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JPS59154898

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DESCRIPTION JPS59154898
[0001]
[1] Purpose of the Invention The present invention relates to a method of manufacturing a
diaphragm for a speaker not only having high vibration damping ability but also having excellent
heat resistance and light transparency. More specifically, a speaker diaphragm formed by
thermoforming a sheet containing a polyolefin resin as a main component is subjected to surface
treatment in advance, a photocurable resin is applied to the diaphragm, and ultraviolet light is
applied to the diaphragm. The present invention relates to a method of manufacturing a
diaphragm for a speaker characterized by completely curing a photocurable resin, and in
addition to exhibiting the effects as described above, it is a lightweight and highly rigid
diaphragm for a speaker. It is intended to be provided. Background of the Invention
Conventionally, speaker diaphragms have been manufactured using paper and pulp as raw
materials, but recently, compositions of inorganic fillers such as mica, talc, graphite and the like
in aluminum foil or synthetic resin or synthetic resin A number of methods have been proposed
to manufacture the diaphragm by molding the sheet of However, in the case of using paper and
pulp as a raw material, there is a problem in rigidity and further there is a defect that the
moisture resistance is poor. Moreover, the rigidity is insufficient with the synthetic resin alone.
Moreover, in the case of the composition, although rigidity improves, since a specific gravity
becomes large, since an output sound pressure level falls in a whole frequency range, it is not
desirable. Furthermore, in the case of metal foils such as aluminum foils, it has the disadvantage
that formability is difficult. From the above, the inventors of the present invention conducted
various searches for obtaining a speaker diaphragm without these drawbacks, and as a result, a
sheet mainly composed of a polyolefin resin is thermoformed. A speaker diaphragm
characterized in that a surface treatment is performed on a speaker diaphragm in advance, a
photocurable resin is applied to the diaphragm, and the photocurable resin is completely cured
by irradiating ultraviolet light. It has been found that the method of the present invention does
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not have the disadvantages as described above, and can be produced on an industrial scale, to
reach the present invention. Effect of Concave Invention The speaker diaphragm obtained by the
method of the present invention exhibits the following effects (features) including the time of its
production. (1) Relative density (density) is relatively small (light weight). (2) High rigidity (high
modulus of elasticity) (3) Excellent weatherability and water resistance. (4) The production
method is relatively simple compared to the commonly used method, and is suitable for
industrial production. V. Detailed Description of the Invention 樹脂 Polyolefin Resin The
polyolefin resin used in the present invention is an ethylene homopolymer having a density of
0900 to 0980 or an α-olefin having 3 to 12 carbon atoms with ethylene (the copolymerization
ratio is high) Random or block copolymers with at least 20% by weight) and propylene tlt
homopolymers or with ethylene or α-olefins having 4 to 7 carbon atoms (copolymerization
proportion at most 20% by weight) It is a block copolymer.
In the practice of the present invention, these polyolefin resins may be used alone or in
combination of two or more. The molecular weight of the polyolefin resin is usually 2 to
1,000,000, preferably 2 to 500,000, and particularly preferably 3 to 400,000. These polyolefin
resins can be obtained by supporting a catalyst system (so-called Ziegler catalyst) obtained from
an M-transfer metal compound and an organoaluminum compound, or by supporting a
chromium-containing compound (for example, chromium oxide) on a carrier (for example, silica).
It is obtained by homopolymerization of the olefins or copolymerisation of the olefins with one
another or of olefins with vinyl compounds using catalyst systems (so-called Phillips catalysts) or
radical initiators (for example organic peroxides). The production methods of the polyolefin
resins are well known. (B) Surface treatment In the surface treatment carried out in the present
invention, a photocurable resin described later is coated on the surface of a diaphragm for a
speaker obtained by thermoforming a sheet of a polyolefin resin manufactured by the method
described later. In particular, the photocurable resin may be in a state in which it can be
completely in close contact with the surface of the speaker diaphragm. However, it is important
to treat it to such an extent that the physical properties of the polyolefin resin which is a raw
material of the speaker diaphragm are not impaired, and the treatment method is widely known
in the field of polyolefin resins. Typical treatment methods include oxidizing low temperature
plasma treatment method and ultraviolet radiation treatment method. The plasma processing
method is a method performed by activating a low pressure gas such as oxygen, argon, or
nitrogen by high frequency or microwave discharge, and contacting the activated gas with the
surface of the speaker diaphragm. Although the processing conditions are not particularly
limited, the output is 0.1 W to 10 KW, the pressure is 0.1 to 10 torr, and the processing time is
generally 10 seconds to 50 minutes, and the output is industrially The process is performed
under conditions such that the IOW to lKW, the pressure is 0.2 to 2 Torr, and the processing
time is 30 seconds to 5 minutes. Moreover, the ultraviolet irradiation processing method is a
method of irradiating the ultraviolet-ray of wavelength 1.800-5.5oo1 on the front and back both
surfaces of the diaphragm for speakers using a quartz mercury lamp. Although the processing
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conditions are not particularly limited, the light source distance is 5 to 30 crn and the processing
time is generally 10 seconds to 3 hours in air, and industrially, the distance between light
sources is 5 to 10 c1 rL and the processing time is 10 It is processed on the conditions which
become -20 seconds.
(C) Photo-Curable Resin The photo-curable resin used in the present invention is a polyester
oligomer having at least two acryloyl or methacryloyl groups at the end or a polyvalent vinyl
monomer having at least two vinyl groups per molecule. It can be obtained from Germany or
from a mixture. The polyester oligomer is obtained by dehydration condensation of a polyhydric
alcohol and a polybasic acid or its anhydride, and the photocurable resin has an acryloyl group
or methacryloyl group at the end of an oligomer having a molecular version of 200 to 3,000. It is
obtained by bonding a group. Polyhydric alcohol generally has 2 to 8 OH groups and 2 to 14
total carbon atoms, and typically includes ethylene glycol, propylene glycol, sodium chloride and
sodium phosphate. , Butanediol, neopentyl glycol. トリメチロールプロパン、ペンタエリスリト
−ル。 ジペンタエリスリトールおよびトリペンタエリスリトールがあげられる。 In addition,
polybasic acids generally have 2 to 10 carbon atoms in total, and representative examples
thereof include 7-tal acid, trimellitic acid, succinic acid, adipic acid, azelaic acid, and sephatic
acid. And maleic acid and fumaric acid. In the case where the end of the oligomer is a hydroxyl
group, it is reacted with acrylic acid, acrylic acid chloride, methacrylic acid, methacrylic acid
chloride etc., and in the case where the terminal end of the amine is a carboxyl group, it is
reacted with hydroxyalkyl acrylate, glycidyl acrylate etc. A polyester oligomer having an acryloyl
group or a methacryloyl group at the end is produced. Furthermore, the polyvalent vinyl
monomer having at least two vinyl groups per molecule means an aromatic polyvinyl compound
such as divinyl ton group divinyl toluene, an alicyclic compound such as divinyl cyclobutane, and
2 to 8 vinyl groups. And polyfunctional (meth) acrylic and allyl compounds having 4 to 30
carbon atoms in total, and representative examples thereof include ethylene glycol di (meth)
acrylate, propylene glycol di (meth) acrylate, Diethylene glycol di (meth) acrylate, triethylene
glycol di (meth) acrylate, butylene glycol di (meth) acrylate, trimethylolpropane tri (meth)
complete acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) Acrylate, di
arylidene pentaerythritol, diallyl polyurethane, diallyl phthalate, diallyl terephthalate, triallyl
isocyanurate, trimethylolpropane diallyl ether, diethylene glycol bis-allyl carbonate and diallyl
like.
In the present invention, as the photocurable resin, those obtained by adding 0.01 to 10 parts by
weight of a photosensitizer per 100 parts by weight of the polyester oligomer or polyhydric vinyl
monomer or a mixture thereof are used. As the photosensitizer, those used for general
photocurable resins can be applied. Representative examples of the photocurable resin include
benzylbenzoin, benzophenone, benzoin methyl ether, benzoin isopropyl ether, methyloln pentoyl
benzoate and thioxane. I. Ultraviolet Curing Treatment In curing the above-mentioned
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photocurable resin using ultraviolet light, a light source which generates ultraviolet light having a
wavelength of 2000 to 4 ° o A may be used. Chemical lamps and xenon lamps are
representative examples of this light source. Mercury lamps, multi-metal lamps, etc. can be
mentioned. The irradiation time is usually 2 seconds to 20 minutes, but it is sufficient if the
curing reaction is completely irradiated, and it is industrially adjusted to 2 seconds to 2 minutes.
(G) Production of Diaphragm for Speaker In order to produce the diaphragm for a speaker of the
present invention, first, a polyolefin resin is formed into a sheet. In this case, the polyolefin resin
may be used as it is, and the stabilizer for oxygen and heat, filler, flame retardant, metal
deterioration inhibitor and lubricant which are generally used in dividing the polyolefin resin. A
small amount of additives may be blended. Moreover, in order to produce a sheet, molding
methods such as an extrusion molding method and a calendar molding method which are used in
the field of polyolefin resins may be applied. The sheet obtained in this manner can be
thermoformed (for example, vacuum formed or pressure formed) to produce a speaker
diaphragm. If the sheet is subjected to the above-mentioned surface treatment before the
thermoforming, the processing effect is lost by the thermoforming, and the photocurable resin is
a diaphragm for a speaker even if the step of applying and curing the photocurable resin is
performed. Not desirable because it does not adhere to It must be carried out at a temperature
above the softening point of the polyolefin resin used to produce the sheet and thermoform the
sheet, but if it is carried out at a temperature below 280 ° C. It is natural that the resin must be
carried out below this temperature because the resin causes thermal degradation (11). In order
to apply the thermosetting resin to the diaphragm for a speaker obtained as described above, a
commonly used application method may be applied.
The application method Toshite may be applied by a roll coater or the like, or by brush coating,
but from the industrial point of view, from the viewpoint of efficiency, the method of application
using an impregnation method or a spray gun is preferred. desirable. The thickness of the
coating is usually 3 to 100 microns, preferably 5 to 80 microns. The diaphragm for a speaker of
the present invention can be manufactured by irradiating the photocurable resin applied in this
manner with ultraviolet rays as described above and completely curing the same. The speaker
diaphragm obtained by the method of the present invention is advantageous in cost because it
has the above-mentioned effects, and the industrial value is large. 0 (Supplies) Examples and
Comparative Examples (12 The present invention will be further described in detail by the
following examples. In Examples and Comparative Examples, the density was measured at 23 °
C. in accordance with JIS K-6758. Moreover, the elastic modulus was measured using the
viscoelasticity measuring apparatus. Example 1 T-die sheet molding of propylene homopolymer
having a melt flow index (measured at 230 ° C. and a load of 2 ° 16 kg according to JIS K6758) of 0.5 fj / 1.0 min. Machine was used to produce a sheet with a resin temperature of 230
° C. and a thickness of 0.3. The obtained sheet was made into a speaker diaphragm (diameter
25 ryn) by vacuum molding (resin temperature 150 ° C.). As a surface treatment of the
diaphragm for the speaker, oxygen is used as a processing gas at room temperature (about 20 °
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C.), and a surface treatment is performed for 2 minutes under a vacuum degree of 1 tnrr using a
plasma treatment apparatus (discharge power 50 W) The Photocurable resin (containing 80
parts by weight of trimethylolpropane triacrylate, 20 parts by weight of dipentaerythritol
hexaacrylate and 0.02 parts by weight of benzoin ethyl ether) on both sides of the treated
speaker diaphragm ) Was uniformly applied by the impregnation method so that the thickness of
the coated surface was 20 microns. The photocurable resin was completely cured by subjecting
both of the coated surfaces to an ultraviolet curing treatment for 30 seconds. Example 2 As a
surface treatment of the speaker diaphragm implemented in Example 1, a quartz mercury lamp
(300 W) is used instead of plasma treatment, and ultraviolet light irradiation treatment is
performed for 2 minutes on both sides under the condition of 6 c IrL of light source distance. In
the same manner as in Example 1 except for the above, a diaphragm for a speaker in which the
photocurable resin was completely cured was manufactured.
Comparative Example 1 The photocurable resin used in Example 1 was applied to both sides of
the speaker diaphragm in the same manner as in Example 1 without performing the surface
treatment carried out in Example 1], and was completely cured. The coating film was not in close
contact with the diaphragm and was treated on the entire surface. Comparative Example 2 The
sheet obtained in Example 1 was subjected to plasma treatment in the same manner as in
Example 1, and then, in the same manner as in Example, a speaker diaphragm was manufactured
by a pressure forming method. Photocurable resin was apply | coated on both surfaces of the
obtained diaphragm for speakers on the same conditions as Example 1, and it hardened | cured
completely. However, the photocurable resin did not adhere to the diaphragm and peeled off
entirely. Example 3 In contrast to the photocurable resin used in Example 1, 40 parts by weight
of neopentyl glycol diacrylate, 20 parts by weight of trimethylolpropane triacrylate, and 4 o T
part of dipentaerythritol A diaphragm for a speaker was produced in the same manner as in
Example 1 except that a photocurable resin consisting of oxaacrylate and 0 parts by weight of
benzophenone was used, and the photocurable resin was completely cured on both sides. 05)
Example 4 Instead of the photocurable resin used in Example 1, 25 parts by weight of
diarylidenepentaerythritol, 25 parts by weight of pentaerythritol tetrathioglycolate, and 50 parts
by weight of trimethylol Under the same conditions as in Example 1, except that a photocurable
resin consisting of propane triacrylate and 0.01 parts by weight of benzophenone was used, a
diaphragm for a speaker in which the photocurable resin was completely cured on both sides
was manufactured. EXAMPLE 5 Instead of the propylene homopolymer used in Example 1,
except using a propylene-ethylene block copolymer (ethylene content: 17% by weight) having a
melt flow index of 0.5 g / 10 min. A sheet was produced in the same manner as in Example 1,
and surface treatment was carried out under the same conditions as in Example 1 to cure the
photocurable resin, thereby producing a speaker diaphragm. Example 606) Instead of the
propylene homopolymer used in Example 1, the melt index (measured in accordance with JIS K6760, at a temperature of 190 ° C and a load of 2.16 kg) of 0.2 g / g Under the same conditions
as in Example 1 except that ethylene polymer (density o, q55. 1 Cr) was used for 10 minutes, a
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diaphragm for a speaker in which the photocurable resin was completely cured on both sides
was manufactured. The density and elastic modulus (ljtjJ modulus) of the speaker diaphragm in
which the photocurable resin obtained in Examples 1 to 6 was cured on both sides and the
speaker diaphragm before the photocurable resin was applied in Comparative Example 1 It was
measured.
The results and specific modulus are shown in Table 1. The adhesion between the cured
photocurable resin and the diaphragm of the speaker diaphragm obtained in each of Examples 1
to 6 was peeled off using a Nichiban cello tape in accordance with the test (JIS K-5400). It
evaluated by measuring the days of the coating film which did not have each, but all were
100/100 and peeling was not able to be recognized. Table 1 Patent Assignee Showa Denko KK
Patent Attorney Patent Attorney Kikuchi Sei-
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