close

Вход

Забыли?

вход по аккаунту

?

JPH0350255

код для вставкиСкачать
Patent Translate
Powered by EPO and Google
Notice
This translation is machine-generated. It cannot be guaranteed that it is intelligible, accurate,
complete, reliable or fit for specific purposes. Critical decisions, such as commercially relevant or
financial decisions, should not be based on machine-translation output.
DESCRIPTION JPH0350255
[0001]
The present invention relates to a resin composition excellent in processability, heat resistance
and rigidity and a diaphragm for a speaker. More particularly, the present invention relates to a
resin composition particularly suitable for injection molding of a speaker diaphragm requiring
thin-wall moldability, high heat resistance and high elasticity, and a speaker diaphragm
comprising the resin composition. [Prior Art] In general, the main characteristics required for a
speaker diaphragm are a lightweight and high rigidity to flatten a sound pressure in a
reproduction frequency band, that is, a large specific elastic modulus, and harmonics In order to
reduce distortion, it can be mentioned that the internal loss (vibration damping property) is large.
Conventionally, for the speaker diaphragm, metal such as paper, aluminum, titanium, beryllium
and polymer material such as thermosetting resin or polypropylene are used, but metal has high
elastic modulus but small internal loss, and polypropylene However, such polymeric materials
have the disadvantage of high internal loss but low elastic modulus. In order to ameliorate these
drawbacks, the polymer material is intended to improve the elastic modulus by using a fiberreinforced composite material, but a material satisfying both high elasticity and high vibration
damping property has not been obtained. . Recently, aromatic thermotropic liquid crystal
polymers have attracted attention as materials that satisfy both the specific elastic modulus and
internal loss, and development of speaker diaphragms using liquid crystal polymers has also
been carried out (e.g. Open Sho 62-149296 etc.). Other characteristics required for the speaker
diaphragm include thin-walled high flowability required for injection molding of a heat-resistant
diaphragm that can withstand the heat generation of the voice coil and a large-sized diaphragm.
However, the liquid crystal polymers currently in use tend to have worse processability as those
having higher heat resistance, and none of them have high heat resistance and high fluidity.
Therefore, in the case where a liquid crystal polymer is currently used for the diaphragm, it is
necessary to use the case where heat resistance is required and the case where fluidity is
11-05-2019
1
required. SUMMARY OF THE INVENTION It is an object of the present invention to provide a
resin composition which is highly fluid and has high heat resistance based on the above
circumstances, and a speaker diaphragm made of the resin 1 composition. [Means for Solving the
Problems] As a result of intensive studies to solve the above problems, the present inventors
have found that fibrous substances can be reduced by minimizing the decrease in heat resistance
associated with high fluidization of liquid crystal polymers. It was found that the blended resin
composition was excellent in fluidity and heat resistance at the time of injection molding. That is,
the present invention is a resin composition comprising a liquid crystal polymer and a fibrous
substance, and the spiral flow length of 0, 5 dragons at 330 ° C. is 200 nus or more, and the
heat distortion temperature (ASTM D-64818, 6 kg / c The present invention relates to a resin
composition characterized in that the filling amount of the fibrous substance is 250% or more
and less than 5% by weight and less than 20% by weight, and a speaker diaphragm made of the
resin composition.
Hereinafter, the present invention will be described in detail. The liquid crystal polymer used in
the present invention comprises an aromatic hydroxycarboxylic acid as a main component and at
least one compound selected from aromatic dicarboxylic acids and aliphatic dicarboxylic acids,
and at least two compounds and aromatic diols and fats. 1 or 2F selected from the family of diols!
Aromatic polyester obtained by copolymerizing the above compounds, and one selected from
aromatic dicarboxylic acids and aliphatic dicarboxylic acids, or two or more compounds selected
from aromatic diols and aliphatic diols Or an aromatic polyester obtained by copolymerizing one
or more compounds. Aromatic hydroxycarboxylic acids such as 4-hydroxybenzoic acid, 3hydroxybenzoic acid, 2-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 5-hydroxy-2-naphthoic
acid Or 4-hydroxy-2-methylbenzoic acid, 4-hydroxy-3-methylbenzoic acid, 4-hydroxy-2phenylbenzoic acid, 2-chloro-4-hydroxybenzoic acid, 3-chloro-4-hydroxybenzoic acid Alkyls of
aromatic hydroxycarboxylic acids such as 6-hydroxy-5-chloro-2-naphthoic acid, 6-hydroxy 7chloro-2-naphthoic acid, 6-hydroxy-5, 7-dichloro-2-naphthoic acid , Allyl, halogen-substituted
compounds and the like. As aromatic dicarboxylic acids, terephthalic acid, isophthalic acid, 4.4diphenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid, diphenylether-4,4'-dicarboxylic acid,
diphenoxyethane-4,4'-dicarboxylic acid Acid, diphenoxybutane-4,4′-dicarboxylic acid,
diphenylmethane-3,4′-dicarboxylic acid, diphenylether-3,3′-dicarboxylic acid,
diphenoxyethane-3,3′-dicarboxylic acid, diphenylethane-3 And aromatic dicarboxylic acids such
as 1,3′-dicarboxylic acid, or alkyl, halogen-substituted products of the above aromatic
dicarboxylic acids such as chloroterephthalic acid, bromoterephthalic acid, methylterephthalic
acid and t-butylterephthalic acid. . Aliphatic dicarboxylic acids include cyclic aliphatic
dicarboxylic acids such as trans-14-cyclohexanedicarboxylic acid, cis-1, 4cyclohexanedicarboxylic acid, 1.3-cyclohexanedicarboxylic acid, and derivatives thereof. As
aromatic diols, hydroquinone, resorcinol, 4.4 = -dihydroxydiphenyl, 4.4′-dihydroxydiphenyl
ether, 3.4 ° -dihydroxydiphenyl, 3.4-dihydroxydiphenyl ether, 4.4 = dihydroxybenzophenone,
3.4 ′ ′-dihydroxybenzophenone, 3.3-dihydroxybenzophenone, 4.4-dihydroxydiphenyl sulfone,
11-05-2019
2
4.4-dihydroxydiphenyl sulfide, 4.4-dihydroxydiphenylmethane, 3.4 ′ ′-dihydroxydiphenyl
sulfone 3.4′-dihydroxydiphenyl sulfide, 3.4′-dihydroxydiphenylmethane, 3.3 ′ ′dihydroxyphenyl sulfone, 3.3-dihydroxydiphenyl sulfide, 3.3-di- Hydroxydiphenylmethane, 2.6naphthalenediol, 1,6 ′ ′-naphthalenediol, 2.2 ′ ′-bis (4-hydroxyphenyl) propane, aromatic
diols such as bis (4-hydroxyphenoxy) ethane, or chlorohydroquinone Alkyls of the above
aromatic diols such as bromohydroquinone, methylhydroquinone, t-butylhydroquinone, 4chlororesorcine, 4-methylresorcin, halogen-substituted aromatic diols and the like can be
mentioned.
Aliphatic diols include trans-1,4-cyclohexanediol, cis-1,4-cyclohexanediol, trans-1,4cyclohexanedimetatool, cis-1,4-cyclohexanedimetatool, trans-1,4, 3-cyclohexanediol, cis-1,2cyclohexanediol, trans-1,3-cyclohexanedimetatool, ethylene glycol, 1,4-butanediol, 1.6hexanediol, And cyclic, linear or branched aliphatic diols such as 8-octanediol and derivatives
thereof. Depending on the compositional ratio in the component and the polymer, and the
sequence distribution, the aromatic polyester composed of the above-described components may
or may not form an anisotropic melt phase. However, the liquid crystal polymers used in the
present invention are limited to aromatic polyesters that can form an anisotropic melt phase.
There is no limitation in particular about the manufacturing method of aromatic polyester which
can form an anisotropic melt phase using said monomer. For example, a typical production
method includes a method in which 4-acetoxybenzoic acid is reacted with 4.4′diacetoxydiphenyl, terephthalic acid and isophthalic acid. The reaction is generally carried out by
starting at low temperature in a nitrogen stream and continuously raising the temperature as the
reaction proceeds. The resulting granular product can be further subjected to a secondary solid
phase polycondensation reaction under reduced pressure or at a temperature of 200 to 350 ° C.
under normal pressure. This operation increases the molecular weight and the properties of the
resulting polyester are significantly improved. Further, in order to promote the above reaction,
0.01 to 1.0% by weight of a catalyst such as, for example, a Lewis acid, hydrogen halide, an
organic acid or a salt of an inorganic acid and a compound of antimony or germanium can be
used. Generally, in order to increase the flowability, the molecular weight may be lowered, but
this alone will cause a decrease in heat resistance and heat stability. In the present invention, in
order to minimize the decrease in heat resistance and thermal stability, an excess of dicarboxylic
acid is reacted with the diol during the reaction, and many of the ends of the polymer chain are
obtained as carboxylic acid end groups. Improve the thermal stability of the polymer product.
The excess amount of dicarboxylic acid to diol varies depending on the types of monomers to be
reacted, but when 4-acetoxybenzoic acid, isophthalic acid, terephthalic acid and 4,4′diacetoxydiphenyl are reacted to obtain a polymer An excess of 13 mol% is preferred.
If the excess amount is less than 8 mol%, a decrease in fluidity may occur, and if the excess
amount exceeds 13 mol%, the heat resistance may decrease and the elastic modulus may
11-05-2019
3
decrease. The spiral flow length of 0 and 5 dragons at 330 ° C. of the liquid crystal polymer is
preferably 250 m + s or more. If the spiral flow length is less than 250 m + s, a short shot may
occur in the case of injection molding of a diaphragm having a large shape, for example, in a
resin composition containing a fibrous material, which is not suitable for the present invention.
The heat distortion temperature of the liquid crystal polymer is preferably 230 ° C. or more.
When the heat distortion temperature is less than 23-0 ° C., the resin composition containing
the fibrous material does not have sufficient heat resistance to withstand the heat generation of
the voice coil even if the speaker diaphragm is obtained There is. The melt viscosity of the liquid
crystal polymer used in the present invention is preferably 100 to 7,000 Boise at a constant
temperature of 320C and a shear rate Iqsec, and more preferably 500 to 3,000 poise. In the case
of 100 boil, heat resistance and heat stability may decrease, and when it exceeds 7000 poise,
flow may decrease. The fibrous material filled in the resin composition according to the present
invention has a tensile modulus of elasticity of 1. It is preferable that OX 10 ′ ′ kg / c− or
more, the fiber diameter 0.1 to 30 μm 1 and the aspect ratio be 3 or more. The tensile modulus
of the fibrous material used is 1. If the OX is less than 106 kg / c, the fiber diameter is outside
the range of 0.1 to 30 μm, or the aspect ratio is less than 3, sufficient high elasticity may not be
obtained in the present invention. As a fibrous substance like the above, carbon fiber. Alumina
fibers, aramid fibers and potassium titanate fibers may, for example, be mentioned. The blending
amount of the fibrous substance is preferably 5% by weight or more and less than 20% by
weight. When the compounding amount is less than 5% by weight, high heat resistance and high
elasticity may not be obtained sufficiently, and when the compounding amount is 20% by weight
or more, vibration damping property is lowered and at the time of molding In some cases, the
flowability of the diaphragm decreases to make it difficult to form the diaphragm. The spiral flow
length of 0, 5 m + s at 330 ° C. of the resin composition according to the present invention is
preferably 200 mm or more. If the spiral flow length is less than 200 m 1 m, for example, a short
shot may occur when injection molding a diaphragm having a large shape, which is not suitable
for the present invention.
Moreover, it is preferable that the heat deformation temperature of the said resin composition is
250 degreeC or more. If the thermal deformation temperature is less than 250 ° C., even if the
speaker diaphragm is obtained by injection molding, it may not have heat resistance enough to
withstand the heat generation of the voice coil. EXAMPLES The present invention will now be
described more specifically by the following Examples and Comparative Examples, but the
present invention is not limited thereto. EXAMPLE 1 4-acetoxybenzoic acid / isophthalic acid /
terephthalic acid / 4.4 "-diacetoxydiphenyl was reacted at a molar ratio of 3.51 0.3310.77 / 1.0
to obtain a liquid crystal polymer. The melt viscosity of the iG liquid crystal polymer was
determined using a flow tester manufactured by Shimadzu Corporation iDJ using a die with a
diameter of 0.5 mm and a capillary length of 2 mm. Measurement-1 temperature at 320 ° C.,
shear rate 10 sec 1,1, It was 400 voices. Further, this liquid crystal polymer was extruded and
granulated at a cylinder temperature of 280 ° C. and a die temperature of 300 ° C. using a
11-05-2019
4
twin-screw extruder (TEX30 SS manufactured by Nippon Steel Corp.) to produce a belet. Next,
the pellet is dehumidified and dried for 2 hours at 120 ° C., and a cylinder temperature of 330
° C., injection pressure 1, 100 kg / cd, injection speed high speed, mold temperature using a 50
ton injection molding machine (l550EP manufactured by Toshiba Machine) When the spiral flow
length of 0.5 mm was evaluated at 150 ° C., it was 363%. A specimen of 127 mm in length, 12.7
mm in width and 3.2 mm in thickness was prepared under the same injection conditions, and the
heat distortion temperature (18, 6 kg / cd) was measured according to ASTM D-648. The This
liquid crystal polymer 90 weight; tri-blend 10% by weight carbon fiber with a fiber diameter of 6
μm (product of Toho Rayon Co., Ltd. [Vesphyt HTAJ)] 4) tensile modulus 2) 4 x 106 kg / cI #
and biaxial extrusion An extrusion granulation was carried out at a cylinder temperature of
280.degree. C. and a die temperature of 300.degree. C. using a machine (manufactured by
Nippon Steel New TEX 30 SS) to make a belet. Next, the pellet is dehumidified and dried at 120
° C. for 2 hours, and then a cylinder temperature of 330 ° C., an injection pressure of 1,100 kg
/ c, an injection speed high speed, a mold using a 50 ton injection molding machine (l550EP
manufactured by Toshiba Machine) The spiral flow length of 0.5 mm was evaluated at a
temperature of 150 ° C., and the results are shown in Table 1. In addition, test pieces of 127
mm in length, 1.2.7 m + s in width and 3.2 mm in thickness are prepared under the same
injection conditions, and the flexural modulus according to ASTM D-790, heat deformation
temperature (18,6 kg / in accordance with ASTM D-648) d) The tan δ was determined by the
vibration lead method.
The results are shown in Table 1. (Example 2) Similar to Example 1, 90% by weight of liquid
crystal polymer, potassium titanate fiber having a tensile modulus of 2.8 × 106 kg / cd and a
fiber diameter of 0.2 to 0.3 μm (manufactured by Otsuka Chemical Co., Ltd.) The flexural
modulus, the thermal deformation temperature and the tan δ were determined in the same
manner as in Example 1 except that the name “Tismo DJ” was 10% by weight. The results are
shown in Table 1. Comparative Example 1 The same as Example 1 except that 75% by weight of
the liquid crystal polymer similar to Example 1 and carbon fibers similar to Example 1 (trade
name "Bethite HTAJ" manufactured by Toho Rayon Co., Ltd.) are 25% by weight. The flexural
modulus, thermal deformation temperature and tan δ were determined by the method of The
results are shown in Table 1. Comparative Example 2 The same as Example 1 except that 97% by
weight of the liquid crystal polymer as in Example 1 and the carbon fiber as in Example 1 (trade
name "Bethite HTAJ" manufactured by Toho Rayon Co., Ltd.) are 3% by weight The flexural
modulus, thermal deformation temperature and tan δ were determined by the method of The
results are shown in Table 1. Comparative Example 3 4-acetoxybenzoic acid / isophthalic acid /
terephthalic acid / 4.4 "-diacetoxydiphenyl was reacted at a molar ratio of 3.510.32010.75/1.0
to obtain a liquid crystal polymer. The melt viscosity of the obtained liquid crystal polymer was
measured by the same method as in Example 1 and found to be 12,000. Further, the same
method as in Example 1 is used except that this liquid crystal polymer is extruded and granulated
at a cylinder temperature of 300 ° C. and a die temperature of 330 ° C. using a twin-screw
11-05-2019
5
extruder (TEX30 SS manufactured by Nippon Steel Corp.) to form pellets. The spiral flow length
and the heat distortion temperature of 0.5 mm were evaluated by the above, and the results were
165 mm and 250 ° C., respectively. Using 90% by weight of this liquid crystal polymer and 10%
by weight of carbon fibers similar to Example 1 (Toho Rayon Co., Ltd., trade name: Bethite HTAJ)
10% by weight, using a twin-screw extruder (TEX30 SS, manufactured by Nippon Steel Corp.) The
spiral flow length, flexural modulus, thermal deformation temperature and tan δ were
determined in the same manner as in Example 1 except that extrusion granulation was
performed at a cylinder temperature of 300 ° C. and a die temperature of 330 ° C. to form
pellets. The results are shown in Table 1. Comparative Example 4 4-acetoxybenzoic acid /
isophthalic acid / terephthalic acid / 4.4 "-diacetoxydiphenyl was reacted at a molar ratio of 3.51
0.3410.77 / 1.0 to obtain a liquid crystal polymer. The melt viscosity of the obtained liquid
crystal polymer was measured by the same method as in Example 1 and found to be 20 poise.
Further, the same method as in Example 1 is used except that this liquid crystal polymer is
extruded and granulated at a cylinder temperature of 255 ° C. and a die temperature of 280 °
C. using a twin-screw extruder (TEX30 SS manufactured by Nippon Steel Corp.) to form pellets.
The spiral flow length of 0.5 關 was evaluated by. Next, the heat distortion temperature was
determined to be 7TllI in the same manner as in Example 1 except that the cylinder temperature
of the 50 ton injection molding machine was set to 300 ° C, and it was 187 ° C. 90 weight% of
this liquid crystal polymer and 10 weight 96 of carbon fiber (Toho Rayon Co., Ltd. trade name
“Beth Fight HTAJ” as in Example 1) are dry-blended using a twin-screw extruder (TEX30 SS
made by Nippon Steel New) The spiral flow length was evaluated in the same manner as in
Example 1 except that extrusion granulation was performed at a cylinder temperature of 255 °
C. and a die temperature of 280 ° C. to prepare pellets. The results are shown in Table 1. Next,
the flexural modulus, the thermal deformation temperature and the tan δ were determined in
the same manner as in Example 1 except that the cylinder temperature of the 50 ton injection
molding machine was set to 300 ° C. The results are shown in Table 1. [Effects of the Invention]
According to the present invention, a resin composition which is excellent in fluidity during
injection molding, has high elasticity, high vibration damping property and high heat resistance,
and is particularly suitable for a speaker diaphragm is obtained. It is possible.
11-05-2019
6
Документ
Категория
Без категории
Просмотров
0
Размер файла
17 Кб
Теги
jph0350255
1/--страниц
Пожаловаться на содержимое документа