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JPS61163945

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DESCRIPTION JPS61163945
[0001]
[Industrial field of application] The present invention relates to a resin composition which is
particularly suitably used as a substitute for wood, pulp paper and the like in applications in
which its mechanical and functional characteristics are used. More specifically, wood, pulp paper,
etc. have high elastic modulus and high internal loss, such as wood used for acoustic equipment
applications, such as wood, which is an alternative to pulp paper, ie, speaker box, record player
cabinet, motor The present invention relates to a mica-filled thermoplastic resin composition
suitably used in applications such as a substrate of an equal drive part or an acoustic diaphragm.
[Prior Art] In applications where wood, pulp paper, etc. have been used conventionally, problems
with wood, pulp paper etc., such as low degree of freedom in design, long time required for
molding and assembly, dry and wet state Recently, development of synthetic wood and synthetic
paper using synthetic resin as a raw material has been advanced in order to solve problems such
as large changes in physical properties. These synthetic woods and synthetic papers are
generally resins containing a filler or a reinforcing material, or low-foam foam resins, and these
materials have already been put to practical use in the fields of furniture, building materials, and
the like. However, materials that reproduce the functional properties of wood, pulp paper, etc.,
such as high elastic modulus / high internal loss, have not been developed yet, and at present,
intensive research and development is being conducted. is there. The inventors of the present
invention have already developed an acoustic diaphragm composed of a resin such as polyolefin,
polyamide, polyester, etc. and mica for an acoustic imaging plate in which pulp paper is mainly
used at present, but the balance of elastic modulus / internal loss There is a need for the
development of further excellent compositions (JP-A-57-154994, -164697.58-3499, -204699,
etc.). Further, although a composition of polyolefin resin / vinyl acetate resin / mica disclosed in
Japanese Patent Application Laid-Open No. 58-172100 is excellent in terms of the balance of
elastic modulus / internal loss, it generates a gas having a molding-specific corrosion property.
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There was a problem of [Problems to be Solved by the Invention] It is an object of the present
invention to develop a thermoplastic resin composition having high elastic modulus, high internal
loss and good moldability which can be substituted for wood, pulp paper and the like. [The
means for solving the problems] The inventors of the present invention have intensively studied
the above problems, and (A) crystalline aliphatic polyolefin resin (3) Aliphatic polyolefin obtained
by copolymerizing acrylic acid alkyl ester or methacrylic acid alkyl ester in the range of 2 & $ mi
(Tsue, Y, 6, 1-5 o to 1 + 20 ° C.), 0 weight average aspect ratio 10 or more The composition
containing mica as an essential component was found to have excellent running performance and
moldability, and the present invention has been completed.
In the present invention, T2 refers to a temperature at which the internal loss becomes maximal
by measuring the temperature dependence of the internal loss at a frequency of 110 Hz using a
Toyo Baldwin dynamic viscoelasticity measuring apparatus, “Pipelon DDV-[[EA] . The weight
average aspect ratio of mica in the present invention is the weight average flake diameter
measured by the following method! And the weight average flake thickness d using the equation
(1). -Heavy chain average aspect ratio = 1 / d (1) Here, the weight average flake diameter j of
mica powder is the wet classification of mica powder using standard sieves of various openings,
and the result is given by Rosin-Rammlar The mesh size j50 of the sieve through which 50
weight and 1 kgk of mica powder used for measurement is plotted on a diagram is determined,
and the value is calculated by (2) from the value. J = V'T juo (2) Also, with respect to the weight
average flake thickness d of mica powder, C, E, water surface single particle film property
reported by Capea et al. (C, E, Capes and R, C0CC0Co1e, Ind, Eng, Chem. Using the occupied area
S on the water surface of the flakes measured according to Fundam, 12.124 (1973)), it is a value
calculated according to equation (3). d =-+ 3) ((1-ε) S where W is the weight of the flake used for
measurement, S is the area occupied by the flake on the water surface, ρ is the specific gravity
of the flake, (1-ε) is the flake It is an occupancy rate when the closest packing state is taken on
the water surface, and 2.5etyct & as the value of 場合 when the flake is mica, 0.9 as the value of
(1-ε), Used. Examples of crystalline aliphatic polyolefins in the present invention include
polyethylene, polypropylene, poly (4-methylpentene-1), and copolymers containing them as main
components, but from the viewpoint of good moldability and inexpensiveness, polypropylene /
polyethylene In addition, polypropylene or ethylene copolymerized polypropylene is more
preferable from the viewpoint of elastic modulus in the room temperature region, high internal
loss, and good heat resistance. As the above-mentioned crystalline aliphatic polyolefin resin, a
compound having a polar group, for example, a resin obtained by copolymerizing maleic
anhydride, acrylic acid, glycidyl methacrylate, or a silane compound having an ethylenically
unsaturated bond can also be used. Crystalline aliphatic polyolefin resins provided with these
polar groups are extremely effective in improving the mechanical performance of the
composition.
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Ethylene as an aliphatic polyolefin / (hereinafter sometimes referred to as “bo” olefin
copolymer) obtained by copolymerizing acrylic acid alkyl ester or methacrylic acid alkyl ester
having Tf in the range of from 1 to 50 ° C. in the present invention -Methyl acrylate, ethyleneethyl acrylate, ethylene-inpropyl acrylate, ethylene-n-propyl acrylate, ethylene-acrylic n -7 'ethyl,
ethylene-n-hexyl methacrylate, ethylene-methacrylate Although n-octyl etc. can be mentioned,
the ethylene-ethyl acrylate copolymer with which the improvement effect of the internal loss in a
room temperature area | region is remarkable by composite with a crystalline aliphatic polyolefin
resin is used preferably. As for the polyolefin copolymer used in this invention, it is desirable for
the copolymerization rate (Hereinafter, it is only called acrylic acid copolymerization rate) of
acrylic acid alkyl ester or methacrylic acid alkyl ester to be in the range of 10-40 weight-. In the
case of using a copolymer having an acrylic acid copolymerization ratio of 5% by weight or less,
the effect of improving the internal loss of the composition is unsatisfactory, while using a
copolymer having an acrylic acid copolymerization ratio of 40% by weight or more In the case
where the miscibility with the polyolefin resin is poor, the heat resistance of the composition also
decreases. The blending ratio of the polyolefin copolymer is preferably 5 to 40% by weight of the
total composition weight, and more preferably 10 to 35% by weight. When the blending ratio of
the copolymer is 5 wt- or less, the internal loss improvement effect of the composition is
unsatisfactory, while when it is 40 wt% or more, the modulus of elasticity and heat resistance of
the composition are unsatisfactory. . As mica used in the present invention, phlogonite,
muscovite, synthetic phlorov logobite, etc. can be widely selected, but the weight average aspect
ratio calculated by equation (1) is 10 or more. It is necessary to be there. A composition using
mica having a weight average aspect ratio of 10 or less can not be used because the modulus of
elasticity and the internal loss are low. The blending ratio of mica in the composition of the
present invention is desirably 10 to 50% by weight, and more desirably 20 to 45% by weight. The
composition containing 10 weight- or less of mica has unsatisfactory elastic modulus and
internal loss, while the composition containing 50 weight- or more of mica has problems in
moldability. It is desirable that the mica used in the present invention be surface-treated with a
silane coupling agent or the like so as to have a good affinity to the matrix resin.
Examples of the silane coupling agent include γ-aminopropyltrimethoxysilane, raminopropyltritoxysilane, and N- (β-aminoethyl) -r-aminopropyltrimethoxysilane. Although there
is no restriction | limiting in particular regarding the compounding ratio of these silane coupling
agents, Generally, it is 0.05-3 weight with respect to the weight of mica. In addition, although
surface treatment agents, such as 7 rank coupling agents, may be used by the method of surfacetreating mica powder beforehand, when melt-kneading resin and mica powder, even if it adds
directly, it exhibits an effect. . A blowing agent can be added to the composition of the present
invention. The type of the foaming agent used in the present invention is not particularly limited,
and examples thereof include azodicarbanamide, dinitrosopentamethylenetetramine, Pv oxybis
(benzenesulfonylhydrazide) and the like. The combined use of these foaming agents and the use
of foaming assistants such as fatty acid metal salts such as calcium stearate and zinc laurate, and
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metal oxides such as zinc oxide, etc. are not limited. The composition using the foaming agent in
the present invention can be foamed during injection molding and extrusion molding, and a
molded article having a specific gravity of 0.7 to 1.1 by foaming exhibits excellent performance
in specific elastic modulus Do. As the material for acoustic parts, the speed of sound is often
regarded as important, but since the speed of sound has a correlation with the specific elastic
modulus, it is particularly preferable to use a foam molded body molded from the composition of
the present invention. There are many. In the composition of the present invention, fillers other
than squid may be used in combination with, for example, glass fibers, talc, calcium carbonate,
barium sulfate, graphite, glass flakes, glass peas, carbon fibers and the like. In addition, it is
possible to add known additives such as colorants, plasticizers, lubricants, antioxidants, copper
inhibitors and the like as necessary. In the composition of the present invention, generally, each
component is kneaded by a single screw extruder, a twin screw extruder, a roll kneader, etc., and
then an injection molding machine, an extrusion molding machine, a compression molding
machine, a calendar molding machine It is supplied as a button, etc., and used as molded articles,
sheets, bars, pipes, etc. of various shapes used for electric machines such as acoustic parts, and
machine applications, but 1 composition “4! I:Ij? And there is no limitation in the
manufacturing method of a molded object. EXAMPLES The present invention will be described
more specifically by the following Examples and Comparative Examples, which should not be
construed as limiting the present invention. Example 1 Melt flowlet) 15 f / 10 min. Low
temperature impact grade polypropylene (hereinafter sometimes referred to as polypropylene
may be abbreviated as PP) (Ube Industries, Ltd. J-815 HK), ethyl acrylate copolymer ratio 25
wt%, T1 is one Ethylene-ethyl acrylate copolymer at 30 ° C. (hereinafter sometimes abbreviated
as EEA) (NUC-6570 manufactured by Nippon Unicar Co., Ltd.), gold mica (weight average aspect
ratio 65) (Szolite 1503 manufactured by Marietta S. C Composition of polypropylene / ethyleneethyl acrylate (to-copolymer / mica / silane coupling agent = 60/10 / 3010.15 (weight ratio))
using γ-7 minopropyl triethoxysilane as a raw material with a Henschel mixer Adjust, mix the
mixture in a single screw extruder, Under conditions in degrees 230 ° C and crosstalk Beret of.
The pellets were molded using an injection molding machine under conditions of a cylinder
temperature of 230 ° C. to obtain test pieces of thickness. Problems such as generation of gas at
the time of molding and corrosion of the molding machine are not recognized. The molded article
was used to measure a dynamic elastic modulus E 'and an internal loss tan δ under the
conditions of a temperature 23 ° C. and a frequency ttoI (z conditions) using a t-o-vibrone
DDVIEA manufactured by Toyo Baldwin. As shown in Table IK, both E 'and tan δ were very
excellent. Example 2 The same experiment as in Example 1 except that the blending ratio of
polypropylene / ethylene-ethyl copolymer / mica / silane coupling agent is 40/20 / 4010.2
(weight ratio) Did. The results are shown in Table IK, and very good values were obtained.
Example 3 Using ethylene / ethyl acrylate copolymer, copolymer having an ethyl acrylate
copolymerization ratio of 8% by weight and Tf of 20 ° C., the compounding ratio of PP / EEA /
mica / silane coupling agent The same experiment as in Example 1 was performed except that
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the ratio was 20/40 / 4010.2 (weight ratio). The results are shown in Table IK, and very good
values were obtained. Comparative Example 1.2.3 Only PP Used in Example 1 (Comparative
Example 1), Composition Composed of 9 PP and Mica Used in Example 1 (Comparative Example
2), EEA and Mica in Example 1 The performance of the composition (Comparative Example 3) is
shown in Table 1. The composition of Comparative Example 1 is low in both E ′ and tan δ, the
composition of Comparative Example 2 is high in E ′ but low in tan δ, and the composition in
Comparative Example 3 is high in tan δ but low in E ′, I was dissatisfied. Example 4 In the case
of Example 1 except using a brand having a weight average aspect ratio of 20 as mica and setting
the blending ratio of PP / EEA / mica / silane coupling agent to 50/10 / 4010.2 (weight ratio)
And did exactly the same experiment. As shown in Table 1, satisfactory results were obtained
with E 'and jan δ. Comparative Example 4 The same experiment as in Example 4 was conducted
except that a grade of weight average aspect ratio 8 was used as mica. As shown in Table 1, the
values of E 'and tanJ are low. Comparative Example 5 The same experiment as in Example 1 was
conducted, except that the blending ratio of PP / EEA / mica / silane coupling agent was
90/10/0/0 (weight ratio). As shown in Table IK, the values of K E 'and tan J were low. Melt Flore
as Example 5 pp. 15 f / 10 min. Homopolypropylene (Ube Industries, Ltd. 1!
The same experiment as in Example 1 was carried out except using 1J-115G). The results showed
satisfactory values for both E 'and tanJ as shown in the surface finishing. Example 6220 Using a
high density polyethylene (Hisex 2200 J, manufactured by Mitsui Petrochemicals) with a melt
index of 5.5 P / 10 min instead, the compounding ratio of high density polyethylene / EEA / mica
/ silane coupling agent is 50 / l O / 4010. The same experiment as in Example 1 was carried out
except that 2 (weight ratio) was used. As the results are shown in Table 1, good values were
obtained for both VcE 'and tanJ. EXAMPLE 7 r-Methacryloxypropyl triethoxysilane ヲ o, s parts
by weight, 100 parts by weight of a melt polypropylene a-flate 5 f / 10 min homopolypropylene
(U-B J-105G), butyl peroxybenzoate 0 After adding 2 parts by weight and thoroughly mixing with
a Henschel mixer, melt mixing is carried out at a cylinder temperature of 240 ° C. using a single
screw extruder, and copolymerized PP of polar group (hereinafter abbreviated as polar PP)
Obtained. The composition of the polar PP is as follows: PP / polar PP / BA / mica / silane
coupling agent = 50/10/10 o / a Olo, 1 s (weight ratio) I did exactly the same experiment. As
shown in Table 1, excellent values were obtained for both K E ′ and tan J O values. Further, the
composition has a tensile strength of 390 kl / d and a thermal deformation temperature of 110
° C., which is a significant improvement over the composition of Example 1 (tensile strength
350 ky / cl, thermal deformation temperature 95 ° C.) was gotten. Examples 8 and 9 EEAO
Using ethylene-isobutyl acrylate copolymer (isobutyl acrylate copolymerization ratio 25 wt%, Tr2 g ° C.) (Example 3) Run as ethylene-methacrylic acid n-octyl ester The same experiment as
that of Example 1 was conducted except that a copolymer (n-octyl methacrylate,
copolymerization ratio: 25 wt fk, Ty-32 ° C) was used (Example 9). As the results are shown in
Table 1, satisfactory values are obtained for both E 'and tan J9. Example 10 The same experiment
as in Example 1 was carried out except using polypropylene of impact type (B-aoxH
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manufactured by Ube Industries, Ltd.) having a melt flow rate of 0.8 P / 10 min as Example 10 to
obtain a belet. The bellet was supplied to an extruder equipped with a sheet die and extruded at a
cylinder temperature of 230 ° C. to obtain a 0.5 day thick sheet. As shown in Table 1, the sheet
had very excellent performances of K E 'and tan J, and was suitably used as an acoustic
diaphragm.
EXAMPLE 11 100 parts of the composition of Example 1 is uniformly mixed with
azodicarbonamide 0.25 F, and the mixed bellet is supplied to an injection molding machine to
carry out injection molding at a cylinder temperature of 210 "C. Obtain foam test pieces. The
specific gravity of the test piece was 0.85, and as shown in Table 1, the foamed test piece had
excellent elastic modulus, specific elastic modulus, and strength. The following experiment was
conducted in exactly the same manner as in Example 1 except that the blending ratio of margin
example 12 PP / EEA / mica was changed to 40/20/40 (weight ratio). Both the dynamic elastic
modulus E d and the internal loss tan δ of the molded product were extremely excellent as in the
molded product of Example 1. In the following, according to the present invention, a synthetic
resin composition with good moldability is provided which is effectively used in applications
where wood, pulp paper and the like have been used conventionally. The molded product made
of the resin composition or molded from the resin composition has high elastic modulus and
internal loss, and gives good properties particularly when used as an acoustic diaphragm.
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