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FIELD OF THE INVENTION The present invention relates to a high rigidity damping material. The
high rigidity damping material is a useful material as a speaker diaphragm in which both rigidity
and damping property are required to be excellent in terms of sound quality. [Conventional
technology] Metal, paper, etc. are conventionally used as a material of a speaker diaphragm, but
since these materials can not satisfy both rigidity and damping property, the speaker vibration
for high sound where the rigidity is regarded as important The metal has been used for the
board, and paper etc. have been used for the bass speaker while the damping property is
emphasized. In recent years, aromatic polyesters which form an anisotropic molten phase having
relatively good rigidity and relatively good damping properties are attracting attention as highly
rigid damping materials, and are beginning to be used as speaker diaphragm materials. However,
while the damping property is required in a wide temperature range from low temperature to
room temperature -C, the damping property in the room temperature region is insufficient. In
order to further improve the sound quality, it is desirable to improve the room temperature
allocation. SUMMARY OF THE INVENTION An object of the present invention is to develop an
aromatic polyester high rigidity damping material that forms an anisotropic molten phase with
good damping properties in a wide range from low temperature to room temperature. is there.
[Means for Solving the Problems] The gist of the present invention is to introduce a
hydroquinone substituted with methyl as a constituent unit into an aromatic polyester forming
an anisotropic melt phase which is insufficient in vibration damping properties in a room
temperature region. It is to improve the shortage. That is, the present invention relates to a
damping material comprising an aromatic polyester which forms an anisotropic melt phase
containing methyl-substituted hydroquinone as a constituent unit. It is desirable that the
aromatic polyester according to the present invention contains 10% by 2% or more, preferably
20% by weight or more of methyl-substituted hydroquinone as a copolymerization component.
As another component of the aromatic polyester, it is possible to form an ester bond
stoichiometrically with one or more kinds of aromatic hydroxycarboxylic acid residues or an
aromatic hydroxycarboxylic acid residue as a main component And at least one aromatic
carboxylic acid residue, aliphatic dicarboxylic acid gc group, aromatic diol residue, aliphatic diol
residue, and one or more aromatic dicarboxylic acid residues Aromatic diol residues, aliphatic
diol residues and the like can be mentioned. As the aromatic hydroxycarboxylic acid, 4hydroquinbenzoic acid, 3-hydroxybenzoic acid, 2-hydroxybenzoic acid, 6-hydroxy-2-naphthoic
acid, 5-hydroxy-2-naphthoic acid and the like can be mentioned. As an aromatic dicarboxylic
acid, terephthalic acid, isophthalic acid, 4.4 ′ ′-diphenyldicarboxylic acid, 26naphthalenedicarboxylic acid, diphenylether-4,4′-dicarboxylic acid, diphenoxyethane-4,4 ° dicarboxylic acid, Diphenoxybutane-4,4′-dicarboxylic acid, diphenylmethane-34′-dicarboxylic
acid, diphenylether-3,3′-dicarboxylic acid, diphenoxyethane-3,3′-dicarboxylic acid,
diphenylethane-3,3′- Dicarboxylic acid etc. are mentioned.
Aliphatic dicarboxylic acids include cyclic aliphatic dicarboxylic acids such as trans -14cyclohexanedicarboxylic acid, cis-1,4-cyclohexanedicarboxylic acid, 13-cyclohexanedicarboxylic
acid, and derivatives thereof. As the aromatic diol, hydroquinone, resorcine, 4.4′dihydroxydiphenyl, 44′-dihydroxydiphenyl ether, 34 ° -dihydroxydiphenyl, 3,4 ° dihydroquine diphenyl ether, 4.4′-dihydroxybenzophenone, 3.4 '-Dihydroxybenzophenone, 3.3'dihydroquinone benzophenone, 4,4 ° -dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl
sulfide, 4,4'-dihydroxydiphenylmethane, 3.4'-dihydroxydiphenyl sulfone, 34' ′ ′ Dihydroxydiphenyl sulfide, 3.4 ° -dihydroxydiphenylmethane, 33 ′ ′-dihydroxydiphenyl
sulfone, 3.3′-dihydroxydiphenyl sulf Deodo, 3.3 'dihydroxydiphenylmethane, 2.6'naphthalenediol, 1.6'-naphthalenediol, 1,6'-naphthalenediol, 2,2 bis (4-hydroxyphenyl) propane,
bis ( 4-hydroxy phenoxy) ethane etc. are mentioned. Aliphatic diols include trans-1,4cyclohexanediol, cis-1,4-cyclohexanian cow diol, trans-co, 4-cyclohexanedimetatool, cis-1,4cyclohexanedimetatool, trans-1 2,3-cyclohexanediol, cis-1,2-cyclohexanediol, trans-1,3cyclohexanedimetatool, ethylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, etc.
Cyclic, linear or branched aliphatic diols and derivatives thereof can be mentioned. The aromatic
polyester comprising the above components is limited to an aromatic polyester capable of
forming an anisotropic melt phase. The molecular weight of the aromatic polyester according to
the present invention is preferably 50,000 to 100,000 in terms of styrene by GPC method. The
molecular weight is a value measured at a flow rate of 013 m1 / min at a temperature of 40 ° C.
using a solvent in which pentafluorophenol and chloroform are mixed at a weight ratio of 1: 2.
There is no limitation in particular about the manufacturing method of aromatic polyester using
the said monomer.
For example, a typical production method includes a method in which 4-hydroxybenzoic acid is
reacted with 4 ° -dihydroxydiphenyl, terephthalic acid and isophthalic acid. Generally, it starts
from low temperature in nitrogen stream, and temperature is raised continuously as the reaction
progresses. The resulting granular product can be further subjected to 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 significantly improves the
properties of the resulting aromatic polyester. Moreover, in order to accelerate | stimulate said
reaction, 0.01 to 1.0 weight% of catalysts, such as a Lewis acid, hydrogen halide, an organic acid,
or the salt of inorganic acid, and the compound of antimony and germanium, can also be used,
for example. The aromatic polyester according to the present invention can be blended with
various substances generally filled in a molding resin composition. Such substances are fibrous
(for example, carbon fiber, glass fiber, aramid fiber, asbestos fiber, potassium titanate fiber, etc.),
scaly (mica, graphite, glass flake, aluminum flake, etc.) or powdery (calcium carbonate, Clay, zinc
sulfate etc.), non-reinforcing fillers, pigments and other colorants, light and heat stabilizers,
nucleating agents, mold release agents, plasticizers, flame retardants, blowing agents and other
specialties Additives, such as polymeric toughening agents, are included. It is preferable that the
compounding quantity of the said filler is 0 to 70 weight%. If the blending amount of the filler
exceeds 70% by weight, the processability is lowered and the damping property is lowered,
which is not preferable. The method of mixing these fillers may be a commonly used technique,
such as a method of kneading with a screw extruder or a Brabender mixer. The material obtained
in this manner is molded by a normal injection molding machine or a press molding machine and
used as a dividing material. [The performance of co-vibration damping property is exhibited
when the energy of the vibration is absorbed by the energy of the thermal motion of the
molecules constituting the molding when the molding is vibrated. In order to improve the
damping property in the room temperature region, it is necessary to make the thermal movement
of molecules active in the room temperature region. The thermal movement of the methylsubstituted hydroquinone monomer is most active around 0 ° C. when vibrating at 10 Hz, and
has an effect of improving the damping property around room temperature. The present
invention will be described in more detail by the following examples, but the present invention is
not limited thereto. EXAMPLE 1 160 moles 9 o 4-hydroxybenzoic acid Iff, 10 mole% terephthalic
acid, 10 mole% isophthalic acid, 10 mole% 4,4′-dihydroxydiphenyl, 10 mole% methylsubstituted hydroquinone with nitrogen flow The reaction is carried out from middle to low
temperature, the temperature is continuously raised as the reaction proceeds, and the resulting
granular raw +1 i 3 is subjected to a secondary solid phase polycondensation reaction at a
temperature of 200 to 350 "C to give An aromatic polyester is obtained which forms an
anisotropic melt phase as shown.
The molecular weight of the above polyester was 10,000 according to GPC method. This
polyester was press-molded at 320 ° C. in the presence of nitrogen using a high-temperature
press-molding machine to obtain a molded article having a length of 5 cm, a width of 5 mm, and
a thickness of 0.5 mm. The loss coefficient (tall δ) of this sample was measured at a
measurement frequency of 10 Hz using a dynamic viscoelasticity measuring device (trade name:
rR5A-IIJ) manufactured by Rheometrics. Table 1 shows measured values of tan δ at -100 ° C, 50 'C1 o "c, 25 ° C., and 50' C ni. Comparative Example 1 Compared with the chemical structure
of the material used in Example 1, the methyl-substituted hydroquinone is not contained as a
constituent unit, and the other constituent units are in common with the structure and
composition ratio shown in the following formula: The aromatic polyester forming the
anisotropic melt phase was polymerized and molded in the same manner as in Example 1, and
tan δ was measured. The measured values of tan δ at -100 ° C, -50 ° C, 0 ° C, 25 ° C and
50 ° C are shown in Table 1. As compared with the example, it can be seen that the tan δ value
is larger in the example at a temperature range of −50 ° C. to room temperature or higher. In
particular, the improvement of tan δ around room temperature is achieved by the improvement
due to the methyl-substituted hydroquinone around 0 ° C. [Effects of the Invention As is
apparent from the above description, the present invention 1 can improve tan δ in a
temperature range from 50 ° C. to a room temperature or higher, and has high rigidity with
excellent damping properties in this temperature range A damping material can be obtained.
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