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JPH04336796

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DESCRIPTION JPH04336796
[0001]
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a
heat-resistant loudspeaker diaphragm for use in an electroacoustic transducer such as a
loudspeaker.
[0002]
2. Description of the Related Art In the past, as the heat-resistant paper in the general paper
market, asbestos (asbestos) paper was representative, but recently there is a strong suspicion of a
carcinogenic substance. From this, it is said that there is almost no new recruiting from the
industry. In recent years, glass fiber paper and carbon fiber paper have been put on the market
as heat-resistant paper, but in most cases, organic materials (polyvinyl alcohol) are used as
fibrous binders. The addition amount is also 10% or more, as predicted from the heating loss
(400 ° C. + 2 hours). Moreover, the fiber paper strength is low, and the tensile strength is 0.5 kg
/ mm 2 or less, and there are few products having a strength higher than this. Some products do
not use organic materials, but strength is such that they support their own weight.
[0003]
[0003] On the other hand, some of the diaphragms for speakers, which are called heat-resistant
paper, are used by adding several percent of heat-resistant fibers (Kevlar fibers, glass fibers, etc.)
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to wood pulp. Considering the maintenance of strength, the addition rate is limited to about 5 to
10%. Further additions have not been realized to significantly reduce the strength of the paper.
Under these circumstances, it can not be said that it is a practical heat-resistant paper. The fiber
paper diaphragm in which high elastic fibers having heat resistance superior to that of cellulose
fibers account for 90% or more is a difficult existence.
[0004]
In the case of a paper-like matrix of high elasticity (elastic modulus and higher than general
purpose fibers) fibers, whether inorganic or organic, in comparison with paper made of cellulose
fibers: The high modulus fiber has nonpolar and inert surface chemical structure, and has a
slightly polar weak amide group (-NHCO-) and imide group (-N = (CO-) 2) in the aromatic
polyamide fiber If present only, there is no strong polar group, i.e., hydroxyl group (-OH), which
can form hydrogen bonds between fibers and significantly improve inter-fiber bond strength.
Therefore, the surface of many fibers is hydrophobic, and these phenomena are also a cause of
low water absorption, low hygroscopicity and good insulation. 2. The contact area between
fibers, which is important for the strength of the paper-like matrix, is small because these fibers
have a high modulus of elasticity, the fibers are rigid, and the crystallinity is high. Also, like
cellulose fibers, it swells and plasticizes in water, and a strength increase effect (CampbellCampbell effect) can not be expected as the contact area between the fibers is expanded. 3.
Most of these high modulus fibers have a small fiber diameter to enhance fiber strength, but the
specific surface area is still smaller than wood pulp (specific surface area 1.0 m 2 / g), and fiber
diameter and density Although depending on the amount, it is about 0.25 m 2 / g, and there is no
improvement in mechanical strength due to the increase in the inter-fiber contact area by the
fibers themselves. 4. Of course, the friction resistance between fibers is small, and it is
impossible to expect the improvement of the internal loss as well as the strength. 5. Since the
inorganic fiber has a small specific surface area and a high fiber density, the settling speed in the
slurry is high, and since the fiber surface is hydrophobic, the uniform dispersibility is not good
either, so it is difficult to obtain a homogeneous paper.
[0005]
【0005】6. Thus, the high elastic fiber is hydrophobic, rigid and has no Campbell effect, so
the moisture content of the paper-like fiber matrix is low, bulky and low in density, and the
surface tension between the fibers does not work and the web (Web (Web = Composite of fiber
and water) Strength is also weak. Therefore, it is also impossible to transfer or peel the web from
the papermaking net during papermaking. High elasticity fiber is not swollen or plasticized by
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2
water, is rigid, is not rigid, does not work surface tension of water, can not expect a Campbell
effect, and is poor in web forming property (consolidation consolidation property) as compared
with cellulose fiber. That is, since the relationship with water is small, it is difficult to obtain
strength like cellulose fiber paper. However, the fiber strength of the high elastic fiber is high, the
elastic modulus is high, and excellent properties such as water resistance, humidity resistance,
heat resistance, flame retardancy, etc. far exceed the properties of cellulose fiber, so Once the
application technology is established, useful fiber paper diaphragms with various properties of
these fibers can be expected.
[0006]
As described above, high elastic inorganic fibers, high elastic organic fibers, etc. are used to form
a strong sheet which can practically withstand, and the condition for obtaining a diaphragm
having a suitable internal loss is the physical properties of the fibers themselves. It is necessary
to devise the characteristics and papermaking technology to be used as finished paper, or to
establish the post-treatment method (secondary treatment). On the other hand, it is necessary to
study the chemical conditions of the fiber itself, the treatment method after forming the paper,
etc. in order to obtain a paper having heat resistance, flame retardancy, water resistance,
moisture resistance and the like.
[0007]
However, considering the strength of the paper as a finished paper with these techniques, it is
very difficult to make it a practical paper comparable to wood pulp, and naturally it is essential
that the interfibers are essential as a speaker diaphragm. I can not expect the rise of internal loss
using the friction resistance of In order to make the paper strength to withstand practical use,
practical vibration plate production is impossible unless addition of a fibrous binder or adhesive
is considered.
[0008]
The mechanical strength of the paper-like matrix is physically related to the strength of the fiber
material, the fiber form (fiber length, cross-sectional shape, fiber diameter), the surface condition
of the fibers, etc., and the method of increasing the density of the formed paper. The actions and
effects of strong paper are as follows. Operation effect a. The fiber form is 1. Strong fiber
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strength: Strong and non-brittle, tough fiber Long fiber length: Decrease in fiber cut surface3.
Thin fiber diameter: Increase in fiber-to-fiber contact area by expansion of specific surface area4.
Cross-sectional shape is ribbon-like: increase in fiber-to-fiber contact area, densification b. The
surface condition of the fiber is
[0009]
5. Having a polar group on the surface: The presence of a strong polar group (−0H) improves
the dry strength by establishing hydrogen bonds between fibers, and also improves the web
strength by the action of a strong surface tension of water. Use of adhesive fiber and adhesive:
Improvement of inter-fiber adhesive strength 7. Adhesiveness with Fibrous Binder, Binder:
Increase in strength by increasing entanglement between fibers 8. It can be plasticized by
absorption of water: Improvement of strength by increasing the contact area (Campbell effect)
between fibers c. Density of finished paper is 9. Packing between fibers with short fibers to
increase the density: Combination of short fibers (milled or fibrillar fibers) or fine substances and
long fibers increases the filling ratio between fibers, and improves web strength and dry strength
10. Covering fibers with a material with a large specific surface area: Increase the contact area
between fibers and improve the web strength and dry strength Various properties such as heat
resistance, flame retardancy, water resistance, moisture resistance, etc. The effects and effects
are as follows in relation to the 11. High binding energy of main chain of molecular structure:
good thermal resistance because high decomposition temperature is required. Containing
nitrogen, phosphorus, halogen, metal element in molecule: Flame retardant, heat resistant 13.
High crystallinity: improvement of water resistance and moisture resistance 14. Surface polarity
is inactive (non-polar): improvement of water resistance, moisture resistance 15. Large diameter,
increase the density of paper: Flame retardance by reducing the contact area with air If the above
conditions are not satisfied, a diaphragm having practical strength and having the abovementioned properties can not be produced.
[0010]
However, although wood pulp is excellent in most of the above conditions, its fiber strength is
inferior to that of high modulus fibers. Thus, the biggest problem with high modulus fiber paper
involves the "how to increase the density of the paper" papermaking technology.
[0011]
The present invention has been made in view of these points, and the object of the present
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invention is to use a high elasticity fiber to obtain excellent flame retardancy or water resistance,
humidity resistance, high strength and high strength. It is an object of the present invention to
provide a heat-resistant speaker diaphragm having elastic modulus and high internal loss.
[0012]
[Means for Solving the Problems] In order to achieve the above object, the heat-resistant speaker
diaphragm of the present invention comprises high-elasticity inorganic fibers and high-elasticity
organic fibers as short fibers or inorganic powders. Super-beaten wood pulp with a large specific
surface area is added as a fibrous binder to make a paper, and further, a silicate compound
having excellent heat resistance, an organic metal polymer compound, an inorganic compound,
an aromatic polyamide, an imide compound, etc. It is characterized in that it is impregnated with
excellent heat resistance, flame resistance or water resistance, humidity resistance and high
strength, high elastic modulus and high internal loss.
[0013]
[Functions] The conditions for producing strong paper with low cohesion fibers such as high
elasticity fibers are strong, long and thin fibers, and the fibers are filled with milled fibers,
fibrillated fibers and fine powder. Therefore, it is necessary to cover with a fibrous material
having a large specific surface area or other material and have a high density.
The present invention increases the fiber-to-fiber filling ratio by combining high-elasticity fiber
short fibers (cut fibers, milled fibers, fibrillated fibers), measures the increase in density of the
formed paper, super-refined wood pulp, and has a large specific surface area The super-beaten
wood pulp (10.0 m 2 / g or more) having 0.5 to 30 parts as a fibrous binder is added to increase
the inter-fiber bonding strength to make a paper.
Furthermore, it is impregnated with a solution of heat resistant silicate having a bonding
performance, an organic metal polymer compound, an organic polyamide, an imide compound,
an inorganic compound or the like to cover the fibers, and has high strength, high elastic
modulus, etc. It is to provide a diaphragm in which physical properties are enhanced to improve
various properties such as heat resistance, flame retardancy, water resistance and humidity
resistance. Since internal loss uses super-beaten wood pulp having a large specific surface area,
the frictional resistance between fibers is improved, and high internal loss can be obtained. In
addition, the ultra-beaten wood pulp has high specific surface area, so it has good dispersibility
and strong cohesion, so it is excellent in the dispersibility of inorganic fibers with high density,
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and it is possible to reduce the settling speed and make a uniform slurry.
[0014]
EXAMPLES The states and types of these highly elastic fibers, materials used in the present
invention, such as an impregnating agent, will be described. The cut fibers are obtained by
setting long fiber bundles (yarns) with a sizing agent, cutting with a rotary blade, and making the
length 1 to 72 mm, and many 1 to 7 mm suitable for papermaking. Longer lengths are used for
nonwovens. It contributes to the improvement of strength and elastic modulus of paper, and
almost all fibers, organic or inorganic, are used. The elastic modulus and the heat resistance
temperature of each fiber are described below. Both are manufacturer catalog values.
[0015]
High elastic inorganic fiber (elastic modulus Ton / mm 2 / heat-resistant temperature ° C.) a.
Glass fiber (7.5 / 650) Fiber diameter: 9.6 microns: Nippon Sheet Glass, Nitto spinning b. Carbon
fiber (24-70 / 1000-1200) Fiber diameter 7 microns: Toho Rayon, Toray, Mitsubishi Kasei c.
Alumina fiber (15-4 / 1200-1600): Dupont, Mitsui Metal Mining, (Al2O3: 80% or more)
Sumitomo Chemical d. Ceramic fiber (16-25 / 1200-1600): Ibiden, Nippon Steel, (SiO 2 / Al 2 O 3
= 4.0-0.1) Isolite e. Silicone carbide SiC fiber (18-20 / 1200): Nippon Carbon "Nicalon" f. Boron
tungsten B / W fiber (40/1600): New chemical and metal silicon carbide carbon SiC / C fiber
(43/1600) Japan g. Titanium silica fiber (20/1300): Ube Industries "Chirano" h. Silicon nitride
fiber (25/1200): Tonen "silicon nitride fiber" i. Cement fiber (-/ 1300): Nippon cement "CMF" j.
Calcium silicate fiber (-/ 1300) CaSiO 3: Onoda cement k. Potassium titanate whisker fiber
(28/1350): Otsuka Pharmaceutical "Tismo" l. Metal fiber (19/1450): Nippon Seisen "Naslon"
High-elasticity organic fiber a. Aromatic polyamide fiber Para-based: Dupont Toray Kevlar "Kebla
(6.3-15.5 / 500)", Sumitomo Chemical "Twalon" (0.8-1.8 / 375) Meta-based: Teijin "Conex" ,
Dupont Toray "Nomex" Unitika "A Pierre" b.
Aromatic polyetheramide fiber (7.1 / 500): Teijin "Technola" c. Liquid crystalline wholly aromatic
polyester fiber (7.6 / 400): Kuraray "Vectran" and polyethylene terephthalate copolymer fiber d.
Polybenzimidazole (PBI) Fiber: Teijin "PBI" Fiber (0.6 / 560) e. Aromatic polyetherimide fibers
(0.45 / 400): Teijin "PEI" f. Aromatic polyamideimide fiber: Rhone-Poulenc "Kelmer" (0.8-1.3 /
380) g. Polyether ether fiber (0.5-1.5 / 350): Teijin "PEEK fiber", Mitsui Toatsu Chemical "Talpa"
h. Polyphenylene sulfone fibers: Kureha, Teijin (0.5-1.0 / 280) i. Phenolic fiber (0.3- / 300):
Nippon Kainol "Kainol" j. Polyparaphenylene benzbisthiazole: USA Air Force (PBT) fiber (25-28 /
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600) k. Ultra-high molecular weight acrylic fiber (2.0 / 140): Asahi Kasei "Cashmillon", Mitsubishi
Rayon l. Polyether sulfone fiber
[0016]
m. Polyoxymethylene fibers (4.0 / 190): Asahi Kasei "tenac" [0016] When milled fibers are cut
fibers cut with a fiber length of 1 to 7 mm and made into a paper-like matrix, the density of the
paper becomes low, The fiber-to-fiber contact area is reduced and the strength is reduced. In
order to prevent the decrease in density and to increase the contact area between fibers, short
milled fibers or fibrillated fibers described below are used for the purpose of filling the gaps
between the cut fibers. Fibers mainly made of high-elasticity fiber scraps to 0.5 to 0.7 mm with a
grinder, and the fiber diameter can be reduced to several microns, and the specific surface area
reaches 0.5 to 4 m 2 / g. In general, it is used as a reinforcing fiber for general-purpose resins,
and it can be used as a web-strength-retaining agent when it is peeled off from a papermaking
net in paper, and works to increase the density of the paper and increase the strength. Inorganic
fibers are more frequently used than organic fibers and used to improve the density of inorganic
fiber paper.
[0017]
【0017】
[0018]
Carbon fiber: For resin mixing For carbon fiber manufacturers Carbon fiber manufacturers: Glass
fiber for paper mixing: Aromatic polyamide fiber for paper: For paper mixing Kevlar pulp Dupont
Toray Kevlar aromatic polyether fiber: For paper mixing Technora pulp Teijin Alumina, ceramic
fiber: for resin mixture All-aromatic polyester fiber for paper companies: paper for paper Vectran
pulp Kuraray [0018] The fibrillated fiber acts as a filler between fibers in the same manner as the
milled fiber, It can increase the density of the paper, but since the specific surface area than the
milled fibers much larger can improve the strength of the interfiber bonding, web strength,
which contributes greatly to the improvement of dry strength.
Wood pulp can increase its specific surface area to several m 2 / g by ordinary beating, but high
modulus fibers do not fibrillate by general beating and can not expand its specific surface area.
Other mechanical methods can be used to increase the specific surface area, or other fibers can
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be used to fibrillate and utilize this. There are a method of fibrillating organic synthetic fibers and
cellulosic fibers to submicrons in a special way to increase the specific surface area, and a
method of using a large specific surface area from the beginning.
[0019]
One of the methods for producing fibrillated fibers (fibrit fibers) is to dissolve a fiber material in
an organic solvent, jet it into a nonsolvent which is being stirred, disperse and fibrillate it. As a
result, the fiber length is 3 to 5 mm, the fiber diameter is up to submicron, and the specific
surface area is about 1 to 10 m 2 / g. This fibrillated fiber is referred to as fibrilt fiber. At present,
this method is only possible with organic synthetic fibers, and has a great effect in increasing the
density of synthetic fiber paper. It is said that it is possible to increase the specific surface area to
several m 2 / g to several 10 m 2 / g by selecting the type of non-solvent. Currently, only metabased aromatic polyamide fibers are possible.
[0020]
【0020】
[0021]
Teijin: "Cornetsk Pulp" Unitika: "Apierre Pulp IAW IBT" Dupont: "Fibrit 102 103" Super beaten
wood pulp is also a method of hyperfibrillating wood pulp, which is a diameter of web-like wood
pulp A high pressure is applied to the gap (slit) between the piston and the cylinder, which are
different from each other, and they are reversely rotated with each other, and repeated several
times to superbeaten to fibrillation along the fiber axis to fibrillate. .
The specific surface area of the resulting ultra-beaten wood pulp reaches 10.0 m 2 / g or more,
and super beating up to 200 m 2 / g is possible. A binder that maintains the shape of fibers with
a large specific surface area, and is effective in improving the paper strength of non-bondable
inorganic and organic fiber paper, and the inter-fiber friction resistance increases due to a
significant increase in the inter-fiber contact area, and internal loss Increases rapidly. By superrefining synthetic fibers and processed fibers in addition to the above-mentioned wood pulp, it is
possible to provide a fibrous binder which improves the strength and the like of the fiber paper.
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[0022]
【0022】a. Ultra-rapid liquid-crystalline thermoplastic all-aromatic polyester fiber Vectran
(Kuraray) is cut into 3 mm, made into a slight web shape, and ultra-beaten in the same manner as
wood pulp to give an ultra-large specific surface area. A beaten Bectran fiber is obtained. This
super-beaten fiber is mixed with super-beaten wood pulp and inorganic fibers such as carbon
fiber, and after paper making, when it is heat-pressed near the melting point of Vectran fiber, the
carbon fibers (inorganic fiber) are thermally bonded and liquid crystal fiber It is possible to
obtain carbon fiber (inorganic fiber) paper which has high internal loss, high strength, high
elasticity, heat resistance and flame retardancy. b. Super beating of Kevlar (Para-based Dupont
Toray), Conex (Meta-based Teijin), Apier (Meta-based Unitika), etc., which are short fibers of
ultra-refined aromatic polyamide of aromatic polyamide fiber, in the same manner as wood pulp
Thus, it is possible to obtain ultra-beaten aromatic amide fibers having a large specific surface
area. When this ultra-beaten fiber is mixed with the super-beaten wood pulp with short fibers, an
aromatic amide fiber paper having strength, heat resistance and flame resistance can be
obtained. c. Chitosan's super-beaten chitosan can also be super-beaten in the same manner as
the above-mentioned wood pulp. Blending with chitosan fiber enables strong biopaper. d.
When the hydroxyl group and methylol group of the super-beaten wood pulp of phosphorylated
wood pulp are phosphated with polyphosphates, phosphoric acid and the like, an extremely
excellent flame retardant pulp can be obtained. This phosphated pulp can be ultra-refined in the
same manner as the above-mentioned wood pulp to obtain a flame-retardant super-refined
phosphated pulp having a large specific surface area. When this ultra-beaten phosphated pulp
and super-beaten wood pulp are mixed with organic high modulus fibers, short fibers such as
high modulus inorganic fibers, or ordinary wood pulp, they have high strength, high modulus,
and heat resistance, Good flame-retardant fiber paper is produced.
[0023]
Although the web strength at the time of papermaking is determined by the water content, the
high elasticity fiber has a low water content as compared with cellulose fiber paper, and the
surface tension of water does not work between the fibers and the web strength is weak. The
corn sheet-forming process is a batch-type, transfer process, and requires a certain level of web
strength. Although the above-mentioned super-beaten wood pulp is useful as a web strength
improver to increase its strength, in particular, heat-resistant inorganic fiber paper has long been
used sepiolite which is a fine needle-like crystal. There is. Add 10% hydrogen peroxide to
sepiolite to make a 3% slurry. The mixture is stirred for 30 minutes with a disintegrator at a
rotational speed of 3000 rpm and completely separated. When 10% of this slurry is added to the
fiber suspension, the strength of the web at the time of papermaking is remarkably improved,
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and it can be easily peeled off from the paper mesh. The pulp having a large specific surface area
thus formed can be a fibrous binder and can be a binder of a high elastic fiber material having
low binding performance. 100% sepiolite paper is also commercially available as heat resistant
paper.
[0024]
The inorganic powder is most effective in increasing the density of the paper, and the physical
properties of the paper are different depending on the shape, and the strength and the modulus
of elasticity become higher as the ratio of asbestos is larger. In particular, mica has a great effect
on these physical properties. Although sepiolite alone becomes paper-like, it has a large specific
surface area and is thus suitable for improving the strength of the web.
[0025]
Granular talc Tancal strength Fibrous asbestos strength Flaky mica glass flake Graphite Flexural
elasticity, internal loss Needle-like sepiolite web strength Impregnation of silicate compounds,
organic metal polymers, inorganic compounds, aromatic polyamides, imide compounds, etc. The
agent, the substance considered for use in the present invention will be described. Of course,
high heat resistance can not be expected with the construction of only the high elastic fiber short
fibers and the ultra-beaten wood pulp as a fibrous binder, and silicates and organometallics can
be used to wrap this super-beat wood pulp. By impregnating the compound, high strength and
high elastic modulus are obtained, and further heat resistance and flame retardancy are provided.
[0026]
As silicate compounds, sodium silicate and potassium silicate are known, but lithium silicate
Li2SiO3 n H20 (Li20 / SiO2 = 7.2-7.8) is different from the above two, and after drying It does
not become water soluble again, does not absorb water, has water resistance and humidity
resistance, and heat resistance does not decrease in weight up to 1000 ° C.
[0027]
The organic metal compound is mainly a compound having a structure in which silicon is
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contained in the main metal and elements of titanium and boron (boron) are bonded thereto.
When the temperature is high, the organic substance disappears, and a large amount of metal
components are formed to be ceramics (metal oxide). Compound name Main chain structure Heat
resistance a. Organometallic polymer compounds ■ Polysilane-Si-Si-450 ° C or higher Silicone
varnishes-Polycarbosilane-Si-C-1000 ° C or higher Nippon Carbon "Nicalocoat" ■ Alcoxidides M
(OR) n M = Ti A material with a small amount of C in R, such as Si, Zr, ZnR = -CnH2n + 1Si(OC2H5) 4, is hydrolyzed in air to form amorphous SiO2, and the heat resistance becomes 400C
or higher. Nippon Synthetic Rubber, Catalyst Chemical, Nippon Soda b. Organic boron-containing,
silicon compounds borosiloxane-B-O-Si-O-800 ° C or higher Organic titanium-containing silicon
compound polytitanocarbosilane-Ti-Si-O-C-1200 ° C or higher Ube Industries "Tyrano coat" d.
Organic nitrogen-containing silicon compound polysilazane-N = Si 1200 ° C or more Tonen-ko
"polysilazane" e. Organic aluminum-containing silicon compound polyaluminoxane-Al-O-1000 °
C or higher Sumitomo Chemical f. Organo sol Alumina sol Al2O3 650 ° C or more Each
company Silica sol SiO2 1200 ° C or more Each company g. Organic phosphazene-N = P (OR) 2400 [deg.] C. or higher As inorganic compounds other than Idemitsu Petrochemical Dainichi
silicon silicon salt, alumina sol, silica sol and the like are also used.
[0028]
The press-dried diaphragm is impregnated with a resin of an aromatic polyamide or an imide
compound, and the compound having a polyamic acid type is cured at a high temperature.
Indicate the typical manufacturing company and product name. a. Aromatic polyamide
compound Unitika "Apiere" b. Aromatic polyimide compounds Toray "Trenees", Dupont "Bail"
Mitsubishi Gas Chemical "BT Resin" c. Aromatic polyamideimide compounds Hitachi Chemical
"HI-400", Sumitomo Electric "Sumisame" AMCO "AMCO AI-10" d. Aromatic polyester imide
compounds Sumitomo Electric "Sumithem F-555" Dainichi Seikei "Telebec" e. Aromatic polyhidatoin compound Sumitomo Bayer "Resser PH-10" f. Aromatic benzimidazole compound
[0029]
g. Aromatic polybenzothiazole compounds h. Aromatic polypyromellitic acid imide compounds
i. Polypalamban acid Tonen "Sollac" [0029] The present invention has high elastic fibers (cut
fibers, milled fibers, fibrillated fibers) excellent in heat resistance and flame retardancy, as
described above, but having a paper-like matrix And adding 0.5-30% as a fibrous binder of ultrabeaten wood pulp having a large specific surface area (10.0 m 2 / g or more) mechanically
11-05-2019
11
super-beaten as described above for practical use. The strength and modulus of elasticity are
increased, and the large specific surface area which can not be obtained with a normal beating
machine, the friction resistance between fibers is significantly improved, the internal loss is
increased, and silicates and organometallic polymers. The diaphragm is impregnated with a
solution of a compound, an inorganic compound, an organic polyamide, an imide compound or
the like to produce a diaphragm having heat resistance and flame resistance.
[0030]
Description of various test evaluation methods Calculated from tensile strength and tensile
modulus stress distortion curve (SS-Curve). 2. Measured and calculated using an internal loss
torsion free reduction visco-elasticity measuring instrument (made by Lesca). 3. The heat loss
rate at 400 ° C. for 2 hours is measured. 4. Flame Retardant According to JIS D 1201
“Flame Retardant Test Method for Organic Materials for Automobile Interiors”. The details will
be described using examples, and the physical properties, heat resistance, and flame retardancy
of fiber paper (diaphragm) will be described in the separate table.
[0031]
Common to the examples are the papermaking agent and the impregnating agent. 1. Paper
making chemicals The pH during paper making was made neutral and the principle was to use
the same medicine as in the manufacture of neutral paper, but when using glass fiber, the same
medicine as for acid papermaking in view of further improvement in strength It was used. In
order to prevent "floating" in the fiber slurry, nonionic and anionic surfactants are added to
improve the wetting of the fiber surface with water, and further, air bubbles in the fiber matrix
are removed. A silicone antifoam was used to remove it. This made it possible to obtain a paper
with uniformity. The polymeric flocculant, sodium polyacrylate, is added to load finely divided
materials into a paper-like matrix. It is used in the case of mica powder, potassium titanate
whisker fiber, cement fiber, calcium silicate fiber and the like.
[0032]
【0032】2. In order to give the diaphragm a better heat resistance and flame retardancy
than the impregnating agent, it is impregnated with a solution of silicate, organometallic polymer
compound, inorganic compound, organic polyamide, imide compound etc. There are many types,
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so in each of the present examples, the following treating agents were mainly used and described
in abbreviated form. Compound name Abbreviation Processing condition Manufacturing
company a. Lithium silicate Li-Si 10% solution First class reagent b. Organometallic polymer
polyborosiloxane B-Si 10% solution Showa Electric Wire Electronics, "borosiloxane" c. Same as
above Polytitanic siloxane Ti-Si 10% solution Ube Industries "Tyrano coat" d. Same as above
Polycarbosilane Si-C 10% solution Nippon Carbon "Nicalo coat" e. Metal alkoxide compound
[0033]
Ethylated silicate Si- (OC2H5) 4 (SiO2) 10% solution Nippon Synthetic Rubber Butylated Titanate
Ti- (OC4H9) 4 (TiO2) 10% solution Mitsubishi Edogawa Chemical f. Aromatic polyamide resin
Apierre Apierre 10% solution Unitika g. Aromatic polyimide resin BT resin BT resin 10% solution
Mitsubishi Gas Chemical The lithium silicates, metal alkoxides, aromatic polyamides, imides, etc.
mentioned above have the compounds only by volatilizing the solvent after impregnation with
the solution. While sufficient heat resistance can be exhibited, organometallic polymer
compounds such as polyborosiloxane, polytitanium siloxane, polycarbosilane and polysilazane
sufficiently exhibit the heat resistance of the compound only by volatilizing the solvent after
impregnation It can not be said that I did. Organometallic compounds have organic properties at
low temperatures, but when treated at high temperatures of 400 ° C. or higher, they become
ceramic and change to inorganic properties. At the time of this ceramicization, the super-beaten
wood pulp which is a fibrous binder added is burned off, and instead, a strong ceramic is formed
between the fibers to improve the strength of the fiber paper. This also improves the heat
resistance and makes the fiber paper ceramic. The treatment method is as follows depending on
the type of the compound.
[0034]
In the case of polycarbosilane, crystals of Nippon Carbon "Nicalocoat" polycarbosilane are
dissolved in an organic solvent such as toluene and xylene at a ratio of 30 to 40%, and the
followings such as ceramic fiber paper and carbon fiber paper are dissolved in this The inorganic
fiber paper shown in Examples 1 to 7 is impregnated and dried at normal temperature for about
1 hour to volatilize most of the organic solvent, and the fiber paper is made to contain 50% or
more. Next, it is pre-baked at 250 ° C. for 30 minutes and then fired gradually to 600 ° C. to
form silicone carbide SiC and to be ceramicized, significantly improving the inter-fiber bond
strength at high temperature, and heat resistant to fiber paper give.
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[0035]
In the case of polysilazane, Tonen "polysilazane" As above, polysilazane is dissolved in an organic
solvent such as toluene or xylene at a concentration of 30 to 40%, and this solution is
impregnated with the inorganic fiber paper shown in Examples 1 to 7 below. Similarly, the
solvent is volatilized and dried at normal temperature to make the fiber paper contain 50% or
more. It is calcined at 250 ° C. for 30 minutes and then calcined at 700 to 800 ° C. to form a
siloxane siloxane SiON (silicon oxynitride) with a yield of 95% to form a ceramic. As a result, the
fiber-to-fiber bond strength at high temperatures is significantly improved, and the fiber paper is
given heat resistance.
[0036]
In the case of polytitanium siloxane, polytitanium siloxane dissolved 30-40% in an organic
solvent such as Ube Industries "tilano coat" toluene, xylene, etc. is impregnated with the
inorganic fiber paper shown in the following Examples 1 to 7 at normal temperature The solvent
is volatilized, 50% or more is contained in fiber paper, and temporary baking is carried out at
250 ° C. for 30 minutes, and then main baking at around 700 ° C. forms ceramic siloxane by
forming titanium siloxane TiOSi with a yield of 96%. . As a result, the fiber-to-fiber bond strength
at high temperature is improved to impart heat resistance to the fiber paper.
[0037]
In the case of polyborosiloxane, the inorganic fiber paper shown in the following Examples 1 to 7
is impregnated with 30 to 40% of polyborosiloxane in the same manner as Showa Electric Wire &
Cable "borosiloxane", After firing and main firing at 600 to 700 ° C., boron carbide BC, boron
siloxane SiOB, etc. are formed between fibers in a yield of 98% to be ceramized. As a result, the
fiber-to-fiber bond strength at high temperature is improved to impart heat resistance to the fiber
paper. It withstands high temperature continuous use at 450 ° C, and can withstand even 1000
° C instantaneously without losing its flexibility even at 600 ° C.
[0038]
EXAMPLE 1 Ceramics staple fibers (Ibiden Ibi wool, electrochemical alsene) produced by a
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blowing method are put into a separator to remove as much as possible the shot (particulate
matter) and the content thereof is 15%. 30 to 70 parts of glass fibers (E type-Glass Nippon Sheet
Glass) cut with a fiber length of 3 mm to 5 mm with short fibers and ultrafine fibers with a fiber
diameter of 6 microns are added. 100 PPM each of surfactant and antifoaming agent which is a
fiber wetting agent are added, 10 to 15 parts of super-beaten wood pulp is added as a fibrous
binder, and 3% slurry is fully disintegrated by a disintegration machine (pulper), Add a
papermaking agent, make pH 4.0, make a paper with a conventional paper machine, and press
dry. A solution of a silicate compound, an organic metal compound or the like is impregnated
with this to improve the heat resistance, strength and elastic modulus, or to improve flame
retardancy and water resistance, and has flame resistance and high elastic modulus dried. A heatresistant speaker diaphragm can be obtained. a. The following are used as the abovementioned fiber material. Ceramic staple fiber (blowing method) shot 15% or less: 70 parts Glass
fiber E-Glass 6 micron diameter 3 mm cut product: 30 parts Super beaten wood pulp: 10 parts b.
The following are used as paper-making chemicals. Wetting strength improver Ethylene urea
resin: 1.50% Size Rosin: 0.50% PH adjustment Dilute sulfuric acid: PH 4.0 c. Impregnation
Treatment In order to improve the flame retardancy, heat resistance and high modulus of
elasticity of the above-mentioned fiber paper, the following impregnation treatment is carried
out. 1. Impregnation of a 10% solution of lithium silicate The fiber paper obtained above is
fully impregnated with a 10% solution of lithium silicate in water, dried at 60 ° C. and then
pressed at 100 ° C. for about 1 minute to correct the shape Do. 2. Impregnation of
Polycarbosilane Solution The crystalline polycarbosilane is dissolved in an organic solvent
toluene 30%, to which the above fiber paper is gently impregnated and dried at room
temperature. When the odor of the organic solvent disappears, temporary baking is performed at
400 ° C. for 60 minutes. Even in this state, it can withstand 300 ° C., but if necessary, it can be
ceramicized by raising it to a higher temperature (2 hours at 600 ° C.).
3. Impregnation of polysilazane solution The fiber paper is fully impregnated with a 30%
toluene solution of polysilazane, dried at room temperature until the odor disappears, and then
temporary baking is carried out at 400 ° C. for 1 hour. Even in this state, it can withstand 300
° C. for a long time, but when treated at a high temperature state of 600 ° C. for 2 hours, it can
be made into fiber paper which can be made into a ceramic paper and can withstand up to about
1000 ° C.
[0039]
Example 2 30 to 70 parts of a ceramic short fiber (shot = non-fibrous particles, content 15% or
less) obtained by the blowing method and having long ceramic fibers cut into 3 mm is added.
Make a 3% slurry and add 100 ppm each of surfactant and antifoam to improve wettability. To
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this, 10 to 15 parts of super-beaten wood pulp is added as a fibrous binder, sufficiently
deaggregated and stirred to obtain a uniform slurry. A paper-making agent is added to give a pH
of 4.0, which is paper-made by a conventional paper machine and press-dried to form a
diaphragm. Furthermore, it can be impregnated with a solution of a silicate compound and an
organic metal compound to obtain a heat-resistant speaker diaphragm having flame retardancy,
high elastic modulus and high rigidity. a. The following are used as the above-mentioned fiber
material. Ceramic staple fiber (blowing method) shot 15% or less: 70 parts Ceramic fiber 6μ × 3
mm cut product: 30 parts Super beaten wood pulp: 10 parts b. The following are used as papermaking chemicals. Wetting strength improver Ethylene urea resin: 1.50% Size Rosin: 0.50% PH
adjustment Dilute sulfuric acid: PH 4.0 c. Impregnation Treatment The fiber paper obtained by
the above operation is treated with the same lithium silicate, polycarbosilane, polysilazane or the
like as in Example 1 to measure flame retardancy, heat resistance and increase in elastic
modulus.
[0040]
Example 3 Ceramic staple fiber 25 parts of a 3 mm glass fiber cut product and 15 parts of
potassium titanate whisker fiber were added to the above 60 parts, and a polymer coagulant
(poly) was used to capture whisker fiber (Otsuka Pharmaceutical Tismo). 100 PPM of sodium
acrylate) and 10 parts of sepiolite are added to this, 10 to 15 parts of super-beaten wood pulp as
a fibrous binder is added, sufficiently disintegrated and stirred, and a predetermined amount of
paper making agent is added, PH4 The resultant is made into a sheet by a conventional paper
machine and press dried to form a diaphragm. Furthermore, a solution of a silicate compound
and an organic metal compound can be impregnated to obtain a heat-resistant speaker
diaphragm having flame retardancy, high elastic modulus, and high rigidity. a. The following
are used as the above-mentioned fiber material. Ceramic staple fiber: 60 parts Glass fiber 6 μ ×
3 mm cut product: 25 parts Potassium titanate whisker fiber: 15 parts Sepiolite: 10 parts Super
beaten wood pulp: 10 parts b. The following are used as paper-making chemicals. Wetting
strength improver Ethylene urea resin: 1.50% Size Rosin: 0.50% Polymer flocculant Sodium
polyacrylate: 100 PPM PH adjustment Dilute sulfuric acid: PH 4.0 c. Impregnation treatment The
fiber paper obtained by the above operation is treated with a lithium silicate salt to measure
flame retardancy, heat resistance and high modulus.
[0041]
Example 4 Acrylonitrile (PAN) carbon fiber (Toho rayon, Vesphyt) is cut into 7 μ × 3 mm, and
30 to 50 parts of milled carbon fiber (Nippon Sheet Glass Dona Carbo) and 3% slurry are added
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thereto. Then, 100 PPM of a surfactant and an antifoaming agent are added to improve
wettability, and 10 to 15 parts of super-beaten wood pulp as a fibrous binder are added,
sufficiently disintegrated and stirred. This is formed into a sheet by a conventional paper
machine and press dried to form a diaphragm. Furthermore, it can be impregnated with a
solution of a silicate compound and an organic metal compound to obtain a heat-resistant
speaker diaphragm having flame retardancy, high elastic modulus and high rigidity. a. The
following are used as the above-mentioned fiber material. Carbon fiber 3 mm cut product: 50
parts Milled carbon fiber: 50 parts Super beaten wood pulp: 10 parts b. The following are used as
paper-making chemicals. Infiltration strength improver Epoxy polyamide resin: 1.50% Size Dimer
acid ester: 0.50% PH: 6.5 c. Impregnation Treatment The fiber paper obtained by the above
operation is treated with the same lithium silicate, polycarbosilane, polysilazane or the like as in
Example 1 to measure flame retardancy, heat resistance and increase in elastic modulus.
[0042]
[Example 5-1] PAN-based carbon fiber: 25 parts of the 7 μ × 3 mm cut product, milled carbon
fiber, and 50 parts of mica for paper making (Nippon Mica) added to 25 parts of 0.5 to 0.7 mm A
3% slurry was prepared, to which 100 PPM each of surfactant and antifoam as a wetting agent
were added, and 100 PPM of a polymer flocculant sodium polyacrylate was added to sufficiently
capture mica powder. To this, 10 to 15 parts of super-beaten wood pulp, which is a fibrous
binder, is added, sufficiently deagglomerated with a peptizer, and stirred to form a uniform
slurry. A predetermined amount of a paper making agent is added to this, and paper making is
performed with a normal paper machine, followed by press drying to form a vibrating plate.
Further, if necessary, it is impregnated with a solution of a silicate compound, an organic metal
polymer compound and an inorganic compound to improve various properties such as flame
retardancy, water resistance, humidity resistance, etc., high strength, high elastic modulus, high
internal A heat-resistant speaker diaphragm having a loss can be obtained. a. The following
are used as the above-mentioned fiber material. Carbon fiber 7μ × 3 mm cut product: 25 parts
Milled carbon fiber: 25 parts Mica for papermaking: 50 parts Super beaten wood pulp: 10 parts
b. The following are used as paper-making chemicals. Wetting strength improver Epoxy
polyamide resin: 1.50% Size Dimer acid ester: 0.50% PH: 6.5 c. Impregnation Treatment The fiber
paper obtained by the above operation is treated with the same lithium silicate, polycarbosilane,
polysilazane or the like as in Example 1 to measure flame retardancy, heat resistance and
increase in elastic modulus.
[0043]
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Example 5-2 PAN-Based Carbon Fiber 20 to 50 parts of mica for papermaking (Nippon Mica) is
added to the 7 μ × 3 mm cut product to make a 3% slurry. A surfactant and an antifoamer are
added as 100% each as a wetting agent to this, 10 to 15 parts of ultra-beaten wood pulp is added
as a fibrous binder, and the mixture is sufficiently deagglomerated and stirred by a disintegrator.
To this, a paper-making chemical is added, and paper-making is carried out with a normal paper
machine, followed by press drying to form a diaphragm. Furthermore, it can be impregnated with
a solution of a silicate compound, an organic metal polymer compound or the like to obtain a
heat-resistant speaker diaphragm having high strength, high elastic modulus and high internal
loss. a. The following are used as the above-mentioned fiber material. Carbon fiber 7μ x 3mm
cut product: 70 parts Papermaking mica: 30 parts Super beaten wood pulp: 10 parts b. The
following are used as paper-making chemicals. Wetting strength improver Epoxy polyamide
resin: 1.50% Size Dimer acid ester: 0.50% PH: 6.5 c. Impregnation Treatment The fiber paper
obtained by the above operation is treated with the same lithium silicate, polycarbosilane,
polysilazane or the like as in Example 1 to measure flame retardancy, heat resistance and
increase in elastic modulus.
[0044]
EXAMPLE 6 A polymer flocculant (sodium ariacrylate) 100 PPM and 10 parts of sepiolite are
added to a 5 to 7 mm cut product of cement fiber (Nippon Cement CMF), to which super beaten
wood as a fibrous binder is added. 10 to 15 parts of pulp is added, sufficiently deaggregated and
stirred, a predetermined amount of paper making agent is added, the mixture is made by a
common paper machine, and it is pressed and dried to form a diaphragm. Furthermore, a
solution of a silicate compound and an organic metal compound can be impregnated to obtain a
heat-resistant speaker diaphragm having flame retardancy, high elastic modulus, and high
rigidity. a. The following are used as the above-mentioned fiber material. Cement fiber: 100
parts Sepiolite: 10 parts Super beaten wood pulp: 10 parts b. The following are used as papermaking chemicals. Wetting strength improver Epoxy polyamide resin: 1.50% Size Dimer acid
ester: 0.50% Polymeric flocculant Sodium polyacrylate: 100 PPM PH: 6.5 c. Impregnation
treatment Not impregnated in this study.
[0045]
Example 7 100 PPM of a polymer coagulant (sodium polyacrylate) and 10% of sepiolite added to
calcium silicate fiber (Onoda cement) and 10 to 15 parts of super beaten wood pulp as a fibrous
binder The mixture is sufficiently disintegrated and stirred, a predetermined amount of paper
making agent is added, and paper making is performed with a normal paper machine, followed
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by press drying to obtain a diaphragm. Furthermore, a solution of a silicate compound and an
organic metal compound can be impregnated to obtain a heat-resistant speaker diaphragm
having flame retardancy, high elastic modulus, and high rigidity. a. The following are used as
the above-mentioned fiber material. Calcium silicate: 100 parts Sepiolite: 10 parts Super beaten
wood pulp: 10 parts b. The following are used as paper-making chemicals. Wetting strength
improver Epoxy polyamide resin: 1.50% Size Dimer acid ester: 0.50% Polymeric flocculant
Sodium polyacrylate: 100 PPM PH: 6.5 c. Impregnation Treatment The fiber paper obtained by
the above treatment is treated with the same lithium silicate, polycarbosilane, polysilazane or the
like as in Example 1 to measure flame retardancy, heat resistance, and increase in elastic
modulus.
[0046]
Example 8-1 Liquid crystalline wholly aromatic polyester fiber Bectran HT 5.0 De × 3 mm cut
product (Kuraray), PAM type carbon fiber 3 mm cut product (Toho rayon) 50 to 100 parts and
milled 50 to 100 parts of carbon fiber (Nippon Sheet Glass) and the like are added, and 100 PPM
each of surfactant and antifoaming agent as a wetting agent are added to make a 3% slurry. To
this, 10 to 15 parts of super-beaten wood pulp are added, sufficiently deaggregated and stirred
with a disintegrator, a paper-making chemical is added, paper making is carried out with a
normal paper machine, and press-dried. High strength, high elasticity, high internal loss by
pressing liquid crystal wholly aromatic polyester fiber and bonding between carbon fibers by
pressing with temperature 300 to 350 ° C and pressure 4.0 Kg / cm2 with the next press
machine It can be set as the diaphragm for heat-resistant speakers of flame retardance, and it has
it. If necessary, the above properties can be further improved by impregnating with a solution of
a silicate compound, an organic metal polymer compound or the like. a. The following are
used as the above-mentioned fiber material. Vectlan HT 5.0 De × 3 mm cut product: 40 parts
Carbon fiber 7 μ × 3 mm cut product: 30 parts Milled carbon fiber: 30 parts Super beaten
wood pulp: 10 parts b. The following are used as paper-making chemicals. Wetting strength
improver Epoxy polyamide resin: 1.50% Size Dimer acid ester: 0.50% PH: 6.5 c. Impregnation
treatment The above fiber paper is hot pressed with a press at a temperature of 350 ° C., a
pressure of 4 kg / cm 2 and a time of 5 minutes to melt the liquid crystalline thermoplastic
wholly aromatic polyester fibers and bond the carbon fibers together. In some cases, the strength
between fibers is increased. Furthermore, this can provide the fiber paper with the large internal
resistance and heat resistance of this liquid crystalline fiber.
[0047]
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EXAMPLE 8-2 A milled carbon fiber (Nippon Sheet Glass Dona Carbo) is added to a short carbon
fiber (Toho Rayon, Vesphit), and a super-beaten liquid crystalline wholly aromatic polyester as a
fibrous binder is added thereto. Add fibers (Clera, Bectran HT101) and super-beaten wood pulp,
add 100 ppm each of surfactant and antifoam as a wetting agent to make a 3% slurry, and
sufficiently disintegrate and stir with a disintegrator. This slurry is formed into a sheet by a
conventional paper machine and press dried to form a diaphragm. Next, the press temperature is
set to 300 to 350 ° C., and the pressure is set to 4 kg / cm 2 or more. This melts super-refined
wholly aromatic polyester fibers, bonds the carbon fibers together, increases the fiber-to-fiber
strength, has high strength, high elasticity, high internal loss, and is for flame-resistant heatresistant speakers It can be a diaphragm. If necessary, the above properties can be further
improved by further impregnating with a solution of silicate, organic polymer compound,
inorganic compound and the like. a. The following are used as the above-mentioned fiber
material. Carbon fiber 7 μ × 3 mm cut product: 50 parts Milled carbon fiber 0.5 to 0.7 mm: 50
parts Super beaten liquid crystalline wholly aromatic polyester fiber: 30 parts Super beat wood
pulp: 10 parts b. The following are used as paper-making chemicals. Wetting strength improver
Epoxy polyamide resin: 1.50% Size Dimer acid ester: 0.50% PH: 6.5 c. Impregnation treatment
The above fiber paper is hot pressed with a press at a temperature of 350 ° C., a pressure of 4
kg / cm 2 and a time of 5 minutes to melt the liquid crystalline thermoplastic wholly aromatic
polyester fibers and bond the carbon fibers together. In some cases, the strength between fibers
is increased. Furthermore, this can provide the fiber paper with the large internal resistance and
heat resistance of this liquid crystalline fiber.
[0048]
EXAMPLE 8-3 Milled carbon fibers were added to 3 mm short fibers of carbon fibers (Toho
rayon, Vesphit) and liquid crystalline wholly aromatic polyester fibers (Clera, Vectran HT) As a
binder, super-beaten liquid crystalline wholly aromatic polyester fibers (Clera, Bectran HT) and
super-beaten wood pulp are added, and as a wetting agent, 100 PPM each of surfactant and
antifoam are added to make 3% slurry. The mixture is sufficiently deaggregated by a
deagglomeration machine to form a uniform slurry, which is formed into a diaphragm by a
conventional paper machine. Next, it is pressed with a temperature of 300 to 350 ° C. and a
pressure of 4 kg / cm 2 or more by a pressing machine. This melts super-refined wholly aromatic
polyester fibers, bonds the carbon fibers together, increases the fiber-to-fiber strength, has high
strength, high elasticity, high internal loss, and is for flame-resistant heat-resistant speakers It
can be a diaphragm. If necessary, the above properties can be further improved by further
impregnating with a solution of silicate, organic polymer compound, inorganic compound and
the like. a. The following are used as the above-mentioned fiber material. Carbon fiber 7μ x
3mm cut product: 25 parts Liquid crystalline wholly aromatic polyester fiber 3mm cut product:
50 parts Milled carbon fiber 0.5 to 0.7 mm: 25 parts Super beaten liquid crystalline all aromatic
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polyester fiber: 30 parts Super Beaten wood pulp: 10 parts b. The following are used as papermaking chemicals. Wetting strength improver Epoxy polyamide resin: 1.50% Size Dimer acid
ester: 0.50% PH: 6.5 c. Impregnation treatment The above fiber paper is hot pressed with a press
at a temperature of 350 ° C., a pressure of 4 kg / cm 2 and a time of 5 minutes to melt the
liquid crystalline thermoplastic wholly aromatic polyester fibers and bond the carbon fibers
together. In some cases, the strength between fibers is increased. Furthermore, this can provide
the fiber paper with the large internal resistance and heat resistance of this liquid crystalline
fiber.
[0049]
Example 9 Para-Aromatic Polyamide Fiber Kevlar (Dupont Toray) 149 1.5 De × 3 mm cut
product with 50 to 100 parts of milled fiber of para-based aromatic polyetheramide fiber
Technola (Teijin) Add 100 ppm each of surfactant and antifoam as a wetting agent to make a 3%
slurry. To this, 10 to 15 parts of super-beaten wood pulp are added, sufficiently stirred with a
disintegrator and deaggregated, chemicals for paper making are added, paper making is carried
out with a usual paper machine, and press drying is carried out. Furthermore, it can be
impregnated with a solution of a silicate compound, an organic metal polymer compound or the
like to obtain a heat-resistant, flame-retardant, high-strength heat-resistant speaker diaphragm.
a. The following are used as the above-mentioned fiber material. Para-based aromatic amide
fiber short fiber Kevlar 149 1.5De × 3 mm cut product: 50 parts Para-based aromatic ether
amide fiber milled fiber Technola pulp: 50 parts Super beaten wood pulp: 10 parts b. The
following are used as paper-making chemicals. Wetting strength improver Epoxy polyamide
resin: 1.50% Size Dimer acid ester: 0.50% PH: 6.5 c. Impregnation treatment The abovementioned fiber paper is impregnated with 10% bismaleimido fiber (Mitsubishi Gas Chemical, BT
resin), 10% aromatic polyamide fiber (UNITICA, APIER Varnish), 10% lithium silicate solution and
dried at 60 ° C. or less Provides flame retardancy and heat resistance.
[0050]
[Example 10] 50 to 100 parts of milled fiber of Kevlar is added to para-based aromatic polyamide
fiber Kevlar 149 1.5 De × 3 mm cut product, and 100 PPM each of surfactant and antifoaming
agent as a wetting agent Add 3% slurry. To this, 10 to 15 parts of super-beaten wood pulp are
added, sufficiently stirred with a disintegrator and deaggregated, chemicals for paper making are
added, paper making is carried out with a usual paper machine, and press drying is carried out.
Furthermore, it can be impregnated with a solution of a silicate compound, an organic metal
polymer compound or the like to obtain a heat-resistant, flame-retardant, high-strength heat-
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resistant speaker diaphragm. a. The following are used as the above-mentioned fiber material.
Para-based aromatic amide fiber short fiber Kevlar 149 1.5De × 3 mm cut product: 50 parts
Para-based aromatic polyamide fiber milled fiber Kevlar pulp: 50 parts Super beaten wood pulp:
10 parts b. The following are used as paper-making chemicals. Wetting strength improver
Epoxypoamide resin: 1.50% Size Dimer acid ester: 0.50% PH: 6.5 c. Impregnation treatment The
above-mentioned fiber paper is impregnated with 10% bismaleimido fiber (Mitsubishi Gas
Chemical, BT resin), 10% aromatic polyamide fiber (UNITICA, APIER Varnish), 10% lithium
silicate solution and dried at 60 ° C. or less Provides flame retardancy and heat resistance.
[0051]
As described above, according to the present invention, super-beaten wood pulp having a large
specific surface area is added as a fibrous binder to short fibers of high elasticity inorganic fibers
and high elasticity organic fibers, or inorganic powder. Paper, which is further impregnated with
a silicate compound having excellent heat resistance, an organic metal compound, an inorganic
compound, an aromatic polyamide, an imide compound, etc., so that it has excellent flame
retardancy, water resistance and humidity resistance. It is possible to obtain a heat-resistant
speaker diaphragm having high strength, high elastic modulus and high internal resistance. 【
Table 1】 【Table 2】
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