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JPH05328485

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DESCRIPTION JPH05328485
[0001]
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an
acoustic vibration member, and more particularly to an acoustic vibration member having an
extremely high elastic modulus and a light weight with excellent acoustic characteristics.
[0002]
2. Description of the Related Art Currently, titanium or alumina is used for a central speaker
dome as a diaphragm of a speaker of an audio device. And for the speaker cones in the vicinity,
polypropylene or the like in which paper or mica is dispersed is used. Generally, the physical
properties required for the diaphragm include a light so that sound can be easily transmitted and
a high elastic modulus. Both of these can be represented by one characteristic value of sound
velocity. Therefore, it can be said that the characteristic of the diaphragm is better as the sound
velocity is larger, and in terms of the characteristic value alone, diamond is the best quality
material. However, making a single crystal of diamond thin and having a large area is practically
impossible. And, as an alternative to this, a polycrystalline film is produced by the CVD (Chemical
Vapor Deposition) method, but it has not been realized yet with a sufficient area and at a low
cost. On the other hand, the thin film made of resin has the advantages of being light and having
excellent formability. On the other hand, it has the disadvantage of low hardness and low
modulus of elasticity. In order to compensate for this, inorganic fillers such as mica are added to
improve the mechanical properties, but this is not sufficient and satisfactory products are
desired.
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[0003]
Therefore, in view of the above situation, the present inventors have intensively researched to
develop an acoustic vibration member with excellent quality by solving the drawbacks of the
conventional method. As a result, it has been found that a phosphazene-based resin obtained by
polymerizing a curable phosphazene compound is very effective, and an acoustic vibration
member having desired properties can be obtained. The present invention has been completed
based on such findings. That is, according to the present invention, after a paper or cloth is
impregnated with a curable composition containing a curable phosphazene compound as a main
component and press-molded, or alternatively, the paper or cloth is pre-formed to have a curable
phosphazene compound as a main component The present invention provides an acoustic
vibration member comprising a cured product obtained by impregnating a curable composition
as described above and then polymerizing and curing the curable phosphazene compound to
integrate phosphazene resins. .
[0004]
First, in the present invention, various papers can be used as the paper to be used for
impregnating the curable composition containing the curable phosphazene compound as a main
component. Specific examples thereof include high quality paper, rice paper, impregnated base
paper, kraft paper, synthetic pulp paper, synthetic fiber paper, non-pulp nonwoven paper, and
synthetic pulp non-woven paper. Further, as the cloth for impregnation, for example, woven or
non-woven fabric of synthetic fiber such as nylon, vinylon, tetron, woven or non-woven fabric of
natural fiber such as cotton, silk, etc., woven or non-woven fabric of various artificial fibers Be
The thickness of the paper and cloth for impregnation is not particularly limited and may be
arbitrarily selected, and it is desirable to be as thin as possible within the range where the
mechanical strength permits. For example, the basis weight may be selected in the range of 10 to
200 g / m 2.
[0005]
The paper or fabric is impregnated with a curable composition containing a curable phosphazene
compound as a main component and pressed and molded, or alternatively, the paper or fabric is
preformed to have a curable phosphazene compound as a main component After impregnating
the curable composition, the curable phosphazene compound is polymerized and cured to
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integrate the phosphazene resin, whereby the acoustic vibration member of the present invention
can be obtained. Phosphazene resin (hereinafter referred to as PPZ) which is integrated by curing
on paper or cloth. ) Is a curable phosphazene compound as an essential component, and, if
necessary, a monomer that is copolymerizable with the curable phosphazene compound as a
main component, and a curable composition prepared by blending other additives is polymerized.
It is a polymer obtained by Here, as the curable phosphazene compound, for example, a
compound represented by the general formula (I)
[0007]
[Wherein, A represents a polymerizable and curable group, and B represents a non-polymerized
and curable group. Further, a and b indicate real numbers satisfying 0 <a, 0 ≦ b and a + b = 2.
The phosphazene compound etc. which have a repeating unit represented by these are
mentioned, and there exist various things by the kind of each substituent. In the formula, A
represents a polymerization curing group, and this polymerization curing group means a
functional group which is cured by reaction by irradiation with ultraviolet light, visible light or
electron beam, use of a chemical curing agent or heating. And usually a group having a reactive
double bond. There exist various things as group which has this reactive double bond. For
example, a functional group containing an acryloyl group, a methacryloyl group, a vinyl group or
an allyl group can be mentioned. The functional group containing an acryloyl group or the
functional group containing a methacryloyl group is an acryloyloxy group or a methacryloyloxy
group, and further, a general formula (II)
[0009]
Wherein R 1 represents a hydrogen atom or a methyl group, and R 2 represents an alkylene
group (including branched alkylene groups) having 1 to 12 (preferably 1 to 5) carbon atoms. ] Is
represented.
[0010]
Specific examples of the group represented by the general formula (II) include 2-hydroxyethyl
methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl
methacrylate, 3-hydroxybutyl methacrylate, 4-hydroxy Butyl methacrylate, 5-hydroxypentyl
methacrylate, 6-hydroxy-3-methylhexyl methacrylate, 5-hydroxyhexyl methacrylate, 3-hydroxy-
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2-t-butylpropyl methacrylate, 3-hydroxy-2, 2-dimethylhexyl methacrylate, 3 Residues obtained by
removing a hydrogen atom from hydroxyl groups in methacrylates such as -hydroxy-2-methyl-2ethylpropyl methacrylate and 12-hydroxydodecyl methacrylate, 2-hydroxyethyl acrylate, 2hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 3-hydroxybutyl
acrylate, 4-hydroxybutyl acrylate, 5-hydroxypentyl acrylate, 6-hydroxy-3-methyl Hexyl acrylate
5-hydroxyhexyl acrylate, 3-hydroxy-2-t-butylpropyl acrylate, 3-hydroxy-2,2-dimethylhexyl
acrylate, 3-hydroxy-2-methyl-2-ethylpropyl acrylate and 12-hydroxy The residue which remove |
eliminated the hydrogen atom from the hydroxyl group in acrylates, such as dodecyl acrylate,
can be mentioned. Particularly preferred groups are 2-hydroxyethyl methacrylate residue and 2hydroxyethyl acrylate residue. Moreover, the functional group containing this acryloyl group or
methacryloyl group is a group represented by the general formula (III) in addition to the one of
the above-mentioned general formula (II)
[0012]
[Wherein, R 1 and R 2 are as defined above. ], That is, a residue obtained by removing a
hydrogen atom from the hydroxyl group of hydroxyalkyl-substituted (meth) acrylamide, and
further represented by the general formula (IV)
[0014]
Wherein R 1 is as defined above. And the residue obtained by removing one hydrogen atom from
the amino group of acrylamide or methacrylamide. Furthermore, as the functional group
containing an allyl group, in addition to the allyl group itself, for example, there is an allyloxy
group (CH2 = CH-CH2O-), but not limited to this allyloxy group, a wide range of general formulas
(V) to VII)
[0016]
Wherein R 1, R 3 and R 4 are as defined above. And a residue obtained by removing a hydrogen
atom from the hydroxyl group of an allyl compound having one hydroxyl group. As specific
examples of the functional groups represented by the general formulas (V) to (VII),
[0018]
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There are residues obtained by removing a hydrogen atom from the hydroxyl group in an allyl
compound such as, for example. On the other hand, B in the general formula (I) has the general
formulas (VIII) and (IX) as described above.
[0020]
[Wherein, M represents an oxygen atom, a sulfur atom or an imino group, and R 5 represents an
alkyl group having 1 to 18 carbon atoms or a halogenated alkyl group having 1 to 18 carbon
atoms. R6 to R10 each independently represent a hydrogen atom, a halogen atom, an alkyl group
having 1 to 4 carbon atoms or a halogenated alkyl group having 1 to 4 carbon atoms. ]
Represents a group represented by Specific examples of the general formula (VIII) include an
alkoxy group such as methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy
group, hexyloxy group, heptyloxy group, octyloxy group and the like, halogen (eg fluorine,
chlorine, Brominated with similar alkoxy, methylthio, ethylthio, propylthio, butylthio, pentylthio,
heptylthio, octylthio etc. alkylthio groups such as bromine, etc., substituted with halogen (eg
fluorine, chlorine, bromine etc.) Similar alkylthio groups, methylimino groups, ethylimino groups,
propylimino groups, butylimino groups, pentylimino groups, hexylimino groups, hexylimino
groups, heptylimino groups, alkylimino groups such as octylimino groups; A similar substituted
alkyl Luimino group etc. can be mentioned. Specific examples of the group of the formula (IX)
include phenoxy group, thiophenyl group, halogenated phenoxy group (2, 4, 6-tribromophenoxy
group, 4-bromophenoxy group, 2-chlorophenoxy group, 2, 4 -Dichlorophenoxy group etc.) and
halogenated thiophenyl group (4-chlorophenylthio group etc.), or aniline and halogenated aniline
(2-chloroaniline, 2,4-dichloroaniline, 2,4,6-tribromoaniline etc.) The residue etc. which removed
the hydrogen atom from the amino group of these can be mentioned.
[0021]
In addition, a and b in the above general formula (I) may be real numbers satisfying 0 <a ≦ 2, 0
≦ b <2, and a + b = 2, but preferably 0.6 ≦ a ≦ 2, 0 ≦ b ≦ 1.4. Substituent A is a group that
exerts a curing action when polymerizing (curing) the phosphazene compound of the general
formula (I), and Substituent B controls the physical properties of the polymer and also controls
the polymerization performance. It is a group that exhibits a regulatory action. However, such
phosphazene compounds are excluded from the subject matter of the present invention, since
those having a = 0 do not have curability. However, one with a = 2, b = 0, ie, the general formula
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[0023]
[Wherein, A is as defined above. The phosphazene compound which has a repeating unit
represented by these can be utilized as a raw material in this invention, and can make this
invention more effective at the point of hardenability. Preferred examples of the curable
phosphazene compound used in the present invention are those having a repeating unit of the
above general formula (I), but the degree of polymerization thereof is 3 or more, preferably in the
range of 3 to 10,000, more preferably Is in the range of 3 to 18, and in particular 3 or 4 or a
mixture thereof is optimum. There are also those in which the repeating units of the general
formula (I) are linked (polymerized) in a chain-like manner, but preferably they are cyclically
bonded (polymerized). A specific example of such a curable phosphazene compound is as shown
by the following formula.
[0025]
Such curable phosphazene compounds can be produced by various methods and are not
particularly limited. For example, when it is desired to introduce a group represented by the
general formula (II) as the substituent A, a hydroxyalkyl (meth) acrylate corresponding to the
general formula (II), that is, a general formula
[0027]
[Wherein, R 1 and R 2 are as defined above. When it is desired to introduce a group represented
by the general formula (III) as the substituent A using the hydroxyalkyl (meth) acrylate
represented by
[0029]
Wherein R 1 and R 2 are as defined above. When it is desired to introduce a group represented
by general formula (IV) as substituent A using hydroxyalkyl (meth) acrylamide represented by
[0031]
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[Wherein, R 1 is as defined above. When it is desired to introduce a group represented by any
one of the general formulas (V) to (VIII) as the substituent A, using a (meth) acrylamide
represented by the formula
[0033]
Wherein R 1, R 3 and R 4 are as defined above. Or allyl alcohol, allyl phenol, allyl ester of
hydroxybenzoic acid or a derivative thereof. On the other hand, in the group represented by the
general formula (VIII) introduced as the substituent B, when M is an oxygen atom, the general
formula [wherein R 5 is the same as above. When M is a sulfur atom, the formula is as defined
above, wherein R 5 is as defined above. When M is an imide group, a compound of the general
formula R5 NH2 wherein R5 is as defined above. The alkylamine represented by these, the
halogenated alkylamine, or its derivative (s) is used. In the group represented by the general
formula (IX) introduced as the substituent B, when M is an oxygen atom, the general formula
[0035]
[Wherein, R 6 to R 10 are as defined above. When M is a sulfur atom, a general formula
[0037]
[Wherein, R 6 to R 10 are as defined above. When M is an imide group, a compound of the
general formula
[0039]
[Wherein, R 6 to R 10 are as defined above. The aniline represented by these] or its derivative (s)
is used. The compound forming the substituent A and the compound forming the substituent B
are shown in the form of a cyclic compound represented by chlorophosphazene [formula (NPCl2)
n] or a formula Cl4 P. (NPCl2) n-1 .NPCl3. The desired phosphazene compound of the general
formula (I) can be obtained by reaction with the chain compound (n is an integer of 3 or more,
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preferably 3 to 18) or the like. In addition, when the compound which forms said substituent B is
alcohol, mercaptans, phenols, or thiophenols, alkali metals, such as sodium metal and metallic
potassium, are made to react beforehand, alcoholates, phenolates, mercaptide , And may be
stored as thiophenolates. Moreover, it is preferable to use dehydrohalogenating agents, such as
tertiary amine, in the reaction of the compound which forms the above-mentioned substituents A
and B, respectively, and chloro phosphazene. Examples of this tertiary amine include
trimethylamine, triethylamine, triisopropylamine, tri-n-propylamine, tri-n-butylamine and
pyridine, among which pyridine is preferred. Furthermore, this reaction is usually carried out in
an organic solvent. Examples of the organic solvent include benzene, toluene, xylene, chloroform,
cyclohexane, methylene chloride, tetrahydrofuran, 1,4-dioxane and the like. These can be used
alone or in combination. In the curable phosphazene compound obtained by the above reaction,
it is preferable that all chlorine atoms of chlorophosphazene as a raw material be substituted
with the above-mentioned substituents, but chlorine may partially remain.
[0040]
In the present invention, the phosphazene resin (PPZ) contains, as an essential component, the
above-mentioned curable phosphazene compound and, if necessary, a monomer copolymerizable
with the above-mentioned curable phosphazene compound (monomer for copolymerization)
Alternatively, it is a polymer obtained by impregnating a curable composition containing an
ultraviolet absorber, an antistatic agent, an antifogging agent, a lubricant and the like as another
additive, and polymerizing and curing a curable phosphazene compound. As a monomer
copolymerizable with this curable phosphazene compound (monomer for copolymerization),
there are a silicone-modified curable compound, a polymerizable prepolymer, and an acryloyl
group, a methacryloyl group, a vinyl group or an allyl group. The compound which has a reactive
double bond, such as a polymerizable monomer, can be mentioned. Here, the silicone-modified
curable compound is not particularly limited as long as it is a compound having a silicone (silane)
group and preferably a (meth) acrylate group in one molecule.
[0041]
Specific examples of the silicone-modified curable compound include silicone-modified urethane
acrylate, (meth) acryloxysilane compounds, and (meth) acrylate-modified polysiloxane. Moreover,
as a (meth) acryloxysilane compound, (gamma)-methacryloxy propyl trimethoxysilane, (gamma)methacryloxy propyl methyl dimethoxysilane etc. are mentioned, for example. Examples of
(meth) acrylate-modified polysiloxanes include compounds containing a silicone (silane) group
and a (meth) acrylate group in one molecule. The mixing ratio of the curable phosphazene
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compound to the silicone-modified curable compound is not particularly limited, and may be
appropriately selected according to the type of the silicone-modified curable compound. Usually,
20 to 99.5 parts by weight of a curable phosphazene compound and 0.5 to 80 parts by weight of
a silicone-modified curable compound. Preferably, 40 to 99 parts by weight of a curable
phosphazene compound and 1 to 60 parts by weight of a silicone-modified curable compound.
[0042]
Specific examples of the polymerizable monomer having an acryloyl group, a methacryloyl
group, etc. include methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth)
acrylate and 2-hydroxy. Monofunctional groups such as propyl (meth) acrylate, 1,3-butanediol di
(meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, ethylene
glycol di (Meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth)
acrylate, tetraethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene
glycol di (meth) acrylate , A bifunctional group such as hydroxypentyl ester neopentyl glycol di
(meth) acrylate, and a trifunctional group such as trimethylolpropane tri (meth) acrylate,
pentaerythritol tri (meth) acrylate and dipentaerythritol hexa (meth) acrylate The above
polyfunctional compounds can be mentioned.
[0043]
Specific examples of the polymerizable prepolymer include polyester (meth) acrylate,
polyurethane (meth) acrylate, epoxy (meth) acrylate, polyether (meth) acrylate, melamine (meth)
acrylate and oligo (meth). Acrylate, alkyd (meth) acrylate, polyol (meth) acrylate, silicon (meth)
acrylate and the like prepolymers having at least one (meth) acryloyl group can be mentioned.
Particularly preferred prepolymers are polyester, epoxy and polyurethane (meth) acrylates.
Examples of the polyester (meth) acrylate include ethylene glycol; 1,4-butadiol; 1,6-hexanediol;
diethylene glycol trimethylolpropane; dipropylene glycol; polyethylene glycol; polypropylene
glycol; pentaerythritol; dipentaerythritol, etc. A polyester is obtained from a polyhydric alcohol
and a polybasic acid such as phthalic acid, adipic acid, maleic acid, trimellitic acid, itaconic acid,
succinic acid, terephthalic acid and alkenyl succinic acid, which is then (meth) acrylated Are
listed.
[0044]
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Examples of the (meth) acrylated compounds include adipic acid / 1,6-hexanediol / (meth) acrylic
acid type, phthalic anhydride / propylene oxide / (meth) acrylic acid type, trimellitic acid /
diethylene glycol / acrylic acid Mention may be made of polyester (meth) acrylates such as those
of the family. An epoxy (meth) acrylate esterifies the epoxy group of an epoxy resin with (meth)
acrylic acid, and makes a functional group a (meth) acryloyl group. Specific examples thereof
include bisphenol A-epichlorohydrin type epoxy resin / (meth) acrylic acid type, phenol novolakepichlorohydrin type epoxy resin / (meth) acrylic acid type, alicyclic epoxy resin / (meth) acrylic
acid type and the like. Epoxy (meth) acrylate is mentioned. Specifically, for example, by reacting
an isocyanate compound such as tolylene diisocyanate with a (meth) acrylate having a hydroxyl
group such as 2-hydroxyethyl (meth) acrylate as the above-mentioned polyurethane (meth)
acrylate can get. In this case, the central portion of the molecule has a polyester structure, and
isocyanate groups are often disposed at both ends to (meth) acrylate. Moreover, as a urethane
compound, oil-modified polyurethane resin type | system | group, moisture-curable polyurethane
resin type | system | group, block type polyurethane resin type | system | group, catalyst curing
polyurethane resin type etc. are mentioned, for example. Specific examples of the epoxy
compound include those obtained by adding an appropriate curing agent to an epoxy resin, those
esterified by reaction of an epoxy resin and a fatty acid, and those obtained by using an epoxy
resin and an alkyd resin in combination. . Specific examples of the silicone compound include, for
example, a precondensed product obtained by mixing monomethyl or monoethyltrichlorosilane
with a small amount of dimethyldichlorosilane and diethyldichlorosilane and reacting them. The
obtained precondensate is usually dissolved in an appropriate solvent, and, if necessary, a curing
accelerator such as a soluble fatty acid salt or zinc octoate is added and used.
[0045]
The acoustic vibration member of the present invention is obtained by impregnating a paper or a
cloth with a curable composition containing the curable phosphazene compound as a main
component, polymerizing and curing the curable phosphazene compound to integrate
phosphazene resins. It consists of a hardened | cured material obtained. Although a room
temperature curing method can be used to impregnate and cure a curable composition
containing this curable phosphazene compound as a main component, a heat curing method and
active energy can be taken into consideration in view of the properties of the resulting cured
resin. It is preferable to use a method of curing by irradiating a ray (visible light, ultraviolet light,
electron beam, X-ray, γ-ray, etc.). Therefore, when preparing a curable composition having this
curable phosphazene compound as a main component, the method of preparation is changed
depending on the curing method after polymerization or copolymerization of the curable
phosphazene compound. That is, when performing the said superposition | polymerization or
copolymerization, when using a heat-hardening method, it is preferable to use the compound of a
peroxide type and an azo compound individually or in combination as a polymerization initiator
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as needed. Here, specific examples of the peroxide compound include, for example, benzoyl
peroxide; p-chlorobenzoyl peroxide; 2,4-dichlorobenzoyl peroxide; t-butyl hydroperoxide; di-tbutyl Peroxide; dicumyl peroxide; t-butylperoxyacetate; t-butylperoxybenzoate and the like can be
mentioned. Other peroxides (persulfates, redox systems) can also be used, and examples of such
persulfates include ammonium persulfate, potassium persulfate, etc., and as a redox system,
hydrogen peroxide-metal salts , An organic peroxide-metal salt, an organic peroxide-aliphatic or
alicyclic polyamine compound, an organic peroxide-dimethylaniline, a potassium dichromatemetal oxide, etc., and as an azo compound, an aromatic diazoamino compound And aromatic
diazothioethers, aromatic diazooxy compounds, aliphatic diazo compounds and the like. In
addition, although it changes with conditions, such as impregnation of a curable composition,
and an application quantity, in a heat-hardening method, what is necessary is just to make it
harden | cure completely at 100-150 degreeC and 10 to 120 minutes.
[0046]
On the other hand, when the above polymerization or copolymerization is carried out, a
polymerization initiator (photosensitizer) should be used, if necessary, when using a curing
method by active energy rays such as ultraviolet rays, electron rays or visible rays. Is preferred.
As such a polymerization initiator, various ones can be used. Specifically, for example, 1hydroxycyclohexyl phenyl ketone, dibenzoyl, benzoyl, benzoin methyl ether, benzoin ethyl ether,
p-chlorobenzophenone, p-methoxybenzophenone, benzoyl peroxide, di-t-butyl peroxide,
camphorquinone and the like Can be mentioned. These initiators can be used alone or in
combination. The blending amount of these polymerization initiators is usually in the range of
0.05 to 5.0 parts by weight with respect to 100 parts by weight of the curable phosphazene
compound. In this curing method using active energy rays, for example, in the case of ultraviolet
light, ultraviolet light having a wavelength of 200 to 550 nm may be irradiated for 1 second or
more, preferably 3 to 300 seconds. Here, the integrated light quantity of the irradiation beam is
usually 50 to 5,000 mJ / cm @ 2. The amount of polymerization initiator used is usually selected
in the range of 0.1 to 5.0 parts by weight with respect to 100 parts by weight of the curable
compound.
[0047]
Here, an example of the component composition of the curable composition prepared by
impregnating in paper or cloth is as follows. (A) Curable phosphazene compound 100 parts by
weight (b) Monofunctional monomer and / or polyfunctional monomer copolymerizable with the
curable phosphazene compound 0 to 100 parts by weight (c) water or organic solvent
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Compounded water (d) photo initiator or thermal polymerization initiator 0.05 to 5 parts by
weight [to 100 parts by weight in total of (a) and (b)] (e) other additives such composition The
curable composition of the present invention is prepared by sufficiently stirring and dispersing it
with a generally used dispersing / stirring machine, as in the preparation of a paint in coating. As
the dispersion / stirring machine used for the preparation of the curable composition, various
ones can be used. Specific examples thereof include sand mills, roll mills, ball mills, ultrasonic
dispersers, and microfluidizer dispersers.
[0048]
In order to impregnate the curable composition thus prepared into paper or cloth, a method of
applying to a paper or cloth, a method of impregnating into a paper or cloth, an impregnated
body obtained by impregnating the curable composition. Furthermore, a method of applying a
curable composition (a cured product as shown in FIG. 1 can be obtained. )などいずれであって
もよい。 The paper or cloth coated and impregnated with the curable composition is, for
example, sandwiched by a plate having a smooth surface, pressed under a load, and then cured
by the heat curing method, photo curing method or the like. The cured product of the invention
can be obtained. In the case of the photo-curing method, it may be cured by applying a load
between a smooth and transparent plate which has a good UV transmittance like PET. Further, in
the case of a heat curing method, it may be cured at the same time as applying a load as in a hot
press. A load of 10 to 150 kg / cm2 is sufficient. When the load is applied too much, it becomes
too thin, and when the load is too small, the surface becomes uneven, which is not preferable.
Then, when impregnating the curable composition into paper or cloth, the paper or cloth may be
preformed, and then the curable composition may be applied, impregnated and cured. A coater
(for example, a spin coater, a gravure coater, a roll coater, a roll coater, a curtain coater, a bar
coater) generally employed in ordinary dipping or coating for applying and impregnating the
curable composition onto paper or cloth After coating and impregnating with a blade coater, a
doctor coater, a spray coater, etc.), water and solvent are removed if necessary. Then, a cured
product can be obtained by curing by the above-mentioned curing method and integrating
phosphazene-based resins, and for example, it can be applied to a speaker cone of a speaker (see
FIG. 2) for acoustic equipment. It can be used for high quality acoustic vibration members.
[0049]
In the cured product of the present invention, an inorganic filler can be added to the curable
composition for the purpose of improving the strength, hardness, elasticity and the like. Various
inorganic fillers can be used as the inorganic filler. Specific examples include ceramics (SiC, Si3
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N4, Al2 O3, TiC, SiO2 etc.), natural minerals (talc, clay, mica etc.), their diamonds, carbon
(including carbon fibers), glass fibers etc. Be The particles of these inorganic fillers have an
average particle size of about 500 μm or less, preferably 0.1 to 100 μm. The inorganic filler is
used in an amount of 5 to 950 parts by weight, preferably 10 to 150 parts by weight, per 100
parts by weight of the curable phosphazene compound. In order to prepare a curable
composition using such an inorganic filler, it may be sufficiently stirred and dispersed by a
dispersing / stirring device generally used for dispersing a coating pigment. As the dispersion /
stirring machine, various ones can be used. Specific examples thereof include sand mills, roll
mills, ball mills, ultrasonic dispersers, and microfluidizer dispersers.
[0050]
The present invention will now be described in more detail by way of Preparations and Examples.
Production of a Curable Phosphazene Compound A 1-liter flask equipped with a thermometer, a
stirrer, a dropping funnel and a condenser is a hexachlorocyclotriphosphazene [cyclic compound
of the formula (NPCl2) 3], hereinafter abbreviated as 3PNC. 58 g (0.167 mol), 50 ml of toluene
and 158 g (2.0 mol) of pyridine were added and stirring was started. Next, 2-hydroxyethyl
methacrylate (hereinafter referred to as HEMA). ) (143 moles) was gradually dropped from the
dropping funnel. The mixture was heated to 80 ° C. in a warm bath and reacted for 8 hours
under stirring. Then, 400 cc of toluene was added, the precipitated crystals and the catalyst were
filtered off, and the filtrate was washed with water. After the filtrate is dried using sodium sulfate,
the catalyst is removed by distillation under reduced pressure to obtain 136 g of 1,1,3,3,5,5-hexa
[2- (methacryloyloxy) ethoxy] cyclotriphosphazene as a yellow liquid. The The yield was 91%.
[0051]
EXAMPLE 1 The curable phosphazene compound obtained in the preparation example was
impregnated at a ratio of 50 g / m @ 2 into a sheet of base paper 100 mm.times.100 mm basis
weight of 30 g / m @ 2. Then, it was molded by applying a load of 20 kg / cm @ 2 and then cured
by ultraviolet irradiation with a total light quantity of 500 mJ / cm @ 2. The thickness of the
obtained sheet was 65 μm. And this sheet was transparent, and from the microscopic
observation of its cross section, it was a structure having paper at the center of the sheet and
having a cured resin layer of phosphazene compound above and below it. The phosphazene
compound permeates sufficiently between the fibers of the paper to form a strong bond. A test
piece of 5 mm × 10 mm was prepared from this sheet, and the tensile elastic modulus was
measured. As a result, it was 1.0 × 10 10 Pa and the density was 1.1 g / cm 3. Moreover, this
sound velocity was 3,020 m / sec, and it was an acoustic vibration member of excellent quality.
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[0052]
Example 2 Example 1 was carried out in the same manner as in Example 1 except that diamond
fine particles having a particle size of less than 1 μm were blended with the curable
phosphazene compound obtained in Production Example so that the content would be 10% by
weight. The obtained sheet had a tensile modulus of 3.2 × 10 10 Pa and a density of 1.2 g / cm
3. Moreover, this sound velocity was 5,160 m / sec, and it was an acoustic vibration member of
excellent quality. The tensile modulus of elasticity was measured using a universal material tester
manufactured by Instron.
[0053]
As described above, according to the present invention, it is possible to obtain a cured product
which is extremely high in tensile modulus, light in weight, and excellent in acoustic
characteristics with high sound velocity. Therefore, the acoustic vibration member of the present
invention is widely and effectively used as a diaphragm of a speaker of various acoustic devices.
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14
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