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DESCRIPTION JPS5184249
5 Jan. 1, 1955, General Secretary of Patent Office 1, Title of Invention ■ Japan Patent Office 0
JP-A-51-842490 Published Japanese Patent Application 51. (1976) 7.23 Japanese Patent
Application No. 50-8329 Office Serial Number 646555 Specification 1, Title of Invention 1, Title
of Invention Speaker cone paper
Speaker cone paper 2, i Ming and 3, patent applicant Osaka City Higashi-ku 1-chome 11th (300)
Teijin Ltd. Representative Oya Shozo 4; agent Tokyo Chiyoda-ku Uchiyukicho 2-chome 1st (Iino
Building )
5. Detailed Description of the Invention The invention, the speaker cone gKllI. j! More
specifically, the present invention relates to a speaker cone paper made of pulp particles having
heat resistance and comprising a solvent-soluble aromatic polymer and short fibers. One of the
four most important characteristics representing speaker performance is frequency
characteristics. The target of the reproduction limit of the stuttering is the sound resonance
frequency fh and To '), the output sound pressure mv at a frequency of fb or more: the mass of
the voice coil mo: the mass of the cone 82 = the stiffness at the top of the cone I am scolded.
Therefore, in order to make the output sound pressure characteristics good up to the high-pass
range, K needs to increase fh. For this purpose, it is necessary to increase the stiffness of the top
of the cone or increase the stiffness of the voice coil, the core 7 (D mass. Here the stiffness line at
the top of the cone. -Half cone angle of two cones h: cone thickness 冨: represented by Young's
modulus equation of cone, but α can not be too small in relation to cone forming, so the value of
112 has a limit. EndPage: Generally speaking, the treble-playing limit of the treble range. il
present value: medium diameter ρ of cone. : Expressed by the density of corn. Therefore, the
sound production frequency fh indicates the propagation velocity in the cone shape cone. You
can get a stormy speaker cone paper with a frequency of aS. It is used as a conventional corn
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paper material and mainly used for natural cellulose pulp and pyroelectricity *, such as gold aS
etc. In particular, natural cellulose pulp is widely used. However, the speaker cone paper mainly
composed of such natural cellulose pulp is inferior in heat resistance, incombustibility is also
sterile, and frequency characteristics are not good. Recently, as an attempt to reform such points,
Japanese Patent Publication No. 45-. No. 23505, threat jI 48-25515, describes a method of
mixing lumber with a large elastic modulus. However, the speaker cone paper obtained by such a
method is not preferable because it has a conductive round shape and a large amount of heat. As
a result of keen research to eliminate such defects, the present 814 person has the heat
resistance, and the pulp particles and the binding chain consisting of solvent-soluble aromatic
group 1 coalescing are coaxial or parallel from each other. A speaker cone which is excellent in
p% flame resistance and heat resistance and has only this characteristic by mixing and
fabricating a short fiber composed of a carbon-ring aromatic compound homo or copolyamide
having a long carbon content. There is nothing to get paper, but this invention is completed.
That is, the present invention has a heat resistance and a bulky particle in which 50 to 95 weight
of par 1 particles consisting of solvent-soluble aromatic group 1 and a bonding chain extend
coaxially or in a parallel direction from each aromatic ring. Short fibers of the formula aromatic
homo or copolyamide! It is speaker cone paper which carries out pressure heating of the paperlike thing obtained by carrying out all mixed papermaking to 11115-50 m weight-. The heatresistant, solvent-soluble aromatic X-based paste used in the present invention has a weight of at
least 3 and more, preferably 7 and more, in '+ tit. 1. Aromatic polyamide (condensation
polyamide of 1 & active-active castings such as acid halides for the filtration of dicarboxylic acid
having 11 aromatic rings) and diamine having aromatic ring. Example EVA, terephthalic acid,
isophthalic acid etc. as dicarboxylic acid, metaphenylene diamine as diamine, 4.4′cyaminodiphenyl ether, 4.4′-diaminodiphenylmethane, xylylenediamine, N-methyl-baraphenylenediamine, etc. It may be a homopolymer consisting of a pair of dicarboxylic acids and
diamines of 、, and it is possible to use one or more of the compounds of either or both of the
Dicarphone 1ll component and the diamine fraction] It may be l [4r polymer. As typical ones, for
example, polymetaphenylene iso 7 thalamide, poly metaxylene terephthal and or meta phenylene
diamine, in 7 tar 鈑 and terephthalic acid co-weight polymer, poly N methyl para phenylene ter 7
thal amide Is illustrated. (2J A polyamide that has been activated and condensed over the course
of an aminocarboxylic acid that has a positive impact. For example, it is possible to use
homopolymers of only 樵 with 2 amino acids or meta amino amino acid ア ミ ン, valaamine
methyl benzoic acid, etc. as an aminocarboxylic acid, and a copolymer of 7 or more
minocarboxylic acid chains with two or more poles. Even if there is a storm. As an alternative, for
example, condensation of para-aminobenzoic acid can be used. EndPage: 2 (3) Polyamide
copolymerized with the above (11 (2). For example, polyamides obtained by condensing three
components of metaphenylene diamine, inphthalic acid chloride and no (acid chloride acid
chloride hydrochloride) may be mentioned as an alternative. 2, including ii! Elemental
polyheterophilic compound (1) Aromatic polyamideimide wherein X is an alkylene having 1 to 6
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carbon atoms, γ-alkylidene, cycloalkylene or cycloalkylidene group. It is -O-, -8-, -802-, -N "" N-+N.ident.N-.
Repeating units of 30% by weight and 15% by weight are polyamide pentimidazole, aromatic
polyimide, aromatic polyamide polyazole such as polyoxazole. −ポリオキサジアゾール。
Polyazoles, polythiadiazole polypentazoles such as polybenzimidazole. ポリペンゾチアゾール。
Polybenzoxazole, polyhydantoin, vorino clavano (acid, polyquinazoline dione, polyquinazolone.
Botakinokinarin and polyoxazinone are also great. The polyamideimide of the above formula is
composed of at least 70 moles, preferably at least 85 moles, and Xa-CH2-, -0-, -802-Y, and a
methyl group for Xa-CH2-, -0- and -802-Y; The methoxy group m or n is preferably 0 or 1. The
polyamideimides contain 30 mol-, in particular 15 mol-, of recurring units. Here, R is an organic
group having 2 to 15 longitudinal atoms, R is an organic group having 1 to 10 carbon atoms, Y is
Y, Y is same or different, and each is 1 to 6 carbon atoms And a hydrocarbon group having a
halogen atom, an aryloxy group having 1 to 5 carbon atoms, and a carboalkoxy group having 2
to 10 carbon atoms. It is at least one selected from alkoxycarbonyl groups having 1 to 5
longitudinal atoms. m and n are the same-or different because they are different. ∼3である。
Precursors of pentagons i 1 element poly complex caged compounds + 11 polymers having units
represented by formula 1 (fm & isomer of polyamide imide) (2) aromatic polyhydrazides,
aromatic ureas (3) aromatic poly Amide hydrazide-containing polyamide hydrazide. These may
have an inert substituent such as a methyl group, an alkoxyl group or a halogen atom. It is also
possible to use these precursors by copolymerizing aromatic dicarboxylic acids such as
isophthalic acid and terephthalic acid, benzophenone tetracarboxylic acid anhydride, pyromellitic
EndPage: triacid anhydride and the like. (4) polyazoles, such as poloxazole. Polio Now Sadiazole,
Polythiazole. Polydeadiazoles (5) Polybenzazoles, such as Polybenzimidazole, Polybenzothiazole.
'-1) Poly 67 Zooxazo 1 Polyquinazoline dione, Polyquinanro / (7) Polyquinosarline, Horioki Fuji
715 :, 1 屯 麺 Polyether polyphenylene oxide, Polyarylene oxide Pulp particles of the present
invention are as follows: Manufactured by
The heat resistant aromatic group 1 as described above is dissolved in a suitable **, and the filler
is added thereto, or the heat resistant aromatic polymer is mixed at one time. It is obtained by
adding fillers and precipitating as fine surface particles. As a solvent used in the abovementioned method, although one united component 1 m in valve particles is dissolved, a watersoluble solvent insoluble in the filler is preferable, and such a solvent may be used as such #r
medium. For example, enemy enemies, non-hydrohydrogen acid 9 fuming sulfuric acid, chlor
sulfuric acid. Flor (itl + 1, non-root solvent such as polyphosphorus or N-methyl-2-pyrrolidone, N,
N-dimethylformamide. N、N−ジメチルアセトアミド、ジメチルスルホキシド。 There are 8
such as methyl methacrylate, tetramethyl urea and so on! Solvents are preferred. The inorganic
solvent or the organic solvent can be used as a mixture. In addition, by adding an inorganic salt
such as lithium chloride or calcium chloride to the above-mentioned solvent, it is possible to use
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a melt-curvature in which the layering property to one unit is increased. The concentration of the
polymer in the solution is different depending on the polymer si's and the amount of polymer Ji
[Di], but preferably 2 to 15 wt-%. As a precipitating agent used in the present invention, a liquid
or a 紘 soluble salt which is 紘 compatible with the company's polymer-dissolved tILofI #
medium, but which is non-soluble for one combination is preferable. Such precipitants differ
according to the [K of the solvent used. In the case of using an organic solvent as a solvent 1),
water may be used alone or in combination with glycerin, ethylene di "glycol, glycerin-water
mixture, ether acetate or salts of 1111 or tli21! Water soluble in II or more, even 1m is ugly. ここ
に、MはLitManKnMg+CanSr。 Bat1itbZn+Ax+N1Xは
O1+Br+’MO5,C! 115c! 00. BONn represents an integer of 1 to 4. An
example of such inorganic salts is calcium chloride. Lithium chloride, sodium chloride,
magnesium chloride. Zinc chloride, strontium chloride, aluminum chloride. Chlorinated # 12 tin,
nickel chloride, calcium bromide. Calcium nitrate, zinc nitrate, aluminum nitrate. Sodium
butyrate, potassium thiocyanate, thiocyanic acid calcium, etc. are mentioned, and in particular
calcium chloride, lithium chloride, aluminum chloride. There are calcium thiocyanate release,
sodium acetate release. Among these, calcium chloride-hydrogen precipitants are preferred
because they are easy to handle, inexpensive and expensive.
Among the above-mentioned precipitants, hydrogen books are suitable for use as soot. When an
inorganic solvent is used as the solvent, it is possible to use, as the precipitant used, water alone
or an aqueous precipitant in which the used inorganic S medium is diluted with water. In the case
of non-invention, it is also possible to have inorganic heat-resistant filler particles in the particles.
Such filler particles are, for example, mica, mica, anupest, crow fibers, glass flakes. EndPage: 4
quartz powder, talc, alumina, calcium sulfate. Longitudinal calcium, kaolin clay, diatomaceous
earth. There are feldspar powder, mochi magnesium, magnesium oxide and so on. In the
production of pulp particles in the present invention, the filler is mixed with the raw material in 1
vII & in advance in the solution obtained by adding the filler when dissolving the united body, or
in the mixing of the polymer. (1) The combined solution is subjected to high-speed agitation in a
precipitating agent to desolvate the solution, and at the same time it produces a shearing or
beating action. Paper Spread from Pulp Particles and Short Fibers Produced by the Method As
described above Papermaking is carried out by a wet method using a long screen type companylike circular mesh type paper machine like a pigeon building made from conventional natural
pulp It is ugly. In the present invention, short fibers used conveniently for papermaking of Hull 1
particles usually have a fineness of cL 5 to 10 denier. It is desirable that the fiber length is 1 to
20 battles. As a polymer constituting a short fiber composed of a carbon denatured aromatic
homo or copolyamide in which a connecting chain extends coaxially or in parallel from each
aromatic ring, an aromatic ring in which the connecting chain is coaxial Although these aromatic
rings may have a direct conversion group, the direct conversion group must be such that it does
not cause an undesirable reaction in one reaction and in the processing step. As such a
substituent, for example, a halogen group (eg, CLBr, F) + lower alkyl group (eg, methyl, ethyl, in
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7). n-) dropyr) Lower alkoxy (for example, methyl, ethoxy) cyano group, acetyl group, nitro group
can be mentioned. The polymer chain is composed of an amide bond (-CONH-) and an aromatic
ring, but does not meet the conditions described above, eg, the aromatic polyamide bond does
not extend coaxially from the aromatic ring, Those which do not extend in parallel (for example,
meta orientation), urea bonds, ester bonds, and combinations such as hydrazide bonds which
contain bonds other than amide bonds such as about 10 mol. Such polymers which can be used
are poly (p-benzamido) poly (p-phenylene terephthalamide) poly (2-talolo p-phenylene
terephthalamide) -po!
J (p-phenylene-2,6-naphthalene dicarboxylic acid amide) port! J (2,6-dichloro-p-phenylene-2,6naphthalenedicarboxamide) ester! J (p, p'-phenylene benzamide) poly (1,5-suethylene
terephthalamide) regular aromatic copolyamide (e.g. copolymer of p, p'-diaminobenzanilide-tele7
thalamide) random cobo Lia (such as p-benzamido on) / p-phenylene terephthalamide 50150
and the like. These polymers are used as homopolymers alone, copolymers alone, mixtures of
homopolymers, mixtures of homopolymers and copolymers, and mixtures of copolymers. As the
short fibers which can be used together with the above-mentioned short fibers, respective ones
are possible, and for example, the following fibers can be mentioned. 1. Short fiber aromatic
polyamide consisting of aromatic polyamide is the same as above. 2. A short fiber nitrogencontaining poly complex fished compound consisting of tiii basic hybrid double poly compound
is the same as the above-mentioned short fiber nitrogen-containing poly complex bulky
compound consisting of a precursor of the same & palm-containing poly complex woody stack
compound Precursors the same as above. 4, one-fiber aromatic polyether consisting of aromatic
polyether same as above. EndPage: As a short-fiber aromatic polyester consisting of 5 & aromatic
polyester, (i) polyethylene-2,6-naphthalate and / or polyethylene-47-naphthalate offshore)
ethylene-2,6-naphthalate unit and / or ethylene 7-- 2.7-copolyester having at least 85 moles of 7
units of tare. As a copolymerization component of the co-composite polyester, a copolyester
using an aromatic dicarboxylic acid as an acid component is preferably used. tri (1) polyethylene2,6-naphthalate and / or polyethylene-2,7-naphthalate and / or (i ethylene-2,6-naphthalate and /
or ethylene / 2,7-naphthalate unit 85 Blended polyester containing copolyester contained above.
1) Polyethylene terephthalate 幡) Blended polyester containing a copolyester containing at least
85 moles of ethylene terephthalate units. In this case, a copolymerized polyester using an
aromatic dicarboxylic acid as an acid component as a copolymerized component of the
copolymerized polyester is preferably used 6H (1) polyethylene terephthalate and / or Oi)
ethylene terephthalate unit all 85 moles or more Blended polyester containing copolyester
possessed by the government.
Short fibers consisting of 6 inorganic compounds As short fibers consisting of inorganic
compounds crow * M, asbestos fibers, rock wool. Mineral wool, fused silica fiber, vitreous silica
fiber, basalt fiber, kaolin fiber, bauxite fiber, kayanite fiber #! In addition, there are inorganic
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fibers such as boron-based squeezing, potassium titanate sterilization, magnesia fibers, etc., and
whiskers such as alumina, silicon ilicide, etc. 2 Natural Fibers As natural fibers, preferred are
cellulose fibers, regenerated cellulose fibers and cellulose acetate fibers. Such short fibers can be
used singly or in combination of two or more of Fi. After drying, the sheet obtained as described
above can be made into excellent nucleated paper by heating with a press by means such as a
heat breath or heat roll. The temperature for pressurization is preferably 140 to 320 ° C., and
the pressurization pressure is preferably 200 wc 11 or less. Hereinafter, measurement methods
will be described with respect to raw characteristic values in the present invention. It was
measured at 30 ° C. as 0.5 II / 10 − once in logarithmic viscosity core concentration a
commercial or N-methyl-2-pyrrolidone. Measured by the method of 1 strength and strength L: J
8 P 811 M, and (- Tensile elongation t: Measured according to the method of J. SP8132 and
represented by. Elastic modulus: The rigidity and the torsional free damping-logarithmic damping
factor of the motion were determined for a strip-like sample in a torsional confusive white
damping vibration measuring apparatus. Oxygen index: according to ASTM D2B63-70],
supported by the upper ignition, to determine the percentage of oxygen when it continues
burning about 1.51. The invention will now be described by way of example. EndPage: 6 Example
1 Trimellitic 駿 Anhydride, 44'-Diaminodiphenylmethane, 44'-Diphenyl Dimethane Diisosyanate
Obtained from Polyamideimide (Summer-Logarithmic Viscosity α 8 in Methyl-2-Pyrrolidone) 59,
95 Ii Pulp particles were obtained by introducing N-methyl-2-pyrrolide / into * t into a 60% by
weight aqueous solution of N-methyl-2-pyrrolidone in a homomixer stirring at high speed.
Further, to the above polyamideimide solution is added 9317 mica which has passed through a
60 mesh Tights-1 standard sieve, and introduced into a 60 weight -1 N-methyl-2-pyrrolidone
aqueous solution in a homomixer in the same manner as described above to obtain pulp
particles. Obtained. These pulp particles are designated A61.2, respectively. A dispersion
obtained by dispersing the above-mentioned pulp particles in water and a powder 9 (p. A
dispersion of 7 erentere 7 tal amide) fibers (fineness 1.8 da, I 1 M long 5) was mixed in various
proportions, and paper making was carried out, and hot pressing was carried out in a drying
oven at 250 ° C. for 200 floors to obtain paper.
The results are shown in the first row. In Table 1,% 1-1-2-2-2-6-4 have large values of 0
logarithmic attenuation rate and rigidity sK within the scope of the present invention. A2-1 is a
case where there are many pulp particles, rigidity, Ft is excellent, but log attenuation rate is
inferior. When the amount of the pulp particles is too small (2-5), the logarithmic attenuation
rate is large, but the rigidity 1, r2; and the tensile elongation 1N is inferior. As a reference, the
merits of commercially available speaker cone paper mainly composed of Heaven @ * Ru p-sparg
are shown. EXAMPLE 2 High speed stirring of a solution containing polymetaphenylene iso 7
taland (logarithmic viscosity 1, 8 in sulfuric acid sulfate) 717 in 95 fI of N-methyl-2-pyrrolidone
in a homomixer in place of the polyamide of Example 1 Pulp particles were obtained by
introducing into 40% by weight of fM solution of N-methyl-2-pyrrolidone water. In nine places,
the logarithmic attenuation factor α12 rigidity B 50 X 10 "乍-7 kt 7 x 10 '-/-measured on a
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paper consisting of 70% by weight of such pulp particles and 30% by weight of poly (pphenylene terephthalamide) fibers similar to Example 1. sec)] show excellent nine characteristics.
EXAMPLE 3 In 42-2 in Example 1, a poly (P-phenylene tele7 thalamide) fiber substitute CK
polymetaphenylene isophthalic acid is wet spun from a summer-methyl-2-pyrrolidone solution
and spun out Measured for paper using short fibers (fineness 2de) cut into lengths of 5 絽,
logarithmic attenuation factor α12 rigidity v2.6 × 10 ′ ′ Example 4 42-3 in Example 1 and
commercially available corn When the paper is left at 210 ° C. for 2 hours, the results in Table
3 can be obtained. EndPage: 7 Table 5 Compared to commercially available speaker cone paper,
the deterioration due to the heat treatment was extremely small and the heat resistance was
excellent. Example 5 A sample of rot 2-3 of Example 1 was measured by means of upward
ignition using an OTR-1 flammability tester manufactured by Toyo Rika Kogyo Co., Ltd. according
to the method of M.TMD. 2B 65-70, 3aO, flame retardancy Was very mourning. As a comparison,
the oxygen index of commercially available speaker cone paper was measured at 9 points and 2
tO. Patent applicant Teijin shares voice agent patent attorney before 1) net, Hakuho 5l-84249 (8
'1 EndPage: 8
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