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The present invention relates to an acoustic diaphragm having a high upper limit frequency band
and a wide reproduction frequency band. [Prior Art] Materials generally used as acoustic
diaphragms are lightweight, have high elasticity, have moderate internal 1-part loss, and have a
large ratio of Young's modulus E to density ρ, that is, a large propagation speed fτ 7 Is
required. Heretofore, natural fibers such as valves, polymer films / foams, metal plates and the
like have been used as the material f [of the diaphragm for sound. However, the diaphragm using
pulp fiber t · 1k has a large internal loss, but has a small elastic modulus, is easily affected by
temperature Gj, and has a drawback that the sound quality and characteristics are easily
changed. In addition, since the diaphragm made of the polymer film and the foam is inferior in
elastic modulus, it is not satisfactory as a diaphragm for sound. The metal plate has a
disadvantage that the elastic modulus is relatively high but the internal loss is small. Therefore,
good frequency characteristics could not be obtained depending on the acoustic diaphragm made
of these materials. Also, an acoustic diaphragm using glass fiber, carbon fiber, or silicon carbide
fiber having high elasticity has been proposed. But these mineral jJ! Since the internal loss of
fibers is small, it is difficult to f, 1) good frequency # -7. [Section to be Solved by the Invention:
BE] The present invention solves the drawbacks of the conventionally used materials, has a high
high frequency limit, a wide reproduction frequency band, and can reproduce delicate, good
sound quality. It is in providing a board. [Means for Solving the Problems] The present invention
provides an acoustic device comprising a vibration substrate and a ceramic layer formed by
applying a ceramic heat resistant paint to all or part of the surface of the vibration substrate and
then heat treatment. Provide a diaphragm. Examples of the material of the vibration substrate
used in the present invention include metals such as aluminum and titanium, glass fibers, carbon
fibers, inorganic fibers such as silicon carbide fibers, and polyimide resins. As the ceramic heatresistant paint in the present invention, generally used is one containing an organic silicon
compound as a binder and containing fine powders such as oxides, nitrides and carbides as an
inorganic filler, or further containing a silicon resin. Be As the organosilicon compound,
polycarbosilane or polymetallocarbosilane is preferable. Polycarbosilane is composed of the
following bonding units (A) (A):-(S 1 -CH 2)-and the following bonding units (B) (B):-(Si-3i)-, and
each silicon element And the lower chain has a lower alkyl group, a phenyl group or a hydrogen
atom independently of each other, and the ratio of the total number of bonding units of (A) to the
total number of bonding units of (B) is 20 = 1 to 1 It is in the range of 1:20 and has a number
average molecular wind of 400 to 50.000.
Polymetallocarbosilane is represented by the following (C) (C):-(S1-CHz) -R,-(wherein, R7 and R2
may be the same or different, and independently of each other, a lower alkyl group, a phenyl
group or A carbosilane-bonded unit of hydrogen atom) and at least one of the following (D) <D):(M-0)-(wherein M is at least one selected from the group consisting of Ti, Zr, Cr and MO) (C) and
(D) consisting of one or more elements, and in some cases at least one part of each of the above
elements has at least one lower alkoxy group or phenoxy group as a side Wi group) A polymer in
which each bonding unit is randomly bonded in the main chain, and / or at least a part of the
silica f /: atom of the bonding unit of the (C) is a bonding unit of the (D) A polymer in which a
polycarbosilane moiety obtained by bonding of each element to an oxygen atom and thereby
obtaining a chain of bonding units of (C) is crosslinked by the bonding unit of (D), An
organometallic polymer comprising a ratio of the total number of binding units in (1) to the total
number of binding units in (D) in the range of 1 = 1 to 10 = 1 and a number average molecular
weight of 400 to 50,000 is there. The inorganic filler used in the present invention is at least one
selected from the group consisting of oxides, borates, phosphates, silicates, silicides, borates,
nitrides, and carbides, and It illustrates below. Boric acid, magnesium, aluminum, silicon, calcium,
titanium, vanadium, chromium, manganese, sub-button, zirconium, molybdenum, cadmium, tin,
antimony, barium, tungsten, button, bismuth oxide, carbide, nitride, Silicides, porides, lithium,
sodium, potassium, magnesium, calcium, nitrous S (borates of one, phosphates, silicic acid, etc.
The silicone resin used in the present invention is silicone oil, silicone rubber, silicone oil or the
like. 10 to 900 parts by weight of the inorganic filler is preferably added or 50 to 5001 iJt parts
with respect to 100 parts by weight of the organic silicon oxide compound. Alternatively, silicone
(A fat 10 to 900 parts by weight, preferably 50 to 500 parts by weight is added. The mixture is
dissolved or dispersed in a suitable solvent such as benzene, toluene, xylene or the like to obtain
a paint. The heat resistant paint is disclosed in Japanese Patent Application Laid-Open Nos. 6248773, 1-m Sho 62-54768, and Sho-sho 62-235370 filed by one of the present applicants. .
The heat resistant paint is applied to the surface of the diaphragm at least 50% of the surface
area by a method such as brushing, spraying, immersion or the like. The thickness of the coating
layer after drying is preferably 20 to 100 μm. After drying, the ceramic layer is formed on the
diaphragm surface by baking and curing for 30 to 90 minutes at a temperature of preferably
200 to 400 ° C. In addition to the present invention, there is also known an acoustic diaphragm
in which alumina powder or carbon powder is plasma-sprayed on a vibrating substrate and then
heat treated to form a ceramic layer. On the other hand, it is difficult to form a ceramic and has
poor adhesion to the substrate. The diaphragm for sound of the present invention can apply a
dome to various diaphragms, such as a speaker, a cone type speaker, and a pawn type speaker. 1
and 2 show an example in which the ceramic layer 3 of the present invention is formed on the
cone-shaped diaphragm 1 and its center cap 4, and FIGS. 3 and 4 show the dome-shaped
diaphragm 5. An example is shown in which the ceramic layer 3 of the present invention is
formed, and 2 indicates an edge. Hereinafter, the present invention will be described based on
examples. Reference Example 5! In an N-type flask, 11400 g of anhydrous xylene as 2.51 is
placed, heated to the boiling point of xylene under a nitrogen gas flow, and dropwise added with
dimenaldichlorosilane 11 over 1 hour. I made a thing. The precipitate is filtered and washed first
with methanol and then with water. 1120 g of white powdery polydimethylsilane was obtained.
By charging 400 g of the polydimethylsilane described above into a 31 m flask equipped with a
gas inlet pipe, a stirrer, a cooler and a distillation pipe and heating at 420 ° C. under nitrogen
stream (5017 sin) while stirring. The distillation receiver contained 350 g of a clear, colorless,
slightly viscous liquid, and the number average molecular weight of this liquid was 470 as
measured by vapor pressure osmometry (VPO method). Also, measurement of far-infrared
absorption of this substance shows that the composition is mainly composed of-(SiC + 42)bonding unit and-(Si-3i)-bonding unit, and an organic gay cord polymer having a hydrogen atom
and methyl absorption in the side chain of silicon. It confirmed that it was. Next, 400 ml of xylene
was added to a mixture of 40 g of this organosilicon polymer and 20 g of titanium
tetrainpropoxide to form a mixed solution consisting of homogeneous phases, and the reaction
was allowed to reflux while stirring at 130'C for 1 hour under nitrogen gas flow. went. After
completion of the refluxing reaction, the temperature was further raised to distill off xylene as a
solvent, and polymerization was carried out at 300 ° C. for 0 hours to obtain an organometallic
crosslinked polymer containing silicon and titanium.
The number average molecular weight of this polymer was 1185 as measured by the vPo
method. The polymer obtained here from the gel permeation chromatograph and the infrared
absorption spectrum has a partial disappearance of the S i -1-1 bond in the organosilicon
polymer, and the silicon atom of this portion is titanium tetraiso10. It is bonded to the titanium
atom and the oxygen atom of the oxo-oxide, thereby partly containing -0-Ti (OCzHy) 3 group in
the side chain of the organosilicon polymer, and partly the organosilicon polymer is-(Tie)- A
bond-crosslinked polytitanocarbosilane, a conversion rate of a 5t-II bond in the polymer and / or(Sj C112) -linked unit and-(Si-3i) of an organosilicon polymer moiety It was recognized that the
ratio of the total number of -binding units to the total number of -O-Ti (oC3l-17) 3 and -TiObinding units was about 6: 1. The above reaction product was dissolved in xylene to form a 50%
solids solution. The 1250% solution of polytitanocarbosilane obtained in Example Reference
Example 50, 50-foot portion, silicon carbide 3o! "1 part and 20 fffiffi parts of silicone varnish
were mixed to obtain a heat resistant paint. The paint was applied to the entire surface of an
aluminum cone-shaped diaphragm as shown in FIG. 1 with a brush and dried at 100 ° C. The
thickness of the coating layer after 92 cycles was 50 μm. After drying, it was baked at a
temperature of 200 ° C. for 60 minutes to be cured. The frequency characteristic of the
obtained diaphragm is shown in FIG. In the figure, 1 is the diaphragm of the present invention,
and 2 is the one to which the heat resistant paint is not applied. As is clear from the nature of
this item 1, the diaphragm of the present invention has a high upper limit frequency. According
to the acoustic diaphragm provided with the ceramic layer of the present invention, the ceramic
layer has a high elastic modulus, the transmission speed is high, and the high frequency limit
frequency can be made high. In addition, since the reproduction frequency band is wide, and the
characteristics during reproduction and harmonic distortion can be reduced, it is possible to
reproduce delicate, good sound quality. Furthermore, since the acoustic diaphragm of the present
invention forms a ceramic layer, it has an effect of being excellent in high temperature resistance,
oxidation resistance, chemical resistance, moisture resistance and weather resistance.
Furthermore, the acoustic diaphragm of the present invention can be easily ceramized to form a
ceramic layer, and is excellent in adhesion to the acoustic substrate.
Brief description of the drawings
1 to 4 show cross-sectional views of the acoustic diaphragm of the present invention, and FIG. 5
is a graph showing frequency characteristics of the acoustic diaphragm of the present invention
and a conventional acoustic diaphragm.
1: Cone-shaped diaphragm 3; Ceramic layer 5: Dome-shaped diaphragm Apply for Ube Industries,
Inc. 1 other person
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