KR100728900B1 - Conductive piezoelectric plastic film and film speaker for emission using it - Google Patents

Abstract

A conductive piezoelectric plastic film and a film speaker for emission using the same are provided to secure high electric conductivity and transparency and to apply auditory and visual effects at the same time by forming a functional layer on one surface of the plastic film or between the films. The conductive piezoelectric plastic film(100) is composed of a piezoelectric plastic film(10); organic conductive polymer layers(20) formed on both sides of the piezoelectric plastic film; and a mesh type metal layer(30) formed on one or both surfaces of the piezoelectric plastic film where the organic conductive polymer layers are formed. The organic conductive polymer layer is made of an organic conductive polymer composition consisting of soluble conductive polymers of 50~85wt.%, a fluorine adhesive binder of 2~8wt.%, an acryl-urethane binder of 2~10wt.%, a solvent of 10~30wt.%, and a cross-linking agent of 0.1~5wt.%.

Description

Conductive piezoelectric plastic film and film speaker for emission using it}

1 is a cross-sectional view of a conductive piezoelectric plastic film according to the present invention.

Figure 2a is a schematic diagram of a speaker sound device including a flexible film speaker for light emission according to the present invention.

FIG. 2B is a view showing a coupling relationship between respective parts of the speaker acoustic apparatus shown in FIG.

The present invention relates to a conductive piezoelectric plastic film and a light emitting film speaker using the same, and more particularly, to a piezoelectric plastic film having a high electrical conductivity and transparency by coating the piezoelectric plastic film with an organic conductive polymer composition and coating a metal binder in a mesh form. The present invention relates to a light emitting film speaker (film speaker for emission) manufactured by including a functional layer (a light emitting material, a phosphor, a liquid crystal polymer, etc.) between a film and the prepared transparent film cross section or the film.

As the piezoelectric plastic film, polytetrafluoroethylene (PTEE), Teflon (FEP), polyvinylidene fluoride (PVDF) and the like can be used. In particular, PVDF is known to be the most effective piezoelectric film. The piezoelectric plastic film currently developed is widely used as a microphone, an electroacoustic transducer, a flat panel speaker, a pressure sensor, and an ultrasonic transducer.

In particular, piezoelectric plastic films (especially PVDF) such as microphones and film speakers that can play a role of diaphragm and signal conversion at the same time have to use the entire surface as an electrode, so the conductive function is important for the whole surface. . In other words, the function of the film speaker is to transmit electricity to the piezoelectric plastic film to make the sound by vibrating the film. Therefore, the entire surface of both surfaces of the insulator piezoelectric plastic film must have an excellent conductivity function.

Recently, research has been reported to replace conventional metals or metal oxides using conductive polymers in PVDF films (US Pat. No. 6,573,639). The conductive polymer is an organic conductive material, and is known as a next-generation metal electrode replacement material because it has excellent solubility in various solvents and has excellent conductivity.

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The present invention has been made to solve the above problems, and an object of the present invention is to provide a conductive piezoelectric plastic film having high electrical conductivity and transparency.

It is also an object of the present invention to provide a functional light emitting film speaker capable of simultaneously providing an auditory effect and a visual effect by including a functional layer between the cross section or the film of the conductive piezoelectric plastic film.

In order to achieve the above object, the present invention provides a piezoelectric plastic film, an organic conductive polymer layer formed on both surfaces of the piezoelectric plastic film, and a metal layer in the form of a mesh formed on one or both surfaces of the piezoelectric plastic film on which the organic conductive polymer layer is formed. It provides a conductive piezoelectric plastic film comprising.

The present invention also forms a functional layer made of a light emitting material, a liquid crystal polymer, or a phosphor between one end of the conductive piezoelectric plastic film or between the films, and light emission formed by forming electrode layers on both sides of the conductive piezoelectric plastic film having the functional layer formed thereon. Provide film speakers.

Hereinafter, the present invention will be described in more detail with reference to the accompanying drawings.

1 is a cross-sectional view of a conductive piezoelectric plastic film according to the present invention.

Referring to FIG. 1, after the high frequency treatment is performed on the piezoelectric plastic film 10, which is an insulator, the organic conductive polymer composition is coated on both sides thereof by a gravure method, and thermally cured at 70 to 90 ° C. for 3 minutes. ) And the metal binder 30 is formed by coating a metal binder in a mesh form on one or both surfaces of the piezoelectric plastic film on which the organic conductive polymer layer 20 is formed, thereby having excellent electrical conductivity and transparency according to the present invention. The piezoelectric plastic film 100 may be manufactured.

The organic conductive polymer layer 20 is functional with the same series of fluorine-based adhesive binders in order to increase the adhesion of the water-soluble conductive polymer that gives high electrical conductivity to the piezoelectric plastic film, and the piezoelectric plastic film containing hydrophobic fluorine functional groups. It may be made of an organic conductive polymer composition comprising a crosslinking agent. As an example of the present invention, the organic conductive polymer composition may include 50-85% by weight of a water-soluble conductive polymer, 2-8% by weight of a fluorine-based adhesive binder, 2-10% by weight of an acrylic urethane binder, 10-30% by weight of a solvent, and a crosslinking agent of 0.1. -5% by weight.

As the water-soluble conductive polymer, water-soluble polyaniline, water-soluble polypyrrole, water-soluble polythiophene, poly (3,4-ethylenethiophene), derivatives or copolymers thereof, and? -Conjugated electrically conductive polymer can be used.

The fluorine-based adhesive binder is at least one monomer selected from the group consisting of tetrafluoroethylene, hexafluoropropylene, trifluoroethylene or ethylene / tetrafluoroethylene copolymer, tetrafluoroethylene-hexafluoropropylene copolymer , Vinylidene fluoride, derivatives thereof, copolymers, and fluorine-urethane.

The solvent is dimethyl sulfoxide (DMSO), dimethylformamide (DMF), N-methyl-2-pyrrolidinone (NMP), 2-butanone, 4-methyl-2-pentanone, methyl alcohol, ethyl alcohol , Isopropyl alcohol, isobutyl alcohol, t-butyl alcohol, benzyl alcohol, ethylene glycol and other polar solvents, preferably dimethyl sulfoxide (DMSO), N-methyl-2-pyrrolidinone (NMP), isopropyl Alcohol and the like.

The crosslinking agent is a polyfunctional aziridine-based crosslinking agent having a low curing temperature (100 ° C. or less) while being able to easily crosslink famine under the influence of an anion included in the conductive polymer or binder.

As the multifunctional aziridine crosslinking agent, one containing at least two nitrogen atoms in the molecular crosslinking agent may be used. For example, N- (aminoethyl) aziridine, N-aminoethyl-N-aziridylethylamine, N , N-bis-2-aminopropyl-N-aziridylethylamine, N-3,6,9-triazanoylaziridine, and the like, and it is preferable that three aziridine functional groups are contained in the molecular crosslinking agent.

As the piezoelectric plastic film 10, polytetrafluoroethylene, polyvinyl fluoride, polytrifluoroethylene, polytrifluorochloroethylene, ethylene / tetrafluoroethylene copolymer, tetrafluoroethylene-hexafluoro Propylene copolymer, polyvinylidene fluoride (PVDF), derivatives and copolymers thereof may be selected and used, preferably PVDF.

As the metal of the metal binder, a conductive material made of a metal having a conductivity such as gold, silver, copper, nickel, zinc, or an alloy thereof is preferable. The metal layer 30 may be formed by coating a metal binder with a mesh (which can be manufactured in various shapes and intervals) through screen printing on a piezoelectric plastic film having an organic conductive polymer layer formed thereon. Screen printing is possible in various forms such as square, circle, rhombus.

Figure 2a is a diagram schematically showing a speaker sound device including a film speaker according to the present invention. FIG. 2B is a diagram illustrating a coupling relationship between parts of the speaker sound device illustrated in FIG. 2A.

Referring to the drawings, an acoustic apparatus including a light emitting speaker unit according to the present invention includes an audio input signal, an amplifier for amplifying the signal, a power supply for supplying power to the audio and amplification apparatus, A light emitting device for inputting a signal and a light emitting speaker unit. In the light emitting film speaker using the transparent conductive piezoelectric plastic film of the present invention, electrode layers (metals such as silver and copper) 150a and 150b are formed on both surfaces of the conductive piezoelectric plastic film 100, and the conductive layer 150b is formed. The light emitting layer 140 is formed by coating aluminum quinoline (Alq ₃ , which is commonly used in a light emitting layer of an organic EL, or a ZnS compound) as a light emitting body on a piezoelectric plastic film, and then forming an electrode layer 150c on the light emitting layer 140. Can be. Electrode layers 150a and 150b formed on both surfaces of the transparent conductive piezoelectric plastic film 100 are connected to an amplifier, and electrode layers 150b and 150c formed on upper and lower surfaces of the light emitting layer 140 are connected to a light emitting device. When a voltage difference occurs at both ends of the electrode layers 150a and 150b disposed on both surfaces of the transparent conductive piezoelectric plastic film 100, the conductive piezoelectric plastic film 100 may generate a mechanical vibration. In addition, when a predetermined voltage is applied to the electrode layers 150b and 150c formed on the upper and lower surfaces of the light emitting layer 140, light emission may occur to produce a visual effect.

In the light emitting film speaker of the present invention, the light emitting display device was capable of using a driving voltage of 110 V or less, and the luminance characteristic was 70 cd / m 2 or more. The sound from the sound level meter (Az Instrument, Az8921) showed more than 80dB at 1KHz.

In addition, a transparent liquid crystal polymer layer was added to the transparent conductive piezoelectric plastic film cross section or between the films to manufacture a flexible film speaker capable of liquid crystal display. The liquid crystal polymer is a liquid crystal display polymer composed of 10-30% by weight of ferroelectric liquid crystal and antiferroelectric liquid crystal and 70-90% by weight of urethane acrylate, acrylate or methacrylate polymerization polymer. Formed. In the case of the liquid crystal display flexible film speaker manufactured as described above, it may be equipped with a function capable of adjusting hearing and visually. The liquid crystal display of the present invention can use a driving voltage of 20-110V, and has a transmittance of 75% or more, a viewing angle of 120 degrees, and a response time of 80 ms.

Inorganic materials that can be used as light emitting materials include ZnS: Mn / CdSSe, ZnS: TbOF, ZnS: TbS, AnS: TbS, SrS: Ce, KCaGa ₂ S ₄ : Ce, SrS: Cu, SiC, InGaAIP, InGaN, etc. The low molecular weight organic material may include blue andrasene, phenyl substituted cyclopentadiene derivatives, LiPBO and DPVBi, yellow 1,2-phthalo-perinon derivatives, and yellow quinoline (Alq ₃ ). There is this. Representative polymer organic materials include poly (p-phenylenevinylene), poly (p-phenylene), polythiophene and derivatives thereof. In addition, all organic-inorganic light emitting materials can be used. The liquid crystal polymer may be a liquid crystal display polymer composed of 10 to 30% by weight of the ferroelectric liquid crystal and semi-ferroelectric liquid crystal and 70 to 90% by weight or more of urethane acrylate, acrylate or methacrylate polymerization polymer, and the thickness is 10 to 40㎛. It can form a degree layer.

Hereinafter, the present invention will be described in detail by the following examples. However, the embodiments do not limit the technical scope of the present invention.

Example  One

70% by weight of water-soluble conductive polymer (Baytron pH), 7% by weight of ethylene / tetrafluoroethylene copolymer, 7% by weight of acryl-urethane binder, fluorine adhesive binder, 10% by weight of solvent DMSO, 5% by weight of NMP, crosslinking agent A conductive coating solution was prepared using 0.5 wt% of CX-100 (Bayer Co.) and 0.5 wt% of a wetting agent. The prepared conductive coating solution was coated on a PVDF 80 μm film, which is an insulator, by a gravure method, and thermally cured at 80 ° C. for 3 minutes to prepare a transparent conductive piezoelectric plastic film having excellent adhesive strength. The silver binder, which is a metal, was coated on the PVDF film, which is a piezoelectric plastic film coated with the conductivity, in a mesh form (2 mm each) through screen printing to obtain excellent conductivity (surface resistance: 0.5Ω / sq.) And A conductive PVDF film, which is a conductive piezoelectric plastic film with transparency (> 85%), was prepared. Surface resistance was measured according to the ASTM D257 measurement method, the transparency was measured in the visible light (550nm) region using a UV photometer (Simazu Co.).

The light emitting layer was formed on the conductive PVDF film by screen printing an inorganic material, a ZnS compound binder, which is a light emitting material. A dielectric layer was formed on the light emitting layer, and silver paste (or carbon paste), which is an electrode layer, was screen printed and dried at 60 ° C. to manufacture a light emitting film speaker unit. The light emitting film speaker according to the present invention showed a luminance characteristic of 70 cd / m ² at a driving voltage of 110 V, and an acoustic sound of 80 dB at 1 KHz.

Example  2

In the production of the conductive piezoelectric plastic film, the conductive coating solution was performed in the same manner as in Example 1. Excellent conductivity (surface resistance: 0.5Ω / sq.) By coating a silver binder, which is a metal, on the produced film in a mesh form (2 mm each horizontally) through screen printing on a PVDF film, which is a piezoelectric plastic film coated with the conductive coating solution. A conductive PVDF film, which is a conductive piezoelectric plastic film having transparency and transparency (> 85%), was prepared.

The conductive PVDF film was coated with a single molecule Alq ₃ as a luminescent material to form a light emitting layer, and again, a silver paste (or carbon paste, ITO) as an electrode layer was screen printed and dried at 60 ° C. to manufacture a light emitting film speaker unit. The light emitting film speaker according to the present invention showed a luminance characteristic of 50 cd / m ² at a driving voltage of 10 V, and an acoustic sound of 82 dB at 1 KHz.

Example  3

In the production of the conductive piezoelectric plastic film, the conductive coating liquid was carried out in the same manner as in Example 1. Excellent conductivity (surface resistance: 0.5Ω / sq.) By coating a silver binder, which is a metal, on the produced film in a mesh form (2 mm each horizontally) through screen printing on a PVDF film, which is a piezoelectric plastic film coated with the conductive coating solution. A conductive PVDF film, which is a conductive piezoelectric plastic film having transparency and transparency (> 85%), was prepared.

60 wt% of PDLC (polymer dispersed liquid crystal, E-7 (Merck Co.) and urethane acrylate oligomer Ebercryl-270 (SK-UCB) and acrylic monomer 2-EHA (Aldrich Co.) were prepared in the conductive PVDF film. 40 wt% of a photocurable binder mixed at a weight ratio of 1 to 3)], and a PVDF film coated with a conductive polymer is adhered thereon, and then cured by irradiation with ultraviolet (365 nm, 10 mW / cm ² ). A liquid crystal display film speaker unit having a thickness of 15 μm was manufactured. Using the liquid crystal display flexible film speaker unit prepared above, it was possible to manufacture a liquid crystal display flexible film speaker simultaneously having a function capable of acoustic and visual adjustment. The liquid crystal display of the liquid crystal display flexible film speaker exhibited a transmittance of 10% to 85% when on-off at a driving voltage of 110V and a response speed of 80ms. The sound was 82dB at 1KHz.

Comparative example  One

In the production of the conductive piezoelectric plastic film, the conductive coating liquid was carried out in the same manner as in Example 1. The prepared conductive coating solution was coated on a PVDF 80 μm film, which is an insulator, by a gravure method, and thermally cured at 80 ° C. for 3 minutes to prepare a transparent conductive piezoelectric plastic film having excellent adhesive strength. Excellent conductivity (surface resistance: 0.5Ω / sq.) By coating a silver binder, which is a metal, on the produced film in a mesh form (2 mm each horizontally) through screen printing on a PVDF film, which is a piezoelectric plastic film coated with the conductive coating solution. A conductive PVDF film, which is a conductive piezoelectric plastic film having transparency and transparency (> 85%), was prepared. A metal speaker (silver, copper, etc.) was printed on the front and rear surfaces of the prepared conductive piezoelectric plastic PVDF film to prepare a film speaker unit.

The acoustic sound of the piezoelectric plastic speaker prepared above was 85dB at 1KHz.

According to the present invention, the conductive polymer layer and the metal layer of the mesh form are formed on the piezoelectric plastic film, so that the conductive and transparent piezoelectric plastic film can be prepared, and the functional layer (light emitting material, By manufacturing a light emitting film speaker including a phosphor, and a liquid crystal polymer), a film speaker having many applications can be manufactured that can simultaneously provide a visual effect to an auditory effect. Various applications are applicable to display-related speakers, advertising banners, posters, various indoor interiors, various play equipment, various communication equipments, electrical and electronic parts, and the like.

Claims (8)

A conductive piezoelectric plastic film comprising a piezoelectric plastic film, an organic conductive polymer layer formed on both surfaces of the piezoelectric plastic film, and a metal layer in a mesh form formed on one or both surfaces of the piezoelectric plastic film on which the organic conductive polymer layer is formed. . According to claim 1, wherein the organic conductive polymer layer is 50-85% by weight of the water-soluble conductive polymer, 2-8% by weight of the fluorine-based adhesive binder, 2-10% by weight of the acrylic-urethane binder, 10-30% by weight of the solvent and crosslinking agent 0.1 A conductive piezoelectric plastic film comprising an organic conductive polymer composition containing -5% by weight. The method of claim 2, wherein the water-soluble conductive polymer is selected from water-soluble polyaniline, water-soluble polypyrrole, water-soluble polythiophene, poly (3,4-ethylenethiophene) and derivatives or copolymers thereof and π-conjugated electrically conductive polymer. Conductive piezoelectric plastic film, characterized in that one. The method of claim 2, wherein the fluorine-based adhesive binder is at least one monomer selected from the group consisting of tetrafluoroethylene, hexafluoropropylene, trifluoroethylene or ethylene / tetrafluoroethylene copolymer, tetrafluoroethylene- A conductive piezoelectric plastic film, which is selected from hexafluoropropylene copolymer, vinylidene fluoride, derivatives thereof, copolymers, and fluorine-urethane. The conductive piezoelectric plastic film according to claim 2, wherein the crosslinking agent is a multifunctional aziridine-based crosslinking agent. The method of claim 1, wherein the piezoelectric plastic film is polytetrafluoroethylene, polyvinyl fluoride, polytrifluoroethylene, polytrifluorochloroethylene, ethylene / tetrafluoroethylene copolymer, tetrafluoroethylene-hexa A conductive piezoelectric plastic film, which is selected from the group consisting of fluoropropylene copolymer, polyvinylidene fluoride, derivatives and copolymers thereof. The conductive piezoelectric plastic film of claim 1, wherein the metal layer is formed by coating a metal binder made of gold, silver copper nickel, zinc, or an alloy thereof. A conductive layer formed of a light emitting material, a liquid crystal polymer, or a phosphor is formed between a cross section or a film of the conductive piezoelectric plastic film according to any one of claims 1 to 7, wherein the functional layer is formed of the conductive piezoelectric plastic film A light emitting film speaker characterized by forming an electrode layer on both sides.

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