用量为所述主体树脂重量的1％～10％。
根据本发明的一些实施例，所述促进剂包括壬基酚。
根据本发明的一些实施例，所述促进剂用量为所述主体树脂重量的1％～5％。
根据本发明的一些实施例，所述中空玻璃微球的粒径为110μm～150μm，密度为0.08g/cm 3-1.5g/cm 3，添加量为所述主体树脂和所述固化剂总重量的15％～40％。
根据本发明的一些实施例，所述泡沫材料密度在0.35g/cm 3～0.8g/cm 3，模量在8GPa～40GPa之间。
本发明第二方面实施例的振动板，其包括泡沫材料层，所述泡沫材料层采用本发明第一方面所述的泡沫材料。
根据本发明的一些实施例，其还包括：至少一层基材层，所述基材层设在所 述泡沫材料层的外表面。
根据本发明的一些实施例，所述基材层采用铝箔、工程塑料、碳纤维、芳纶纤维复合材料中的至少一种。
根据本发明的一些实施例，所述振动板的厚度为0.04mm～0.25mm。
本发明第三方面实施例的扬声器，其包括发声振膜，以及用于连接和支撑所述发声振膜的振动板，所述振动板为本发明第二方面所述的振动板；所述振动板和所述发声振膜之间可通过胶膜或胶水粘结。
本发明第一方面实施例的泡沫材料的制备方法，包括：
将所有原料混合后，进行第一阶段升温，进行发泡反应；
之后接着进行第二阶段升温，进行固化反应；
然后再继续进行第三阶段升温，进行保温稳定；
最后冷却。
根据本发明的一些实施例，所述第一阶段升温的终点温度为140℃～150℃，所述第二阶段升温的终点温度为150℃～180℃，所述第三阶段升温的终点温度为180℃～200℃。
根据本发明的一些实施例，所述第一阶段升温的升温速率为0.8℃/min～1℃/min，所述第二阶段升温的升温速率为2℃/min～3℃/min，所述第三阶段升温后的保温时间为2h～3h。
根据本发明的一些实施例，控制所述发泡反应使发泡比达到1.5～3.5。
与现有技术相比，本发明选用氰酸酯类树脂、双马来酰亚胺类树脂等作为主体树脂，再加入化学发泡剂，化学发泡剂发生化学反应生成氮气和/或二氧化碳等环保性气体，由此使得主体树脂进入发泡状态而形成多孔结构，不仅保留了上述树脂良好的粘接性能，还保留了氰酸酯和双马来酰亚胺类树脂的低吸水率和优良耐热性等特性，而且材料发泡后具有低密度和高模量、高强度等特点。当上述发泡材料应用于振动板时，可以显著提高振动板的结构强度和高频性能。
附图说明
通过阅读下文优选实施方式的详细描述，各种其他的优点和益处对于本领域普通技术人员将变得清楚明了。附图仅用于示出优选实施方式的目的，而并 不认为是对本实用新型的限制。而且在整个附图中，用相同的参考符号表示相同的部件。在附图中：
图1为本发明提供一种振动板的结构示意图；
图2为本发明提供另一种振动板的结构示意图；
图3为实施例制作的振动板的剖面图；
图4为对比例制作的振动板的剖面图；
图5为振动板的扬声器FR曲线图；
图6为本发明提供的一种扬声器组件的结构图；
图7为本发明提供的另一种扬声器组件的结构图。
具体实施方式
下面将结合实施例对本发明的实施方案进行详细描述，但是本领域技术人员将会理解，下列实施例仅用于说明本发明，而不应视为限制本发明的范围。实施例中未注明具体条件者，按照常规条件或制造商建议的条件进行。所用原药、试剂或仪器未注明生产厂商者，均为可以通过市售购买获得的常规产品或者可以根据现有技术制备得到。
本发明提供的泡沫材料主要由原料经过发泡、固化而成，所述原料包括：
主体树脂、化学发泡剂和固化剂；
其中，所述主体树脂包括氰酸酯类树脂和双马来酰亚胺类树脂中的至少一种；所述化学发泡剂受热发生化学反应生成氮气和/或二氧化碳以使所述原料进入发泡状态。
该材料选用氰酸酯类树脂、双马来酰亚胺类树脂等主体树脂作为主体树脂，再加入化学发泡剂，从而产生多孔结构，不仅保留了这类树脂良好的粘接性能，还保留了氰酸酯类树脂和双马来酰亚胺类树脂低吸水率和优良耐热性等特性，而且材料发泡后具有低密度和高模量、高强度。
经测试，本发明得到的泡沫材料密度在0.35g/cm 3～0.8g/cm 3，模量在8GPa～40GPa之间。
需要进行说明的是，上述主体树脂可以是单独使用氰酸酯类树脂或双马来酰亚胺类树脂，或者二者的组合，或者两种以上的氰酸酯类树脂组合，或者两种以 上的双马来酰亚胺类树脂组合等，本发明对此不作具体限制。
本发明选用的发泡剂为化学发泡剂。添加化学发泡剂可以在一定温度下产生氮气和/或二氧化碳，气体膨胀产生泡孔结构，同时主体树脂发生固化反应导致结构硬化，最终使泡孔形态得到固定，因发泡剂分解产生的气体通常为氮气或二氧化碳等无毒的环保性气体，具有很好的环保性。优选的化学发泡剂包括N-亚硝化合物、偶氮化合物、酰肼类化合物、碳酸盐类化合物中的至少一种。其中，N-亚硝化合物包括但不限于N,N-二亚硝基五次甲基四胺、N,N-二甲基-N,N-二亚对苯二甲酰胺等，偶氮化合物包括但不限于偶氮二甲酰胺、偶氮二异丁腈、偶氮二甲酸异丙酯、偶氮二甲酸二乙酯、二偶氮胺基苯、偶氮二甲酸呗等；酰肼类化合物包括但不限于4,4-二磺酰肼二苯醚、对苯磺酰肼、3,3-二磺酰肼二苯砜、4,4-二苯二磺酰肼、1,3-苯二磺酰肼等，碳酸盐类化合物包括但不限于碳酸氯钠等。发泡剂更优选包括N-亚硝化合物和偶氮化合物中的至少一种，进一步地，化学发泡剂可以为偶氮二异丁腈。
对于发泡剂的用量可根据主体树脂的类型及泡沫材料性能等各方面要求调整。当泡沫材料用于制作扬声器的振动板时，所述化学发泡剂的用量优选为所述主体树脂和所述固化剂总重量的5％～40％，例如可以是5％、10％、15％、20％、25％、30％、35％、40％等，其中更优选12％～20％，例如可以是12％、13％、14％、15％、16％、17％、18％、19％、20％，更优选15％～20％。
对于固化剂，适用于主体树脂的固化剂类型有很多，包括典型的脂肪族胺类(如乙烯基三胺DETA、乙二胺EDA、三乙烯四胺、二丙烯三胺DPTA等)、芳香胺类(如间苯二胺、二氨基二苯基甲烷、联苯胺等)、酰胺基胺类、环氧树脂等等。考虑到泡沫材料用于发声振动板时，需要兼顾湿热性能、刚性和模量等性能，优选选用环氧树脂作为固化剂，环氧树脂本身既具有粘接性，又可以与氰酸酯类树脂和双马来酰亚胺类树脂等发生交联反应，起到很好地固化作用，即环氧树脂与氰酸酯类树脂/双马来酰亚胺类树脂组合可以达到协同增效的作用。
可选地，环氧树脂可以包括典型的环氧树脂E51、环氧树脂E44、环氧树脂E128等，优选地，环氧树脂可以为环氧树脂E51。
固化剂的用量优选为所述主体树脂重量的10％～35％，例如10％、15％、17％、20％、22％、25％、27％、29％、30％、33％、35％等，其中优选25％～30％，具体 可以是25％、26％、27％、28％、29％、30％。
在本发明的泡沫材料中还可以引入催化剂、促进剂和中空玻璃微球中的至少一种。也就是说，泡沫材料中可以加入催化剂、促进剂和中空玻璃微球中的任意一种，泡沫材料中又可以加入催化剂、促进剂和中空玻璃微球中的任意两种，泡沫材料中还可以同时加入催化剂、促进剂和中空玻璃微球，可以根据实际的使用需求选择设置，本发明对此不做限制。其中，中空玻璃微球具有降低密度、保持材料强度等作用，催化剂和促进剂可以促进树脂固化反应。
为了提高泡沫材料的刚性和模量等性能，优选采用乙酰丙酮钴作为催化剂，促进树脂固化，其用量优选为所述主体树脂重量的1％～10％，例如1％、2％、3％、4％、5％、6％、7％、8％、9％、10％等。
优选以壬基酚作为促进剂，其与固化剂一起可以更好的促进树脂固化，也有利于改善泡沫材料的综合性能，其用量优选为所述主体树脂重量的3％～5％，例如3％、3.5％、4％、4.5％、5％等。
中空玻璃微球优选粒径为110μm～150μm，密度为0.08g/cm3-1.5g/cm3，添加量为所述主体树脂和所述固化剂的总重量的15％～40％，例如15％、20％、22％、25％、27％、29％、30％、33％、35％、40％等。
在发明的一个具体示例中，中空玻璃微球的粒径为130μm，填充密度为1g/cm 3，中空玻璃微球的添加量为所述主体树脂和所述固化剂的总重量的19％或28％。
在一些优选的实施方式中，泡沫材料主要由以下原料经过发泡、固化而成：
按重量份计，主体树脂100份、环氧树脂E51 20～30份、偶氮二异丁腈10～20份、中空玻璃微球25～35份、乙酰丙酮钴1～2份、壬基酚3～5份；
其中，所述主体树脂包括氰酸酯类树脂和双马来酰亚胺类树脂中的至少一种，优选包括双酚A型氰酸酯树脂、双酚E型氰酸酯树脂中的至少一种。
例如下文所示的多种实施例方式。
泡沫材料主要由以下原料经过发泡、固化而成：
按重量份计，主体树脂100份、环氧树脂E51 20份、偶氮二异丁腈20份、中空玻璃微球25份、乙酰丙酮钴1～2份、壬基酚5份。
或者，按重量份计，主体树脂100份、环氧树脂E51 30份、偶氮二异丁腈 10份、中空玻璃微球35份、乙酰丙酮钴1份、壬基酚5份。
或者，按重量份计，主体树脂100份、环氧树脂E51 20份、偶氮二异丁腈10份、中空玻璃微球25份、乙酰丙酮钴1份、壬基酚3份。
或者，按重量份计，主体树脂100份、环氧树脂E51 30份、偶氮二异丁腈20份、中空玻璃微球35份、乙酰丙酮钴2份、壬基酚5份。
或者，按重量份计，主体树脂100份、环氧树脂E51 25份、偶氮二异丁腈15份、中空玻璃微球30份、乙酰丙酮钴1.5份、壬基酚3.5份。
或者，按重量份计，主体树脂100份、环氧树脂E51 25份、偶氮二异丁腈15份、中空玻璃微球30份、乙酰丙酮钴1.2份、壬基酚4份。
或者，按重量份计，主体树脂100份、环氧树脂E51 25份、偶氮二异丁腈15份、中空玻璃微球30份、乙酰丙酮钴1.7份、壬基酚4.5份。
另外，为了获得不同性能的泡沫材料，还可以通过控制制备工艺条件或原料用量调整发泡比。本发明所指的发泡比是：发泡后材料厚度与发泡前材料厚度的比值。
本发明还提供了以上泡沫材料的制备方法，该方法通过加热方式使发泡和固化二者协同进行，最终所得复合振动板具有较好的可靠性(耐湿热性能)、刚性和模量，具有较好的声学性能。
具体地，包括：
将所有原料混合后，进行第一阶段升温，进行发泡反应；
之后接着进行第二阶段升温，进行固化反应；
然后再继续进行第三阶段升温，进行保温稳定；
最后冷却。
通过三个阶段的升温可以保证材料充分发泡和固化，具有更可靠的耐湿性、刚性和模量。其中，第一阶段升温主要是完成发泡过程；第二阶段升温阶段主要完成固化反应，使第一阶段发泡形成的结构得到固定，并同时伴随少量的发泡反应；第三阶段升温阶段使材料完全固化，以确保第二阶段得到的材料在耐热、力学性能上最大化。
其中，优选地，所述第一阶段升温的终点温度为140℃～150℃；例如，第一阶段升温的终点温度可以为140℃、143℃、145℃、150℃等。所述第二阶段升 温的终点温度为150～180℃；例如，第二阶段升温的终点温度可以为150℃、155℃、160℃、165℃、170℃、175℃、180℃等；所述第三阶段升温的终点温度为180℃～200℃，例如，第三阶段升温的终点温度可以为180℃、185℃、190℃195℃、200℃等。
更优选地，所述第一阶段升温的升温速率为0.8℃/min～1℃/min(例如，可以是0.8℃/min、0.9℃/min、1.0℃/min等)，所述第二阶段升温的升温速率为2℃/min～3℃/min(例如，可以是2℃/min、2.5℃/min、3℃/min等)，所述第三阶段升温后的保温时间为2h～3h(例如，可以是2h、2.5h、3h等)。
优选的，控制所述发泡反应使发泡比达到1.5～3.5(例如，可以是1.5、1.7、2.0、2.3、2.5、3.0、3.5等)。
另外，原料的混合顺序分阶段的，发泡剂和任选助剂最后加入，例如：第一阶段：先将氰酸酯、双马来酰亚胺一种或多种与固化剂、任选中空玻璃微球混合；第二阶段，在第一阶段基础上再加入发泡剂和其他任选助剂等进行第二阶段混。
另外，本发明的泡沫材料用于制作扬声器振动板时，更适于现用现发泡，即选定表层(可以是铝箔、工程塑料、碳纤维、芳纶纤维复合材料中的至少一种)和芯层材料，芯层采用本发明上文所述的泡沫材料，然后制备：固定下表层，将芯层材料的原料置于下表层上，覆盖上表层，然后进行热压贴合，热压贴合采用上文所述的“三阶段升温法”，之后三层材料被牢固结合在一起，得到声学振动板。
综上，本发明提供的一种优选振动板，其包括位于两个表层的基材层，以及位于两个所述基材层之间的泡沫材料层；所述泡沫材料层上文所述的泡沫材料；所述基材层优选采用铝箔、工程塑料、碳纤维、芳纶纤维复合材料中的至少一种；所述振动板的厚度优选为0.04～0.25mm。
上述振动板中各层的厚度可灵活调整。
对于基材层，工程塑料可以为PEN、PET、PEI、LCP、PI等工程塑料，厚度≥3μm；碳纤维复合材料可以为单向碳纤维预浸料，碳纤维编织布预浸料、短切碳纤维类预浸料、碳纤维纸等碳纤维材料，厚度20-400μm；芳纶纤维厚度20-400μm；箔类材料可以为软铝、硬铝、铝合金等，厚度在7μm-40μm之间。
当然，本发明的泡沫材料还可以制成只有一层基材层的振动板，即所述基材 层设在所述泡沫材料层的其中一个外表面。在发泡时，泡沫材料层的另一表面可以固定在一个可离型的板材上，待发泡结束后移除该离型板材即可。
或者，本发明的泡沫材料制成没有基材层的振动板，即只有一层泡沫材料层。在发泡时，泡沫材料层的两个表面都固定在一个可离型的板材上，待发泡结束后移除两面的离型板材即可。
利用上文所述的任意振动板还可进一步形成扬声器组件，其包括发声振膜，以及用于连接和支撑所述发声振膜的振动板，所述振动板和所述发声振膜之间可通过胶膜或胶水粘结。发声振膜可以由工程塑料(如PEEK，PAR等)、弹性体材料(如TPU、TPEE、硅橡胶等)、胶膜(如丙烯酸酯类胶、有机硅类胶等)等中的一种或多种材料复合组成，厚度在20-500μm之间。
综上，与现有技术相比，本发明达到了以下技术效果：
(1)提供一种能够兼具轻质多孔结构和粘结性能的泡沫材料；
(2)泡沫材料还具有优异的耐湿性，吸水率低；
(3)泡沫材料还具有更高的刚性和模量，机械强度高；
(4)减少了振动板的层数，从而简化了制备工艺流程；
(5)采用三阶段升温方式可以进一步改善材料的模量、强度等性能。
下文结合实施例具体展开说明。
实施例1
a)按重量计，双酚A型氰酸酯树脂(2,2'-二(4-氰氧苯基)丙烷)100份，环氧树脂E51 30份，空心玻璃微球25份(粒径为110μm，密度为1.1g/cm 3)，在一定温度下混合均匀，然后再与催化剂乙酰丙酮钴1.5份、壬基酚4.5份、AIBN20份混合均匀，得到发泡胶树脂的原料。
b)将上述发泡胶树脂制作成胶膜，通过热压贴合将铝箔与上述原料粘接在一起，结构为铝箔/发泡胶树脂/铝箔，经过发泡和固化工艺，再通过冲裁可制得声学振动板。
发泡和固化过程为：先升温至150℃，升温速率0.8℃/min-1℃/min，进行发泡反应；然后升温至180℃，升温速率2℃/min-3℃/min；最后升温至200℃保温2h-3h。最后得到的发泡比为1.5。
根据模具不同，该实施例得到的振动板的结构可以是如图1所示的异形板(图中示意为凸包结构)，或者图2所示的直板，都包括上下两个表层和中间发泡层，其剖面图均如图3，以表层为铝箔为例，包括铝箔11、发泡层12、铝箔11。
实施例2
a)按重量计，双酚A型氰酸酯树脂(2,2'-二(4-氰氧苯基)丙烷)60份，双酚E型氰酸酯树脂(1,1-双(4-氰氧苯基)乙烷)40份，环氧树脂E51 25份，空心玻璃微球(同实施例1)35份混合均匀，然后再与乙酰丙酮钴1.2份、壬基酚3.5份、AIBN15份经搅拌混合均匀，得到发泡胶树脂的原料。
b)将上述发泡胶树脂制作成胶膜，通过热压贴合将铝箔与上述原料粘接在一起，结构为铝箔/发泡胶树脂/铝箔，经过发泡和固化工艺，再通过冲裁可制得振动板，振动板同样可以为图1至3所示的结构。
发泡和固化过程为：先升温至150℃，升温速率0.8℃/min-1℃/min，进行发泡反应；然后升温至180℃，升温速率2℃/min-3℃/min；最后升温至200℃保温2h-3h。最后得到的发泡比为1.5。
对比例1
使用常规环氧胶膜和PMI，通过热压贴合将铝箔与PMI泡沫粘接在一起，结构为五层结构，即铝箔/胶/PMI/胶/铝箔(胶为环氧树脂E51)，经过固化工艺(160℃固化2h)，再通过冲裁可制得声学振动板，其剖面结构如图4，包括铝箔3、胶4、PMI5、胶4、铝箔3。
测试上述三种振动板的性能，结果如表1所示(E/ρ为模量密度比；三个振动板所用的铝箔的厚度相同，均为10μm；吸湿率：吸湿后样品重量与吸湿前样品重量之比)。
表1
Figure PCTCN2022095614-appb-000001
Figure PCTCN2022095614-appb-000002
通过性能对比数据可以看出，在铝箔厚度以及振动板总厚度一致的情况下，采用本发明的发泡材料具有更高的模量，相对于对比例1，实施例1和实施例2的模量密度比E/ρ分别提高了35.0％、27.5％，具有非常明显的性能优势。
同时还测试了相同结构尺寸下(指振动板的长度、宽度、R角和厚度)，采用实施例1与对比例1制备振动板的扬声器FR曲线如图5所示，图中曲线表明：使用常规PMI时，fh为4000Hz，fr在5000Hz-170000Hz之间波动较大，采用本发明的发泡材料制作振动板，fh更高达到4500Hz，高频扩展性更好，fr曲线在5000Hz-170000Hz部分也更平滑，具有更好的高频性能。
上述实施例的振动板可以用于发声装置，例如常见的扬声器组件，如图6或7所示，包括发声振膜2，以及用于连接和支撑所述发声振膜2的振动板1；所述振动板1和所述发声振膜2之间可通过胶膜或胶水粘结。
以上所述，仅为本发明较佳的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，可轻易想到的变化或替换，都应涵盖在本发明的保护范围之内。因此，本发明的保护范围应以所述权利要求的保护范围为准。

Claims (17)

  1. 一种泡沫材料，其特征在于，主要由原料经过发泡、固化而成，所述原料包括：
    主体树脂、化学发泡剂和固化剂；
    其中，所述主体树脂包括氰酸酯类树脂和双马来酰亚胺类树脂中的至少一种，所述化学发泡剂受热发生化学反应生成氮气和/或二氧化碳以使所述原料进入发泡状态。
  2. 根据权利要求1所述的泡沫材料，其特征在于，所述化学发泡剂包括N-亚硝化合物、偶氮化合物、酰肼类化合物、碳酸盐类化合物中的至少一种。
  3. 根据权利要求2所述的泡沫材料，其特征在于，所述化学发泡剂包括偶氮二异丁腈；
    和/或，所述化学发泡剂为所述主体树脂和所述固化剂总重量的5％～40％。
  4. 根据权利要求3所述的泡沫材料，其特征在于，所述化学发泡剂的用量为所述主体树脂和所述固化剂总重量的12％～20％。
  5. 根据权利要求1所述的泡沫材料，其特征在于，所述固化剂包括环氧树脂；
    和/或，所述固化剂的用量为所述主体树脂重量的10％～35％。
  6. 根据权利要求1所述的泡沫材料，其特征在于，所述泡沫材料的原料还包括：催化剂、促进剂和中空玻璃微球中的至少一种。
  7. 根据权利要求6所述的泡沫材料，其特征在于，
    所述催化剂包括乙酰丙酮钴；
    和/或，所述催化剂的用量为所述主体树脂重量的1％～10％；
    和/或，所述促进剂包括壬基酚；
    和/或，所述促进剂用量为所述主体树脂重量的1％～5％；
    和/或，所述中空玻璃微球的粒径为110μm～150μm，密度为0.08g/cm 3-1.5g/cm 3，添加量为所述主体树脂和所述固化剂的总重量的15％～40％。
  8. 根据权利要求1-7中任一项所述的泡沫材料，其特征在于，所述泡沫材料密度在0.35g/cm 3～0.8g/cm 3，模量在8GPa～40GPa之间。
  9. 一种振动板，其特征在于，包括：泡沫材料层，所述泡沫材料层采用权利要求1-8任一项所述的泡沫材料。
  10. 根据权利要求9所述的振动板，其特征在于，还包括：至少一层基材层，所述基材层设在所述泡沫材料层的外表面。
  11. 根据权利要求10所述的振动板，其特征在于，所述基材层采用铝箔、工程塑料、碳纤维、芳纶纤维复合材料中的至少一种。
  12. 根据权利要求9所述的振动板，其特征在于，所述振动板的厚度为0.04～0.25mm。
  13. 一种扬声器，其特征在于，其包括发声振膜，以及用于连接和支撑所述发声振膜的振动板，所述振动板为权利要求9-12任一项所述的振动板；所述振动板和所述发声振膜之间可通过胶膜或胶水粘结。
  14. 权利要求1-8任一项所述的泡沫材料的制备方法，其特征在于，包括：
    将所有原料混合后，进行第一阶段升温，进行发泡反应；
    之后接着进行第二阶段升温，进行固化反应；
    然后再继续进行第三阶段升温，进行保温稳定；
    最后冷却。
  15. 根据权利要求14所述的制备方法，其特征在于，所述第一阶段升温的终点温度为140℃～150℃，所述第二阶段升温的终点温度为150℃～180℃，所述第三阶段升温的终点温度为180℃～200℃。
  16. 根据权利要求14或15所述的制备方法，其特征在于，所述第一阶段升温的升温速率为0.8℃/min～1℃/min，所述第二阶段升温的升温速率为2℃/min～3℃/min，所述第三阶段升温后的保温时间为2h～3h。
  17. 根据权利要求14或15所述的制备方法，其特征在于，控制所述发泡反应使发泡比达到1.5～3.5。
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