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DESCRIPTION JP2009065476
An object of the present invention is to provide a speaker edge having a thickness of 200 μm or
less and excellent in both internal loss and flexibility, which is obtained by injection molding, for
a small speaker such as a mobile phone or a personal computer required to be thin. Component
(A) Polystyrene-hydrogenated polybutadiene-polystyrene triblock copolymer (a-1), polystyrenehydrogenated polyisoprene-polystyrene triblock copolymer (a-2) and polystyrene-water 100
parts by mass of at least one selected from butadiene / isoprene copolymer-polystyrene triblock
copolymer (a-3), 2 to 20 parts by mass of component (B) polyolefin, and 70 to 300 parts of
component (C) oil A speaker edge having a thickness of 200 μm or less obtained by injection
molding a composition containing part. 【Selection chart】 None
スピーカーエッジ
[0001]
The present invention relates to a speaker edge with excellent internal loss and flexibility.
[0002]
The diaphragm of the speaker is supported by the speaker edge.
Such a speaker edge is required to have a high internal loss so as to be able to absorb the extra
vibration of the diaphragm, and as a material therefor, ethylene-acrylate copolymer rubber (see
Patent Document 1) ), Polyurethane foams (see, for example, Patent Document 2), thermoplastic
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1
elastomers having a mixture of a styrene-based thermoplastic elastomer and polypropylene as a
main component (see, for example, Patent Document 3), and the like have been developed. In
addition, as a vibration damping material, for example, a low hardness and high durability
vibration damping material is known that contains, for example, a polystyrene-hydrogenated
polybutadiene-polystyrene triblock copolymer, polypropylene, and a paraffin oil (for example, ,
Patent Document 4).
[0003]
Patent Document 1: Japanese Patent Application Publication No. 08-275288 Patent Document 2:
Japanese Patent Application Publication No. 08-033095 Patent Document 2: Japanese Patent
Application Publication No. 2004-269756 Patent Document 2: Japanese Patent Application
Publication No. 2000-169826
[0004]
However, the material described in Patent Document 1 has a problem that it lacks flexibility.
The material described in Patent Document 2 is a foam, and the foam usually has a problem that
the dimensional change at the time of sound output is larger than other materials, so the
durability is poor and the problem of not being able to withstand long-term use as a speaker
edge is there. The material described in Patent Document 3 states that a speaker edge of 10 to
300 μm or less can be manufactured. However, as described in Patent Document 3, when this
material is used, a method of producing a speaker edge by secondary molding using a heating
mold after forming pellets into a sheet shape is inevitable. There are a lot of manufacturing
processes. Also, the flexibility of the resulting sheet is not satisfactory and there is room for
further improvement. Moreover, although the material excellent as a vibration-proof material is
described in patent document 4, there is no description about being very effective as a speaker
edge, and it is said that especially the thin speaker edge of 200 micrometers or less is
manufactured. About the thing, it is hard to imagine from the compounding ratio of each
ingredient of patent documents 4 usually.
[0005]
The present inventors focused attention on the above problems, and as a result of intensive
studies on a speaker edge damping material capable of directly producing a speaker edge having
a thickness of 200 μm or less by injection molding, the component (A) specified hydrogenated
styrene If it is a composition containing a base elastomer, component (B) polyolefin and
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2
component (C) oil and mixing each component at a specific ratio, a speaker edge having a
thickness of 200 μm or less excellent in internal loss and flexibility They found that they could
be manufactured by injection molding, and completed the present invention.
[0006]
That is, the present invention is as follows: [1] Component (A) Polystyrene-hydrogenated
polybutadiene-polystyrene triblock copolymer (hereinafter abbreviated as SEBS).
(A-1), polystyrene-hydrogenated polyisoprene-polystyrene triblock copolymer (hereinafter
abbreviated as SEPS). ) (A-2) and polystyrene-hydrogenated butadiene / isoprene copolymerpolystyrene triblock copolymer (hereinafter abbreviated as SEEPS). ) Obtained by injection
molding a composition containing 100 parts by mass of at least one selected from (a-3), 2 to 20
parts by mass of component (B) polyolefin and 70 to 300 parts by mass of component (C) oil
Loudspeaker edge, a speaker edge obtained by injection molding a composition further
comprising component (D) polyphenylene ether in the composition according to [2] [1], [3]
component (D) polyphenylene ether, The speaker edge according to [2], which is a polyphenylene
ether / polystyrene based alloy, a polyphenylene ether / polypropylene based alloy, or a
polyphenylene ether / polyamide based alloy, [4] the content of the component (D) is the
component (A) 100 It describes in [2] or [3] which is 10 to 100 parts by mass with respect to
parts by mass. Speaker edge, [5] the speaker edge according to any one of [1] to [4], wherein the
component (B) polyolefin is polypropylene, the hardness (Shore of the composition according to
[6] [1] The speaker edge according to [1], obtained by injection molding a composition wherein
A) is 3 to 50 degrees, [7] Component (A) polystyrene-hydrogenated butadiene / isoprene
copolymer-polystyrene triblock Damping material for speaker edge containing 100 parts by mass
of copolymer (a-3), 2 to 20 parts by mass of component (B) polyolefin and 70 to 300 parts by
mass of component (C) oil, [8] component (D) ) The vibration damping material for a speaker
edge according to [7], containing polyphenylene ether, [9] component (D) polyphenylene ether is
a polyphenylene ether The vibration damping material for a speaker edge according to [8], which
is a rubber / polystyrene based alloy, a polyphenylene ether / polypropylene based alloy, or a
polyphenylene ether / polyamide based alloy, [10] Component (B) the polyolefin is
polypropylene, [ The vibration damping material for a speaker edge according to any one of 7] to
[9], is provided.
[0007]
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According to the present invention, both internal loss and flexibility are excellent, and a speaker
edge having a thickness of 200 μm or less can be easily manufactured by injection molding, so
that a small size such as a mobile phone or a personal computer is required. It can provide a
speaker edge used for a speaker. By using the speaker made with the speaker edge of the present
invention, distortion of sound can be suppressed, and good sound quality can be maintained over
a long period of time.
[0008]
The speaker edge of the present invention comprises at least one selected from component (A)
SEBS (a-1), SEPS (a-2) and SEEPS (a-3), component (B) polyolefin and component (C) oil It is
obtained by injection molding a composition containing the specific ratio.
[0009]
First, the component (A) will be described.
The SEBS of (a-1) is not particularly limited, but the content of polystyrene block is preferably 10
to 70% by mass, more preferably 20 to 65% by mass, and the hydrogenation rate of
polybutadiene block is preferably 50 mol% or more, more preferably 70 to 100 mol%. Moreover,
there is no restriction | limiting in particular in a weight average molecular weight, It is
preferable that it is 60000-400000. There is no restriction | limiting in particular about the
manufacturing method of this SEBS, A conventionally well-known method can be used. Also, such
SEBS is commercially available, for example, "Tuftec (registered trademark) H1272" (trade name,
manufactured by Asahi Kasei Chemicals Corporation, weight average molecular weight 60000,
polystyrene block content 30%), "Septon (registered trademark) 8007" (Brand name, Kuraray Co.,
Ltd., weight average molecular weight about 80,000, polystyrene block content 30%), "Septon
(registered trademark) 8104" (brand name, Kuraray Co., Ltd., polystyrene block content 60%),
etc. , These may be used. In addition, the weight average molecular weight is monodispersed
polystyrene by gel permeation chromatography [GPC: Tosoh HLC-8020, column: Tosoh GMH-XL
(two in series), detector: differential refractometer (RI)]. As a standard, it is the value taken out in
polystyrene conversion of each polymer, and so on. The SEPS of (a-2) is not particularly limited,
but the content of polystyrene block is preferably 10 to 70% by mass, more preferably 10 to 40%
by mass, and the hydrogenation rate of polyisoprene block is preferably Is 50 mol% or more,
more preferably 70 to 100 mol%. Moreover, there is no restriction | limiting in particular in a
weight average molecular weight, However, It is preferable that it is 60000-400000. There is no
restriction | limiting in particular about the manufacturing method of this SEPS, A conventionally
well-known method can be used. In addition, such SEPS is commercially available, for example,
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"HYBLER (registered trademark) 7125" (trade name, manufactured by Kuraray Co., Ltd.,
polystyrene block content 20%), "HYBLER (registered trademark) 7311" (trade name, Inc. Made
by Kuraray, polystyrene block content 12%), “Septon (registered trademark) 2007” (trade
name, made by Kuraray Co., Ltd., weight average molecular weight about 80,000, polystyrene
block content 30%), “Septon (registered trademark) 2063” (Trade name, manufactured by
Kuraray Co., Ltd., polystyrene block content 13%) and the like may be used.
Although there is no restriction | limiting in particular as SEEPS of (a-3), The content rate of a
polystyrene block becomes like this. Preferably it is 10-70 mass%, More preferably, it is 20-40
mass%, The hydrogenation of butadiene / isoprene copolymer block is carried out The rate is
preferably 50 mol% or more, more preferably 70 to 100 mol%. Moreover, there is no restriction |
limiting in particular in a weight average molecular weight, It is preferable that it is 60000400000. There is no restriction | limiting in particular about the manufacturing method of this
SEEPS, A conventionally well-known method can be used. In addition, such SEEPS is
commercially available, for example, "Septon (registered trademark) 4077" (trade name,
manufactured by Kuraray Co., Ltd., weight average molecular weight about 300000, polystyrene
block content 30%), "Septon (registered trademark) 4033" (Trade name, manufactured by
Kuraray Co., Ltd., polystyrene block content 30%) and the like may be used.
[0010]
Examples of the component (B) polyolefin include polyethylene, polypropylene, ethylene /
propylene copolymer, propylene / 4-methyl-1-pentene copolymer, poly (4-methyl-1-pentene),
polybutene-1 and the like. Be Among them, melt flow rate (hereinafter abbreviated as MFR)
measured according to JIS K 7210 [190 ° C., 21.18 N (2.16 kgf)] from the viewpoint of
processability and heat resistance. It is preferable to use the polyolefin which is 0.1-100 g / 10
minutes, and it is more preferable to use the polyolefin which is 0.5-50 g / 10 minutes.
Moreover, it is preferable that it is a polypropylene. Such polyolefins are commercially available
and, for example, "Novatec (registered trademark) BC05B" (trade name, component:
polypropylene, manufactured by Nippon Polypropylene Corp.), M1600 (trade name, component:
polypropylene, manufactured by Sun Aroma Co., Ltd.), Boulon (Registered trademark, component;
polybutene-1, manufactured by Mitsui Chemicals, Inc.) and the like may be used. The content of
the polyolefin is 2 to 20 parts by mass with respect to 100 parts by mass of the component (A),
and preferably 5 to 20 parts by mass from the viewpoint of processability.
[0011]
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Polystyrene can be used in combination with the component (B) polyolefin for the purpose of
improving processability and heat resistance. As the polystyrene, those obtained by known
production methods can be used, and they may be produced by any of radical polymerization
method and ion polymerization method. The weight average molecular weight of the polystyrene
is preferably 5,000 to 500,000, more preferably 10,000 to 200,000, and the molecular weight
distribution is preferably 5 or less. Examples of the polystyrene include polystyrene, styrenebutadiene block copolymer having a styrene unit content of 60% by mass or more, rubberreinforced polystyrene, poly α-methylstyrene, poly p-t-butylstyrene and the like. One type may
be used alone, or two or more types may be used in combination. When using polystyrene
together, it is preferable that it is polyolefin / polystyrene = 95/5-85/15 (mass ratio).
[0012]
Examples of the component (C) oil include paraffinic oil, naphthenic oil, silicone oil, aromatic oil,
vegetable oil and the like. Among these, paraffin oil and silicone oil are preferable from the
viewpoint of compatibility. In particular, the paraffinic oil preferably has a kinematic viscosity
(40 ° C.) of 100 to 10000 mm <2> / S from the viewpoint of bleed suppression. The kinematic
viscosity can be measured in accordance with JIS K2283. As paraffinic oil, for example, Diana
Process Oil PW380 (trade name, manufactured by Idemitsu Kosan Co., Ltd., molecular weight
750, dynamic viscosity (40 ° C.) 380 mm <2> / S), “Lucant (registered trademark) HC-180”
(trade name) A brand name, Mitsui Chemicals, Inc. make, molecular weight 1500, dynamic
viscosity (40 degreeC) 2500 mm <2> / S) etc. are mentioned. As silicone oil, what is marketed
can be used. Examples of vegetable oils include castor oil, cottonseed oil, linseed oil, rapeseed oil,
soybean oil, palm oil, coconut oil, peanut oil, wax, pine oil, olive oil and the like. One of these may
be used alone, or two or more may be used in combination as long as the compatibility is good.
The content of oil is 70 to 300 parts by mass with respect to 100 parts by mass of the
component (A), and the combination of flexibility, processability, mechanical strength, hardness,
and suppression of bleeding due to long-term use of the speaker edge, etc. As it considers, it is
preferable that it is 70-270 mass parts.
[0013]
When manufacturing the speaker edge of this invention, it can be added to said component (A)(C), and the above-mentioned component (D) polyphenylene ether can be contained. The
polyphenylene ether has the following general formula
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[0014]
<img class = "EMIRef" id = "203279160-00002" />
[0015]
(Wherein, R <1>, R <2>, R <3> and R <4> each independently represent a hydrogen atom, a
halogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group.
It is a homopolymer which consists of a repeating unit represented by these, or a copolymer
containing the said repeating unit, and an alloy with polystyrene, a polypropylene, or a
polyamide is also included in this invention. In this general formula, as a halogen atom which R
<1> -R <4> represents, a chlorine atom, a bromine atom, an iodine atom etc. are mentioned, for
example. Moreover, as a C1-C5 alkyl group which R <1> -R <4> represents, a methyl group, an
ethyl group, a propyl group, a butyl group, a pentyl group is mentioned, for example. As the
polyphenylene ether, known ones can be used, and as a homopolymer, for example, poly (2,6dimethyl-1,4-phenylene ether), poly (2-methyl-6-ethyl-1) , 4-phenylene ether), poly (2,6-diphenyl1,4-phenylene ether), poly (2-methyl-6-phenyl-1,4-phenylene ether), poly (2,6-dichloro-1) And 4phenylene ether). As the copolymer, for example, 2,6-dimethylphenol and a monovalent phenol
(eg, 2,3,6-trimethylphenol or 2-methyl-6-butylphenol) And polyphenylene ether copolymers such
as copolymers thereof. Component (D) polyphenylene ether is commercially available. For
example, it is possible to use “Zyron (registered trademark)” series manufactured by Asahi
Kasei Chemicals Corporation, “Noryl (registered trademark)” series manufactured by Japan GE
Plastics Co., Ltd., etc. it can. By including the component (D), the heat resistance of the speaker
edge is improved. When the component (D) is contained, the content thereof is not particularly
limited, but it is preferably 10 to 100 parts by mass with respect to 100 parts by mass of the
component (A).
[0016]
When manufacturing the speaker edge of the present invention, other additives may be added in
addition to the components (A) to (D) as long as the object of the present invention is not
impaired. Examples of such additives include pigments such as ceramic, carbon black, amber,
shenna, kaolin, nickel titanium yellow, cobalt blue, pramaster gray, quinophthalone,
diketopyrrolopyrrole, quinacridone, dioxazine, phthalocyanine blue, phthalocyanine green, etc.
Flame retardant: Antiaging agent: Antistatic agent: Antibacterial agent: Antioxidant: Talc, silica,
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calcium carbonate, magnesium carbonate, aluminum hydroxide, barium sulfate, glass fiber, glass
powder, inorganic hollow filler such as glass balloon, ceramic powder , Inorganic fillers such as
mica: organic fillers such as cork powder, wood powder, graphite etc: release agents such as
stearic acid: light stabilizers: tackifiers such as rosin derivatives (tackifier): "Leostomer (registered
trademark) ) B (Trade name, Riken Technos Co., Ltd.) adhesive elastomers, such as: coumarone
resins, coumarone - indene resins, and phenolic terpene resins. When an additive is added, the
amount used is preferably 20 parts by mass or less, and more preferably 5 parts by mass or less,
with respect to 100 parts by mass of component (A). In addition, when manufacturing the
speaker edge of this invention, in order not to reduce the acoustic characteristic of the speaker
edge obtained, it is preferable not to contain a crosslinking agent.
[0017]
As a method of mixing a component (A)-(C), and a component (D) and the said additive as needed,
and producing a pellet, a single-screw kneader, a twin-screw kneader, a Banbury mixer,
Brabender, a kneader, for example A method of obtaining pellets (composition) by melt-kneading
preferably at 100 to 300 ° C. using a high shear type mixer or the like can be used. In
particular, in order to sufficiently mix the oil of the component (C) with the respective
components, although it is not particularly limited, it may be mixed by the following method. For
example, a twin screw kneader having a total screw length / cylinder diameter = 30 or more,
preferably 50 to 70, and a ratio of the length of the kneading zone to the total screw length of
30% or more, preferably 40 to 70% is prepared. A polymer of a twin-screw kneader prepared by
adding a part or all of the component (C) to the components (A) and (B) and, if necessary, the
component (D) and the additive, and mixing them beforehand Bleeding in which the component
(C) is sufficiently mixed into the composition by feeding from the inlet and, if there is the
remaining component (C), melt-kneading by feeding from the polymer inlet or the side feed port
It is possible to obtain difficult pellets. In addition, a part or all of the component (C) may be
simultaneously added to the components (A) and (B) and, if necessary, the component (D) and the
additive without mixing. It may be fed from a polymer inlet.
[0018]
In the pellet (composition) thus obtained, a speaker edge obtained by injection molding a pellet
having a hardness (Shore A) of 3 to 50 degrees is particularly preferable because of its excellent
flexibility and processability.
[0019]
In the present invention, a speaker edge having a thickness of 200 μm or less is obtained by
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injection molding (mold temperature: 30 to 100 ° C., resin temperature: 150 to 190 ° C.) using
the pellets obtained as described above. It can be made.
[0020]
EXAMPLES The present invention will next be described in more detail by way of examples,
which should not be construed as limiting the invention thereto.
[0021]
<Examples 1 to 5 and Comparative Examples 1 and 2> Each component is mixed in advance
according to the composition (unit: mass part) shown in Table 1, and then a twin screw kneader
(TEM 58 BS type manufactured by Toshiba Machine Co., Ltd., total screw length) Kneaded at 180
° C with / cylinder diameter = 62.5, ratio of length of kneading zone to total screw length =
62%) and cut with a cutter while extruding in a strand shape to obtain a composition (pellet) .
The hardness and internal loss (Tan δ) of the obtained pellets were measured as follows, and are
shown in Table 1.
Further, the pellets were injection-molded under a production condition of a mold temperature of
80 ° C. and a resin temperature of 170 ° C. to prepare a sheet of 200 μm.
Table 1 shows whether or not the sheet could be produced.
[0022]
(1) Hardness Measured in accordance with JIS K6253 (Type A). (2) Internal loss (Tan δ) A sheet
having a length of 40 mm, a width of 5 mm and a thickness of 2 mm was prepared and used as a
sample. About this sample, distance between chucks 2 mm, dynamic strain 1%, frequency 60 Hz,
measurement temperature -30 to 50 ° using a viscoelastic spectrometer "RDA III"
(manufactured by Rheometric Scientific F Co., Ltd.) Dynamic viscoelasticity measurement was
performed under the measurement conditions of C, and the internal loss (loss tangent) at the
temperature shown in Table 1 was measured.
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[0023]
[0024]
<* 1>: manufactured by Kuraray Co., Ltd., triblock copolymer consisting of polystyrenehydrogenated butadiene / isoprene copolymer-polystyrene, weight average molecular weight
about 300000, polystyrene block content 30% <* 2>: Asahi Kasei Chemicals shares Triblock
copolymer consisting of polystyrene-hydrogenated polybutadiene-polystyrene, weight average
molecular weight about 60000, polystyrene block content 30% <* 3>: Component:
polypropylene, MFR50 (g / 10 min), Nippon Polypropylene Corporation Made in company <* 4>:
component; polypropylene, MFR 30 (g / 10 min), manufactured by Sun Aroma Co., Ltd. <* 5>:
manufactured by Asahi Kasei Chemicals Co., Ltd. <* 6>: paraffin oil, molecular weight 750,
manufactured by Idemitsu Kosan Co., Ltd. <* 7>: Paraffin oil, molecular weight 1500, Mitsui
Chemicals, Inc. <* 8>: SH200-10 cs (trade name), manufactured by Toray Dow Corning Co., Ltd.
<* 9>: component; manufactured by Cytec Japan Co., Ltd. <* 10>: component; manufactured by
Chiba Specialty Chemicals Co., Ltd. <* 11>: component; Made in Japan
[0025]
As shown in Table 1, in Comparative Example 1, the processability was very poor, and it was
impossible to produce a 2 mm thick sheet itself, and it was not possible to measure the internal
loss.
In Comparative Example 2, although a sheet with a thickness of 2 mm could be produced,
although the internal loss could be measured, the internal loss was small, and the sheet with a
thickness of 200 μm could not be produced, so the processability was insufficient. It can be said
that
That is, with the material of Comparative Example 2, it can not be said that the speaker edge of a
cellular phone or the like, which is required to be thinned, can not be manufactured by injection
molding. On the other hand, in Examples 1-5, internal loss is high compared with a comparative
example. Furthermore, a sheet having a thickness of 200 μm or less can be produced by
injection molding, and the processability is extremely excellent. Therefore, the speaker edge of
the present invention is particularly effective as a speaker edge used for a small speaker such as
a mobile phone or a personal computer.
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[0026]
Both internal loss and flexibility are excellent, and a speaker edge with a thickness of 200 μm or
less can be manufactured by injection molding, and it can be used as a speaker edge used for
small-sized speakers such as mobile phones and personal computers that require thin film is
there.
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