JP3011963B2 - Manufacturing method of polymer composite vibration damping material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a polymer composite vibration-damping material that can be used as, for example, a diaphragm material, a sound-absorbing material, a sound-insulating material, or a vibration-insulating material of a speaker, and its manufacture. About the method.

[Prior Art] For example, the acoustic characteristics of a speaker greatly depend on the physical properties of its diaphragm material. Determined sound velocity, that is, longitudinal wave propagation velocity (E / ρ) ^1/2 is large, vibration is attenuated quickly, internal loss η is large to suppress unnecessary resonance, and density ρ is It needs to be small. Conventionally, in order to satisfy such conditions more, besides paper such as natural pulp,
Metals such as aluminum, titanium, and beryllium, inorganic materials such as ceramics and glass fibers, and organic polymer materials such as polyethylene, polypropylene, aramid fibers, and liquid crystal polymers have been used.

Further, as the sound absorbing material, the sound insulating material, or the vibration damping material, conventionally, materials such as araswool, rubber, urethane foam, concrete, and metal have been used.

[Problems to be Solved by the Invention] However, the above-described conventional diaphragm materials for speakers have not been able to sufficiently satisfy the above-mentioned conditions required as diaphragm materials for speakers. That is, for example, in the case of metals and inorganic materials, the Young's modulus E is large, but the internal loss η is very small. On the other hand, in a polymer material, η is large but E is small. For this reason, it is extremely difficult to simultaneously satisfy the specific elastic modulus and the internal loss, which are contradictory physical properties, with only such a single material. In order to solve this problem, a composite material combining a metal or an inorganic material and an organic polymer material has been studied. However, since such multi-component, heterogeneous composite materials have remarkably different properties on the surface of the material, good mixing cannot be expected only by ordinary mixing and kneading. Attempts have been made to improve the dispersibility and strengthen the bonding force by modifying the polymer and improving the molding machine, but no satisfactory results have been obtained.

In addition, conventional sound absorbing materials, sound insulating materials, and vibration damping materials also have, for example, those having a sound absorbing effect have a small sound insulating and vibration damping effect, and those having the sound insulating and vibration damping effect have a sound absorbing effect. Was small. For this reason, there is no material that can provide an appropriate sound absorbing effect and at the same time, an appropriate sound insulating effect and vibration damping effect.

The present invention has been made under the above-mentioned background,
For example, it is an object of the present invention to provide a method for producing a polymer composite vibration damping material that can be used as a diaphragm material, a sound absorbing material, a sound insulating material, or a vibration damping material of a speaker.

[Means for Solving the Problems] The present invention has solved the above-mentioned problems by adopting the following configurations.

(1) A method for producing a polymer composite vibration damping material in which a polymer substance is adhered to a base material, wherein the base material is anodized using an electrolyte in which a monomer of the polymer substance is present. Thereby, a polymer composite vibration damping material in which a base material and a polymer substance are compounded is obtained.

(2) The method for producing a polymer composite vibration damping material according to claim 1, wherein the monomer of the polymer substance is a vinyl monomer, an aromatic compound, a heteroaromatic compound, a polynuclear aromatic compound, or active methine. A composition comprising at least one compound selected from the group consisting of:

(3) The method for producing a polymer composite vibration damping material according to claim 1 or 2, wherein the base material is selected from the group consisting of aluminum, magnesium, beryllium, titanium, tantalum, scandium, silicon, tungsten, yttrium, vanadium, and zirconium. A configuration including at least one of the following.

[Action] According to the above-described configuration, the polymer composite system in which the base material and the polymer material are complexed by anodizing the base material using the electrolytic solution in which the polymer material monomer is present. Since the vibration material is obtained, a polymer substance is firmly attached to the base material, and a polymer composite vibration-damping material having both the properties of the base material and the properties of the polymer substance is obtained. Can be.

[Example] (Example 1) In this example, aluminum was used as a base material, and polymethyl methacrylate (PMMA) was used as a polymer substance.
An anodizing of the base material using an electrolytic solution in which a polymer material monomer (methyl methacrylate) is present to cause an electrolytic polymerization reaction, and the polymer in which the base material and the polymer material are composited. This is an example of obtaining a composite vibration damping material. The specific conditions are as follows.

Base material 99.9% pure aluminum plate (50mm x 100mm x 0.2mm) Polymer substance Polymethyl methacrylate (PMMA) Electrolyte solution 1.0% methyl methacrylate dissolved in 5% oxalic acid aqueous solution to make 500ml solution Electrolytic polymerization Method The surface of the substrate was degreased with acetone, and electrolysis was performed in the electrolytic solution using this as an anode.

Electropolymerization conditions Electrolyte temperature; 25 ° C Current density; 4.5 A / dm ² Electrolysis time; 2 hours Polymerization reaction Oxidized film with innumerable pores with a diameter of about 100 to 1000 Methyl electropolymerization was initiated, and a polymer was formed at a polymerization rate of 30% in the pores and on the surface, resulting in a composite of aluminum, aluminum oxide, and polymethyl methacrylate (PMMA).

The physical properties of the composite thus obtained were as follows.

Internal loss (η) Example: 0.065 aluminum alone; 0.005 PMMA alone; 0.064 pulp paper; 0.030 Specific elastic modulus (E / ρ) Example: 2.0 × 10 ¹¹ cm ² / sec ² aluminum alone; 1.1 × 10 ¹¹ cm ² / sec ² PMMA alone; 2.8 × 10 ¹⁰ cm ² / sec ² pulp paper; 5.0 × 10 ¹⁰ cm ² / sec ² As is clear from the above results, according to this example,
It can be seen that a polymer composite vibration-damping material having larger values for both the internal loss and the specific elastic modulus than the conventional material can be obtained. That is, it can be seen that a material having optimal characteristics for the diaphragm of the speaker was obtained by appropriately utilizing the characteristics of both the base material and the polymer substance.

The method of this embodiment can be applied to any material as long as the base material is a substance that can be anodized and the polymer monomer can cause electrolytic polymerization. Thus, by selecting the type of the base material and the polymer substance and the degree of polymerization, it is possible to obtain a polymer composite vibration damping material having appropriate characteristics according to the application.

In addition, the substance which can be used as a base material other than the above-mentioned aluminum is as follows.

A simple substance of magnesium, beryllium, titanium, tantalum, scandium, silicon, tungsten, yttrium, vanadium or zirconium, or an alloy or compound containing at least one of these.

Further, the monomers of the polymer substance which can form the polymer composite material by electrolytic polymerization with these base materials are as follows.

* Vinyl monomers such as methyl methacrylate, styrene, vinyl acetate and acrylonitrile, and mixtures thereof.

* Aromatic compounds such as benzene, aniline, and phenol and derivatives thereof.

* Heteroaromatic compounds such as pyrrole, thiophene and furan.

* Polynuclear aromatic compounds such as phthalocyanine.

* Compounds having active methine such as acetylene derivatives.

Further, the following can be used as the electrolytic solution.

Solvent: water, alcohol, acetonitrile, nitrobenzene, dichloromethane, dimethylformamide, dimethylsulfoxide and a mixed solution thereof.

Electrolyte; sulfuric acid, phosphoric acid, hydrochloric acid, oxalic acid, chromic acid,
Ammonium borate, sulfamic acid, formic acid, potassium dichromate, nickel sulfate, tin sulfate, tetraalkylammonium salts, zinc acetate, lithium acetate and mixtures thereof.

(Second embodiment) In this embodiment, a polymer in which a base material and a polymer material are composited by immersing a base material anodized in a solution in which the polymer material is dissolved, and then drying and removing the solvent is used. This is an example of obtaining a composite vibration damping material. Specifically, it is as follows.

10 g of commercially available polyvinyl chloride powder was dissolved in tetrahydrofuran to prepare a 5% solution, and the previously produced aluminum anodic oxide was immersed in the solution and dried to remove the solvent. An aluminum anodic oxide composite of 8.0% by weight of vinyl chloride was obtained.

The physical properties of the composite thus obtained were as follows.

Internal loss (η) Example: 0.082 Aluminum anodic oxide alone; 0.017 Polyvinyl chloride alone; 0.098 Pulp paper; 0.030 Specific elastic modulus (E / ρ) Example: 1.6 × 10 ¹¹ cm ² / sec ² Aluminum anode Oxide alone; 1.7 × 10 ¹¹ cm ² / sec ² Polyvinyl chloride alone; 6.3 × 10 ⁹ cm ² / sec ² Pulp paper; 5.0 × 10 ¹⁰ cm ² / sec ² Molecular substances are
What is necessary is just to be able to be dissolved in a suitable solvent, for example, the following can be mentioned.

Thermoplastic resin Polyethylene, polypropylene, polyvinyl chloride, polystyrene, polymethyl methacrylate, polyacrylate, polyvinylidene chloride, polyvinyl acetate, polyacrylonitrile and their copolymers, various nylons, polyesters, polyurethanes, fluorine resins, silicone resins , Polyacetal, polycarbonate, polyphenylene oxide, polyphenylene sulfide, polyarylate, polyimide, aromatic polyamide.

Thermosetting resin Phenolic resin, urea resin, melamine resin, alkyd resin, epoxy resin, unsaturated polyester resin, furan resin, aniline resin.

Synthetic rubber Styrene / butadiene rubber, ethylene / propylene rubber, nitrile rubber, butyl rubber, chloropyrene rubber,
Silicon rubber, fluoro rubber, thiocol and others.

Synthetic fiber Nylon, polyester, acrylic fiber, vinylon,
Carbon fiber and others.

(Third Example) In this example, a polymer composite vibration damping material in which a substrate and a polymer substance are composited is obtained by attaching a polymer film to a substrate by heat fusion. Specifically, it is as follows.

A titanium anodic oxide composite of 10 wt% of polypropylene can be obtained by thermally fusing a 0.05 mm thick polypropylene film to the surface of the anodic oxide of the titanium plate at a temperature of 190 ° C. and a fusing pressure of 2 kg.

The polymer substance to which the method of this embodiment can be applied is as follows:
Any material can be used as long as it can be formed into a film and can be heat-sealed, and a polymer material substantially the same as that in the second embodiment can be used.

In addition to the above-described embodiments, a method in which the above-mentioned polymer emulsion of the thermoplastic resin, rubber and synthetic resin is applied to an anodized base material and dried, or a method in which a thermosetting resin, a crosslinked rubber and a natural fiber are used. (Cotton, silk, wool, hemp, etc.)
The polymer composite vibration-damping material can also be obtained by laminating an anodized base material with an adhesive, or mixing and curing on an anodized base material such as a two-component epoxy resin.

[Effects of the Invention] As described above in detail, the present invention provides a composite of a base material and a polymer substance by anodizing the base material using an electrolytic solution containing a monomer of the polymer substance. Since the polymerized composite vibration damping material is obtained, the polymer substance is firmly adhered to the base material, and both the properties of the base material and the properties of the polymer substance are properly utilized. This makes it possible to obtain a polymer composite vibration-damping material having characteristics optimal for a desired control material.

Claims (3)

(57) [Claims] 1. A method for producing a polymer composite vibration damping material having a polymer substance adhered to a substrate, wherein the substrate is anodically oxidized using an electrolytic solution containing a monomer of the polymer substance. A method of producing a polymer composite vibration damping material, wherein a polymer composite vibration damping material in which a base material and a polymer substance are compounded is obtained. 2. The method for producing a polymer composite vibration damping material according to claim 1, wherein the monomer of the polymer substance is a vinyl monomer, an aromatic compound, a heteroaromatic compound, a polynuclear aromatic compound, or A method for producing a polymer composite vibration-damping material, comprising at least one compound having active methine. 3. The method according to claim 1, wherein the base material is aluminum, magnesium, beryllium, titanium, tantalum, scandium, silicon, tungsten, yttrium, vanadium or zirconium. A method for producing a polymer composite vibration damping material, characterized by comprising at least one of the above.