WO2019210645A1 - 硅油改性聚氨酯弹性体振膜以及扬声器单体 - Google Patents

硅油改性聚氨酯弹性体振膜以及扬声器单体 Download PDF

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Publication number
WO2019210645A1
WO2019210645A1 PCT/CN2018/110121 CN2018110121W WO2019210645A1 WO 2019210645 A1 WO2019210645 A1 WO 2019210645A1 CN 2018110121 W CN2018110121 W CN 2018110121W WO 2019210645 A1 WO2019210645 A1 WO 2019210645A1
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silicone oil
diaphragm
polyurethane elastomer
functional group
modified polyurethane
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English (en)
French (fr)
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王婷
吴增勋
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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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/61—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/6505—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6511—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38 compounds of group C08G18/3203
    • 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
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes

Definitions

  • the present invention relates to the field of electroacoustic conversion technology, and more particularly to a silicone oil modified polyurethane elastomer diaphragm and a speaker unit.
  • Thermoplastic polyurethane elastomers have good resilience, excellent chemical stability, high temperature resistance and dimensional stability. As a diaphragm, TPU can improve the sound quality of the low frequency band and high frequency band of the speaker to obtain excellent listening effects.
  • the existing TPU-containing diaphragm is more hydrophilic.
  • the phenomenon of the moisture content of the diaphragm containing TPU increases with the increase of the environmental humidity, that is, there is obvious moisture absorption. This phenomenon affects the modulus and quality of the diaphragm, causing the F o of the speaker to be unstable.
  • a silicone oil modified polyurethane elastomer diaphragm comprises: reacting an isocyanate, a silicone oil with an active hydrogen functional group, and a chain extender into a solvent, wherein an active hydrogen functional group of the silicone oil reacts with an isocyanate group of the isocyanate to form a polyurethane prepolymer, The chain extender reacts with a functional group on the polyurethane prepolymer to form the diaphragm after curing.
  • the silicone oil with an active hydrogen functional group comprises at least one of an alkylhydroxysilicone oil, an aminosilicone oil, and a hydroxysilicone oil.
  • the silicone oil with an active hydrogen functional group is added in an amount of more than 0% and less than or equal to 20% by mass of the added amount of the raw material.
  • the solvent is at least one of acetone, toluene and tetrahydrofuran.
  • the chain extender is a polyol.
  • the chain extender has a chain extension coefficient of 0.5 to 1.0.
  • the isocyanate comprises at least one of TDI, MDI, and NDI.
  • reaction temperature is from 50 ° C to 100 ° C.
  • a diaphragm includes at least one of an engineering plastic film layer and a film layer, and a silicone oil-modified polyurethane elastomer film layer; wherein: the isocyanate, the silicone oil with an active hydrogen functional group, and a chain extender are added to the solvent.
  • a loudspeaker unit is provided.
  • the monomer includes the diaphragm provided by the present invention.
  • the silicone oil molecule having an active hydrogen functional group contains a linear siloxane group.
  • the linear siloxane group has a large intermolecular distance.
  • the interaction between the siloxane chains is small, the molar volume is large, the surface tension is small, and the hydrophobicity is enhanced, so that the hydrophobicity of the diaphragm can be improved, thereby effectively improving the variation of the diaphragm with the season and the instability of F o .
  • the diaphragm has good weather resistance.
  • silicone oil with active hydrogen functional group is a common release agent, which contains a linear siloxane group to modify the ordinary thermoplastic polyurethane elastomer, so that even if the molding temperature of the diaphragm is high, due to the silicone oil composition The role of the sticking head is not easy to occur. This makes the forming structure of the diaphragm more stable.
  • the silicone oil having an active hydrogen functional group contains a Si-O-Si bond. This bond has a large bond angle and is easily rotated between the Si atom and the O atom, so that the segment is very soft. This makes the silicone oil modified polyurethane elastomer diaphragm have good flexibility.
  • the bond energy of the Si-O bond is large, which makes the silicone oil-modified polyurethane elastomer diaphragm less susceptible to oxidation and ultraviolet light resistance than the conventional thermoplastic polyurethane elastomer (TPU) diaphragm.
  • silicone oil-modified polyurethane elastomer diaphragm has high thermal stability.
  • FIG. 1 is a cross-sectional view of a diaphragm in accordance with an embodiment of the present invention.
  • FIG. 2 is a cross-sectional view of a double film diaphragm in accordance with an embodiment of the present invention.
  • Figure 3 is a cross-sectional view of a three-membrane diaphragm in accordance with one embodiment of the present invention.
  • FIG. 4 is a cross-sectional view of a five-membrane diaphragm in accordance with an embodiment of the present invention.
  • a silicone oil-modified polyurethane elastomer diaphragm 1 comprises: reacting an isocyanate, a silicone oil with an active hydrogen functional group, and a chain extender into a solvent, wherein in the solvent, an active hydrogen functional group of the silicone oil reacts with an isocyanate group of the isocyanate to form a polyurethane prepolymerization. body.
  • the chain extender reacts with a functional group on the polyurethane prepolymer to expand the molecular chain and increase the molecular weight. After curing, a silicone oil-modified polyurethane elastomer diaphragm 1 is finally obtained.
  • isocyanate is a generic term for various esters of isocyanic acid.
  • Active hydrogen refers to hydrogen contained in a functional group of an organic molecule.
  • the functional group having an active hydrogen includes a hydroxyl group, an amino group, an alkyl group and the like.
  • the silicone oil with an active hydrogen functional group includes at least one of an alkylhydroxysilicone oil, an aminosilicone oil, and a hydroxysilicone oil.
  • the type of the silicone oil is not limited to the above, and those skilled in the art can select according to actual needs.
  • the chain extender refers to a substance which can react with a functional group on a linear polymer chain to expand the molecular chain and increase the molecular weight.
  • the chain extender includes an ether chain extender, an alcohol chain extender, and the like.
  • a polyol or the like for example, the polyol includes butylene glycol, polyether diol, polyester diol, and the like.
  • the above chain extender has excellent performance.
  • the chain extender is not limited to the above, and those skilled in the art can select according to actual needs.
  • the chain extender has a chain extension coefficient of from 0.5 to 1.0.
  • the larger the chain extension coefficient the larger the molecular weight of the formed polymer; conversely, the smaller the chain extension coefficient, the smaller the molecular weight of the formed polymer.
  • the range of the chain extension coefficient is such that the elasticity of the formed diaphragm is good.
  • the reaction temperature of the above reaction is from 50 ° C to 100 ° C. At this temperature, the above reaction is more sufficient, and the curing speed is moderate, which is advantageous for the formation of the diaphragm.
  • the molding method of the diaphragm can be cast molding, injection molding, or the like.
  • the diaphragm is a folded ring diaphragm or a flat diaphragm. Those skilled in the art can make settings according to actual needs.
  • the silicone oil molecule with an active hydrogen functional group contains a linear siloxane group.
  • the linear siloxane group has a large intermolecular distance. The interaction between the siloxane chains is small, the molar volume is large, the surface tension is small, and the hydrophobicity is enhanced, so that the hydrophobicity of the diaphragm can be improved, thereby effectively improving the variation of the diaphragm with the season and the instability of F o .
  • the diaphragm has good weather resistance.
  • the silicone oil having an active hydrogen functional group is a common mold release agent, and the linear siloxane group contained therein is modified to a general thermoplastic polyurethane elastomer, so that the molding temperature of the diaphragm is high. Due to the action of the silicone oil component, the phenomenon of sticking the head is not easy to occur. This makes the forming structure of the diaphragm more stable.
  • the silicone oil having an active hydrogen functional group contains a Si-O-Si bond. This bond has a large bond angle and is easily rotated between the Si atom and the O atom, so that the segment is very soft. This allows the silicone oil-modified polyurethane elastomer diaphragm 1 to have good flexibility.
  • the bond energy of the Si-O bond is large, which makes the silicone oil-modified polyurethane elastomer diaphragm 1 less susceptible to oxidation than the ordinary thermoplastic polyurethane elastomer (TPU) diaphragm, and is resistant to ultraviolet light.
  • silicone oil-modified polyurethane elastomer diaphragm 1 has high thermal stability.
  • the silicone oil with an active hydrogen functional group is added in an amount greater than 0% and less than or equal to 20% by mass of the raw material added.
  • the greater the amount of silicone oil added the greater the effect on the elasticity of the diaphragm. This mass fraction makes the membrane hydrophobic and the elasticity of the diaphragm is good.
  • the solvent is at least one of acetone, toluene, and tetrahydrofuran.
  • the solubility of the isocyanate, the silicone oil having an active hydrogen functional group, and the chain extender is good, the reaction is more sufficient, and the reliability of the formed diaphragm is good.
  • the isocyanate includes at least one of TDI (toluene diisocyanate), MDI (diphenylmethane diisocyanate), and NDI (naphthyl diisocyanate).
  • TDI toluene diisocyanate
  • MDI diphenylmethane diisocyanate
  • NDI naphthyl diisocyanate
  • a diaphragm is provided.
  • the diaphragm is a composite diaphragm comprising at least one of an engineering plastic film layer 2 and a film layer 3 and a silicone oil-modified polyurethane elastomer film layer 1.
  • the method comprises the steps of: adding an isocyanate, a silicone oil with an active hydrogen functional group, and a chain extender to a solvent, wherein an active hydrogen functional group of the silicone oil reacts with an isocyanate group of the isocyanate to form a polyurethane prepolymer.
  • the chain extender reacts with a functional group on the polyurethane prepolymer to form a silicone oil-modified polyurethane elastomer film layer 1 after curing.
  • the diaphragm is less prone to sticking to the die.
  • the material of the isocyanate, the silicone oil with an active hydrogen functional group, and the chain extender may be, but is not limited to, the material in the above diaphragm.
  • the engineering plastic film layer 2 has the characteristics of high strength and can significantly increase the modulus of the diaphragm.
  • the engineering plastic film layer 2 is compounded with the silicone oil-modified polyurethane elastomer, the two are bonded together using an adhesive.
  • materials for making the engineering plastic film layer 2 include polyimide (PI), polyethylene terephthalate (PET), polyphenylene sulfide (PPS), polyethylene naphthalate.
  • PI polyimide
  • PET polyethylene terephthalate
  • PPS polyphenylene sulfide
  • PEN Alcohol esters
  • PET polyethylene terephthalate
  • PEEK polyetheretherketone
  • POM polyoxymethylene
  • PPO polyphenylene ether
  • PBT polybutylene terephthalate
  • the film layer 3 has a viscosity, so that the film layer 3 can form a good bonding force with the silicone oil-modified polyurethane elastomer film layer 1.
  • the film layer 3 has a damping effect and can absorb the energy of the diaphragm when vibrating to reduce the noise of the speaker.
  • the adhesive film layer 3 is an acrylic film, a polyurethane film or a silicone film.
  • the above film has good adhesion and damping properties.
  • FIG. 2 is a cross-sectional view of a double film diaphragm in accordance with an embodiment of the present invention.
  • Figure 3 is a cross-sectional view of a three-membrane diaphragm in accordance with one embodiment of the present invention.
  • 4 is a cross-sectional view of a five-membrane diaphragm in accordance with an embodiment of the present invention.
  • the double film diaphragm includes an engineering plastic film layer 2 and a silicone oil modified polyurethane elastomer film layer 1.
  • the two film layers 1, 2 are bonded together by an adhesive.
  • the silicone oil-modified polyurethane elastomer film layer 1 has good elasticity.
  • the engineering plastic film layer 2 has good rigidity. The two are combined to give the diaphragm the right elasticity and modulus.
  • the three-layer diaphragm includes a film layer 3 located at the center and a silicone oil-modified polyurethane elastomer film layer 1 attached to the upper and lower sides of the film layer 3.
  • the film layer 3 has a viscosity, which makes it easy to adhere the film layer 3 to the silicone oil-modified polyurethane elastomer film layer 1.
  • the diaphragm has good elasticity, strength and damping properties.
  • one silicone oil-modified polyurethane elastomer film layer 1 of the above-mentioned three-film diaphragm is replaced with an engineering plastic film layer 2.
  • the engineering plastic film layer 2 is directly bonded to the film layer 3.
  • the diaphragm has good elasticity, modulus and damping characteristics.
  • the five-layer diaphragm includes two silicone oil-modified polyurethane elastomer layers 1, two adhesive layers 3, and an engineering plastic film layer 2, wherein the engineering plastic film layer 2 is located on the diaphragm. Central.
  • the two adhesive film layers 3 are respectively attached to the upper and lower surfaces of the engineering plastic film layer 2.
  • Two silicone oil-modified polyurethane elastomer film layers 1 are respectively attached to the outer surfaces of the two film layers 3.
  • the diaphragm has good elasticity, modulus and damping characteristics.
  • the structure of the diaphragm is not limited to the above several embodiments, and the silicone oil-modified polyurethane elastomer film layer 1 can be used as a surface layer or an intermediate film layer of the diaphragm.
  • the silicone oil-modified polyurethane elastomer film layer 1 can be used as a surface layer or an intermediate film layer of the diaphragm.
  • Those skilled in the art can select the number of layers of the composite film layer and the thickness of each film layer according to actual needs. For example, 2 layers, 3 layers, 4 layers, 5 layers, 6 layers, and the like.
  • a speaker unit includes the diaphragm provided by the present invention.
  • the speaker unit includes a vibration system and a magnetic circuit system.
  • the vibration system includes a diaphragm, a voice coil, and a composite layer.
  • the diaphragm is a folded ring diaphragm.
  • the voice coil and composite layer are located at the center of the diaphragm of the folding ring.
  • the magnetic circuit system includes a magnetic conductive plate, a magnet, and a washer. The magnet is fixed to the magnetic conductive plate. The Huasi is placed on the magnet. The free end of the voice coil is inserted into the magnetic gap of the magnetic circuit system.
  • the speaker unit has the characteristics of good weather resistance and stable sounding effect.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Diaphragms For Electromechanical Transducers (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

本发明公开了一种硅油改性聚氨酯弹性体振膜以及扬声器单体。该振膜包括：将异氰酸酯、带有活泼氢官能团的硅油和扩链剂加入到溶剂中进行反应，其中，硅油的活泼氢官能团和异氰酸酯的异氰酸基团反应，以生成聚氨酯预聚体，扩链剂与聚氨酯预聚体上的官能团发生反应，固化后形成所述振膜。该振膜具有耐候性良好，不易粘模头的特点。

Description

硅油改性聚氨酯弹性体振膜以及扬声器单体 技术领域
本发明涉及电声转换技术领域，更具体地，涉及一种硅油改性聚氨酯弹性体振膜以及扬声器单体。
背景技术
热塑性聚氨酯类弹性体(TPU)具有良好的回弹性能、优异的化学稳定性能、耐高低温性能以及尺寸稳定性等特点。TPU作为振膜能够提高扬声器低频带及高频带的音质，以获得优异的听音效果。
现有的含有TPU的振膜的亲水性较强。随着季节变化环境湿度发生变化，造成了含有TPU的振膜随着环境湿度的增加，含水率升高的现象，即有明显的吸湿现象。这种现象影响振膜的模量和质量，造成扬声器的F o不稳定。
此外，含有TPU的振膜在成型过程中，如果成型温度过高，会出现振膜粘着模头的现象，这使得振膜结构无法达到理想的状态。
因此，需要提供一种技术方案，以解决上述技术问题。
发明内容
本发明的一个目的是提供一种硅油改性聚氨酯弹性体振膜的新技术方案。
根据本发明的第一方面，提供了一种硅油改性聚氨酯弹性体振膜。该振膜包括：将异氰酸酯、带有活泼氢官能团的硅油和扩链剂加入到溶剂中进行反应，其中，硅油的活泼氢官能团和异氰酸酯的异氰酸基团反应，以生成聚氨酯预聚体，扩链剂与聚氨酯预聚体上的官能团发生反应，固化后形成所述振膜。
可选地，所述带有活泼氢官能团的硅油包括烷羟基硅油、氨基硅油和 羟基硅油中的至少一种。
可选地，所述带有活泼氢官能团的硅油的加入量占加入量的原料的质量百分比大于0％且小于等于20％。
可选地，所述溶剂为丙酮、甲苯和四氢呋喃中的至少一种。
可选地，所述扩链剂为多元醇。
可选地，所述扩链剂的扩链系数为0.5-1.0。
可选地，所述异氰酸酯包括TDI、MDI和NDI中的至少一种。
可选地，反应温度为50℃-100℃。
根据本发明的第二个方面，提供了一种振膜。该振膜包括工程塑料膜层和胶膜层中的至少一种以及硅油改性聚氨酯弹性体膜层；其中，包括：将异氰酸酯、带有活泼氢官能团的硅油和扩链剂加入到溶剂中进行反应，其中，硅油的活泼氢官能团和异氰酸酯的异氰酸基团反应，以生成聚氨酯预聚体，扩链剂与聚氨酯预聚体上的官能团发生反应，固化后形成所述硅油改性聚氨酯弹性体膜层。
根据本发明的第三个方面，提供了一种扬声器单体。该单体包括本发明提供的所述振膜。
根据本公开的一个实施例，带有活泼氢官能团的硅油分子中含有线性硅氧烷基。线性硅氧烷基的分子间距离较大。硅氧烷链之间相互作用小，摩尔体积大，表面张力小，具有疏水性，故能够提高振膜的疏水性，从而有效改善振膜随季节的变化，F o不稳定的现象。该振膜的耐候性良好。
此外，带有活泼氢官能团的硅油是一种常见的脱模剂，将其含有的线性硅氧烷基对普通热塑性聚氨酯弹性体进行改性，这样即使振膜的成型温度很高，由于硅油成分的作用，故不容易出现粘模头的现象。这使得振膜的成型结构更稳定。
此外，带有活泼氢官能团的硅油中含有Si-O-Si键。这种键的键角大，Si原子和O原子之间容易旋转，从而使链段十分柔软。这使得硅油改性聚氨酯弹性体振膜具有良好的柔顺性。
此外，Si-O键的键能大，这使得硅油改性聚氨酯弹性体振膜相比于普通热塑性聚氨酯弹性体(TPU)振膜，不易被氧化，并且耐紫外光照射。
此外，硅油改性聚氨酯弹性体振膜的热稳定性高。
通过以下参照附图对本发明的示例性实施例的详细描述，本发明的其它特征及其优点将会变得清楚。
附图说明
被结合在说明书中并构成说明书的一部分的附图示出了本发明的实施例，并且连同其说明一起用于解释本发明的原理。
图1是根据本发明的一个实施例的振膜的剖视图。
图2是根据本发明的一个实施例的双膜层振膜的剖视图。
图3是根据本发明的一个实施例的三膜层振膜的剖视图。
图4是根据本发明的一个实施例的五膜层振膜的剖视图。
附图标记说明：
1：硅油改性聚氨酯弹性体振膜或膜层；2：工程塑料层；3：胶膜层。
具体实施方式
现在将参照附图来详细描述本发明的各种示例性实施例。应注意到：除非另外具体说明，否则在这些实施例中阐述的部件和步骤的相对布置、数字表达式和数值不限制本发明的范围。
以下对至少一个示例性实施例的描述实际上仅仅是说明性的，决不作为对本发明及其应用或使用的任何限制。
对于相关领域普通技术人员已知的技术、方法和设备可能不作详细讨论，但在适当情况下，所述技术、方法和设备应当被视为说明书的一部分。
在这里示出和讨论的所有例子中，任何具体值应被解释为仅仅是示例性的，而不是作为限制。因此，示例性实施例的其它例子可以具有不同的值。
应注意到：相似的标号和字母在下面的附图中表示类似项，因此，一旦某一项在一个附图中被定义，则在随后的附图中不需要对其进行进一步讨论。
根据本发明的一个实施例，提供了一种硅油改性聚氨酯弹性体振膜1。 该振膜包括：将异氰酸酯、带有活泼氢官能团的硅油和扩链剂加入到溶剂中进行反应，其中，在溶剂中，硅油的活泼氢官能团和异氰酸酯的异氰酸基团反应形成聚氨酯预聚体。扩链剂与聚氨酯预聚体上的官能团发生反应，以使分子链扩展、分子量增加。固化后，最终得到硅油改性聚氨酯弹性体振膜1。
具体地，异氰酸酯是异氰酸的各种酯的总称。可选地，异氰酸酯包括单异氰酸酯(R-N＝C＝O)、二异氰酸酯(O＝C＝N-R-N＝C＝O)以及多异氰酸酯等。
活泼氢是指有机物分子的官能团中所含的氢。带有活泼氢的官能团包括羟基、氨基和烷基等。可选地，带有活泼氢官能团的硅油包括烷羟基硅油、氨基硅油和羟基硅油中的至少一种。硅油的种类不限于上述几种，本领域技术人员可以根据实际需要进行选择。
扩链剂是指能与线性聚合物链上的官能团反应，以使分子链扩展、分子量增大的物质。可选地，扩链剂包括醚类扩链剂、醇类扩链剂等。例如，多元醇等。例如，多元醇包括丁二醇、聚醚二醇、聚酯二醇等。上述扩链剂的性能优良。扩链剂不限于上述几种，本领域技术人员可以根据实际需要进行选择。
优选地，扩链剂的扩链系数为0.5-1.0。扩链系数越大，则形成的聚合物的分子量越大；反之，扩链系数越小，则形成的聚合物的分子量越小。该扩链系数的范围使得形成的振膜的弹性良好。
优选地，上述反应的反应温度为50℃-100℃。在该温度下，上述反应更充分，并且固化速度适中，有利于振膜的成型。
振膜的成型方式可以采用流延成型、注塑成型等。振膜为折环振膜或者平板振膜等。本领域技术人员可以根据实际需要进行设置。
在本发明实施例中，带有活泼氢官能团的硅油分子中含有线性硅氧烷基。线性硅氧烷基的分子间距离较大。硅氧烷链之间相互作用小，摩尔体积大，表面张力小，具有疏水性，故能够提高振膜的疏水性，从而有效改善振膜随季节的变化，F o不稳定的现象。该振膜的耐候性良好。
此外，带有活泼氢官能团的硅油是一种常见的脱模剂，将其含有的线 性硅氧烷基对普通热塑性聚氨酯弹性体进行改性，这样即使振膜的成型温度很高。由于硅油成分的作用，故不容易出现粘模头的现象。这使得振膜的成型结构更稳定。
此外，带有活泼氢官能团的硅油中含有Si-O-Si键。这种键的键角大，Si原子和O原子之间容易旋转，从而使链段十分柔软。这使得硅油改性聚氨酯弹性体振膜1具有良好的柔顺性。
此外，Si-O键的键能大，这使得硅油改性聚氨酯弹性体振膜1相比于普通热塑性聚氨酯弹性体(TPU)振膜，不易被氧化，并且耐紫外光照射。
此外，硅油改性聚氨酯弹性体振膜1的热稳定性高。
在一个例子中，带有活泼氢官能团的硅油的加入量占加入的原料的质量百分比大于0％且小于等于20％。硅油的加入量越大，则对振膜的弹性影响越大。该质量分数使得振膜的疏水性良好，并且振膜的弹性良好。
在一个例子中，溶剂为丙酮、甲苯和四氢呋喃中的至少一种。在上述溶剂中，异氰酸酯、带有活泼氢官能团的硅油和扩链剂的溶解性良好，反应更充分，形成的振膜的可靠性良好。
可选地，异氰酸酯包括TDI(甲苯二异氰酸酯)、MDI(二苯基甲烷二异氰酸酯)和NDI(二异氰酸萘酯)中的至少一种。上述异氰酸酯均能与带有活泼氢官能团的硅油以及扩链剂反应，以形成硅油改性聚氨酯弹性体材料。
根据本发明的另一个实施例，提供了一种振膜。该振膜为复合振膜，包括工程塑料膜层2和胶膜层3中的至少一种以及硅油改性聚氨酯弹性体膜层1。其中，包括：将异氰酸酯、带有活泼氢官能团的硅油和扩链剂加入到溶剂中进行反应，其中，硅油的活泼氢官能团和异氰酸酯的异氰酸基团反应，以生成聚氨酯预聚体。扩链剂与聚氨酯预聚体上的官能团发生反应，固化后形成硅油改性聚氨酯弹性体膜层1。
该振膜的疏水性良好，从而有效改善了振膜随季节的变化F o不稳定的现象。
此外，该振膜不容易出现粘模头的现象。
异氰酸酯、带有活泼氢官能团的硅油和扩链剂的材料可以是但不局限 于上述振膜中的材料。
工程塑料膜层2具有强度高的特点，能显著提高振膜的模量。当工程塑料膜层2与硅油改性聚氨酯弹性体进行复合时，采用粘结剂将二者贴合在一起。
可选地，用于制作工程塑料膜层2的材料包括聚酰亚胺(PI)、聚对苯二甲酸乙二醇酯(PET)、聚苯硫醚(PPS)、聚萘二甲酸乙二醇酯(PEN)、聚对苯二甲酸乙二醇酯(PET)、聚醚醚酮(PEEK)、聚甲醛(POM)、聚苯醚(PPO)和聚对苯二甲酸丁二醇酯(PBT)中的至少一种。
胶膜层3具有粘性，故胶膜层3能够与硅油改性聚氨酯弹性体膜层1形成良好的贴合力。
此外，胶膜层3具有阻尼的效果，能吸收振膜在振动时的能量，以降低扬声器的杂音。
可选地，胶膜层3为丙烯酸类胶膜、聚氨酯类胶膜或者硅胶类胶膜。上述胶膜的粘结性和阻尼性良好。
图2是根据本发明的一个实施例的双膜层振膜的剖视图。图3是根据本发明的一个实施例的三膜层振膜的剖视图。图4是根据本发明的一个实施例的五膜层振膜的剖视图。
如图2所示，该双膜层振膜包括工程塑料膜层2和硅油改性聚氨酯弹性体膜层1。两个膜层1,2通过粘结剂粘接在一起。硅油改性聚氨酯弹性体膜层1具有良好的弹性。工程塑料膜层2具有良好的刚度。二者复合在一起使振膜兼具合适的弹性以及模量。
如图3所示，该三膜层振膜包括位于中部的胶膜层3和贴合在胶膜层3的上、下两侧的硅油改性聚氨酯弹性体膜层1。胶膜层3具有粘性，这使得胶膜层3与硅油改性聚氨酯弹性体膜层1的贴合变得容易。该振膜具有良好的弹性、强度以及阻尼特性。
在其他示例中，将上述三膜层振膜中的一个硅油改性聚氨酯弹性体膜层1替换为工程塑料膜层2。工程塑料膜层2直接贴合在胶膜层3上。该振膜具有良好的弹性、模量以及阻尼特性。
如图5所示，该五膜层振膜包括两个硅油改性聚氨酯弹性体膜层1、 两个胶膜层3以及一个工程塑料膜层2，其中，工程塑料膜层2位于振膜的中部。两个胶膜层3分别贴合在工程塑料膜层2的上、下两个表面上。两个硅油改性聚氨酯弹性体膜层1分别贴合在两个胶膜层3的外侧表面上。该振膜具有良好的弹性、模量以及阻尼特性。
振膜的结构不限于上述几种实施方式，硅油改性聚氨酯弹性体膜层1可以作为振膜的表层或者中间膜层。本领域技术人员可以根据实际需要选择复合膜层的层数以及每个膜层的厚度。例如，2层、3层、4层、5层、6层等。
根据本发明的又一个实施例，提供了一种扬声器单体。该扬声器单体包括本发明提供的振膜。例如，扬声器单体包括振动系统和磁路系统。振动系统包括振膜、音圈和复合层。振膜为折环振膜。音圈和复合层位于折环振膜的中心部。磁路系统包括导磁板、磁铁和华司。磁铁被固定在导磁板上。华司被设置在磁铁上。音圈的自由端插入磁路系统的磁间隙中。
该扬声器单体具有耐候性良好、发声效果稳定的特点。
虽然已经通过例子对本发明的一些特定实施例进行了详细说明，但是本领域的技术人员应该理解，以上例子仅是为了进行说明，而不是为了限制本发明的范围。本领域的技术人员应该理解，可在不脱离本发明的范围和精神的情况下，对以上实施例进行修改。本发明的范围由所附权利要求来限定。

Claims (10)

  1. 一种硅油改性聚氨酯弹性体振膜，其特征在于，包括：将异氰酸酯、带有活泼氢官能团的硅油和扩链剂加入到溶剂中进行反应，其中，硅油的活泼氢官能团和异氰酸酯的异氰酸基团反应，以生成聚氨酯预聚体，扩链剂与聚氨酯预聚体上的官能团发生反应，固化后形成所述振膜。
  2. 根据权利要求1所述的硅油改性聚氨酯弹性体振膜，其特征在于，所述带有活泼氢官能团的硅油包括烷羟基硅油、氨基硅油和羟基硅油中的至少一种。
  3. 根据权利要求1或者2所述的硅油改性聚氨酯弹性体振膜，其特征在于，所述带有活泼氢官能团的硅油的加入量占加入量的原料的质量百分比大于0％且小于等于20％。
  4. 根据权利要求1-3中的任意一项所述的硅油改性聚氨酯弹性体振膜，其特征在于，所述溶剂为丙酮、甲苯和四氢呋喃中的至少一种。
  5. 根据权利要求1-4中的任意一项所述的硅油改性聚氨酯弹性体振膜，其特征在于，所述扩链剂为多元醇。
  6. 根据权利要求1-5中的任意一项所述的硅油改性聚氨酯弹性体振膜，其特征在于，所述扩链剂的扩链系数为0.5-1.0。
  7. 根据权利要求1-6中的任意一项所述的硅油改性聚氨酯弹性体振膜，其特征在于，所述异氰酸酯包括TDI、MDI和NDI中的至少一种。
  8. 根据权利要求1-7中的任意一项所述的硅油改性聚氨酯弹性体振膜，其特征在于，反应温度为50℃-100℃。
  9. 一种振膜，其特征在于，包括工程塑料膜层和胶膜层中的至少一种以及硅油改性聚氨酯弹性体膜层；其中，包括：将异氰酸酯、带有活泼氢官能团的硅油和扩链剂加入到溶剂中进行反应，其中，硅油的活泼氢官能团和异氰酸酯的异氰酸基团反应，以生成聚氨酯预聚体，扩链剂与聚氨酯预聚体上的官能团发生反应，固化后形成所述硅油改性聚氨酯弹性体膜层。
  10. 一种扬声器单体，其特征在于，包括如权利要求1-9中的任意一项所述的振膜。
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