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JP2012065295

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DESCRIPTION JP2012065295
The object of the present invention is to provide an extremely light weight and a self-charging
property by friction, so that it is not necessary to apply a high voltage for charging, dust and dirt
do not easily adhere, and dust and dirt attached are caused by vibration. An object of the present
invention is to provide a new speaker diaphragm that can construct an electrostatic speaker
system by being able to easily remove dust, and thus capable of stably maintaining a charged
state. The film for speaker vibration has at least a part of the surface of a polymer film covered
with an amorphous fluorine-based film, and the mass per unit area is 5 mg / dm or more and
150 mg / dm or less It is characterized by [Selected figure] Figure 1
Film for speaker diaphragm
[0001]
The present invention relates to a diaphragm for a speaker, and more particularly to a film for a
speaker diaphragm suitable for use in an electrostatic speaker or an ultrasonic speaker.
[0002]
In recent years, along with the miniaturization and high functionality of ultra thin film type
displays using liquid crystal devices and organic EL devices, and mobile communication terminals
such as mobile phones, the size reduction, film thickness reduction, and power saving of the
speakers mounted And sound quality improvement requirements are increasing.
04-05-2019
1
In particular, since the electrostatic speaker system has flexibility, it can be expected as a useful
speaker system for an organic EL display. However, as a problem of the electrostatic speaker, it is
necessary to apply a high potential to the vibrating film to charge it, which leaves a problem of
safety. Also, if used for a long time in a dry environment, dust adheres to the surface of the
vibrating film, which affects the sound quality and volume, and furthermore, when left in a high
humidity environment for a long time, the charged vibrating film is discharged and charged And
the sound is less likely to be emitted.
[0003]
As a method of solving such a problem, a method of suppressing the influence of humidity by
using a film obtained by treating the surface of a polymer film with a conductive polymer as a
vibrating film (Patent Document 1) or a member having a dust collecting function Proposed a
method to suppress adhesion of dust by installing it (Patent Document 2), a method to make it
difficult to generate a discharge by not forming a conductive film formed on the surface of the
vibrating film (Patent Document 3), etc. It is done. Patent Document 1: Japanese Patent
Application Publication No. 7-046697 Patent Document 2: Japanese Patent Application
Publication No. 2008-148195 Patent Document 2: Japanese Patent Application Publication No.
2010-016603
[0004]
However, the method of using the film obtained by treating the polymer film surface with the
conductive polymer as the vibrating film to suppress the influence of humidity can take measures
against the humidity, but dust and dirt associated with aging with use It is necessary to apply a
high potential in order to deposit or to charge, and it is not a fundamental measure. In addition,
in a method of installing a member having a dust collection function to suppress adhesion of dust
and dirt, and a method of making it difficult to generate a discharge by not forming a conductive
film formed on the surface of a vibrating film, etc. Although the structure becomes complicated
and the speaker system becomes thick, or the discharge can be partially mitigated, it is
impossible to prevent the discharge from the vibrating membrane surface, and furthermore, the
system should apply a high potential. In the current situation, it is not a fundamental
improvement because
[0005]
Therefore, the present invention has been made to solve the above-mentioned problems, and it is
04-05-2019
2
extremely lightweight and has a self-charging property by friction, so that it is not necessary to
apply a high voltage for charging, and dust And dust are less likely to be attached, and the
attached dust and dirt can be easily removed by vibration, so that the charged state can be stably
maintained, thereby providing a new diaphragm for a speaker capable of constructing an
electrostatic speaker system. It is to do.
[0006]
That is, in the first invention, at least a part of the polymer film surface is covered with the noncrystalline fluorine-based film, and the mass per unit area is 5 mg / dm <2> or more and 150 mg
/ dm <2> or less It is a film for speaker diaphragms characterized by being.
[0007]
By combining a polymer film and a non-crystalline fluorine-based film to form a film for a
speaker diaphragm, it is possible to form a film suitable for a speaker diaphragm film that is light
in weight and excellent in strength and excellent in chargeability. Can.
[0008]
The second invention is a film for a speaker diaphragm characterized in that the arithmetic
average roughness Ra of the surface coated with the non-crystalline fluorine-based film is 5 nm
or more and 500 nm or less.
[0009]
Furthermore, according to the third invention, in the first or second invention, a fine particle
layer containing inorganic fine particles or polymer fine particles is provided between the
polymer film surface and the non-crystalline fluorine-based film. It is a film for speaker
diaphragms characterized by being formed.
[0010]
Furthermore, according to a fourth aspect of the present invention, there is provided the film for
a speaker diaphragm according to the third aspect, wherein the inorganic fine particles and the
polymer fine particles are dielectrics.
[0011]
Furthermore, in the fifth invention according to the third or fourth invention, the inorganic fine
particles are coated with a silane monomer having an unsaturated bond, and the inorganic fine
04-05-2019
3
particles in the fine particle layer are silane monomers of each other. The speaker diaphragm
film is characterized in that the unsaturated bond or the reactive functional group is chemically
bonded.
[0012]
Furthermore, in the sixth invention according to any of the third to fifth inventions, the inorganic
fine particles are coated with a silane monomer having an unsaturated bond portion, and the
inorganic fine particles in the fine particle layer are the inorganic fine particles. A film for a
speaker diaphragm characterized in that it is fixed to the surface of the polymer film by
chemically bonding the unsaturated bond or reactive functional group of a silane monomer
coating the fine particles with the polymer film. is there.
[0013]
Furthermore, according to a seventh invention, in any of the third to sixth inventions, the fine
particle layer contains a binder component having water repellency, which is a film for a speaker
diaphragm.
[0014]
The film for a speaker diaphragm according to the present invention is excellent in selfchargeability since a non-crystalline fluorine-based film excellent in dielectric property is formed
on the surface of the polymer film and further containing fine particles made of a dielectric. Also,
since it is easily frictionally charged by the vibration of the vibrating film, it is not necessary to
apply a high potential, and the charging of the vibrating film can be maintained for a long time,
and electric shock due to the high potential or noise does not occur for a long time It will not be
difficult to get out.
[0015]
Furthermore, fine irregularities are formed on the surface of the non-crystalline fluorine-based
film by the fine particle layer made of inorganic fine particles and organic fine particles, so
adhesion of dust and dirt to the surface is suppressed. Even if dust or dirt adheres, the contact
area becomes extremely low and it is easily detached from the surface of the vibrating membrane
by the vibration of the vibrating membrane, so even if it is used for a long time, the change in
sound quality or the reduction in volume etc. It can be suppressed.
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Therefore, it is possible to provide a film for a speaker diaphragm which can construct a new
electrostatic speaker system with high safety which does not require a transformer or the like to
which a high voltage is applied.
[0016]
Furthermore, in the film for speaker diaphragms in the present invention, the mechanical
properties of the polymer film are greatly improved by forming the non-crystalline fluorine-based
film on the polymer film surface.
That is, in the stress-strain characteristics, it was found that the elongation was significantly
improved as the strength inherent to the polymer film was improved.
The thin film capable of converting a slight potential change to a large displacement by the
improvement of mechanical properties can provide a very useful material for the practical design
of a lightweight speaker diaphragm film.
[0017]
1 is a cross-sectional view of a film for a speaker diaphragm of Embodiment 1. FIG.
5 is a cross-sectional view of a speaker diaphragm film of Embodiment 2. FIG.
FIG. 7 is a cross-sectional view of a film for a speaker diaphragm of Embodiment 3.
FIG. 14 is a cross-sectional view of a film for a speaker diaphragm of Embodiment 4.
[0018]
First Embodiment Hereinafter, a film for a speaker diaphragm according to an embodiment of the
present invention will be described in detail.
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[0019]
FIG. 1 is an enlarged view of a part of a cross section of a speaker diaphragm film 100 according
to an embodiment of the present invention.
The film 100 for a speaker diaphragm according to the present embodiment is configured by
coating the non-crystalline fluorine-based film 2 on the surface of a base 1 which is a main
portion of a speaker diaphragm.
Although FIG. 1 shows the state in which the entire surface of the substrate 1 is covered with the
non-crystalline fluorine-based film 2, it is sufficient if only at least a part of the surface of the
substrate 1 is covered. The arrangement may be sea-island-like sea or island.
[0020]
The substrate 1 of the speaker diaphragm film 100 of the present embodiment is a film or sheet
made of a polymer.
As the material, for example, polyethylene resin, polypropylene resin, polystyrene resin,
polymethylpentene resin, polyvinylidene chloride resin, methyl polyacrylate resin, polyamide
resin, polyimide resin, polyethylene terephthalate resin, poly Butylene terephthalate resin,
polyarylate resin, polyether phenyl ether sulfone resin, polyvinylidene fluoride resin, PVF (poly
vinyl fluoride), FEP (fluorinated ethylene propylene copolymer), ETFE (ethylene tetra
fluoroethylene), Examples thereof include thermoplastic resins such as PTFE
(polytetrafluoroethylene) and PVDF (poly vinylidene difluoride), and melt liquid crystal polymers
such as polyarylate and PPTA (Poly (p-phenylene terephthalamide)).
If the thickness of the film made of these polymers is 1.0 μm or less, there may be a problem
with handling, and if it is 10 μm or more, the mass becomes high, so high energy is required to
vibrate the vibrating film. Since the power consumption tends to be high and the power
consumption tends to be high, the thickness is preferably 1.0 μm or more and 10 μm or less.
04-05-2019
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[0021]
As an example of the material of the non-crystalline fluorine-based film 2 of the present
embodiment, Cytop (equal strength trademark) (trade name: manufactured by Asahi Glass Co.,
Ltd.) or Teflon AF ("Teflon" is a registered trademark) (product) Name: manufactured by DuPont
Co., Ltd., tetrafluoroethylene-perfluorodioxole copolymer (TFE / PDD) (manufactured by Mitsui /
Dupont Fluorochemicals Co., Ltd.), etc. are used.
These fluorine-based resins are non-crystalline and can be dissolved in a specific solvent because
the unit of their molecular structure is cyclic or contains a cyclic structure.
[0022]
Using this characteristic, a uniform fluorine-based film 2 can be easily formed on the surface of
the substrate 1 by a method such as a spin coating method, an immersion method, or a spray
method. In addition, since the fluorine-based film 2 formed of these materials has a low dielectric
constant and a low water absorption rate and excellent moisture resistance, it is easy to be
charged, and it is difficult to be discharged due to the environment even if it is charged. And can
exhibit excellent characteristics as the speaker diaphragm 100. If the thickness of the noncrystalline fluorine-based film 2 is 0.01 μm or less, the characteristics that are difficult to
discharge after charging tend to be unstable, and if it is 5.0 μm or more, the characteristics such
as chargeability are almost the same. Since a constant state is exhibited, it is not preferable from
the point that excessive energy is required for vibration due to the mass of the vibrating film
becoming large, the material cost becomes high, etc. Therefore, the thickness of the fluorinebased film 2 is preferably 0.01 μm or more and 5.0 μm or less. In particular, the diaphragm
film in the present invention needs to have a mass per unit area of 5 mg / dm <2> or more and
150 mg / dm <2> or less. If the mass is 150 mg / dm <2> or more, high energy is required to
vibrate the vibrating film, and if 5 mg / dm <2> or less, the strength as the vibrating film is
insufficient or the handling becomes difficult. Absent.
[0023]
Moreover, the film 100 for a speaker diaphragm of this embodiment is perpendicular to the MD
(Machine Directrion: flow direction of the resin) and TD (Transverse Directrion: MD) of the film
measured by the test of the tensile properties according to JIS K 7127. The strength (N) in the
04-05-2019
7
direction is preferably 7 N or more in both the MD and TD directions. From the application of a
film for a speaker diaphragm, if it is about 7 to 80 N in both the MD direction and the TD
direction, it can be supplied as a material suitable for practical design.
[0024]
Moreover, as for the elongation (%) measured by the same test, it is preferable that either MD
direction or TD direction is 5% or more. In particular, if the elongation in either the MD direction
or the TD direction is 10% or more and 50% or less, a slight potential change can be converted
into a large displacement, and a film for a speaker diaphragm with high energy efficiency can be
configured.
[0025]
Second Embodiment Next, a speaker diaphragm film 200 according to a second embodiment of
the present invention will be described in detail with reference to FIG.
[0026]
FIG. 2 is an enlarged view of a part of the cross section of the speaker diaphragm film 200
according to the embodiment of the present invention.
The speaker diaphragm film 200 according to the present embodiment is configured by coating
the non-crystalline fluorine-based thin film 2 on the surface of the base 1 forming the main body
of the speaker diaphragm film, and the speaker diaphragm The surface of the film 200 has
minute asperities 3. The film 200 for a speaker diaphragm on which the unevenness 3 is formed
has an arithmetic average roughness Ra of 5 nm or more and 500 nm or less. The minute
irregularities on the surface of the film 200 for a speaker diaphragm according to the present
embodiment are formed by embossing the surface of the polymer film substrate 1,
nanoimprinting, physical methods such as oxygen plasma, or chemical etching, etc. Formed by
the chemical method of Due to the unevenness, dust and dirt charged on the surface of the film
200 for the speaker diaphragm are less likely to come in contact with the surface of the film, so
they are easily detached by the vibration of the film 200 for the speaker diaphragm and dust And
accumulation of dust can be suppressed. Although FIG. 2 also shows that the non-crystalline
fluorine-based film 2 covers the entire surface of the substrate 1, it is sufficient to cover at least a
part of the surface of the substrate 1 as shown in FIG. It is similar.
04-05-2019
8
[0027]
Third Embodiment Next, a speaker diaphragm film 300 according to a third embodiment of the
present invention will be described in detail with reference to FIG.
[0028]
FIG. 3 is an enlarged view of a part of the cross section of the speaker diaphragm film 300
according to the embodiment of the present invention.
The film 300 for a speaker diaphragm according to this embodiment has a fine particle layer
formed of inorganic fine particles 4a or organic (polymer) fine particles 4b containing a binder
component 5 on the surface of a base 1 forming the main body of the film 300 for a speaker
vibration plate. An amorphous fluorine-based film 2 is formed on the surface of the fine particle
layer. Here, the inorganic fine particles 4a or the organic fine particles 4b containing the binder
component 5 are introduced to form minute unevenness on the surface of the substrate 1, and
adhere to the surface of the film 200 for a speaker diaphragm due to the unevenness. The dust
and dirt can be easily detached and its accumulation can be suppressed.
[0029]
Examples of the inorganic fine particles 4a used for the speaker diaphragm film 300 according to
the embodiment of the present invention include Al2O3, TiO2, ZrO2, SnO2, FeO, Fe2O3, Fe3O4,
Sb2O3, PbO, CuO, CuO, NiO, Ni3O4, Ni2O3. And single inorganic oxides such as CoO, Co3O4,
Co2O3, WO3 and CeO2. Further, as composite oxides, for example, BaTiO 3, SrTiO 3, ZnFe 2 O 4,
SiO 2 · Al 2 O 3, SiO 2 · B 2 O 3, SiO 2 · P 2 O 3, SiO 2 · P 2 O 5, SiO 2 · TiO 2, SiO 2. · B 2 O 3, Al
2 O 3 · P 2 O 5, Al 2 O 3 · CeO 2, Al 2 O 3 · Fe 2 O 3, TiO 2 · CeO 2, TiO 2 · CeO 2, TiO 2 · ZrO 2,
SiO 2 · TiO 2 · ZrO 2, Al 2 O 3 · TiO 2 · ZrO 2, SiO 2 · Al 2 O 3 · TiO 2, SiO 2 · TiO 2 · CeO 2 And
KNbO3-NaNbO3-based ferroelectric ceramics, (Bi1 / 2Na1 / 2) TiO3-based ferroelectric ceramics,
tungsten bronze-type ferroelectric ceramics and the like. These inorganic fine particles 4a may be
used alone or in combination of two or more, and the particle diameter of these inorganic fine
particles 4a may be 10 nm to 500 nm. In addition, a particle diameter means volume average
particle diameter, and unless otherwise indicated in this specification, let an average particle
diameter be a volume average particle diameter.
04-05-2019
9
[0030]
In addition, as the polymer particles 4b used for the speaker diaphragm film 300 according to
the embodiment of the present invention, for example, polyethylene resin, polypropylene resin,
polystyrene resin, polymethylpentene resin, polyvinylidene chloride resin, Examples thereof
include polyimide resins, polyethylene terephthalate resins, polybutylene terephthalate resins,
polyarylate resins, polyvinylidene fluoride resins, PVF, FEP, ETFE, and thermoplastic resins such
as PTFE and PVDF. These polymer fine particles 4b may be used alone or in combination of two
or more. The particle diameter of these polymer fine particles 4b may be 10 nm to 1.0 μm.
[0031]
Further, the binder component 5 is contained in the thin film made of the inorganic fine particles
4a or the polymer fine particles 4b of the film 300 for a speaker diaphragm of the present
embodiment. As the binder component 5, for example, vinyltrimethoxysilane,
vinyltriethoxysilane, vinyltriacetoxysilane, N-β- (N-vinylbenzylaminoethyl) -γaminopropyltrimethoxysilane, N- (vinylbenzyl) Hydrochloride of 2-aminoethyl-3aminopropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxy Silane, 3glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3methacryloxypropylmethyldiethoxysilane, 3-meta Examples include silane monomers such as
cryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3isocyanatopropyltriethoxysilane and the like.
[0032]
Furthermore, even in the case where the binder component 5 is a water-repellent compound,
particularly in the case where the non-crystalline fluorine-based film 2 covers a part of the
surface of the substrate 1, even in a high humidity environment, etc. The charge of the vibrating
film can be maintained for a long time, which is more preferable. As the water-repellent
compound 5 as the binder component 5, for example, stearic acid acrylate, reactive silicone oil,
dimethyl silicone oil, methylphenyl silicone oil, methyl hydrogen silicone oil, reactive silicone
oligomer, for example, Matsushita Electrical appliance Sangyo Co., Ltd. Frescer D is used.
04-05-2019
10
[0033]
Furthermore, as the water-repellent compound 5, as a fluorine-based compound, an acrylic
monomer having a perfluoroalkyl group, for example, 2- (perfluoropropyl) ethyl acrylate or 2(perfluorobutyl) ethyl acrylate 2- (perfluoropentyl) ethyl acrylate, 2- (perfluorohexyl) ethyl
acrylate, 2- (perfluoroheptyl) ethyl acrylate, 2- (perfluorooctyl) ethyl acrylate, 2- (perfluoro octyl)
ethyl acrylate, Fluoronolyl) ethyl acrylate, 2- (perfluorodecyl) ethyl acrylate, 3-perfluorohexyl-2hydroxypropyl acrylate, perfluorooctylethyl methacrylate, 3-perfluorooctyl-2-hydroxypropyl
ester Acrylate and, 3-perfluorodecyl-2-hydroxypropyl acrylate are used.
[0034]
Further, as the water-repellent compound 5, other fluorine compounds such as 2perfluorooctylethanol, 2-perfluorodecylethanol, 2-perfluoroalkylethanol, and perfluoro can be
used as the fluorine compound. (Propyl vinyl ether), perfluoroalkyl iodide,
perfluorooctylethylene, 2-perfluorooctylethyl phosphonic acid and the like may be used.
[0035]
Furthermore, as the compound 5 having water repellency, as a fluorine-based compound, a silane
coupling agent having a perfluoroalkyl group, for example, CF 3 (CH 2) 2 Si (OCH 3) 3 or CF 3
(CF 2) 5 (CH 2) 2 Si (OCH 3) 3, CF 3 (CF 2) 7 (CH 2) 2 Si (OCH 3) 3, CF 3 (CF 2) 11 (CH 2) 2 Si
(OCH 3) 3, CF 3 (CF 2) 15 (CH 2) 2 Si (OCH 3) 3 , CF 3 (CF 2) 7 (CH 2) 2 Si (OC 2 H 5) 3, CF 3
(CH 2) 2 SiCH 3 (OCH 3) 2, CF 3 (CF 2) 2 (CH 2) 2 SiCH 3 (OCH 3) 2, CF 3 (CF 2) 5 (CH 2) 2 SiCH
3 (OCH3) 2, CF3 (CF2) 7 (CH2) 2SiCH3 (OCH3) 2, CF3 (CF2) 7 (CH) 2) 2SiCH 3 (OC 2 H 5) 2, CF
3 (CF 2) 7 (CH 2) 2 Si (OCH 3) 3, CF 3 (CF 2) 7 (CH 2) 2 Si (OC 2 H 5) 3, CH 3 (CF 2) 9 (CH 2) 8
Si (OC 2 H 5) ), CF 3 (CF 2) 7 CONH (CH 2) 3 Si (OCH 3) 3, CF 3 (CF 2) 7 CONH (CH 2) 2 SiCH 3
(OCH 3) 2, and oligomers having a perfluoroalkyl group and a silanol group, for example, KP801M You may use (made by Shin-Etsu Chemical Co., Ltd.), X-24-7890 (made by Shin-Etsu
Chemical Co., Ltd.), perfluorobuteryl vinyl ether and its polymer, fluoroolefin copolymer, etc.
[0036]
The binder component 5 is preferably added in an amount of 0.1% by mass or more and 40% by
mass or less with respect to the inorganic fine particles 4a or the polymer fine particles 4b in the
fine particle layer.
0.1If it is less than mass%, it is not sufficient to firmly fix the inorganic fine particles 4a or the
04-05-2019
11
polymer fine particles 4b, and if it exceeds 40 mass%, the effect of forming fine irregularities on
the surface of the non-crystalline fluorine-based film is become weak.
[0037]
Fourth Embodiment Next, a speaker diaphragm film 400 according to a fourth embodiment of
the present invention will be described in detail with reference to FIG.
[0038]
FIG. 4 is an enlarged view of a part of the cross section of the speaker diaphragm film 400
according to the embodiment of the present invention.
In the film 400 for a speaker diaphragm according to the present embodiment, a fine particle
layer formed of inorganic fine particles 4a containing a binder component is formed on the
surface of a base 1 forming the main portion of the film 400 for a speaker vibration plate. A noncrystalline fluorine-based film 2 is formed.
The surface of the inorganic fine particle 4a is coated with a silane monomer 6, and the silane
monomer is bonded on the surface of the substrate 1 by a chemical bond 7 (covalent bond) to
hold the inorganic fine particle 4a firmly.
In FIGS. 3 and 4, the non-crystalline fluorine-based film 2 covers the entire fine particle layer
formed of the inorganic fine particles 4 a or the organic fine particles 4 b containing the binder
component 5 formed on the surface of the substrate 1. Although it may be shown in FIG. 1 and
FIG.
[0039]
Furthermore, as a form in which at least a part of the surface of the substrate 1 is covered with a
non-crystalline fluorine-based film, a non-crystalline fluorine-based resin coexists in the inside of
a fine particle layer composed of the inorganic fine particles 4a or the organic fine particles 4b It
is also good. That is, a film in which inorganic fine particles and a fluorine-based film are mixed
may be formed on the substrate 1 as a fluorine-based film. Even in this case, similar effects can
04-05-2019
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be obtained with respect to the chargeability, dust resistance, and the like.
[0040]
Here, the reason why the silane monomer 6 orients and bonds the unsaturated bond or reactive
functional group toward the outside of the inorganic fine particle 4a will be described in detail.
This is because the silanol group which is one end of the silane monomer 6 is hydrophilic, so it is
easily attracted to the surface of the inorganic fine particle 4a, which is also hydrophilic, while
the unsaturated bond or reactive functional group of the opposite end is Because it is
hydrophobic, it tends to leave the surface of the inorganic fine particles 4a. For this reason, since
the silanol group of the silane monomer 2 is covalently bonded to the surface of the inorganic
fine particles 4a by a dehydration condensation reaction, the silane monomer 6 tends to be
oriented with the unsaturated bond portion or the reactive functional group facing outward.
Therefore, for many silane monomers 6, the unsaturated bond or the reactive functional group
and the surface of the substrate 1 can be obtained by directing the unsaturated bond or the
reactive functional group to the outside and covalently bonding to the inorganic fine particles 4a.
Form a chemical bond.
[0041]
That is, the film 400 for a speaker diaphragm, in which the fine particle layer of the inorganic
fine particles 4a used in the present embodiment is formed, uses the silane monomer 6 excellent
in the reactivity having the unsaturated bond portion or the reactive functional group. The noninorganic fine particles 4 a are fixed on the substrate 1 by forming a chemical bond 7 between
the silane monomer 6 on the surface of the inorganic fine particles 4 a facing the substrate 1 and
the surface of the substrate 1. Furthermore, since the plurality of inorganic fine particles 4a on
the substrate 1 are also bonded to each other by the chemical bond 7 between the silane
monomers 6 on the surface of the inorganic fine particles 4a, the inorganic fine particles 4a are
fixed to the substrate 1 more firmly.
[0042]
Examples of the unsaturated bond or reactive functional group possessed by the silane monomer
6 covalently bonded to the inorganic fine particles 4a by dehydration condensation include a
vinyl group, an epoxy group, a styryl group, a methacrylo group, an acryloxy group and an
isocyanate group.
04-05-2019
13
[0043]
As an example of the silane monomer 6 used by the film 400 for speaker diaphragms in which
the thin film which consists of the inorganic fine particle 4a used by this embodiment was
formed, vinyl trimethoxysilane, vinyl triethoxysilane, vinyl triacetoxysilane, N- β- (Nvinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane, hydrochloride of N- (vinylbenzyl) -2aminoethyl-3-aminopropyltrimethoxysilane, 2- (3, 4 epoxycyclohexyl) ) Ethyltrimethoxysilane, 3glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyl
Dimethoxysilane, 3- Methacryloxypropyltrimethoxysilane, 3methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3acryloxypropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane and the like can be
mentioned.
[0044]
The amount of the silane monomer coated on the surface of the inorganic fine particles 4a may
be 0.1% by mass or more and 10% by mass or less based on the inorganic fine particles 4a, and
10% by mass or more The strength is almost constant, and 0.1 mass% or less is not preferable
because a sufficient strength can not be obtained.
[0045]
Next, the manufacturing method of the film 400 for speaker diaphragms of 4th Embodiment of
this invention is demonstrated.
First, the inorganic fine particles 4a in which the silane monomer 6 is chemically bonded to the
surface are mixed and dispersed in a dispersion medium such as methanol, ethanol, MEK (methyl
ethyl ketone), acetone, xylene, toluene or the like.
Here, in order to promote dispersion, surfactants, mineral acids such as hydrochloric acid and
sulfuric acid, and carboxylic acids such as acetic acid and citric acid may be added as necessary.
Subsequently, the inorganic fine particles 4a are crushed and dispersed in a dispersion medium
using an apparatus such as a bead mill, a ball mill, a sand mill, a roll mill, a vibration mill, or a
homogenizer to prepare a slurry containing the inorganic fine particles 4a.
04-05-2019
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[0046]
The covalent bond between the inorganic fine particles 4a and the unsaturated monomer or the
silane monomer 6 having a reactive functional group can be formed by a conventional method.
For example, the silane monomer 6 is added to the dispersion, and then refluxing is performed.
The silane monomer 6 is covalently bonded to the surface of the inorganic fine particles 4a by
dehydration condensation reaction to form a thin film composed of the silane monomer 6 while
heating at the above, or the silane monomer 6 is dispersed in the dispersion liquid obtained by
pulverization. Alternatively, after adding silane monomer 6 and pulverizing into fine particles by
pulverization, solid-liquid separation and heating at 100 ° C. to 180 ° C. to share silane
monomer 6 on the surface of inorganic fine particles 4 a by the dehydration condensation
reaction A method of bonding, and then grinding and crushing and redispersion may be
mentioned.
[0047]
Here, after adding the silane monomer 6 to the dispersion obtained by pulverizing under reflux
or pulverizing, or adding the silane monomer 6 and pulverizing by pulverizing, solid-liquid
separation is carried out to 100 ° C. When the silane monomer 6 is covalently bonded to the
surface of the inorganic fine particles 4a by heating at 180 ° C., the amount of the silane
monomer 6 depends on the average particle diameter of the inorganic fine particles 4a, but the
amount of the inorganic fine particles 4a is If it is 0.01% to 40.0% by mass with respect to the
mass, the bonding strength between the inorganic fine particles 4a and the substrate 1 does not
have any practical problem.
In addition, there may be an excess of silane monomer 6 not involved in bonding.
[0048]
Subsequently, the slurry in which the inorganic fine particles 4a obtained as described above are
dispersed is applied to the surface of the substrate 1 to be fixed. Specific methods for applying
the slurry in which the inorganic fine particles 4a are dispersed include spin coating, dip coating,
spray coating, cast coating, bar coating, microgravure coating, and gravure coating, which are
generally performed. It may be used, and is not particularly limited as long as application suitable
for the purpose can be performed.
04-05-2019
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[0049]
Then, if necessary, the dispersion medium is removed by heat drying or the like to chemically
bond the substrate 1 and the inorganic fine particles 4a. Specifically, by forming a chemical bond
7 between the silane monomers 6 on the surface of the inorganic fine particles 4 a, the inorganic
fine particles 4 a are bonded to each other, and the bonded inorganic fine particles 4 a are
formed between the silane monomer 6 and the substrate 1 surface. The compound is fixed on the
substrate 1 by forming a chemical bond 7 of
[0050]
In the present embodiment, as a method of chemically bonding 7 the substrate 1 and the silane
monomer 6, it is preferable to use a bonding method by graft polymerization.
[0051]
The graft polymerization used in the embodiment includes, for example, graft polymerization
using a peroxide catalyst, graft polymerization using heat or light energy, graft polymerization by
radiation (radiation graft polymerization), etc., and the shape and form of the substrate or silane
monomer It is appropriately selected and used according to
A chemical bond between the surface of the inorganic fine particles 4 a and the silane monomer
6 can be formed by the treatment with a peroxide catalyst, the treatment with heat or light
energy, and the treatment with radiation.
[0052]
Here, in order to carry out graft polymerization of the silane monomer 6 efficiently and
uniformly, the surface of the substrate 1 is previously subjected to corona discharge treatment,
plasma discharge treatment, flame treatment, chromic acid, perchloric acid, etc. A hydrophilic
treatment such as a chemical treatment with an aqueous oxidizing acid solution or an alkaline
aqueous solution containing sodium hydroxide or the like may be performed.
[0053]
04-05-2019
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Through the above steps, a fine particle layer composed of the inorganic fine particles 4 a
strongly bonded to the silane monomer 6 is formed on the substrate 1.
Since the inorganic fine particles 4a are strongly bonded to the substrate 1 by the silane
monomer 6, peeling and the like can be suppressed, and high durability is maintained.
[0054]
Next, an amorphous fluorine-based film 2 is formed on the substrate 1 or the formed fine particle
layer. The non-crystalline fluorine-based film 2 is made of, for example, Cytop (trade name: made
by Asahi Glass Co., Ltd.), Teflon AF ("Teflon" is a registered trademark) (trade name: made by
DuPont Co., Ltd.), tetrafluoro Ethylene-perfluorodioxole copolymer (TFE / PDD) (manufactured by
Mitsui Dupont Fluorochemicals Co., Ltd.) or the like can be used. Since these non-crystalline
fluorine-based resins are soluble in a specific fluorine-based solvent, the type of solution can be
obtained by selecting the type of fluorine-based resin, the degree of polymerization and solid
content concentration, and the type of fluorine-based solvent. It is possible to widely change the
viscosity and solid content concentration. The fluorine-based film 2 has a thin film formed of the
inorganic fine particles 4a or the organic fine particles 4b formed directly on the surface of the
substrate 1 by various methods usually used for thin film formation such as immersion method,
spray method and spin coating method. It forms on the surface with unevenness.
[0055]
Next, the present invention will be more specifically described by way of examples. However, the
present invention is not limited to only these examples.
[0056]
<Production of Film for Speaker Vibrator> (Example 1) For PET film (made by Toray Industries,
Inc., thickness 1.4 μm), CT-solv. 100E (made by Asahi Glass Co., Ltd.) as a fluorine-based coating
material ) Was applied by immersion and dried at 100 ° C. for 1 minute to produce a film for a
speaker diaphragm of Example 1.
04-05-2019
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[0057]
(Example 2) It produced by the method similar to Example 1 except having made the base |
substrate into a PET film (Toyobo Co., Ltd. product, 6.9 micrometers in thickness).
[0058]
Example 3 Teflon AF (“Teflon”) obtained by diluting PET film (made by Toray Industries, Inc.,
thickness 1.4 μm) with Nobek (Sumitomo 3 M Corporation HFE-7200) as a fluorine-based
coating material "A registered trademark" (Dupont's AF 1601 SOL FC 100ML 6%) was applied by
immersion and dried at 100 ° C. for 1 minute.
[0059]
(Example 4) It produced by the method similar to Example 1 except having made the base |
substrate into the film which gave the embossing.
[0060]
(Example 5) 10.0% by mass relative to methanol of zirconia fine particles (Nippon Denko Co., Ltd.
product PCS) which is inorganic fine particles, 3-methacryloxypropyltrimethoxysilane (Shin-Etsu
Chemical Co., Ltd. product) as a silane monomer After 5.0% by mass of KBM-503) was added to
the fine particles to adjust the pH to 4.0 with hydrochloric acid, a solution containing the
adjusted fine particles was pulverized and dispersed to an average particle diameter of 20 nm by
a bead mill.
Then, solid-liquid separation was performed by a lyophilizer, and heating was performed at 120
° C. to chemically bond the silane monomer to the surface of the zirconia fine particles by a
dehydration condensation reaction to form a coating.
[0061]
Add 3 mass% of silane monomer-coated zirconia fine particles prepared by the above method to
methanol, and add tetramethoxysilane (Shin-Etsu Chemical Co., Ltd., KBM-04) as a binder
component to the silane monomer-coated zirconia fine particles The slurry was dispersed by
15.0% by mass and ground and dispersed again by a bead mill.
04-05-2019
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The average particle size of the fine particles in the slurry was 20 nm.
In addition, an average particle diameter here means the thing of volume average particle
diameter.
[0062]
Moreover, after the surface of a PET film (Toray Industries, Inc., thickness 1.4 μm) was
hydrophilized by corona treatment, the above-mentioned slurry whose solid content was adjusted
to 5% by mass was applied and dried at 100 ° C. for 1 minute .
[0063]
Thereafter, the zirconium oxide fine particles were bonded to the surface of the PET film by graft
polymerization of a silane monomer by irradiating the slurry with a PET film with an electron
beam for 5 Mrad at an acceleration voltage of 200 kV.
[0064]
Furthermore, Cytop was applied by immersion on the obtained inorganic fine particle thin film
and dried at 100 ° C. for 1 minute.
[0065]
(Example 6) A methanol dispersion of PTFE fine particles, which is polymer fine particles
(Kitamura Co., Ltd., KD-800AS, particle size 0.3 μm) is adjusted to a solid content of 5% by mass,
and fluorine resin (central glass (central glass ( Cefral coat CC-04) manufactured by Co., Ltd. was
added to the fine particles so as to be 20% by mass to prepare a slurry.
[0066]
Further, the surface of a PET film (manufactured by Toray Industries, Inc., thickness 1.4 μm)
was hydrophilized by corona treatment, and the prepared slurry was applied and dried at 100 °
C. for 1 minute.
[0067]
Furthermore, Cytop was applied by immersion on the fine particle layer made of the obtained
polymer fine particles, and dried at 100 ° C. for 1 minute.
04-05-2019
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[0068]
(Example 7) 5% by mass of solid content of PTFE fine particles (Kitamura Co., Ltd., KT-500L,
particle size 0.3 μm), which are polymer fine particles, is dispersed in Nobek (Sumitomo 3M Co.,
Ltd. HFE-7200) A slurry is prepared by adding 15% by mass of fluorocarbon resin (Central Glass
Co., Ltd., Cefral coat CC-04) to the fine particles and 5% by mass of Cytop as a fluorinated coating
material to the fine particles. did.
[0069]
Further, the surface of a PET film (manufactured by Toray Industries, Inc., thickness 1.4 μm)
was hydrophilized by corona treatment, and the prepared slurry was applied and dried at 100 °
C. for 1 minute.
[0070]
(Comparative example 1) It produced by the method similar to Example 5 except having made
the binder component 100 mass% with respect to the PTFE fine particles.
[0071]
(Comparative example 2) The characteristic was evaluated in the state as it is, without processing
aluminum foil (made by Toyo Aluminum Co., Ltd. product, 6.0 micrometers in thickness).
[0072]
(Comparative example 3) The characteristic was evaluated in the state as it is, without processing
a PET film (Toray Industries Co., Ltd. product, 1.4 micrometers in thickness).
[0073]
(Comparative example 4) The characteristic was evaluated in the state as it is, without processing
a PVDF film (Kureha Co., Ltd. product, 4.0 micrometers in thickness).
[0074]
(Comparative example 5) It produced by the method similar to Example 1 except having made
the base | substrate into a PVDF film (Kureha Co., Ltd. product, thickness 12 micrometers).
04-05-2019
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[0075]
The following tests were performed on the above examples and comparative examples to
evaluate the characteristics.
[0076]
(Charge Amount) For charge amount, cut each sample to a size of 10 × 10 cm, rub the feather
with a feather and charge the test sample, then connect a Coulomb meter (NK-1001)
manufactured by Kasuga Electric Co., Ltd. It measured using the electrostatic charge measuring
device (Faraday cage type KQ-1400).
Furthermore, after the measurement, the test sample was allowed to stand for one week in an
environment of 50 ° C. and humidity 90% RH (Relative Humidity), and then the charge amount
was measured again.
[0077]
(Surface Roughness) Arithmetic mean roughness Ra was measured as a surface roughness state
of the fine asperity layer with a stylus type surface roughness meter (DEKTAK3030ST,
manufactured by ULVAC, Inc.).
[0078]
(Dustproofness) Dustproofness was evaluated using a cotton linter (1.5 μm in diameter, 1 mm or
less in length manufactured by Japan Air Cleaning Association) which is relatively similar to dust
in indoor and indoor sections of homes and buildings.
The test sample (10 × 10 cm) was evenly sprinkled with cotton linters, lightly shocked, and the
weight was measured to measure and evaluate the weight difference between the test samples
before and after the cotton linter was attached.
At that time, the amount of charge was measured before and after adhesion of cotton linters.
04-05-2019
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[0079]
(Sound Output State) Each sample was used as a diaphragm, an electrode was used as a mesh
plate of SUS 325, and an electrostatic speaker was used where the buffer member was a PET
non-woven fabric.
The output state of the sound of the speaker was evaluated by a noise level meter (NL-20
manufactured by Lion Corporation).
At that time, in the case of 80 dB or more, the sound output was evaluated as (○), the case of 40
dB or more and less than 80 dB (Δ), and the case of less than 40 dB as (×).
[0080]
(Stress-strain property) According to the test method of tensile property of JIS K 7127, parallel to
MD (Machine Directrion: flow direction of resin) and TD (Transverse Directrion: direction
orthogonal to MD) direction of film to be measured A strip sample of each direction was cut out
so as to have a width of 50 mm and a grip interval of 200 mm, and used as a test piece.
Each sample is set in a tensile tester RTG-1210 (manufactured by A & D), and an S-S curve, which
is a curve of elongation and tensile load when applying tensile load at a speed of 100 mm / min,
at a yield point The load and elongation are shown in Table 1 as strength [N] and elongation [%].
[0081]
Tables 1 to 3 show the results of the above evaluation test.
[0082]
[0083]
[0084]
04-05-2019
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[0085]
From the above results, as shown in Examples 1 to 6, by forming a film containing a noncrystalline fluorine resin on the film surface, it can be understood that discharge can be
suppressed and sound output is stabilized with time. .
[0086]
Furthermore, it was confirmed that adhesion of cotton dust can be suppressed and discharge can
be suppressed by forming a minute uneven shape on the film surface and setting the surface
roughness to 5 nm or more and 500 nm or less.
[0087]
On the other hand, as shown in Comparative Examples 1 to 4, it can be seen that the sound
output is lowered in the case of a substrate having poor charging characteristics or having
conductivity.
It can be seen that Comparative Example 4 using a PVDF film which is a crystalline fluororesin is
clearly easier to discharge than Examples 1 to 6 in which a film containing a non-crystalline
fluororesin is formed on the film surface.
In addition, in Comparative Examples 1 and 3 in which the surface roughness is 500 nm or more,
cotton linters are easily attached, and therefore, it was confirmed that the electric charge was
easily discharged and the durability was inferior.
Further, Comparative Example 5 is not preferable because the mass per unit area is large and the
sound output is poor even in the charged state.
[0088]
As for mechanical properties, in Examples 1, 3 and 5 in which the non-crystalline fluorine-based
film was formed on the polymer film surface, the strength was about 20 to 50% and the
04-05-2019
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elongation was higher than Comparative Example 3 of the polymer film alone. The degree is
improved 4.7 to 7.5 times.
It was confirmed that the mechanical characteristics could be improved, in particular, slight
potential change due to remarkable elongation improvement could be converted into large
displacement, and practical design of thin film and lightweight speaker diaphragm film could be
possible due to strength improvement. .
[0089]
Therefore, it was confirmed that the film obtained in the present invention is a useful film for a
speaker diaphragm, which has excellent charging characteristics and can maintain performance
over a long period of time.
[0090]
100, 200, 300, 400 film for speaker diaphragm 1 base 2 fluorine-based film 4 a inorganic fine
particle 4 b polymer fine particle 5 binder
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