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DESCRIPTION JPS5184248
Patent Office Secretary 1, Title of Invention 0 Japanese Patent Publication No. 517-842480
Published Japanese Patent Publication No. 51. (1976) 7.23 Japanese Patent Application
Publication Go-g3zs [phase] Application dated date, (197, r) /, 2 / inside agency number 646555
specification 1, title of the invention 1, title of the invention speaker cone paper
Sispeaker corn paper 2 invention and representative Oyama Soza 4 4, agent Tokyo Chiyo 1] 1
ward 2 Uchiyukicho 2-chome 1st (Iino Building) [Fa] Japan Patent Office
DETAILED DESCRIPTION OF THE INVENTION The present invention relates to speaker cone
paper. More specifically, pulp particles and glass flakes which are heat resistant and formed from
solvent soluble aromatic polymers. Speaker cone paper K11 l consisting of short fibers. One of
the most important characteristics representing the performance of the thermal beaker is
frequency characteristics. It is the high-pitched resonance frequency fh that is the target of the
high-pitched playback limit? The output sound pressure decreases at frequencies above 'h. Here,
fh is represented by mv: mass of voice coil: mass of cone 8: stiffness of cone top. Therefore, it is
necessary to increase fb in order to improve the output sound pressure characteristics up to the
high tone range. For this purpose, the voice coil, the mass of the cone / J1 can be reduced, or the
stiffness at the top of the cone can be increased. Here, the stiffness at the top of the cone is
expressed by the equation of s = πBh2 white ingα: cone half apex angle h: cone thickness E:
cone Young's modulus, α can be too small in relation to cone forming. Not so-so there is a limit
to the value of 82. • Treble resonance frequency EndPage, which generally represents the
reproduction limit of the high range, expressed in terms of μar 'support-free cone eigenvalue ra:
mini cone diameter C C: cone density Be Therefore, the high-pitched resonance frequency fh
indicates the speed of propagation in the shape of a cone in a single-piece computer. That is, by
stacking one, it is possible to obtain speaker cone paper having good frequency characteristics in
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the A range ρC. It is also necessary for the speaker cone to have a reasonable internal loss. As
conventional corn paper materials, mainly natural cellulose pulp, foam-containing resin, metal
foil and the like, in particular, natural cellulose pulp is widely used. Speaker cone paper mainly
composed of natural cellulose pulp is inferior in heat resistance, poor in flammability, and poor in
nine-frequency characteristics. Recently, as an attempt to improve such a point, Japanese Patent
Publication No. 45-23505,% Open Sho 48-25515, a method of mixing a carbon fiber with a large
elastic modulus is described in the official gazette. However, speaker cone paper obtained by
such a method is not preferable because it has high conductivity. In order to reduce the density
of the speaker cone paper and increase the rigidity, a foaming agent as described in Japanese
Patent Publication No. 47-29724 was mixed. For speakers with high rigidity and moderate
internal loss, including micro closed cells in which a thermosetting adhesive mixed with highly
rigid fibrous glass, mica fine powder and natural mineral fine powder is laminated on a textured
cloth piece A diaphragm is known.
However, although the adhesive agent of an amino type, a phenol type, and a polyester type resin
is used for this speaker diaphragm, its heat resistance is inferior. As a result of keen research to
eliminate such drawbacks, the present inventor has obtained heat resistance and, by mixing pulp
particles made of an aromatic polymer soluble in a medium, glass flakes and short fibers, the #
flammability It is possible to obtain a speaker knack paper excellent in heat resistance and
excellent in characteristics, and the present invention is completed. That is, 1) The present
invention is heat resistant, solvent soluble aromatic polymer, or 40 to 90% by weight of pulp
particles, etc., glass + 1 flavor 5 to 50% by weight, short fibers 10 to 30 '111! Speaker cone
paper which is heated by ts-ILL, ml; 2, 'The initial tensile resistance of the glass, ie the Young's
modulus, is 7,000 immediates / 鵡 2, the other common polymeric substances are roughly: zoo =
2 oo OKf /. It is possible to observe an increase in the Young's modulus of the paper when the
glassy flaky substance with such a high Young's modulus is mixed into the paper structure. As
the glass flakes used in the present invention, those of the type of glass generally used by
Company 9 can be used. For example, low alkali / lime / alumina / borosilicate glass or E glass,
soda / lime / borosilicate glass or 0 glass, soda / lime / borosilicate glass t or A glass (alkali
glass), soda tatami lime The glass flakes referred to as glass or A glass (alkali glass), soda / boro /
silicate glass or A glass (alkali glass), etc. is in the form of a film or flake, and has a particle size of
1 tm or less and is 90 weight -It is desirable to occupy the above. If swn or more accounts for
90% by weight or more, it is not preferable because papermaking becomes difficult and
mechanical properties of one paper are degraded. If the particles of glass flakes are too large. If
necessary, 5 to 30% by weight of the 9 sheets of glass flakes is preferably used by grinding
according to a known method. When the amount of glass flakes is less than 5% by weight, the
effect of the addition of glass flakes can not be recognized, and the loss of the important
characteristics of Bi-EndPage: 2-car corn paper is small. Not desirable. On the other hand, if it
exceeds 30% by weight, the loss increases but it is not desirable because the rigidity decreases. In
the present invention, the heat-resistant, solvent-soluble aromatic polymer is used, and the
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entanglement and bonding of the pulp particles are not significantly destroyed.
° ':) Fat by stuffing with glass flakes. Moreover, accompanying with this, a phenomenon that
excessive air gaps are included in the weave of nine papers, as a result, the internal beat of the
sound increases, and the relative increase in density also decreases and the light It becomes a
trap. An 11-thermal, solvent-soluble aromatic polymer used in the present invention is a film
which has a solubility of at least triple lid, preferably 7N varnish at room temperature, and forms
a stable solution Has formation ability. It means a polymer, and the followings are exemplified.
(1) A combination polyamide of a dicarboxylic acid having an aromatic ring, preferably a highly
active derivative such as a pyrogenic acid, and a diamine having an aromatic ring. For example,
terephthalic acid as tId dicarboxylic acid. Meta phenylene diamine, 4.4'- diamino diphenyl ether
as in 7 tal 1 L diamine; Even if it is a homopolymer consisting of -dicarboxylic acid and -diamine
using r-diaminodiphenylmethane, xylylenediamide, 1 /, N-methyl- 2-7 enylene diamine, etc., the
dicarboxylic acid component And may be a copolymer consisting of two or more compounds
selected from the diamine component + one or both of PJ. As typical ones, for example,
polymetaxylene terephthalamide, polymetaxylene terephthalamide, or a copolymer of
metaphenylene diamine, isophthalic acid and terephthalic acid, poly N methyl paraphenylene
rephthalamide temple are exemplified. (2) A polyamide obtained by activating and condensing an
aminocarboxylic acid having an aromatic ring in a favorable manner. For example,
homopolymers from only one of p- or m-aminobenzoic acid, p-aminomethyl sylphamic acid, etc.
added as an aminocarboxylic acid, even if it is a homopolymer from only one, a condensation
product of two or more kinds of rose amino acid There are five (3) above-mentioned pills
obtained by copolymerizing the above-mentioned ill + 21 and an amide. Representative examples
are metaphenylene diamide / l iso 7 thalso chloride, valaamine benzoic acid- * chloride,
polyamide obtained by condensing three components of base salt. [Lambda] -N-containing polypolycyclic cyclic compound fil aromatic polyamideimide wherein X is a group selected from
alkylene / alkylidene having 1 to 6 carbon atoms and cycloalkyl. Here, R is an organic group
having 1 to 10 carbon atoms, and Y and Y 'may be the same or different, each being a
hydrocarbon group having 1 to 6 carbon atoms, and a halogen atom.
Allyloxy (aryloxy) group having 1 to 3 carbon atoms. Carboalkoxy groups having 2 to 10 carbon
atoms. An alkoxycarbonyl group having 1 to 5 carbon atoms. Or at least one selected from m and
n may be the same or different. Q−5である。 EndPage: 3 The polyamideimide of the above
formula is constituted of at least 70 mol, preferably 85 mol or more, and in particular, X is -CH,-,
-0-1-80, -Y, Y 'is a methyl group, a halogen atom , Methoxy group. ffi and fl are preferably 0 or l.
The polyamideimides contain 30 mol%, in particular 15 "% 2 carbon; jO repeat units. Here, R is
an alkylene group having 2 to 15 carbon atoms. である。 The repeating units of 30 mol,
especially 15 mol, are polyamidepetzimidazole, aromatic polyimide, aromatic polyamide
polyazole such as polyoxazole. Polyoxadiazoles, polythiazoles, polythiadiazoles Polybenzazoles
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such as polybenzimidazole, polybe / zothiazole,-polybenzoxazoles, polyhydantoins, polyparabanic
acids, polyquinazolinediones, polyquinazolones. It may also contain polyquinoxali /,
polyoxazinone. 3. Precursor of “fdJ polyheterocyclic compound” Polymer having unit 1
(precursor of polyamide imide) (precursor of polyamide imide) (2) Aromatic polyhydrazide,
Polyamide hydrazide having aromatic polyurea 131 aromatic polyamide hydrazide. These may
have an inert substituent such as a methyl group, an alkoxyl group or a halogen atom. ':' F1 we
precursor 1 against ia 72 sialic acid, kerber. Taro acid and other aromatic dicarboxylic acids, and
7 Nontetracarboxylic acid anhydride, pyromellitic; precursor copolymerized with acid anhydride
etc. can also be used. (2) Polyazoles such as polyoxazoles, polyoxadiazos-polythiazoles,
polythiadiazoles) polybenzazoles 1 such as polybenzimidazoles, polybenzothiazoles,
polybenzoxazoles (4) polyhydantoins, polyparabanic acids, polyquinazolinediones Polyazole (5)
Polyquinoxali / I Polyoxazinone 4, Aromatic Polyether Polyene Enylene Oxide, Polyarylene Oxide
The pulp particles of the present invention are produced by the following method. The aromatic
polymer having heat resistance as described above is dissolved in an appropriate solvent, and the
filler is added thereto, or the above-mentioned filling is carried out during polymerization of the
aromatic polymer having heat resistance. It is obtained by introducing the material and
introducing the polymerized mixture into a suitable precipitant to precipitate as fine particles.
As a solvent used in the above-mentioned method, a solvent which dissolves the polymer
component in pulp particles but is insoluble in a filler and soluble in water is preferable. As such
a solvent, for example, sulfuric acid. Inorganic solvents such as hydrofluoric acid 1 fuming
sulfuric acid, chlorsulfuric acid, 70 sulfuric acid, polyphosphoric acid, or N-EndPage: 4-tyl-2pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl Organic solvents such
as sulfoxide, hexamethylphosphoramide and tetramethylurea are preferred. The inorganic
solvent or the organic solvent can be used as a mixture. Medium systems can be used. The
polymer concentration in the solution is one polymer type. Depending on the degree of
polymerization of the polymer, approximately 2 to 15% by weight is desirable. As the precipitant
used in the present invention, a liquid or solution which is miscible with the solvent of the
polymer solution but is a nonsolvent for the 9 polymers is desirable. Such precipitants depend on
the type of solvent used. When an organic word medium is used as a solvent, water alone or
glycerin, ethylene glycol-, glycerin-water mixture, ether temple may be used, or one or two or
more kinds of salts represented by Mxn may be perplexed. Even if it is water soluble, it is too
cold here 0 9M is Li, Na, K + Mg, Ca, 8r, Ba, 8n + Zn, Al. iX represents eL + 'Br, NO, CH3COO,
8CNn represents an integer of 1 to 4; As these inorganic salts, for example, calcium chloride,
sodium chloride, magnesium chloride, zinc chloride, strontium chloride, aluminum chloride,
stannic chloride, nickel chloride, calcium bromide, calcium nitrate and the like. Zinc nitrate,
aluminum nitrate, sodium acetate, potassium thiocyanate, calcium thiocyanate and the like can
be mentioned, particularly calcium chloride. Lithium chloride, aluminum chloride, calcium
thiocyanate, sodium acetate and the like are opened. Among these, calcium chloride-water based
precipitants are preferred because they are easy to handle and inexpensive. Among the above-
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mentioned precipitants, aqueous ones are particularly preferable. When an inorganic solvent is
used as the solvent, it is possible to use, as the precipitant used, water alone or an aqueous
precipitator obtained by diluting the used inorganic solvent with water. At the same time, it
causes shearing or beating action. 1; Papermaking from pulp grains j and short fiber made by the
above method is carried out using a long mesh type or a circular mesh type paper machine as in
the case of making paper from conventional natural pulp It is good to make paper by wet
method.
It is desirable that the short fibers used when making pulp particles in the present invention be
heat resistant fibers. 1 Normally, the fineness is 0.5 to 10 deniers, and the fiber length is 1 to 20.
. As the polymer, various materials can be used to form such heat-resistant fibers. For example,
the following fibers can be mentioned. l, the short fiber aromatic polyamide consisting of
aromatic polyamide is the same as the above. The short fiber nitrogen-containing
polyheterocyclic compound consisting of λ-like nitrogen polyheterocycle is the same as above.
3. The precursor of the short fiber nitrogen-containing polyheterocyclic compound consisting of
the precursor of the nitrogen-containing polyheterocyclic compound is the same as above. 4. A
short-chain aromatic polyether consisting of aromatic polythylene-ter is the same as the above
05, and as a short-fiber aromatic polyester consisting of aromatic polyester, (i) polyethylene-2,6naphthalate and / or polyethylene- 2,7-naphthalate (ro) ethylene-26-naphthalate unit and He /
also he ethylene-λ 7-naphthalate single EndPage: a copolyester containing 85 moles or more of
the 5-position. As a copolymerization component of the copolyester, a copolyester using an
aromatic dicarboxylic acid as an acid component is preferably used. (Iii) (I) polyethylene-2,6naphthalate and / or polyethylene-.lambda.7-naphthalate and / or (11) ethylene-2,6-naphthalate
and / or-] are ethylene-2,7-naphthalate units. Mixed polyesters containing copolyesters
containing 2 or more molchi. 2) Polyethylene terephthalate (E) Mixed polyester containing
copolymerized polyester containing one or more ethylene terephthalate units in tssmo. In this
case, a copolymer polyester using an aromatic dicarboxylic acid as an acid component as a
copolymer component of the copolymer polyester is preferably used. (C) A copolyester
containing (1) polyethylene terephthalate and / or (I) ethylene terephthalate unit or more and
having ss molt or more is contained. 6. Short Fibers Composed of Inorganic Compounds As short
fibers composed of inorganic compounds, glass fibers, aspe) fQj, rock wool. Mineral fiber-Fused
silica fiber, glassy silica, fiber, basalt fiber, kaolin fiber, bauxite fiber, kayanite fiber, boron fiber,
potassium titanate fiber, inorganic fiber such as magnesia embroidery fiber, alumina, silicon
nitride There are whiskers, etc. 7 Natural Fibers As natural fibers, preferred are fiber,
regenerated fiber and cellulose acetate fiber.
Such short fibers can be used by blending 1 m or 2 槓 or more. The sheet as described above can
be made into excellent speaker cone paper by heating the sheet after drying by means of a press
such as a heat press or a heat roll. The temperature for pressurization is suitably 140 ° C to 320
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° C. The pressure applied is preferably 200 Kp / c + w ′ ′ or less. The following describes the
measurement method for lR11 with respect to the characteristic value of the main bag in the
present invention. J log, viscosity: measured in concentrated sulfuric acid or N-methyl-2pyrrolidone at 30 ° C. as concentration 0,5 / n 106 iu. Tensile strength: Measured by the
method of JIS 8113 and represented by 97 m ′ ′. Tensile elongation: Measured according to
the method of JISP8132 and expressed as a degree. Stiffness yI &: In the torsional free damped
vibration measuring apparatus, the rigidity G for a strip-like sample. The logarithmic damping
factor of the torsional free damping oscillation was determined. In an isotropic material, Young's
modulus E has a relationship of E = 3 G with rigidity G. Oxygen index: The lower support was
made according to ASTMD 286-70, and the percentage of oxygen when burning was continued
for about 1.51 by the upper flame was determined. Hereinafter, the present invention will be
described in detail by way of examples. EXAMPLE 1 Polyamideimide obtained from ト リ trimellitic anhydride, 4.4'-diaminodiphenylmethane, 4.4'-diphenylmethane diisocyanate
(logarithmic viscosity 0.8 in N-methyl-2-pyrrolidone) A solution containing 5 t in 957 F of Nmethyl-2-pyrrolidone was introduced into a 60% by weight aqueous solution of N-methyl-2pyrrolidone in a high-speed stirring homomixer to obtain pulp particles. EndPage: 6 father Add
9.39 mica, which has passed through a 60 mesh Tyler standard sieve, to the above
polyamideimide solution and introduce it into a 60 weight aqueous N-methyl-2-pyrrolidone
aqueous solution in a homomixer in the same manner as above to obtain pulp particles I got The
pulp pulp particles are respectively N1m1.2. A dispersion obtained by dispersing the abovementioned pulp particles in water, glass flakes and polymetaphenylene inphthalamide from Nmethyl-2-pyrrolidone # #! The fibers obtained by Yuka wet spinning and drawing were cut into
lengths of 5 silks, and a short dj and miscellaneous aqueous dispersions were mixed to make a
sheet. The results are shown in Table 1. The sheet was dried at 100 ° C. and heat pressed at
230 ° C., 2004 / cIK ′ ′ to obtain a paper with a thickness of about 100 μ. In the first
clothing sheet, Nl1-1.2-2, 2-3 are within the scope of the present invention. “1れている。
In the case where the addition amount of glass flakes is too small, the rigidity and V * are good
but the reduction ratio of the number of logarithms is small. % 2-4 is excellent in the logarithmic
decay rate when the amount of glass flakes is too large, but the 1illI ratio and f-8 are not good.
The characteristics of commercially available speaker corn paper mainly composed of natural
cellulose pulp are shown as a reference. Example 2 Table 2 shows the results when the mixing
ratio of polymetaphenylene inphthalamide fibers was changed under the same conditions as in
Example 2-3, Example 2-3. In Table 2, when the amount of the polymetaphenylene
inphthalamide fiber is too large, the logarithmic attenuation factor, the rigidity and the X / '¥ are
too small. 1 '& L 23.2' + 2-7 are within the scope of the present invention. Log reduction rate,
rigidity rate, J D is excellent. ^11! 12-8 is not preferable because when the number of
polymetaphenylene isophthalamide fibers is too small, the logarithmic decrement is too small.
EXAMPLE 1 Instead of the polyamideimide of Example 1, polymetabiocene isophthalamide (! A
solution containing 1/8 logarithmic viscosity 1.8 in sulfuric acid 7P in 932 N-methyl-2-
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pyrrolidone is introduced into an aqueous solution of 4ofit% N-methyl-2-bi] rolidone stirred at
high speed in a homomixer Pulp particles were obtained. Measured on a paper consisting of 40
weight jts of pulp particle, 30 weight% of glass flakes, and 30 weight% of polymetaphenylene iso
7 thalamide fiber, where the logarithmic decrement is 0.10 rigidity 18 (L 7 X 10 ′ ′, fr 1 . End
page: 7 to IX1G ', showing excellent characteristics. EXAMPLES The results shown in Table 3
were obtained by leaving the rice cake 2-2 and commercial corn paper in Example 1 at 210'CJ
for 2 hours. Table 3 & 11 & L2-2 is hardly deteriorated by the above treatment, but the
commercially available speaker cone paper is deteriorated seriously. Example 5: The oxygen
index of the sample in Example 4 is measured by means of upward ignition using a Toyo Rika
Kogyo 0N-1 flammability tester according to the method of A8TM D 2863-70, and it is a flame
retardant at 54.0. Was very good. As a comparison, it was 21.0 where the oxygen index of
commercially available speaker cone paper was measured. Patent applicant Teijin Limited
EndPage: 8
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