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The present invention relates to a method of manufacturing a diaphragm for an all-carbon
acoustic device. More specifically, it is lighter and more elastic than conventional diaphragms for
speakers and microphones, and it is excellent in rigidity, so deformation due to external force is
small, distortion of sound is small, and reproduction range is wide, The present invention relates
to a method of producing an all-carbon diaphragm that can produce clear sound quality and is
suitable for the age of digital audio. Generally, it is desirable that the following conditions be
satisfied as a diaphragm for a speaker or the like. (1) The density is low. (2) The Young's modulus
is large. (3) The propagation speed of the longitudinal wave should be large. (4) The internal loss
of vibration is moderately large. (5) It is stable against changes in external air conditions and is
free from deformation or deterioration. (6) The manufacturing method is simple and inexpensive.
Zunawa, wide frequency range (()) can be reproduced faithfully over a wide range ((, efficient, to
be clear sound quality, high rigidity, creep due to external stress In order to increase the speed of
sound from the equation of V = F, / V (V: sound velocity, E: Young's coefficient, :: density) in
history, a material with small density and high Young's modulus is required. Ru. Conventional
swing jlfj, materials such as paper (pulp), plastic, aluminum, ram, titanium, magnesium, beryllium,
holon and the like are used as the base 4A to which glass fiber or carbon fiber is compounded, or
gold j Alloy, gold), boronitrides, metal carbides, metal borides, etc. were used. However, paper,
plastics and their composite materials have a low ratio of Young's modulus to density, so that the
speed of sound is slow, and the split vibration is caused in a specific mode and the frequency
characteristics in the high frequency band are significantly reduced. It is difficult to obtain good
sound quality, and moreover, it is easily influenced by the external environment such as
temperature and humidity, and has a defect such as qualitative deterioration of the material or
fatigue over time to deteriorate the characteristics. On the other hand, when a metal plate such
as aluminum, magnesium 1 or titanium is used, the sound velocity is fast and the performance is
excellent, but the internal loss of vibration is small to cause a sharp resonance phenomenon in
the quotient frequency region or the fatigue over time such as creep of material In addition,
boron, beryllium and their nitrides, carbides, borides, etc. are + A agents having excellent
physical constants, and they are used as diaphragms. Since the reproduction limit is lower than
the audio frequency band, the signal in the audio band can be correctly reproduced without a
transient phenomenon and natural sound quality can be expressed.
However, these materials are extremely high filli] and industrially, the processing is extremely
limited by the national law, and the conventional diaphragm manufacturing method by roll
rolling and press forming has poor practicality, C, C, D, D, P, ν, D1, etc., it is necessary to use the
vapor deposition method that requires advanced technology14, so the processing cost is
extremely expensive, and there are drawbacks such as difficulty in manufacturing a large-sized
speaker SUMMARY OF THE INVENTION In view of the above-mentioned disadvantages of the
conventional diaphragm material, the present invention provides a diaphragm consisting
essentially of carbon consisting of a carbon / carbon composite material, which makes use of the
excellent physical properties of carbon. It is in. As is well known, carbon has extremely wide
physical and chemical properties ranging from crystalline carbon such as tire monde and
graphite to amorphous carbon such as carbon black and charcoal. We have researched
intensively to express various functional properties aimed at by designing and combining these
carbon materials according to the required + XX ability, and a carbon / carbon composite family
of all-carbon diaphragms The manufacturing method is completed. The present inventors have
found that the theoretical elastic modulus of graphite crystal is 1020 GPa and has a very high
elastic modulus as compared to other materials, and carbon fibers obtained from two industries
have a low modulus of 39 ~ Focusing on the fact that the elastic modulus of an ultrafine pencil
lead composed of a natural graphite / carbon binder is from BO to 150 Gtla, and it also extends
to 441 to 706 GPa with 98 GPa and ultra-high modulus products. In order to form a carbon thin
film in which resin carbon is used as a matrix and carbon powder such as natural graphite having
a high elastic modulus is compounded into an arbitrary shape, the invention was carried out.
Furthermore, control of the amount tan δ (vibration internal loss coefficient) representing the
size of Young's modulus and internal loss by changing the type, particle size, shape and packing
ratio of the graphite powder, or the type and blending ratio of carbon powder to be composited.
Discovered that it is possible to do. As the raw material of the carbonaceous matrix used in the
present invention, it is possible to use pitch, tar, 44 = 1 fat or the like used as a raw material for
carbides, but the reason for selecting the thermosetting resin is in particular The degree of
formation is high (the strength of the formed form is at ease, and it can be ringed), and further
carbonization can be prevented without causing any complicated pretreatment when carbonizing.
By performing the process easily. Furthermore, by kneading the carbon powder and resin to be
filled before adding the curing agent with a kneader or the like having a sufficiently high shear
force, the resin, carbon 'a, and powder are mechanochemically acting. It is because it is easy to
disperse it highly and it is easy to obtain a stable raw material pace [• on storage before use.
As the thermosetting resin to be used in the present invention, furan 44 (jI Fi 1 + phenol rays 11
JI + ds, xylene 441 II effect 1, polyimide resins, polyamino 1-imide resin cheek, hismaleimide
resin, etc. can be used However, as a) good for the j jyo charge adjustment, shaping, shape at the
time of firing, 1) work 1) 1 is economically advantageous, it is a furfurilated I-le / turfural / nor
system, Furan (A1 fat) 'J1 of furfural / area type etc. and phenol tree j1 th f of resol type, novolac
type etc. (or mixed 4 Mf JIFi thereof is preferred. Next, natural carbon black powder used in the
present invention includes natural graphite, artificial graphite, quino graphite, super ^ II elastic
modulus graphite fiber, carbon black, charcoal 15 or the like, and mainly exhibits high elastic
modulus function For this purpose, highly crystallized natural graphite and [elastic modulus
graphite fiber are preferable, and for the purpose of increasing internal loss, it is preferable to
add carbon blank, charcoal powder or the like which is amorphous]. Furthermore, in order to
balance and design these high elastic modulus and internal '911 tf4 loss characteristics, it is
carried out by changing the type and blending ratio of the carbon powder to be added. Further,
the particle size of the graphite powder used is preferably an average particle diameter of 0.1 to
200 μm or preferably U7, and the ultra-high modulus graphite fiber has a fiber length of 3 or
less. Next, a method of manufacturing a diaphragm according to the present invention will be
described. After pre-dispersion in a high-speed stirrer such as a Henschel mixer, carbon 'jl 45)
powder to be combined with a thermosetting 4AJ monomer or precondensing polymer without
adding a curing agent is pre-dispersed, and then a Hall mill, three bottles of ml- The mixture is
sufficiently kneaded using a high shear force kneader such as a double reel or the like to obtain a
stable composition like a paste. Next, a predetermined amount of a curing agent is added to the
paste-like acid and the mixture is kneaded with a high-speed agitator or a three-roll mill to
disperse the curing agent, and the air / package removed by intervention through a vacuum
deasphalting apparatus is removed. Do. The obtained raw material composition is preformed into
a film or sheet 1- of a desired thickness by a coater or a calender roll using a hack sheet having
t1 Tachibana old j 俯. Next, remove the hacksea 1- in the area (+3 stage) that does not cure the
film or the sheet j or plastic ('f itself) and remove the press molding machine, vacuum molding
machine, molding machine L1-molding machine, etc. It is molded into a desired diaphragm shape.
At this time, it is necessary to appropriately heat and increase the plasticity · 11 and make the
curing reaction proceed (-).
After the buildup is fully cured 7 and then demolded to take out the form. iiJられた41. In
a heated air oven (': after curing Jfj after molding, the molding is collected in a baking oven &.
]L C. In an inert gas phase such as nitrogen or alkoncus, carbonization is performed by
heating and burning at 1000 ° C. to 1000 ° C. 7. 11. In this baking and carbonizing step,
heating up gradually at a temperature rising rate of 50 ° C./hour or less (preferably 20 °
C./hour or less) up to 500 ° C. or preventing deformation and preventing defects such as cracks
11. It is important for In the region of 500 ° C. or higher, heating is performed at a temperature
rising rate of 20 to 200 ° C. / 肋 (preferably for economic reasons, 50 to 100 ° C./hour), and
the uniformity of the carbonization reaction is further increased. 6 '([For maintaining the
temperature at the maximum temperature for 1 to 5 minutes, then let it naturally cool and bake
it. Hereinafter, the present invention is shown by d ≠ 釧 by implementation jul + 4, but it is not
limited to this range. Xjt-Example-1 Initial condensation product of furfuryl alcohol / furfural
resin (1) (Tachi Chemical Industries, Ltd. 9 VF-302) 60% by weight and 40% by weight of natural
ring-shaped graphite (average particle diameter 1 μm) r) 1 After blending into a ナ ー ー ミ ー
ミ ー and dispersing it uniformly, using a water-cooled three-roll mill for ink mixing, the viscosity
is further adjusted by 1) mixing, and the viscosity is adjusted. It is. Obtained original] '1-1 base Ito 11 100% 100% solid, as a curing agent p-1- luensulphonic acid 50% methanol? A degassing
operation was carried out by passing it through a vacuum degassing machine with sufficient
addition of Ib, 6 wt%, and stirring sufficiently at room temperature using a high speed pommizer.
The obtained paste composition is applied to a hack sheet having a release film by a coater
having a doctor blade set to a film thickness of 200 μm, and is pre-cured to have sufficiently
flexible plasticity (B stage state ) Preformed sheet 1- (r-7). Next, remove the hack sea 1 · and mold
it into a dome shape with a vacuum forming machine using an IS-human shape mold having a
bore of GO mmφ, heat cure with warm air at 80 ° C, and demold to obtain a formed structure It
is 1M. This molded product is further post-cured in an air oven at 150 ° C. for 5 hours, placed
in a baking furnace, heated at a temperature rising rate of 500 ° C. ° C./hour in a nitrogen gas
atmosphere furnace, The heating temperature is 500 ° C. to 11000 ° C., and the temperature
is increased at 50 ° C./hr. Subsequently, after holding at 1000 ° C. for 3 hours, natural cooling
was performed to complete the firing.
In this way, all-carbon dome-shaped vibration control & J having a diameter of 52 鰭 φ, a
thickness of 100 μm, a weight of 400 曙 and a blowout rate of 175 GPa, an acoustic velocity L1.
Those showing physical properties of Okm / sec, density 1.45g / cta are listed. 70% by weight of
“S j” (-I resol based phenol resin (PL-2818 manufactured by Gunei Chemical Co., Ltd.) and
carhon black (Mitsubishi Kasei Co., Ltd.% MA-8> 30 FJX amount%) in the same manner as
Example 1 The raw material paste composition was obtained by processing. Next, the same
operation was performed by a coater to make 1911 j 500 μm preforming sheet 1-. After the
sheet was dried, the back sheet was removed and the resulting sheet was molded into a cone
shape of 3 Q cmφ in diameter and hardened by a press molding machine equipped with all the
molds at 150 ° C. and demolded to obtain a formed body. The resulting green body was fired to
1200 ′ ′ C in the same manner as in Example 1 to obtain an all carbonaceous cone-shaped
diaphragm. The diaphragm thus obtained has the following characteristics: diameter i: 25.4
cmφ, diameter I: 27 (Ium, weight i 20.5 g, Young's modulus 126 GPa, sound velocity 9.5 km /
sec, density 1.40 g /- The The results obtained by comparing the characteristics obtained by the
present invention with a conventional diaphragm material are shown in the following table.
Characteristics Speed of sound Young's modulus Density Internal loss MMv (k1 n / se Lee (GPa L
mountain L to phantom-uP night)-') aluminum 5.1 70.0 2.7 titanium 4.9 + 10.0 4.5 7 gnesium
5.1 44.0 1.72-3 Helirium 12.2 270.0 1.8 Polyp 1 "Pyrene l, 3 1.5 0.9 GO1 Loss (Pal) 1.0 to 0.2 to
0.2 20 to 2.4 4.0 0.7 60 Examples] 11.0 175.0 1.45 8 to 10 Examples 29.5 126.0 1.40 10 to 20
Examples as judged from the table In No. 1, the sound speed is almost equal to that of the
helirium, and in both Example 1 and Example 2, the sound speed is about twice that of the
conventional fully-flexible vibration plate. Further, since internal loss (tan δ (A 1> is also several
times to nearly 10 times larger than that of a metal plate), the high-pass resonant frequency
region can be greatly enhanced, and the dynamic range can be expanded. Furthermore, since the
harmonic distortion rate of sound can be lowered by about 1 / 3.10 dll or less by two ", clear
sound quality is 1! ,? ることができるようになった。 Our superior characteristics are digital
audio such as recent compact compact displayers that boast clear sound quality and wide
dynamic range of lty;
Sufficient ability can be exhibited as a dexterous diaphragm. As described above, according to the
present invention, the diaphragm having high performance can be manufactured at low cost G by
a simple process. Patent applicant Ms. Lead Lead writing, Inc. Procedure N City Masaho ':
(Spontaneous) June 1, 1984 Secretary General of Patent Office Kazuo Wakasugi Hall 1,
Indication of the Case Patent Application No. 229378 No. 2, Invention Name All-carbon sound
equipment diaphragm manufacturing method 3, relationship with the case of correction Patent
applicant address Tokyo parts for Higashi Oi 5-chome 23-37 name (595) Mitsubishi Pencil Co.,
Ltd. 4, agent Person's address ■ 104, Chuo-ku, Tokyo, 8-15, No. 10, Ginza Diamond Heights
410, column [Detailed description of the invention], column 6, contents of correction (1) on page
3, line 12 of the specification Correct rV-FE / .rho. to rV-E / .rho.j. (2) On page 5, line 5, correct "",
and correct "j". (3) Correct "all types" on page 12, line 11 to r molds. (4) Correct “Iron (pulp)”
on page 13, line 9 to “Paper (pulp)”. (5) Correct "Displayer" on page 14, line 10 to "Disc
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