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JPH0583789

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DESCRIPTION JPH0583789
[0001]
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a
cone paper used for a diaphragm of an electroacoustic transducer such as a speaker, and more
particularly to a flame retardant speaker cone paper having a flame retardancy.
[0002]
2. Description of the Related Art Inorganic phosphate compounds (ammonium polyphosphate =
contained) which are said to be most effective for cellulosic fibers among flame retardants after
making the flame retardant method for cellulose fiber paper into a conventional form. The flame
retardant paper obtained by this method is impregnated with an aqueous solution of phosphorus:
32%, phosphorus + chisso: 47%), but the flame-retardant paper obtained by this method emits
"stains" at the time of dyeing, corrodes metals, and high temperature With the high humidity,
with the occurrence of wrinkles, the practicality is now questioned.
[0003]
In general, high density paper, size-sized paper, or high-temperature press-dry method is used to
form a honeycomb structure, and many corn papers that have an abnormally high surface
density compared to the inside are The flame retardant solution does not penetrate easily to the
inside, and when ignited, a fire type (flameless combustion) remains between the paper layers,
leading to a complete self-extinguishing property, making it difficult to achieve flame retardancy.
[0004]
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In addition, when solid matter such as inorganic phosphate flame retardant enters cellulose fiber
paper, the flame retardant paper loses its strength, becomes brittle and becomes hard, and its
elongation decreases and there is no toughness (strength × elongation) and durability There is
no
In particular, corn paper and the like easily break when subjected to vibration accompanied by
forced repeated stress.
Although there are organic phosphorus compounds and liquid flame retardants, even the
trimethylphosphorus compounds with the highest phosphorus content are 22%, and they contain
a large amount of carbon element, so their flame retardancy is lower than inorganic phosphorus
compounds. . Also, metal corrosion is a concern.
[0005]
If the hydroxyl group and methylol group of cellulose fiber are esterified with phosphoric acid,
ammonium phosphate, ammonium polyphosphate etc. and phosphorylated, the flame retardancy
(phosphorus content 5.8% or more) increases depending on the phosphorus content. Can be used
as flame retardant paper. The strength, elongation, etc. are very excellent as compared with the
flame-retardant paper impregnated with solid matter such as the above-mentioned inorganic
phosphate compound. This is because phosphorus is organically esterified on the surface of the
cellulose fiber, and the dyeability is good, and neither wrinkles nor metal corrosion occurs.
[0006]
The mechanical properties such as Breaking Length, Tear Strength, etc. show that the
phosphorus compared to that before esterifying as the degree of phosphorylation and
esterification is increased compared to normal untreated wood pulp paper Even if the content is
5.8%, it decreases to 2/3, but it is practical. This decrease is due to the reduction of hydroxyl
groups, methylol groups, and the like in the cellulose fiber by esterification, the reduction of
hydrogen bonds in the paper, and the reduction of strength.
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2
[0007]
The mechanical strength of the paper-like matrix is determined by the sum of the single fiber
strength and the contact area between fibers, but in the case of wood pulp fibers, when the
specific surface property increases, the contact area between fibers also increases and the
number of hydrogen bonds also increases, and the strength increases. It will be. Although there is
a beating method for increasing the fiber-to-fiber contact area, there is a limit to the fiber-to-fiber
contact area being increased to some extent in a normal yergar-type beating machine (150 cc
CSF = Canadian standard freeness and specific surface area 4.0 m 2 / g There is a degree), and
along with the beating, cutting in the fiber width direction and damage in the fiber axial direction
simultaneously progress, and the single fiber becomes short and thin and the strength is
significantly reduced, so that the strength does not increase greatly after all. The ideal way to
improve the strength of the paper is to increase the contact area between fibers while
maintaining single fiber strength or fiber morphology, but there is no refiner capable of such
operation. Therefore, there is a need for a method of separately preparing and adding a material
that increases only the fiber-to-fiber contact area. Generally, resins and rubbers are added, but if
the strength of the film itself is weak, the strength will not be improved either. Such additives are
difficult to use because they are highly contaminating the papermaking net.
[0008]
Ultra-beaten wood pulp obtained by ultra-refining ordinary wood pulp by a special mechanical
method has a very large specific surface area, which is 10.0 m 2 / g or more. Furthermore, by
repeating this refining process, it can also be finally raised to 200 m 2 / g or more. Naturally,
phosphorylated wood pulp can also be super-refined in the same way, resulting in flameretardant super-refined phosphated wood pulp. At this time, since the beating is performed along
the fiber axial direction, the fiber shape is maintained, which is advantageous for measures to
improve the strength of the fiber paper.
[0009]
The flame retardancy of phosphorylated wood pulp paper is influenced by the phosphorus
content and the density of the resulting paper, and the lower the freeness, the lower the density,
so the contact area with air increases. It becomes easy to burn at the same phosphorus content.
Also, the lighter the paper, the lower the dehydrating pressure, the lower the density and the
easier it is to burn. When making low density paper it is necessary to make the phosphorus
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content higher than when making high density paper. The paper used for the speaker diaphragm
has high rigidity and heavy weight (100 g / m2 or more) in order to emphasize the acoustic
characteristics. Therefore, the freeness of pulp is lower than that of ordinary paper, newsprint,
kraft paper, and corrugated paper (500 cc CSF or more), and naturally the density is also low (0.5
g / cm 3 or less). As it is naturally present and the area of contact with air is naturally large, it is
necessary to increase the phosphorus content. If the phosphorus content is increased in advance,
the flame retardancy of the formed paper is not affected by the density of the density, but there
is a limit to the phosphorus esterification of hydroxyl group and methylol group of cellulose fiber
with phosphorus, conversion of 10% or more is difficult, The reaction time is also long and the
economic efficiency is also reduced, so the range of phosphorylation is limited to 5 to 10%. In
this range, it is difficult to make low density paper flame retardant at a low phosphorus content.
[0010]
In the most common fixed cone paper (Fixed Cone), the edges and cones are made of the same
pulp material, and in order to take into account the stiffness of the cones, they are separated by
materials with low freeness as described above. . In the case of the typical fixed cone paper
(aperture 80 to 160 mm), the weight distribution is such that the edge portion (20 to 50 g / m2)
has a cone portion (100 to 100 g) in order to lower the lowest resonance frequency F0
(stiffness). Very thin and thin compared to 160 g / m2). Therefore, during papermaking, the
dewatering pressure is not applied, the density is low and the mechanical strength is also low.
Therefore, the contact area with the air also increases at the edge portion, and the same
phosphorus content tends to burn easily.
[0011]
However, as described above, the fished cone paper should be made of the same pulp material at
both the edge and the cone, and use pulp material in which the phosphorus content is increased
only at the edge where the contact area with air is large. It is impossible. Therefore, not only it
helps to improve the strength of the paper by adding ultra-beaten phosphated wood pulp, which
is refined and the specific surface area is very large at 10.0 m 2 / g or more, and it is filled with
pulp material with low absorptivity It also acts as an agent, reduces the contact area with air, and
improves the flame resistance of the low-density, light-weight edge portion, and can be an
excellent flame-retardant fi xed cone paper.
[0012]
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The internal loss of paper is known to increase with the increase in fiber-to-fiber contact area.
Normally, this internal loss is secured by beating, but the increase in specific surface area can
reach only a few m 2 / g even at relatively high freeness (150 cc CSF) as described above,
compared to the specific surface area of super-beaten wood pulp Much lower. Therefore, a large
internal loss can not be expected with a conventional squeezing method.
[0013]
The present invention has been made in view of these points, and the object of the present
invention is to provide a flame-retardant speaker having excellent flame retardancy, high specific
elasticity, high strength, and high internal resistance due to phosphorylated ester. It is in
providing a diaphragm.
[0014]
[Means for Solving the Problems] In order to achieve the above object, the cone paper for a
flame-retardant speaker of the present invention has an ultra-low specific surface area of 10.0 m
2 / g or more on a phosphorylated flame-retardant phosphated wood pulp. It is characterized in
that it has excellent flame retardancy, high specific elasticity, high strength and high internal loss
by adding beaten phosphated wood pulp as a fibrous binder.
[0015]
In addition, in order to achieve the above object, the cone paper for a flame retardant speaker of
the present invention is impregnated with an organic metal polymer compound, an aromatic
polyamide, or an imide compound and coated to be flame retardant, heat resistant, water
resistant, resistant It is characterized in that various properties such as humidity are improved
and high specific elasticity, high strength, high elastic modulus and high internal loss are given.
[0016]
[Function] A super-beaten phosphated wood pulp having a specific surface area of 10.0 m 2 / g
or more, which is super-beaten separately, maintaining single fiber strength or fiber form with
unbeaten or low beat-up degree of phosphorylated wood pulp. By adding it, the increase in the
contact area between fibers is measured, and it is a flame retardant paper which has large
specific elasticity (stiffness), elastic modulus, strength and internal loss, low repulsion degree and
low density even with low density, ie, difficult A diaphragm for a flame retardant speaker can be
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manufactured.
It compensates for the decrease in strength due to hydrogen bonding which has been reduced by
esterification.
There is no need for a beating process and no need for difficult beating management.
[0017]
[Example] A flame-retardant phosphated wood pulp obtained by treating wood pulp with
ammonium polyphosphate, ammonium phosphate, phosphoric acid or the like to phosphate the
hydroxyl group and methylol group of cellulose, but not beaten normally. Alternatively, single
fiber strength or fiber form is maintained with low freeness, and the same phosphated wood pulp
as a fibrous binder is ultra-refined by a special beating method to a specific surface area of 10.0
m 2 / g or more. 0.5 to 30% of beaten phosphated pulp is added, charged into a disintegrator
(pulper), sufficiently disintegrate, and a slurry having a uniform pulp concentration of 3% is
obtained.
A predetermined amount of papermaking chemicals is added to this, and it is made into a sheet
by a normal paper machine, and high specific elasticity (stiffness), high strength, high internal
loss, low density and light weight which can not be obtained by general beating. Even cone cone
paper is used as a self-extinguishing flame retardant speaker diaphragm.
[0018]
Furthermore, if necessary, in order to further improve various properties such as flame
retardancy, heat resistance, water resistance and humidity resistance, aromatic polyamide, imide
compounds, organic metal polymer compounds, inorganic compounds (silicate compounds), etc.
It can also be impregnated and coated with a solution of
[0019]
Physical properties and performance of paper-made corn paper are measured and evaluated for
the following items.
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1. Tensile strength Kg / mm2: Calculated from the breaking strength with a tensile tester. Tensile
modulus of elasticity Kg / mm 2: Calculated at 0.25% modulus in the stress distortion curve of
the above-mentioned tester. Internal loss Tan δ: Measured according to JIS K-7213 “Torsion
free damping viscoelasticity measuring machine”. Specific elasticity (stiffness) Km: Tensile
modulus divided by density. 5. Basis weight g / m 2: The paper used for measurement was
targeted at 100 ± 10% g / m 2. 2. Flammability performance JIS D 1201 "Combustibility test
method for organic materials for car interior"
[0020]
[Example 1] Phosphorized wood pulp is fully swollen in water, and introduced into a pulperp in
which clean water (low hardness) is embedded to make the pulp concentration 2.7%. Next, 5.0%
or more of ultra-beaten phosphated wood pulp is added and thoroughly stirred for about 20
minutes for complete disintegration. A predetermined amount of papermaking agent is added to
this, and the mixture is stirred for 2 to 3 minutes to make uniform dispersion. Further, water is
added to make a predetermined papermaking concentration. The steps after the press drying
step are the same as in the normal step.
[0021]
a. The following are used as the above-mentioned fiber material. Phosphorylated wood pulp: 95.0
parts or less Super beaten phosphorylated wood pulp: 5.0 parts or more b. The following are
used as paper-making chemicals. Wetting strength improver Epoxy polyamide resin: 1.5 parts
Size dimer acid ester: 0.5 parts PH neutral: 6.5 c. Physical properties and performance obtained
are as follows. Table 1 shows the physical properties when super-beaten wood pulp is added to
unbeaten phosphated wood pulp and the physical properties just for increasing the freeness. As
shown in Table 1, the addition of 10% or more of ultra-beaten phosphated wood pulp to
unbeaten phosphated wood pulp is superior to the physical property of raising the degree of
beating to 150 cc CSF with a beating machine. In particular, the internal loss is a value which
could not be obtained with conventional beaters. d. Flame retardancy test results Test method JIS
D 1201 "Flame retardancy test method for organic materials in automobile interior", 5.0% or
more of ultra-beaten phosphated wood pulp is added, even in the edge area around 20g / m2
basis weight It does not reach the marked line and is self-extinguishing.
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[0022]
Example 2 In order to improve various properties such as flame retardancy, heat resistance,
water resistance, humidity resistance and the like to the diaphragm made in Example 1, an
aromatic polyamide, an imide compound, an organic metal polymer compound It is also possible
to impregnate and coat a solution of an inorganic compound (silicate compound) or the like.
[0023]
1.
Aromatic polyamide, imide compounds Flame retardancy Heat resistance High strength High
modulus a.
Aromatic polyamide resin 〃 〃 b. Aromatic polyamideimide resin 〃 〃 c. Aromatic polyester
imide resin 〃 〃 d. Aromatic polyester amide imide resin 〃 〃 〃 e. Aromatic polyimide resin 〃
〃 f. Aromatic polyhydantoin compounds 〃 〃 〃 g. Aromatic benzimidazole compounds 〃 〃 〃
h. Aromatic polybenzothiazole compound 〃 〃 〃 i. Aromatic polypyrromellitimide compound 〃
〃 〃 j. Silicone imide compound 〃 〃. K. Pyriparaban compound 〃 〃 〃 〃 〃
[0024]
4】2. Organometallic polymer compound Heat resistance Flame retardant High elastic modulus
a. Organic silicon-containing compound 〃 b. Organic boric acid-containing, silicon compound 〃
c. Organic titanium-containing, silicon compounds 〃 d. Organic aluminoxane compound 化合 〃
〃
[0025]
5】3. Inorganic compounds a. Silicate compound Heat resistance Flame retardant high modulus
(sodium, potassium, lithium salt) 〃 〃 b. Organosol Alumina sol 〃 c. シリカゾル 〃 〃 〃
[0026]
As described above, according to the present invention, ultra-refined phosphated wood pulp is
added as a fibrous binder to a phosphate-blocked flame-retardant phosphated wood pulp to form
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a paper, which is pressed and dried. Since paper is used, it is possible to obtain a cone paper for a
flame-retardant speaker having excellent high specific elasticity, high strength and high internal
loss.
[0027]
Furthermore, since the above-mentioned materials are impregnated and coated with an organic
metal polymer compound, an aromatic polyamide, or an imide compound to improve the
properties, various properties such as heat resistance, water resistance, humidity resistance, etc.
are improved, and further higher It is possible to obtain a cone paper for a flame-retardant
speaker having specific elasticity, high strength, high elastic modulus and high internal loss.
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