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JPH06343197

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DESCRIPTION JPH06343197
[0001]
FIELD OF THE INVENTION This invention relates to speaker cone paper.
[0002]
2. Description of the Related Art A speaker cone is required to have high bending rigidity to
obtain high quality, and liquid crystal polymers, carbon fibers, metals and the like are used, but
paper is often used in terms of cost.
[0003]
However, although paper is inexpensive, its low flexural rigidity is considered to be a drawback.
Therefore, the present inventors made various studies to obtain a speaker cone paper having an
improved bending rigidity, and reached the present invention.
[0004]
SUMMARY OF THE INVENTION That is, the subject matter of the present invention comprises a
hydrolyzate of alkoxysilane and an organic compound having two or more functional groups
capable of reacting with two or more hydroxyl groups of the hydrolyzate. The paper is
impregnated with a liquid composition containing H. and then dried, on speaker cone paper.
11-05-2019
1
[0005]
Hereinafter, the present invention will be described in detail.
First, as the hydrolyzate of alkoxysilane in the present invention, a partial hydrolyzate of
tetraalkoxysilane such as tetramethoxysilane, tetraethoxysilane or tetrapropoxysilane is usually
used. The hydrolysis reaction itself can be carried out by a known method, for example, by
adding a predetermined amount of water to the above tetraalkoxysilane and distilling off byproduced alcohol in the presence of an acid catalyst, usually about room temperature to 100
React at ° C. The alkoxysilane is hydrolyzed by this reaction, and a liquid silicate oligomer
(usually having an average degree of polymerization of about 2 to 8, preferably 3 to 6) having
two or more hydroxyl groups is obtained as a hydrolyzate by a condensation reaction.
[0006]
The degree of hydrolysis can be appropriately adjusted depending on the amount of water used,
but in the present invention it is usually selected from about 40 to 90%, preferably about 60 to
80%. The obtained hydrolyzate usually contains 2 to 10% by weight of monomer, but the amount
of monomer is 1% by weight or less, preferably 0.3% by weight or less by a method such as flash
distillation or vacuum distillation. If the monomer is removed, the resulting coating composition
becomes extremely excellent in storage stability, and is also preferable for safety and health.
[0007]
In the present invention, the hydrolyzate is blended with an organic compound having two or
more functional groups capable of reacting with the above-mentioned hydroxyl group of the
hydrolyzate to obtain a liquid composition. As such a reactive organic compound, for example,
those having two or more of a carboxyl group, a hydroxyl group, an amino group, an alkoxy
group and the like can be mentioned (however, except for the above hydrolysate).
[0008]
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(I) Silane coupling agent (generally RSiX3: X is a hydrolyzable group, R is a functional group) (ii)
alkyl alkoxy silicones (iii) polymers such as acrylic resin, epoxy resin, polyester resin, urethane
resin ( iv) Polyhydric alcohols such as 1,4-butanediol, glycerin, catechol, resorcin and the like,
and preferably selected from the group of (i), (iii) and (iv). More specifically, for example, as the
silane coupling agent of (i),
[0009]
Such as methyl acrylate,
[0010]
Epoxy system, etc.
[0011]
And other amino acids,
[0012]
Etc., and the like.
[0013]
Moreover, as alkyl alkoxy silicones of (ii),
[0014]
Etc.
[0015]
Furthermore, as polymers of (iii), for example, the following may be mentioned.
acrylic resin
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[0017]
(B) VP-γ MTS; the above VP structure to which γ MTS (γ-methacryloxypropyl
trimethoxysilane) is added
[0019]
Epoxy resin
[0021]
Polyester resin
[0023]
Polyurethane resin
[0025]
Two or more of the above organic compounds can be used in combination depending on the
purpose.
The combination of the hydrolyzate and the organic compound is carried out as follows.
That is, although an organic solvent is preferably used, it is preferable that the organic solvent be
compatible with both the hydrolyzate and the organic compound, and, for example, alcohols,
glycol derivatives, hydrocarbons, esters, etc. The ketones and ethers can be used alone or in
combination of two or more.
[0026]
Specific examples of alcohols include methanol, ethanol, isopropyl alcohol, n-butanol, isobutanol,
octanol and the like, and glycol derivatives include ethylene glycol, ethylene glycol monomethyl
ether, ethylene glycol monoethyl ether, ethylene glycol mono n- Propyl ether, ethylene glycol
mono n-butyl ether and the like can be mentioned.
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Among them, use of ethanol or methanol gives speaker cone paper which is excellent in physical
properties such as scratch resistance.
[0027]
As hydrocarbons, benzene, kerosene, toluene, xylene and the like can be used, and as esters,
methyl acetate, ethyl acetate, butyl acetate, methyl acetoacetate, ethyl acetoacetate and the like
can be used.
Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and acetylacetone, and
ethers such as ethyl ether, butyl ether, z-methyl cellosolve, ethyl cellosolve, dioxane, furan and
tetrahydrofuran can be used.
[0028]
The amount of the organic solvent used is preferably about 1 to 10 times by weight of the
organic compound from the viewpoint of operability.
At the time of blending, the catalyst is added at least by the time it is impregnated into speaker /
corn paper described later, for example, inorganic acids such as hydrochloric acid, acetic acid,
nitric acid, formic acid, sulfuric acid and phosphoric acid, Organic acids such as acids, organic tin
compounds such as dibutyltin dilaurate, dibutyltin dicutiate, dibutyltin diacetate, and alkali
catalysts such as potassium hydroxide and sodium hydroxide are effective, but particularly
inorganic acids, organic tin compounds and Organic acids are effective.
[0029]
The compounding amount of the hydrolyzate is preferably 50 to 300 parts by weight, more
preferably 100 to 250 parts by weight with respect to 100 parts by weight of the organic
compound.
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Less than 50 parts by weight is not preferable because bending rigidity is reduced, and more
than 300 parts by weight is not preferable because adhesion to the substrate is reduced.
The composition containing the hydrolyzate, the organic compound, the (catalyst) and the
solvent is a liquid composition having a phase difference of not more than 10,000 cps at room
temperature (25 ° C.).
[0030]
In the present invention, the liquid composition is impregnated into paper.
The paper is not particularly limited as long as it can be used for the speaker cone, and, for
example, kraft paper mainly composed of kraft pulp is preferably used.
In addition, the following method is usually employed for the impregnation. For example, soak
the speaker cone paper in the impregnating solution at room temperature for several minutes
and then pull it up. Control of the adhesion amount to the speaker cone paper is performed by
adjusting the viscosity of the impregnating solution. The viscosity is adjusted by diluting with an
organic solvent or an organic solvent.
[0031]
As a method of removing the organic solvent, a method of volatilizing the organic solvent by
heating to 100 ° C. or less or a method of volatilizing the organic solvent at 60 ° C. or less by
vacuum drawing may be mentioned. The dilution of the organic solvent can be carried out, for
example, at room temperature using the above-mentioned organic solvent. The paper
impregnated as described above is then dried. Drying is possible at room temperature but is
usually carried out by heating to about -20 to about 300 ° C, preferably to about -150 ° C in
terms of efficiency.
[0032]
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The drying furnace can use forced air blowing or an open type. The organic solvent is volatilized
by drying, the dehydration condensation reaction of the hydrolyzate and the organic compound
is completed, and the water is also volatilized. Although the intended speaker cone paper is
obtained as described above, the obtained speaker cone paper has high bending rigidity and does
not generate cracks due to the deformation accompanying the generation of sound.
[0033]
The present invention will be further explained in detail by the following examples. In a 500 ml
3-neck round bottom flask equipped with a stirrer, reflux condenser and thermometer, 234 gr of
tetramethoxysilane and 74 gr of methanol are added and mixed, then 22.2 gr of 0.05%
hydrochloric acid is added, and the internal temperature is 65 ° C, Hydrolysis reaction was
performed for 2 hours.
[0034]
Next, the condenser was replaced with an extraction tube, the temperature was raised until the
internal temperature reached 150 ° C., extraction was performed with methanol, and further
condensation was performed by heating at 150 ° C. for 3 hours. Thus, a hydrolyzate was
obtained. The degree of polymerization was 3 to 6 and 10 or more hydroxy groups. A solution
obtained by adding 60 gr of this alkoxysilane hydrolyzate and 60 gr of a hydroxyl groupcontaining epoxy resin to 120 gr of solvent methyl ethyl ketone and 120 gr of toluene and
compatibilizing them was obtained. 1 cc of hydrochloric acid was added as a catalyst to 240 gr of
this solution. Speaker cone paper prepared by the following method was immersed in this liquid
composition (I) at room temperature for 1 minute and then dried at 100 ° C. for 30 minutes.
(Preparation of paper)
[0035]
Pulp composition Kraft pulp 85% Manila hemp 15% Additive sizing agent (waterproofing agent)
5% Paper strength enhancer 3% Freeness (Canada standard) 600 cc Web mesh 80 Mesh press
method: Wet press method pressure 3 kg / cm2 molding temperature The characteristic values
of the paper obtained at 180 ° C. for 15 seconds are as follows.
[0036]
Thickness 320 μm density 0.86 g / cm 3 area density 0.03 g / cm 2 elastic modulus 3.00 × 10
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10 dyn / cm 2 internal loss (tan δ) 0.02
[0037]
Example 2 A solution obtained by adding 100 gr of the alkoxysilane hydrolyzate obtained in
Example 1 and 50 gr of a hydroxyl group-containing acrylic resin to 250 gr of a solvent
isopropylene and 50 gr of a xylene to be compatible was obtained.
2 cc of nitric acid was added as catalyst to 450 gr of this solution.
The same speaker cone paper as in Example 1 was immersed in this liquid composition (II) at
room temperature for 1 minute and then dried at 120 ° C. for 30 minutes.
[0038]
EXAMPLE 3 150 gr of the alkoxysilane hydrolyzate obtained in Example 1 and 50 ccr of a
hydroxyl group-containing polyester resin were added to 200 g of solvent methyl ethyl ketone
and 200 g of toluene to obtain a compatible solution. To 600 gr of this solution, 3 cc of nitric
acid was added as a catalyst. The same speaker cone paper as in Example 1 was immersed in this
liquid composition (III) (MSPE) for 1 minute at room temperature and then dried at 90 ° C. for 2
hours. The characteristic values of the speaker cone paper obtained in Examples 1 to 3 were as
follows.
[0039]
(Example 1) Thickness 330 μm density 1.00 g / cm 3 area density 0.03 g / cm 2 elastic modulus
4.00 × 10 10 dyn / cm 2 tan δ 0.05 (example 2) thickness 380 μm density 0.88 g / cm cm3
area density 0.03 g / cm2 elastic modulus 4.50 × 10 10 dyn / cm 2 tan δ 0.04 (example 3)
thickness 390 μm density 0.80 g / cm 3 area density 0.03 g / cm 2 elastic modulus 4.20 × 10
10 dyn / cm 2 tan δ 0.04
[0040]
That is, there is a speaker with improved internal loss (tan δ) and elastic modulus of the speaker
/ cone paper, and flatness of the sound pressure-frequency characteristic reduced from ± 6 dB
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to ± 3 dB and secondary distortion from −25 dB to −40 dB. It turns out that it can be realized.
[0041]
Example 4 The monomer content of the alkoxysilane hydrolyzate obtained in Example 1 was 5%.
Subsequently, the jacket heated at 100 to 150 ° C. is boiled with tetramethoxysilane oligomer,
and the vaporized monomer is discharged out of the system together with the inert gas.
The amount of monomers in the tetramethoxysilane oligomer thus obtained was 0.2%.
Thereafter, a solution which was completely dissolved in the same manner as in Example 1 was
obtained. This solution does not show thickening even after 6 months and is excellent in storage
stability. The viscosity of the liquid reactive mixed solution obtained in Example 1 was doubled
after 2 weeks.
[0042]
According to the present invention, a speaker cone paper with improved bending rigidity can be
obtained.
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