JP2009235309

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DESCRIPTION JP2009235309
The present invention provides a thermoplastic elastomer composition that can be suitably used
as a material for thin-walled molded articles such as speaker edge members. SOLUTION: (A) An
oil-extended copolymer comprising 50 to 150 parts by mass of a first mineral oil-based softener
with respect to 100 parts by mass of an ethylene-based copolymer and 100 parts by mass of the
ethylene-based copolymer A raw material composition comprising: an ethylene-based copolymer;
and 10 to 50 parts by mass of (B) an α-olefin-based thermoplastic resin relative to 100 parts by
mass of the (A) oil-extended ethylene-based copolymer (C) A thermoplastic elastomer
composition which is obtained by dynamic heat treatment in the presence of a crosslinking agent
and which satisfies a predetermined condition. 【Selection chart】 None
Thermoplastic elastomer composition and molded member
[0001]
The present invention relates to a thermoplastic elastomer composition and a molded member.
More specifically, since the loss tangent (tan δ) is good, it has excellent vibration absorption, has
small anisotropy of tensile elongation at break, and has good oil bleeding property, mechanical
properties and recycling characteristics, for example The present invention relates to a
thermoplastic elastomer composition that can be suitably used as a material of thin-walled
molded articles such as edge members of speakers, and a molded member formed of this
thermoplastic elastomer composition.
[0002]
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The speaker is provided with a diaphragm for generating an electrical signal as a sound that can
be heard by the human ear. That is, when the diaphragm vibrates in accordance with the
electrical signal, the physical vibration of the diaphragm vibrates air so that it sounds as a sound
to the human ear.
[0003]
For example, an annular edge member is fixed to the outer peripheral portion of the diaphragm.
The edge member has a function of improving the acoustic characteristics of the speaker by
suppressing extra vibration of the diaphragm. In order to exert such a function, the edge member
needs to have a large loss tangent (tan δ).
[0004]
Therefore, development of a material capable of forming an edge member having a good loss
tangent (tan δ) has been advanced. For example, a triblock copolymer obtained by
copolymerizing styrene, polystyrene, and vinyl-polyisoprene (see Patent Document 1), rubber,
softener, organic foaming agent, and viscous rubber admixture containing a vulcanizing agent
Products (see Patent Document 2), predetermined amounts of butyl rubber, liquid rubber, and a
thermoplastic elastomer composition (see Patent Document 3) containing a crystalline olefin
resin are proposed.
[0005]
JP-A-7-131888 JP-A-7-240994 JP-A-2005-320524
[0006]
However, although all the materials described in Patent Documents 1 to 3 have sufficient
vibrational absorptivity, that is, good loss tangent (tan δ), the resulting molded member has high
anisotropy, There has been a problem that dimensional defects of the molded member occur.
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In addition, "anisotropy of a shaping ¦ molding member" means the property from which the
tensile elongation at break (EB) of a flow direction and the tensile elongation at break (EB)
perpendicular to a flow differ in a shaping ¦ molding member. In addition, there is a problem that
the added softener bleeds out, a problem that mechanical properties are not sufficient, and a
problem that the material can not be recycled. Therefore, in order to improve the acoustic
characteristics of the speaker, the loss tangent (tan δ) is good, so it has excellent vibration
absorption, the anisotropy of tensile elongation at break is small, the oil bleed property is good,
and it is good. Development of a thermoplastic elastomer composition capable of providing an
edge member (molded member) having various mechanical properties, and a molded member is
desired. In addition, from the viewpoint of environmental consideration, the molded member is
required to have good recycling characteristics.
[0007]
The present invention has been made to solve the problems of the prior art as described above,
and because it has a good loss tangent (tan δ), it has excellent vibration absorption and is
anisotropic in tensile elongation at break. The present invention provides a thermoplastic
elastomer composition capable of forming a molded member which is small, has a good oil
bleeding property, and has good mechanical properties and recycling properties, and a molded
member.
[0008]
Specifically, according to the present invention, the following thermoplastic elastomer
composition and molded member are provided.
[0009]
[1] (A) An ethylene-based copolymer satisfying the following conditions (1) and (2), and 50 to
150 parts by mass of a first mineral oil based on 100 parts by mass of the ethylene-based
copolymer An oil-extended ethylene-based copolymer containing a softener, and 10 to 50 parts
by mass of (B) an α-olefin-based thermoplastic resin with respect to 100 parts by mass of the (A)
oil-extended ethylene-based copolymer The thermoplastic elastomer composition which is
obtained by heat-processing dynamically the raw material composition containing (C) in presence
of a crosslinking agent, and satisfy ¦ fills the conditions of following (3).
(1): The intrinsic viscosity [η] measured at 135 ° C. in decalin solvent is 5.5 to 9.0 dl / g.
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(2) The ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average
molecular weight (Mn) is 3 or less. (3): 120 mm long, 120 mm wide and 2 mm thick sheet-like
test piece obtained by injection molding under the conditions of cylinder temperature 250 ° C.,
mold temperature 50 ° C., injection speed 50 mm / sec. Formula: {Tension at break elongation
in flow direction (EB) / Tension at break perpendicular to flow (EB)} ≦ 1.5 is satisfied.
[0010]
[2] The above-mentioned raw material composition further includes 10 to 30 parts by mass of
(D) a second mineral oil-based softener with respect to 100 parts by mass of the (A) oil-extended
ethylene-based copolymer [1] ] The thermoplastic elastomer composition as described in [].
[0011]
[3] In addition to the loss tangent (tan δ) measured under conditions of a temperature of 25 °
C. and a frequency of 1.0 Hz being 0.1 or more, the limiting viscosity measured by the raw
material composition in a decalin solvent at 135 ° C. (E-1) Ethylene / α-olefin copolymer
rubber having [[] of 1.8 to 2.3 dl / g, (E-2) isobutylene-isoprene copolymer rubber, (E-3) (E) an
oil-extended ethylene copolymer, and (E) ethylene / α, further comprising at least one (E)
vibration damping additive selected from the group consisting of styrene thermoplastic
elastomers; -The (E-1) ethylene with respect to a total amount of 100 mass% of the olefin
copolymer rubber, the (E-2) isobutylene-isoprene copolymer rubber, and the (E-3) styrene
thermoplastic elastomer・ Α-olefin based weight The total amount of the rubber, the (E-2)
isobutylene-isoprene copolymer rubber, and the (E-3) styrenic thermoplastic elastomer is 10 to
30% by mass as described in the above [1] or [2]. Thermoplastic elastomer composition.
[0012]
[4] A molded member obtained by molding the thermoplastic elastomer composition according to
any one of the above [1] to [3].
[0013]
[5] The formed member according to the above [4], which is an edge member disposed on at
least a part of an outer peripheral portion of a diaphragm of a speaker.
[0014]
[6] A method of manufacturing a speaker member, comprising: a diaphragm; and an edge
member disposed on at least a part of an outer peripheral portion of the diaphragm, which is
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described in any one of [1] to [3]. A method of manufacturing a speaker member, comprising the
steps of: injection molding the thermoplastic elastomer composition of claim 1 to form the edge
member, and then attaching the edge member to at least a part of the outer peripheral portion of
the diaphragm.
[0015]
[7] A method of manufacturing a speaker member, comprising: a diaphragm; and an edge
member disposed on at least a part of an outer peripheral portion of the diaphragm, in a mold in
which the diaphragm is disposed therein, The manufacturing method of the speaker member
which has the process of injection-molding the thermoplastic elastomer composition in any one
of said [1]-[3], and arrange ¦ positioning the said edge member in at least one part of the outer
peripheral part of the said diaphragm. .
[0016]
[8] The method for manufacturing a speaker member according to [7], wherein the diaphragm
obtained by injection molding is inserted into the mold, and the diaphragm is disposed inside the
mold.
[0017]
[9] The method for manufacturing a speaker member according to [7], wherein the diaphragm is
injection-molded in the mold, and the diaphragm is disposed inside the mold.
[0018]
The thermoplastic elastomer composition of the present invention comprises 50 to 150 parts by
mass with respect to (A) an ethylene-based copolymer satisfying the conditions (1) and (2), and
100 parts by mass of the ethylene-based copolymer. And 10 to 50 parts by mass of (B) .alpha.olefin based on 100 parts by mass of the oil-extended ethylene-based copolymer containing the
first mineral oil-based softener of the invention and 100 parts by mass of the (A) oil-extended
ethylene copolymer. The raw material composition containing a thermoplastic resin, is obtained
by dynamically heat-treating in the presence of the (C) crosslinking agent, and the condition of
the above (3) is satisfied. Since the (tan δ) is good, it has excellent vibration absorption, has
small anisotropy of tensile elongation at break, and has good oil bleeding, mechanical properties
and recycling characteristics, for example, an edge member of a speaker, etc. Suitable as a
material for thin-walled moldings of It has the effect of being able to
[0019]
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Since the molded member of the present invention is made of the thermoplastic elastomer
composition of the present invention, the loss tangent (tan δ) is good, so it has excellent
vibrational absorptivity and anisotropy of tensile elongation at break It is effective to have small,
good oil bleeding, mechanical properties and recycling characteristics.
[0020]
The manufacturing method of the speaker member of the present invention is excellent in the
adhesion between the diaphragm and the edge portion, since the speaker member is
manufactured using the thermoplastic elastomer composition of the present invention.
In addition, the manufactured speaker member has good loss tangent (tan δ), so it has excellent
vibration absorption, small anisotropy in tensile elongation at break, good oil bleeding, and a
good machine. The effect of providing an edge member having physical properties and recycling
characteristics is exhibited.
[0021]
Hereinafter, the best mode for carrying out the present invention will be described, but the
present invention is not limited to the following embodiments.
That is, it is understood that any of the embodiments described below can be appropriately
modified or improved based on the general knowledge of those skilled in the art without
departing from the spirit of the present invention and also belongs to the scope of the present
invention. It should.
[0022]
[1] Thermoplastic Elastomer Composition: One embodiment of the thermoplastic elastomer
composition of the present invention comprises (A) an ethylene copolymer satisfying the
following conditions (1) and (2), and the above-mentioned ethylene copolymer. An oil-extended
ethylene-based copolymer (hereinafter sometimes referred to as component (A) ) containing
50 to 150 parts by mass of the first mineral oil-based softening agent with respect to 100 parts
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by mass of the united body; A) 10 to 50 parts by mass of (B) α-olefin thermoplastic resin
(hereinafter sometimes referred to as component (B) ) with respect to 100 parts by mass of
the oil-extended ethylene-based copolymer It is obtained by heat-processing dynamically the raw
material composition containing (C) in presence of a crosslinking agent, and satisfy ¦ fills the
conditions of following (3).
Such a thermoplastic elastomer composition has a good loss tangent (tan δ), so it has excellent
vibrational absorptivity, a small anisotropy of tensile elongation at break, a good oil bleed
property, mechanical properties and recycling. It has a characteristic and can be suitably used as
a material of a thin-walled molded product (molded member) such as an edge member of a
speaker, for example.
(1): The intrinsic viscosity [η] measured at 135 ° C. in decalin solvent is 5.5 to 9.0 dl / g.
(2) The ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average
molecular weight (Mn) is 3 or less.
(3): 120 mm long, 120 mm wide, 2 mm thick sheet-like test piece obtained by injection molding
under conditions of cylinder temperature 250 ° C., mold temperature 50 ° C., injection speed
50 mm / sec : {(Tensile elongation at break in the flow direction (EB)) / (tensile elongation at
break in the direction perpendicular to the flow (EB))} ≦ 1.5.
[0023]
[1-1] (A) Oil-Extended Ethylene-Based Copolymer: The oil-extended ethylene-based copolymer (A)
contained in the polymer composition for obtaining the thermoplastic elastomer composition of
the present embodiment is The ethylene-based copolymer satisfying the conditions (1) and (2),
and 50 to 150 parts by mass of the first mineral oil-based softener with respect to 100 parts by
mass of the ethylene-based copolymer.
[0024]
Such a (A) oil-extended ethylene-based copolymer is excellent in rubber elasticity of the
thermoplastic elastomer composition to be obtained because the number of molecular chain ends
having poor deformation recovery is small.
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In addition, (A) the oil-extended ethylene-based copolymer has a low content of the ultra high
molecular weight component having a high melt viscosity, and therefore, the dispersibility with
other components (for example, the α-olefin-based thermoplastic resin (A)) And the mechanical
strength of the resulting thermoplastic elastomer composition is excellent.
In addition, (A) the oil-extended ethylene copolymer, in particular, the ethylene copolymer, has a
low content of low molecular weight components, so the retention of the softener is high, and a
large amount of the first mineral oil softener Can be contained.
Therefore, the thermoplastic elastomer composition obtained is excellent in moldability, and the
anisotropy of tensile elongation at break of molded articles is reduced.
[0025]
The oil-extended ethylene copolymer (A) is preferably obtained by desolvation from a liquid
mixture containing an ethylene copolymer, a first mineral oil softener, and a solvent.
Since the viscosity of the (A) oil-extended ethylene copolymer thus obtained is lower than that of
the ethylene copolymer alone, in addition to the improvement of the dispersibility with other
components, Since the first mineral oil-based softener is uniformly dispersed in the ethylenebased copolymer, there is an advantage that it is difficult for the first mineral oil-based softener
to bleed out.
[0026]
[1-1-1] Ethylene-based copolymer: (A) The ethylene-based copolymer contained in the oilextended ethylene-based copolymer satisfies the conditions of the above (1) and (2).
By including such an ethylene-based copolymer, the (A) oil-extended ethylene-based copolymer
obtained has a small number of molecular chain ends having poor deformation recovery and
contains an ultrahigh molecular weight component having a high melt viscosity. There is an
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advantage that the amount is small.
[0027]
Examples of the ethylene-based copolymer include ethylene / α-olefin binary copolymer,
ethylene / α-olefin / non-conjugated polyene ternary copolymer, and the like.
[0028]
As an alpha-olefin for obtaining an ethylene-alpha-olefin copolymer, a C3-C20 alpha-olefin is
preferable, A C3-C12 alpha-olefin is still more preferable, A C3-C8 alpha is more preferable
Olefins are particularly preferred.
Specific examples of the α-olefin include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene,
1-octene, 1-decene and the like. Among these, propylene, 1-butene, 1-hexene and 1-octene are
preferable from the viewpoint of industrial availability and propylene is particularly preferable.
In addition, these alpha-olefins can be used individually by 1 type or in combination of 2 or more
types.
[0029]
In addition, the content ratio of structural units derived from ethylene in the ethylene / α-olefin
copolymer is preferably 50 to 80% by mass, and 54 to 75% by mass with respect to all structural
units. It is more preferable, and 60 to 70% by mass is particularly preferable. When the content
ratio is in the above range, there is an advantage that the balance between mechanical strength
and flexibility is excellent. When the content ratio is less than 50% by mass, the crosslinking
efficiency tends to decrease (in particular, when an organic peroxide is used as a crosslinking
agent), it is difficult to obtain sufficient mechanical strength. On the other hand, if it exceeds 80%
by mass, the flexibility may be reduced.
[0030]
As an alpha-olefin for obtaining an ethylene alpha-olefin nonconjugated polyene copolymer, the
thing similar to the alpha-olefin for obtaining the said ethylene alpha-olefin copolymer can be
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used. Further, the content ratio of structural units derived from ethylene in the ethylene / αolefin / nonconjugated polyene copolymer is preferably 50 to 80% by mass, and 54 to 75% by
mass with respect to all structural units. It is more preferable that it is, and it is especially
preferable that it is 60-70 mass%. When the content ratio is in the above range, there is an
advantage that the balance between mechanical strength and flexibility is excellent. When the
content ratio is less than 50% by mass, the crosslinking efficiency tends to decrease (in
particular, when an organic peroxide is used as a crosslinking agent), it is difficult to obtain
sufficient mechanical strength. On the other hand, if it exceeds 80% by mass, the flexibility may
be reduced.
[0031]
Examples of non-conjugated polyenes for obtaining ethylene / α-olefin / non-conjugated polyene
copolymer include 5-ethylidene-2-norbornene, dicyclopentadiene, 5-propylidene-2-norbornene,
5-vinyl-2- Cyclic polyenes such as norbornene, 2,5-norbornadiene, 1,4-cyclohexadiene, 1,4cyclooctadiene, 1,5-cyclooctadiene, 1,4-hexadiene, 4-methyl-1,4-hexadiene , 5-methyl-1,4hexadiene, 5-methyl-1,5-heptadiene, 6-methyl-1,5-heptadiene, 6-methyl-1,6-octadiene, 7-methyl1,6-octadiene 5,7,7-dimethyl-1,6-octadiene, 7-methyl-1,7-nonadiene, 8-methyl-1,7-nonadi , 8methyl-1,8-decadiene, 9-methyl-1,8-decadiene, 4-ethylidene-1,6-octadiene, 7-methyl-4ethylidene-1,6-octadiene, 7-methyl- 4-ethylidene-1,6-nonadiene, 7-ethyl-4-ethylidene-1,6nonadiene 6,7-dimethyl-4-ethylidene-1,6-octadiene 6,7-dimethyl-4-ethylidene Linear polyene
having an internal unsaturated bond having 6 to 15 carbon atoms, such as 1,6-nonadiene, 1,5hexadiene, 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,7-octadiene Mention may be made of
α, ω-dienes such as 9-decadiene, 1,10-undecadiene, 1,11-dodecadiene, 1,12-tridecadiene, 1,13tetradecadiene and the like. . Among these, 5-ethylidene-2-norbornene, dicyclopentadiene, 5vinyl-2-norbornene, 7-methyl-1,6-octadiene, 5-methyl-1,4-hexadiene are preferable, and 5ethylidene- Particularly preferred is 2-norbornene. In addition, these nonconjugated polyenes can
be used individually by 1 type or in combination of 2 or more types.
[0032]
The content of the nonconjugated polyene for obtaining the ethylene / α-olefin / non-polyene
copolymer is preferably such that the iodine value of the ethylene / α-olefin / non-polyene
copolymer is 0 to 40. And preferably in an amount of 0 to 30. This iodine value is a value that
serves as a measure of the content of structural units derived from non-conjugated polyene in
the copolymer, and when the iodine value is more than 40, it tends to cause gelation during
kneading. There is a risk that bumps may occur in a molding process such as extrusion.
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[0033]
The ethylene-based copolymer satisfies the condition (1). That is, the intrinsic viscosity [η]
measured at 135 ° C. in decalin solvent is 5.5 to 9.0 dl / g, preferably 5.5 to 8.5 dl / g, 5.5 to 8.
More preferably, it is 0 dl / g, and particularly preferably 5.5 to 7.5 dl / g. Rubber elasticity falls
that the above-mentioned intrinsic viscosity [eta] is less than 5.5 dl / g. On the other hand, when
it is more than 9.0 dl / g, the viscosity becomes too high and the industrial productivity is
lowered. The measurement of the intrinsic viscosity [η] in the present specification can be
performed using, for example, a Ubbelohde viscometer.
[0034]
The ethylene-based copolymer satisfies the condition (2). That is, the value of the ratio (Mw /
Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn)
is 3 or less, preferably 2.8 or less, and is 2.0 to 2.7. Is more preferred. When the ratio of the
weight average molecular weight to the number average molecular weight is more than 3, the
rubber elasticity, the softener retention property, and the molding processability are reduced. In
addition, in this specification, a "weight average molecular weight (Mw)" is the value of
polystyrene conversion measured using gel permeation chromatography.
[0035]
The ethylene-based copolymer preferably has an area ratio of a region having a molecular weight
of 100,000 or less converted to polystyrene in a chromatogram of its gel permeation
chromatography, preferably 3% or less, and 0 to 3%. More preferably, it is particularly preferably
0 to 2.5%. If the area ratio is more than 3%, rubber elasticity and softener retention may be
reduced.
[0036]
Here, a method of calculating the area ratio of a region having a molecular weight of 100,000
or less converted to polystyrene in a chromatogram of gel permeation chromatography will be
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specifically described with reference to FIG. FIG. 1 is a diagram showing a chromatogram
obtained by analyzing an ethylene copolymer by gel permeation chromatography. First, the
integral value of the elution curve 1 of the chromatogram shown in FIG. 1 (the total area
(indicated as ST in FIG. 1) surrounded by the elution curve 1 and the horizontal axis) is
calculated. Next, the integral value (area (indicated as S1 in FIG. 1)) of the portion detected
after time T1 after which the component with a molecular weight of 100,000 converted to
polystyrene is eluted (elution time) is calculated. Next, the formula: (S1 / ST) × 100 is calculated
from these values to obtain the area ratio of the region having a molecular weight of 100,000
or less converted to polystyrene in the chromatogram of gel permeation chromatography .
[0037]
The ethylene-based copolymer can be produced, for example, by appropriately selecting a
method such as a gas phase polymerization method, a solution polymerization method, or a
slurry polymerization method. These polymerization operations may be batchwise or continuous.
In the solution polymerization method or the slurry polymerization method, an inert hydrocarbon
can be used as a reaction medium. As the inert hydrocarbon solvent, for example, aliphatic
hydrocarbons such as n-pentane, n-hexane, n-heptane, n-octane, n-decane, n-dodecane and the
like; alicyclic groups such as cyclohexane, methylcyclohexane and the like Hydrocarbons; and
aromatic hydrocarbons such as benzene, toluene, xylene and the like can be mentioned. In
addition, these hydrocarbon solvents can be used individually by 1 type or in combination of 2 or
more types.
[0038]
Examples of the polymerization catalyst used when producing the ethylene-based copolymer
include an olefin polymerization catalyst comprising a transition metal compound selected from
the group consisting of V, Ti, Zr and Hf and an organic metal compound. be able to. In addition,
the compound of a transition metal and an organometallic compound can be used individually by
1 type or in combination of 2 or more types.
[0039]
As such an olefin polymerization catalyst, for example, a metallocene catalyst comprising a
metallocene compound and an organoaluminum compound, or an ionic compound which reacts
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with the metallocene compound to form an ionic complex, or a vanadium compound and an
organoaluminum compound And Ziegler-Natta catalysts, etc. In addition, hydrogen gas can also
be used as a molecular weight modifier at the time of manufacture of an ethylene-type
copolymer. The amount of hydrogen gas used varies depending on the type of catalyst, amount
of catalyst, polymerization conditions such as polymerization temperature, polymerization
pressure, and polymerization process such as polymerization scale, stirring state, charge method,
etc. For example, a Ziegler-Natta type catalyst is used In solution polymerization, the amount is
preferably 0.01 to 20 ppm, and more preferably 0.1 to 10 ppm, based on the total monomer
components.
[0040]
[1-1-2] First Mineral Oil-Based Softener: (A) The first mineral oil-based softener contained in the
oil-extended ethylene-based copolymer imparts molding processability and flexibility, and It is
used to improve the product appearance. Examples of the first mineral oil-based softener include,
for example, aromatics, naphthenes, and paraffins. Among these, paraffin-based or naphthenebased first mineral oil-based softeners are preferred because they are highly compatible with
ethylene-based copolymers and are therefore excellent in softener retention and weatherability.
[0041]
As the first mineral oil-based softener, specifically, dimethyl phthalate, diethyl phthalate, dibutyl
phthalate, diisobutyl phthalate, dioctyl phthalate, butyl octyl phthalate, di- (2-ethylhexyl)
phthalate, diisooctyl phthalate, diisodecyl Phthalates such as phthalates; Dimethyladipate,
diisobutyladipate, di- (2-ethylhexyl) adipate, diisooctyladipate, diisodecyladipate,
octyldecyladipate, di- (2-ethylhexyl) azelate, diisooctylazelate, Fatty acid esters such as diisobutyl
azelate, dibutyl sebacate, di- (2-ethylhexyl) sebacate, diisooctyl sebacate; trimellitic acid isodecyl
ester Trimellitic acid esters such as trimellitic acid octyl ester, trimellitic acid n-octyl ester,
trimellitic acid isononyl ester; Petroleum-based softening such as aromatic oil, naphthenic oil,
paraffin oil, white oil, petrolatum, and gylsonite Agents; vegetable oil softeners such as castor oil,
cottonseed oil, rapeseed oil, palm oil, coconut oil, rosin; di- (2-ethylhexyl) fumarate, diethylene
glycol monooleate, glyceryl monoricinolate, trilauryl phosphate, tristearyl phosphate, tri- (2ethylhexyl) phosphate, tricresyl phosphate, epoxidized soybean oil, polyether ester, polybutene
oil and the like can be mentioned.
[0042]
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The used amount of the first mineral oil-based softener is 50 to 150 parts by mass, preferably 80
to 140 parts by mass, and 90 to 130 parts by mass with respect to 100 parts by mass of the
ethylene-based copolymer. It is further preferred that
When the amount used is less than 50 parts by mass, the flexibility and the molding
processability decrease. On the other hand, if the amount is more than 150 parts by mass,
stickiness occurs to reduce industrial productivity.
[0043]
The shape of the oil-extended ethylene copolymer (A) may be any shape such as a bale, crumb, or
pellet. Such a (A) oil-extended ethylene-based copolymer is preferably non-crystalline or lowcrystalline from the viewpoint of improving the flexibility and elastic recovery of the resulting
composition. In addition, since the crystallinity degree is related to the density, it is generally
performed to substitute the crystallinity degree with a density that can be measured more easily
than the crystallinity degree. The (A) oil-extended ethylene copolymer contained in the polymer
composition for obtaining the thermoplastic elastomer composition of the present embodiment
has a density of 0.89 g / cm <3> or less preferable. Furthermore, the crystallinity of the ethylene
copolymer as measured by X-ray diffraction measurement is preferably 20% or less, and more
preferably 15% or less. If the degree of crystallinity is more than 20%, the flexibility of the
ethylene copolymer may be reduced.
[0044]
The method for producing the oil-extended ethylene copolymer (A) is not particularly limited. For
example, a mixed liquid containing the ethylene copolymer, the first mineral oil-based softener,
and the solvent is obtained. It can be produced by removing the solvent from the mixture.
Specifically, a predetermined amount of a first mineral oil softener is added to a solventcontaining ethylene copolymer solution obtained by polymerization, and the mixture is kneaded
by a kneader to obtain a kneaded product. And removing the obtained kneaded product by a
method such as a steam stripping method or a flash method, or ethylene copolymer obtained by
drying after polymerization, benzene, toluene, xylene, hexane, heptane The solvent is uniformly
dissolved in a good solvent such as a hydrocarbon solvent such as cyclohexane or a halogenated
hydrocarbon solvent such as chlorobenzene to obtain a solution, and a predetermined amount of
a first mineral oil-based softener in the obtained solution And the mixture is kneaded by a
kneader to obtain a kneaded product, and the obtained kneaded product can be desolvated by a
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method such as a steam stripping method or a flash method. As a kneader, an apparatus usually
used for oil oil expansion of rubber, such as a Banbury mixer, a pressure kneader, or a roll, can
be used.
[0045]
[1-2] (B) α-olefin thermoplastic resin: (B) α-olefin thermoplastic resin contained in the polymer
composition for obtaining the thermoplastic elastomer composition of the present embodiment is
a fluid In addition to affecting the properties, it acts to reinforce the thermoplastic elastomer
composition to enhance mechanical strength and heat resistance. The (B) α-olefin thermoplastic
resin is contained in an amount of 10 to 50 parts by mass with respect to 100 parts by mass of
the (A) oil-extended ethylene copolymer, and is 15 to 45 parts by mass It is more preferable that
it is 20-40 mass parts. When the content of the (B) α-olefin thermoplastic resin is less than 10
parts by mass, the flowability is reduced, and the anisotropy of the tensile elongation at break is
increased. In addition, mechanical properties and heat resistance are reduced. On the other hand,
when it is more than 50 parts by mass, the hardness is increased and the loss tangent (tan δ) is
decreased.
[0046]
The (B) α-olefin-based thermoplastic resin contained in the polymer composition for obtaining
the thermoplastic elastomer composition of the present embodiment is an α-olefin-based
crystalline thermoplastic resin (b1) and an α-olefin-based resin It is preferable to contain at least
one selected from the group consisting of an amorphous thermoplastic resin (b2), and an αolefin based crystalline thermoplastic resin (b1) and an α-olefin based amorphous thermoplastic
resin It is more preferable to contain the resin (b2).
[0047]
[1-2-1] α-olefin crystalline thermoplastic resin (b1): α-olefin crystalline thermoplastic resin (b1)
(hereinafter sometimes referred to simply as crystalline polymer (b1) The main component
is a structural unit derived from an α-olefin.
By containing such a crystalline polymer (b1), the crystal, that is, the crystal structure of the
crystalline polymer (b1) exhibits a reinforcing effect, so that the mechanical strength of the
resulting thermoplastic elastomer composition is obtained. Has the advantage of improving Here,
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15
in the crystalline polymer (b1), having the structural unit derived from α-olefin as the main
component means α- when the total amount of the crystalline polymer (b1) is 100% by mass.
It means that 80 mass% or more is contained of the structural unit derived from an olefin, and it
is preferable that content of the structural unit derived from an alpha-olefin is 90 mass% or
more. When the content of the structural unit derived from the α-olefin is less than 90% by
mass, the content of crystals is reduced, and thus the mechanical strength of the resulting
thermoplastic elastomer composition may be reduced.
[0048]
Whether the crystalline polymer (b1) is a homopolymer of α-olefin or a copolymer of two or
more α-olefins, a copolymer with a monomer which is not α-olefin It may be It may also be a
mixture of two or more of these different polymers and / or copolymers.
[0049]
When the crystalline polymer (b1) is a copolymer, this copolymer may be either a random
copolymer or a block copolymer. However, in the case of a random copolymer, the total content
of structural units excluding the structural unit derived from α-olefin among the structural units
in this random copolymer is 100% by mass of the total amount of random copolymer It is
preferable that it is 15 mass% or less with respect to, and it is still more preferable that it is 10
mass% or less. If the total content of the structural units excluding the structural unit derived
from the α-olefin is more than 15% by mass, the crystallization is inhibited, and it may not be
possible to obtain a sufficient degree of crystallinity. Moreover, in the case of a block copolymer,
the total content of the constituent units excluding the constituent unit derived from α-olefin
among the constituent units in this block copolymer is 100% by mass of the total amount of the
block copolymer It is preferable that it is 40 mass% or less with respect to, and it is still more
preferable that it is 20 mass% or less. If the total content of the structural units excluding the
structural units derived from the above α-olefin is more than 40% by mass, the content of
crystals is reduced, and thus the mechanical strength of the resulting thermoplastic elastomer
composition may be reduced. is there.
[0050]
The crystalline polymer (b1) is not particularly limited as long as it has crystallinity, but as the
12-05-2019
16
crystallinity of the crystalline polymer (b1), the crystallinity degree by X-ray diffraction
measurement is 50% or more Is more preferably 53% or more, and particularly preferably 55%
or more. Here, the degree of crystallinity is a value closely related to the density. That is, for
example, in the case of polypropylene, the density of α-type crystals (monoclinic form) is 0.936
g / cm <3>, the density of smetica-type microcrystals (pseudo-hexagonal form) is 0.886 g / cm
<3>, The density of the crystalline (atactic) component is 0.850 g / cm <3>. In the case of poly-1butene, the density of isotactic crystals is 0.91 g / cm <3>, and the density of amorphous (atactic)
components is 0.87 g / cm <3>. From the relationship between such crystallinity degree and
density, the crystalline polymer (b1) having a crystallinity degree of 50% or more has a density of
0.89 g / cm <3> or more. And as for a crystalline polymer (b1), it is preferable that the density is
0.90-0.94 g / cm <3>. If the crystallinity degree is less than 50%, that is, the density is less than
0.89 g / cm <3>, the heat resistance, the strength, and the like may be reduced.
[0051]
The crystalline polymer (b1) preferably has a maximum peak temperature by differential
scanning calorimetry, that is, a melting point (hereinafter sometimes simply referred to as
Tm ) is 100 ° C. or higher, and 120 ° C. It is more preferable that it is more than. If the Tm
is less than 100 ° C., sufficient heat resistance and strength may not be exhibited.
[0052]
The crystalline polymer (b1) is a polymer obtained by polymerizing a monomer in the presence
of an existing catalyst such as a Ziegler-Natta catalyst or a metallocene catalyst, and when using a
metallocene catalyst as the catalyst, it has a low molecular weight The content of the component
and the low crystalline component can be reduced, which is preferable from the viewpoint of
improving heat resistance and oil resistance.
[0053]
The crystalline polymer (b1) preferably has a melt flow rate (hereinafter sometimes simply
referred to as MFR ) at a temperature of 230 ° C. and a load of 2.16 kg of 0.1 to 100 g / 10
min. And 0.5 to 80 g / 10 min.
If the MFR is less than 0.1 g / 10 minutes, there is a possibility that the kneading processability,
molding processability, etc. of the thermoplastic elastomer composition may be insufficient. On
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17
the other hand, if it is more than 100 g / 10 minutes, the mechanical strength of the molded
article obtained by the thermoplastic elastomer composition may be reduced.
[0054]
From the above points, the crystalline polymer (b1) specifically has a crystallinity of 50% or
more, a density of 0.89 g / cm <3> or more, and an ethylene unit content of 20 mass. %, A Tm of
100 ° C. or more, an MFR of 0.1 to 100 g / 10 min, and a melting point of 140 to 170 ° C.,
polypropylene, a copolymer of propylene and ethylene, or It is particularly preferred to use a
copolymer of propylene, ethylene and 1-butene.
[0055]
[1-2-2] α-Olefin Amorphous Amorphous Thermoplastic Resin (b2): α-Olefin Amorphous
Amorphous Thermoplastic Resin (b2) (hereinafter, referred to simply as amorphous polymer
(b2) In some cases, the main component is a structural unit derived from an α-olefin.
By containing such an amorphous polymer (b2), when the obtained thermoplastic elastomer
composition is injection-fused together with the vulcanized rubber or the thermoplastic
elastomer, the adhesion strength with the adherend is improved. It has the advantage of Here, in
the amorphous polymer (b2), having a constituent unit derived from α-olefin as the main
component means that the total amount of the amorphous polymer (b2) is 100% by mass. It
means that it contains 50 mass% or more of α-olefins, and the content of the structural unit
derived from α-olefins is preferably 60 mass% or more. Adhesion to an adherend when the
obtained thermoplastic elastomer composition is injection-fused together with a vulcanized
rubber or a thermoplastic elastomer if the content of the structural unit derived from α-olefin is
less than 60% by mass There is a possibility that sufficient strength can not be obtained.
[0056]
The above amorphous polymer (b2) is a homopolymer of α-olefin, or a copolymer of two or
more α-olefins, and a copolymer with a monomer which is not α-olefin It may be combined. It
may also be a mixture of two or more of these different polymers and / or copolymers.
[0057]
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18
Examples of the amorphous polymer (b2) include homopolymers such as atactic polypropylene
and atactic poly-1-butene, copolymers of propylene and other α-olefins, 1-butene and other
polymers. Copolymers with α-olefins may, for example, be mentioned. In addition, as a
copolymer of propylene and other α-olefins, the content of a constituent unit derived from
propylene is 50% by mass or more based on the total amount of the copolymer, and the other αolefins are For example, copolymers of ethylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1pentene, 1-octene, 1-decene and the like. In addition, as a copolymer of 1-butene and other αolefins, the content of the structural unit derived from 1-butene is 50% by mass or more based
on the total amount of the copolymer, Examples of the copolymer include α-olefins such as
ethylene, propylene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene and the like.
[0058]
When the above-mentioned amorphous polymer (b2) is a copolymer, this copolymer may be
either a random copolymer or a block copolymer. However, in the case of a block copolymer, αolefins as main components (copolymers of propylene and other α-olefins, and copolymers of 1butene and other α-olefins) The structural units derived from propylene and 1-butene) need to
be bonded in an atactic structure. When the amorphous copolymer (b2) is a copolymer of αolefin having 3 or more carbon atoms and ethylene, the content of the structural unit derived
from the α-olefin is an amorphous co-polymer. It is preferable that it is 50 mass% or more with
respect to 100 mass% of total amounts of a polymer (b2), and it is still more preferable that it is
60-99 mass%.
[0059]
As the above-mentioned amorphous polymer (b2), atactic polypropylene having a content of
structural units derived from propylene of 50% by mass or more, and propylene having a content
of structural units derived from propylene of 50% by mass or more It is particularly preferable to
use a copolymer with ethylene and a copolymer of propylene and 1-butene.
[0060]
The melt viscosity at 190 ° C. of the amorphous polymer (b2) is preferably 50000 cps or less,
more preferably 100 to 300000 cps, and particularly preferably 200 to 20000 cps.
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When the obtained thermoplastic elastomer composition is injection-fused together with a
vulcanized rubber or a thermoplastic elastomer when the melt viscosity is more than 50000 cps,
the adhesive strength with the adherend is lowered, ie, sufficient adhesion There is a possibility
that the sex can not be obtained. The crystallinity of the amorphous polymer (b2) as measured by
X-ray diffraction measurement is preferably less than 50%, more preferably 30% or less, and
particularly preferably 20% or less. When the obtained thermoplastic elastomer composition is
injected and fusion-bonded with a vulcanized rubber or a thermoplastic elastomer when the
degree of crystallinity is more than 50%, the adhesive strength with the adherend is lowered, ie,
sufficient Adhesion may not be obtained.
[0061]
The crystallinity degree of the amorphous polymer (b2) is a value closely related to the density as
in the crystalline polymer (b1), and the density of the amorphous polymer (b2) is 0. It is more
than .85 g / cm <3>, preferably less than 0.89 g / cm <3>, and more preferably 0.85 to 0.88 g /
cm <3>. When the obtained thermoplastic elastomer composition is injected and fusion-bonded
with a vulcanized rubber or a thermoplastic elastomer when the density is 0.89 g / cm <3> or
more, adhesion strength to an adherend is decreased. There is. Moreover, it is preferable that it is
1000-20000, and, as for the number average molecular weight (Mn) of an amorphous polymer
(b2), it is still more preferable that it is 1500-15000. Here, in the present specification, number
average molecular weight (Mn) is a value in terms of polystyrene measured using gel
permeation chromatography.
[0062]
[1-3] (D) Second mineral oil-based softener: The raw material composition is (A) 10 to 30 parts
by mass of (D) the second per 100 parts by mass of the oil-extended ethylene copolymer. It is
preferable to further include a mineral oil-based softener of
[0063]
The (D) second mineral oil-based softener contained in the raw material composition for
obtaining the thermoplastic elastomer composition of the present embodiment imparts fluidity
and reduces the anisotropy of tensile elongation at break, It improves the loss tangent (tan δ).
[0064]
As the second mineral oil-based softener (D), one similar to the first mineral oil-based softener
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20
described above can be suitably used.
[0065]
The blending amount of the second mineral oil-based softener (D) is preferably 10 to 30% by
mass or less, and 11 to 30% by mass with respect to 100 parts by mass of the component (A) as
described above. Is more preferable, and 12 to 30% by mass is particularly preferable.
When the amount is less than 10% by mass, molding processability may be difficult.
On the other hand, if it is more than 30% by mass, the (D) second mineral oil-based softening
material may bleed out to cause appearance defects of the molded product.
[0066]
In addition, the raw material composition for obtaining the thermoplastic elastomer composition
of the present embodiment has an intrinsic viscosity [η] of 1.8 to 2.3 dl / g as measured in a
decalin solvent at 135 ° C. (E -1) At least one kind of (E) selected from the group consisting of
ethylene / α-olefin copolymer rubber, (E-2) isobutylene-isoprene copolymer rubber, and (E-3)
styrenic thermoplastic elastomer And (E) an oil-extended ethylene copolymer, the (E-1) ethylene /
α-olefin copolymer rubber, and (E-2) an isobutylene-isoprene copolymer rubber. And (E-3)
ethylene-α-olefin copolymer rubber and (E-2) isobutylene-isoprene copolymer rubber with
respect to a total amount of 100% by mass of (E-3) styrene thermoplastic elastomer , (E- ) The
total amount of styrene-based thermoplastic elastomer is 10 to 30 wt%, temperature 25 ° C,
loss tangent measured at a frequency of 1.0 Hz (tan [delta) is preferably 0.1 or more.
[0067]
[1-4] (E-1) Ethylene / α-Olefin Copolymer Rubber: (E-1) Ethylene / α-Olefin Contained in the
Raw Material Composition for Obtaining the Thermoplastic Elastomer Composition of the Present
Embodiment The copolymer rubber preferably has an intrinsic viscosity [η] of 1.8 to 2.3 dl / g
as measured in a decalin solvent at 135 ° C., and the content ratio thereof is (A) an oil-extended
ethylene-based co-polymer Total amount of polymer, (E-1) ethylene-α-olefin copolymer rubber,
(E-2) isobutylene-isoprene copolymer rubber, and (E-3) styrene-based thermoplastic elastomer
On the other hand, it is preferable that it is 0-30 mass%.
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21
Since the component (E-1) has a low intrinsic viscosity [η], that is, a small molecular weight, it is
possible to obtain a molded member having an improved loss tangent (tan δ) obtained.
[0068]
In the component (E-1), the above-mentioned intrinsic viscosity [η] is preferably 1.8 to 2.3 dl / g
as described above, and more preferably 1.8 to 2.2 dl / g And 1.9 to 2.2 dl / g are particularly
preferred.
If the intrinsic viscosity [η] is less than 1.8 dl / g, the tensile strength at break may be reduced,
and (D) bleed out of the second mineral oil-based softener may occur. On the other hand, if it
exceeds 2.3 dl / g, the loss tangent (tan δ) may be reduced.
[0069]
There exists a possibility that the anisotropy of tensile breaking elongation may become it large
that the compounding quantity of (E-1) component is more than 30 mass%. In addition, bleed out
of the (D) second mineral oil softener may occur.
[0070]
The component (E-1) can be obtained by copolymerizing ethylene, an α-olefin other than
ethylene, and a non-conjugated diene which is optionally used, as the component (A).
[0071]
[1-5] (E-2) Isobutylene-Isoprene Copolymer Rubber: The (E-2) isobutylene-isoprene copolymer
rubber contained in the raw material composition for obtaining the thermoplastic elastomer
composition of the present embodiment is an isobutylene A rubbery amorphous copolymer with
a low degree of unsaturation containing a structural unit derived from and a structural unit
derived from isoprene, which is derived from its molecular side chain structure and improves loss
tangent (tan δ) is there.
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[0072]
The content ratio of this (E-2) isobutylene-isoprene copolymer rubber is as follows: (A) oilextended ethylene copolymer, (E-1) ethylene / α-olefin copolymer rubber, (E-2) It is preferable
that it is 0-30 mass% with respect to 100 mass% of total amounts with an isobutylene-isoprene
copolymer rubber and a (E-3) styrene-type thermoplastic elastomer.
If the content ratio is more than 30% by mass, bleed out may occur when the second mineral oilbased softener (D) is used.
[0073]
As the component (E-2), specifically, isobutylene, isoprene, and aromatic divinyl compounds (for
example, divinylbenzene etc.) as disclosed in US Pat. What was polymerized can be mentioned.
Further, the component (E-2) includes, for example, JP-A-48-90385, JP-A-53-42289, JP-A-5984901, JP-A-3-131643, and JP-A As disclosed in 2004-091766, an isobutylene-isoprene
copolymer rubber having a conjugated diene unsaturated bond has a functional group such as a
carboxyl group, an acid anhydride group, a hydrosilyl group, an amino group or an epoxy group.
It may be denatured by reacting an unsaturated compound.
[0074]
As commercial products of component (E-2), all trade names are "JSR BUTYL" (manufactured by
JSR Corporation), "Exxon BUTYL, Esso BUTYL" (manufactured by Exxon), "POLYSAR BUTYL"
(manufactured by Bayer Polymers Co., Ltd.) Etc. can be mentioned.
[0075]
The content ratio of the structural unit derived from isoprene in the component (E-2) is
preferably 0.5 to 15 mol%, and is 0.8 to 5.0 mol% with respect to 100 mol% of all the structural
units. Is more preferred.
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23
If the content ratio is less than 0.5 mol%, the crosslinking reaction tends to be delayed, and the
tensile strength at break may not be sufficient. On the other hand, when it is more than 15 mol%,
the crosslink density of the thermoplastic elastomer composition is excessively increased, and the
mechanical properties tend to be lowered.
[0076]
The compounding amount of the component (E-2) is 0 to the total amount of the components (A),
(E-1), (E-2), and (E-3) as described above. It is preferably 30% by mass. When the said
compounding quantity is more than 30 mass%, when (D) 2nd mineral-oil type softening agent is
used, there exists a possibility that the bleed-out may generate ¦ occur ¦ produce. In addition,
mechanical properties may be degraded.
[0077]
The component (E-2) is obtained, for example, by slurry-polymerizing isobutylene and a small
amount of isoprene in methyl chloride at a low temperature of about -100.degree. C. using
anhydrous aluminum chloride as a catalyst and then drying it. You can get it.
[0078]
[1-6] (E-3) Styrenic Thermoplastic Elastomer: The (E-3) styrenic thermoplastic elastomer
contained in the raw material composition for obtaining the thermoplastic elastomer composition
of the present embodiment is derived from styrene The copolymer is a copolymer containing a
constituent unit which is derived from the above and a constituent unit derived from a
conjugated diene, is derived from its molecular side chain structure, and improves the loss
tangent (tan .delta.).
[0079]
As the conjugated diene, for example, butadiene, isoprene, isobutylene and the like can be used.
In addition, it is preferable that the conjugated diene is a hydrogenated type in which the
conjugated diene is hydrogenated, because the heat deterioration resistance and the weather
resistance are improved.
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24
Moreover, the styrenic thermoplastic elastomer may be a block copolymer composed of a soft
segment and a hard segment. In such a case, as a soft segment, for example, a butadiene
polymerization block having a high 1,2- or 3,4-linkage ratio, an isoprene polymerization block
having a high 3,4-linkage ratio, an isobutylene polymerization block, styrene and a conjugated
diene It is preferred to use at least one of the random copolymer blocks. This is because the loss
tangent (tan δ) can be improved.
[0080]
The content ratio of the (E-3) styrenic thermoplastic elastomer is (A) an oil-extended ethylene
copolymer, (E-1) ethylene / α-olefin copolymer rubber, and (E-2) isobutylene- It is preferable
that it is 0-30 mass% with respect to 100 mass% of total amounts of an isoprene copolymer
rubber and a (E-3) styrene-type thermoplastic elastomer. If the content ratio is more than 30% by
mass, bleed out may occur when the second mineral oil-based softener (D) is used.
[0081]
As components (E-3), the following commercial products can be used under the trade names.
Kuraray's "Hybler", "Septon", Kraton Polymers' "Clayton D", "Clayton G", Asahi Kasei's "Tuftec",
"Tuffuprene", "Asaprene", JSR "JSR TR JSR SIS , JSR DYNARON , SIBSTAR
manufactured by Kaneka Corporation, and the like.
[0082]
[1-7] Other Components: In addition to the above-described components, the raw material
composition may, if necessary, contain various additives, fillers, and other (co) polymers such as
polyethylene and polyisobutylene. Etc. can be contained.
[0083]
Additives include, for example, anti-aging agents, anti-oxidants, ultraviolet light absorbers, antistatic agents, weathering agents, non-halogen flame retardants, fillers, antibacterial and
antifungal agents, blocking agents, sealing improvers, A heat stabilizer, a light stabilizer, a
stabilizer such as a copper inhibitor, a metal deactivator, a crystal nucleating agent, a tackifier, a
foaming aid, a colorant (dye, pigment, etc.) and the like can be mentioned.
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25
[0084]
As the filler, for example, metal powder such as ferrite, inorganic fiber such as glass fiber and
metal fiber, organic fiber such as carbon fiber and aramid fiber, composite fiber, inorganic
whisker such as potassium titanate whisker, glass bead, glass balloon Glass flakes, mica, calcium
carbonate, talc, wet silica, dry silica, alumina, alumina silica, calcium silicate, hydrotalcite, kaolin,
diatomaceous earth, graphite, pumice, evo powder, cotton flock, cork powder, sulfuric acid
Barium, fluorine resin, polymer beads, carbon black, cellulose powder, rubber powder, wood
powder and the like can be mentioned.
[0085]
Other (co) polymers include, for example, rubbery polymers such as butadiene rubber, butyl
rubber and NBR, thermoplastic resins such as acrylic resins, thermoplastic elastomers such as
hydrogenated diene polymers, and organopolysiloxanes A modified organopolysiloxane etc. can
be mentioned.
The content ratio of the other polymer is preferably 1 to 50% by mass, more preferably 2 to 45%
by mass, and further preferably 3 to 40% by mass, with respect to 100% by mass of the total
amount of the polymer components. Is particularly preferred.
If the content ratio is less than 1% by mass, the effect of the addition of the other polymer may
not be exhibited.
On the other hand, if it is more than 50% by mass, rubber elasticity may be reduced.
[0086]
Examples of the organopolysiloxane include unmodified organopolysiloxanes such as
dimethylpolysiloxane, methylphenylpolysiloxane, fluoropolysiloxane,
tetramethyltetraphenylpolysiloxane and methylhydrogenpolysiloxane. Further, as the modified
organopolysiloxane, for example, chemically modified with a functional group such as acryl
modified, epoxy modified, alkyl modified, amino modified, amino modified, carboxyl modified,
alcohol modified, fluorine modified, alkyl aral polyether modified, epoxy polyether modified, etc.
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26
Organopolysiloxanes can be mentioned. Among these, since the slidability is remarkably
improved, an unmodified organopolysiloxane having a viscosity at 25 ° C. defined in JIS K 2283
of less than 10000 cSt, and an unmodified organopolysiloxane having the viscosity of 10000 cSt
or more. It is preferable to use in combination with
[0087]
Other polymers may be added to the polymer composition, or may be added after the polymer
composition is dynamically heat-treated in the presence of a crosslinking agent.
[0088]
The thermoplastic elastomer composition of the present embodiment preferably has a loss
tangent (tan δ) of 0.1 or more as measured under conditions of a temperature of 25 ° C. and a
frequency of 1.0 Hz.
While having excellent vibrational absorptivity with a loss tangent (tan δ) of 0.1 or more, it is
possible to form a molded member having excellent dimensional stability, ie, lower anisotropy in
tensile elongation at break. Can. If the loss tangent (tan δ) is less than 0.1, the vibration
absorption of the resulting molded member may be insufficient. Here, as an apparatus for
measuring loss tangent (tan δ), for example, RSA II manufactured by TA Instruments can be
mentioned.
[0089]
[1-8] (C) Crosslinking Agent: The type of the (C) crosslinking agent is not particularly limited, and
at least the component (A) and (D) are subjected to dynamic heat treatment at a temperature
above the melting point of the component (D). It is preferable that it is a compound which can
crosslink a component.
[0090]
As the crosslinking agent (C), for example, organic peroxide, hydrosilylation crosslinking agent,
sulfur, sulfur compound, p-quinone, derivative of p-quinone dioxime, bismaleimide compound,
epoxy compound, silane compound, amino resin, Polyol crosslinking agents, polyamines, triazine
compounds, metal soaps and the like can be mentioned.
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27
Among these, organic peroxides are preferable. In addition, these can be used individually or in
combination of 2 or more types.
[0091]
As the organic peroxide, 1,3-bis (t-butylperoxyisopropyl) benzene, 2,5-dimethyl-2,5-bis (tbutylperoxy) hexyne-3,2,5-dimethyl- 2,5-Bis (t-butylperoxy) hexene-3,2,5-dimethyl-2,5-bis (tbutylperoxy) hexane, 2,2'-bis (t-butylperoxy)- p-isopropylbenzene, dicumyl peroxide, di-t-butyl
peroxide, t-butyl peroxide, p-menthane peroxide, 1,1-bis (t-butylperoxy) -3,3,5-trimethyl
Cyclohexane, dilauroyl peroxide, diacetyl peroxide, t-butylperoxybenzoate, 2,4-dichlorobenzoyl
peroxide, p-chlorobenzoyl Okishido, benzoyl peroxide, may be mentioned di (t-butylperoxy)
perbenzoate, n- butyl-4,4-bis (t-butylperoxy) valerate, and t-butyl peroxy isopropyl carbonate.
[0092]
Among these, 1,3-bis (t-butylperoxyisopropyl) benzene, 2,5-dimethyl-2,5-di (t-butylperoxy)
hexyne-3,2,5-dimethyl-2,5 -Di (t-butylperoxy) hexane, α, α-bis (t-butylperoxy)
diisopropylbenzene, dicumyl peroxide, di-t-butyl peroxide are preferred.
In addition, these can be used individually or in combination of 2 or more types.
[0093]
The amount of the crosslinking agent (C) used is preferably 0.01 to 20 parts by mass, preferably
0.3 to 15 parts by mass, per 100 parts by mass of the total amount of the components (A) and
(B). It is more preferable that it is, and it is especially preferable that it is 0.5-10 mass parts. If the
amount of the crosslinking agent (C) used is less than 0.01 parts by mass, the degree of
crosslinking is insufficient, and the mechanical properties of the resulting thermoplastic
elastomer composition tend to be reduced. On the other hand, when it is more than 20 parts by
mass, the degree of crosslinking becomes excessively high, the molding processability tends to
decrease, and the mechanical properties of the resulting thermoplastic elastomer composition
tend to decrease.
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[0094]
When a crosslinking coagent, a crosslinking accelerator, and the like are used together with the
crosslinking agent (C), the crosslinking reaction can be gently performed, so that uniform
crosslinking can be formed.
[0095]
Examples of crosslinking assistants include sulfur, sulfur compounds (powdered sulfur, colloidal
sulfur, precipitated sulfur, insoluble sulfur, surface-treated sulfur, dipentamethylenethiuram
tetrasulfide, etc.), oxime compounds (p-quinone oxime, p, p ' -Dibenzoylquinone oxime, etc.,
multifunctional monomers (ethylene glycol di (meth) acrylate, diethylene glycol di (meth)
acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate,
polyethylene glycol di) (Meth) acrylate, trimethylolpropane tri (meth) acrylate, diallyl phthalate,
tetraallyloxy ethane, triallyl cyanurate, N, N'-m-phenylenebismaleimide, N, N'toluylenebismaleimide Maleic anhydride, divinylbenzene, are preferably used di (meth) zinc
acrylate and the like) and the like.
Among these, p, p'-dibenzoylquinone oxime, N, N'-m-phenylenebismaleimide, and divinylbenzene
are preferable. These can be used alone or in combination of two or more.
[0096]
When the organic peroxide is used as the crosslinking agent, the amount of the crosslinking aid
used is 10 parts by mass or less based on 100 parts by mass of the total amount of the
components (A), (D) and (B). Is preferably, and more preferably 0.2 to 5 parts by mass. If the
amount of the crosslinking aid used is more than 10 parts by mass, the degree of crosslinking
becomes excessively high, which tends to deteriorate moldability and mechanical properties.
[0097]
[1-9] "Dynamically heat treatment": The thermoplastic elastomer composition of this embodiment
is a polymer composition containing the (A) component and the (B) component in the presence of
a crosslinking agent. It is obtained by heat treatment. Here, "dynamically heat treatment" refers
to both applying a shear force and heating. As an apparatus used for "dynamic heat processing",
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29
a melt-kneading apparatus can be mentioned as a suitable example, for example. The processing
by the melt-kneading apparatus may be either a continuous type or a batch type. Specific
examples of the melt-kneading apparatus include an open-type mixing roll, a non-open-type
Banbury mixer, a single-screw extruder, a twin-screw extruder, a continuous kneader, a pressure
kneader, and the like.
[0098]
Among these, it is preferable to use a continuous melt-kneading apparatus such as a single-screw
extruder, a twin-screw extruder, or a continuous kneader from the viewpoint of economy,
processing efficiency, and the like. In addition, two or more continuous melt-kneading
apparatuses of the same type or different types may be used in combination.
[0099]
The L / D ratio (ratio of screw effective length L to outer diameter D) of the twin-screw extruder
is preferably 30 or more, and more preferably 36 to 80. In addition, as the twin screw extruder,
for example, any twin screw extruder such as one in which two screws are engaged or one in
which two screws are not engaged can be used, but the screws are rotated in the same direction.
It is more preferable that As such a twin-screw extruder, for example, trade name "PCM" (made
by Ikegai Co., Ltd.), trade name "KTX" (made by Kobe Steel, Ltd.), trade name "TEX" (made by
Japan Steel Works, Ltd.), goods Name "TEM" (made by Toshiba Machine Co., Ltd.), brand name
"ZSK" (made by Warner), etc. can be mentioned.
[0100]
The L / D ratio (ratio of screw effective length L to outer diameter D) of the continuous kneader
is preferably 5 or more, and more preferably 10 or more. As such a continuous kneader, trade
name "Mixtron KTX LCM NCM" (made by Kobe Steel, Ltd.), trade name "CIM CMP" (made by
Japan Steel Works, Ltd.), etc. can be mentioned.
[0101]
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It is preferable that it is 120-350 degreeC, and, as for the heat processing temperature at the
time of "dynamically heat-processing", it is still more preferable that it is 150-290 degreeC. The
heat treatment time is preferably 20 seconds to 30 minutes, and more preferably 30 seconds to
25 minutes. In addition, the shear force to be applied is preferably 10 to 20,000 / second in
shear rate, and more preferably 100 to 10,000 / second.
[0102]
The thermoplastic elastomer composition of the present embodiment satisfies the following
condition (3). As described above, by satisfying the following condition (3), since the anisotropy
of tensile elongation at break is small, molding defects such as warpage are less likely to occur,
and there is an advantage that uniform molded articles can be obtained. If the test piece does not
satisfy the above equation, the anisotropy in tensile elongation at break is large, so that molding
defects such as warpage occur and there is a problem that a good molded article can not be
obtained. (3): 120 mm long, 120 mm wide, 2 mm thick sheet-like test piece obtained by injection
molding under conditions of cylinder temperature 250 ° C., mold temperature 50 ° C.,
injection speed 50 mm / sec : {(Tensile elongation at break in the flow direction (EB)) / (tensile
elongation at break in the direction perpendicular to the flow (EB))} ≦ 1.5.
[0103]
Moreover, it is preferable that the thermoplastic elastomer composition of this embodiment is
what satisfy ¦ fills the conditions of following (3-1). (3-1): A sheet-like test piece 120 mm long,
120 mm wide and 2 mm thick obtained by injection molding under the conditions of a cylinder
temperature of 250 ° C., a mold temperature of 50 ° C. and an injection speed of 50 mm / sec.
Equation: {Tension at break elongation in flow direction (EB) / Tension at break perpendicular to
flow (EB)} ≦ 1. 3
[0104]
Here, in the present specification, the flow direction means the flow direction of the
thermoplastic elastomer composition when a sheet-like formed film is formed by injection
molding. Also, "perpendicular to flow" means a direction perpendicular to the flow direction. In
addition, tensile elongation at break (EB) is a test piece when the test piece is pulled and
broken at a tensile speed of 500 mm / min using No. 3 dumbbell in accordance with JIS K6251-
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1993. It means the growth rate.
[0105]
In the thermoplastic elastomer composition of the present embodiment, the melt flow rate
measured at 230 ° C. and a 2.16 kg load is preferably 0.1 to 100 g / 10 min according to JIS K
7210, More preferably, it is 1.0 to 100 g / 10 min. When the melt flow rate is less than 0.1 g /
10 min, moldability may be difficult. On the other hand, there is a possibility that mechanical
strength may fall that it is more than 100 g / 10 minutes.
[0106]
Moreover, it is preferable that it is 20-95, and, as for the thermoplastic elastomer composition of
this embodiment, Duro A hardness 5 seconds after the measurement start measured according to
JISK6253 is 30-90 more preferable. If the Duro A hardness is less than 20, the formed edge
member tends to be easily broken. On the other hand, if it exceeds 95, it becomes difficult for the
speaker having the formed edge member to generate a good sound quality.
[0107]
[2] Method of Producing Thermoplastic Elastomer Composition: The thermoplastic elastomer
composition of the present embodiment is, for example, the above-mentioned (A) oil-extended
ethylene-based copolymer, and (A) oil-extended ethylene-based copolymer A raw material
composition is obtained by kneading 10 to 50 parts by mass of (B) α-olefin thermoplastic resin
with 100 parts by mass with the above-described melt-kneading apparatus, and the obtained raw
material composition is A crosslinker can be added and obtained by dynamic heat treatment
under the conditions (time, temperature, shear force) described above by the melt-kneading
apparatus described above in the presence of the (C) crosslinker.
[0108]
[3] Molding Member: One embodiment of the molding member of the present invention is
obtained by molding the thermoplastic elastomer composition of the present invention.
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Since the molded member obtained in this manner has a good loss tangent (tan δ), it has
excellent vibrational absorptivity, a small anisotropy of tensile elongation at break, a good oil
bleed property, and a good property. It has mechanical properties and recycling characteristics.
[0109]
The molded member of the present embodiment has good loss tangent (tan δ), so it has
excellent vibrational absorptivity, small anisotropy in tensile elongation at break, good oil bleed
property, and good mechanical properties. And since it has a recycling property, it is suitable to
use as an edge member arrange ¦ positioned at at least one part of the outer peripheral part of
the diaphragm of a speaker.
[0110]
The edge member is disposed on at least a part of the outer peripheral portion of the diaphragm
of the speaker, and the edge member can suppress extra vibration of the diaphragm and can
improve the acoustic characteristics of the speaker. .
[0111]
The diaphragm is a plate that is provided in the speaker and performs a predetermined vibration
according to a predetermined electrical signal, and the speaker can generate the given electrical
signal as a sound that can be heard by the human ear.
There are no particular restrictions on the material and shape of the diaphragm, and
conventionally known ones can be used.
Examples of the material of the diaphragm include polyethylene, polypropylene, pulp, aluminum,
titanium and the like. Moreover, as a shape of a diaphragm, a cone type, dome shape, a planar
type etc. can be mentioned, for example.
[0112]
For example, FIG. 2 is an example showing a part of a speaker provided with a disk-shaped
diaphragm 11 and an annular edge member 12 disposed on the outer peripheral portion of the
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diaphragm 11. FIG. 2 is a plan view showing an embodiment of a speaker member manufactured
by the method for manufacturing a speaker member of the present invention.
[0113]
The shape of the edge member is preferably in the form of a sheet, the thickness thereof is
preferably 50 to 500 μm, and more preferably 100 to 400 μm. If the thickness of the edge
member is less than 50 μm, the edge member may be easily broken. On the other hand, if it
exceeds 500 μm, there is a possibility that a speaker that generates a good sound quality can
not be obtained.
[0114]
The molded member of the present embodiment can be manufactured by, for example, various
molding methods such as injection molding, press molding, and extrusion molding.
[0115]
[4] Method of Manufacturing Speaker Member: As an embodiment of a method of manufacturing
a speaker member according to the present invention, a diaphragm and an edge member
disposed on at least a part of an outer peripheral portion of the diaphragm are provided. A
method for producing a speaker member, comprising injection molding the thermoplastic
elastomer composition of the present invention to form an edge member, and then attaching the
edge member to at least a part of the outer peripheral portion of the diaphragm. .
[0116]
As described above, the method for manufacturing the speaker member according to the present
embodiment improves mechanical properties because the adhesion between the diaphragm and
the edge portion is good because the speaker member is manufactured using the thermoplastic
elastomer composition according to the present invention. be able to.
[0117]
The conditions for injection molding are not particularly limited, and can be determined by a
conventionally known method.
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For example, injection molding can be performed under conditions of a cylinder temperature of
180 to 280 ° C., a mold temperature of 20 to 80 ° C., and an injection speed of 10 to 2000
mm / sec.
[0118]
The shape of the edge member to be formed is not particularly limited, and may be a
conventionally known shape.
For example, the shape, thickness, etc. described in [3] molding member can be used.
[0119]
There is no restriction ¦ limiting in particular in the diaphragm used for the manufacturing
method of the speaker member of this embodiment, A conventionally well-known thing can be
selected suitably and can be used.
For example, as a material of the diaphragm, polyethylene, polypropylene, pulp, aluminum,
titanium and the like can be mentioned, and as a shape of the diaphragm, a cone type, a dome
type, a flat type and the like can be mentioned.
[0120]
The method for attaching the edge member to the outer peripheral portion of the diaphragm is
not particularly limited, but an adhesive can be used. The adhesive is not particularly limited in
kind and the like, and conventionally known ones can be used. Examples of the type of adhesive
include solvent type adhesives, aqueous type adhesives, hot melt type adhesives, reactive type
adhesives and the like.
[0121]
Another embodiment of a method of manufacturing a speaker member according to the present
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invention is a method of manufacturing a speaker member including a diaphragm and an edge
member disposed on at least a part of an outer peripheral portion of the diaphragm. Injection
molding of the thermoplastic elastomer composition of the present invention into a speaker
member forming mold in which the diaphragm is disposed, and the step of arranging the edge
member on at least a part of the outer peripheral portion of the diaphragm It is.
[0122]
Thus, by using the thermoplastic elastomer composition of the present invention, the speaker
member manufactured by the method of manufacturing the speaker member of the present
embodiment has a good loss tangent (tan δ), so excellent vibration absorption is obtained. It has
the advantage of having an edge member having a small anisotropy in tensile elongation at
break, a good oil bleed property, and good mechanical properties and recycling properties.
In addition, since the adhesion between the diaphragm and the edge portion is further improved,
there is an advantage that mechanical properties can be further improved. In addition, for
example, after the diaphragm and the edge member are separately formed, the process can be
simplified as compared with a method in which the diaphragm and the edge member are bonded
together using an adhesive or the like.
[0123]
The method for manufacturing a speaker member according to the present embodiment includes
the steps of injection molding a material for forming a diaphragm on a diaphragm forming mold
to obtain a diaphragm, and using the obtained diaphragm as a speaker member forming gold.
Preferably, the method further comprises the step of arranging inside the mold. Such a
manufacturing method, so-called insert molding, is a highly versatile manufacturing method.
Specifically, in the insert molding method, two molding machines and two molds (a mold for
forming the diaphragm and a mold for forming the speaker member) are prepared, and first, the
first molding machine and the vibration are prepared. A diaphragm may be manufactured using a
plate forming mold, and then the manufactured diaphragm may be inserted into a speaker
member forming mold and the edge portion may be molded using a second molding machine. it
can.
[0124]
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Further, according to the method of manufacturing the speaker member of the present
embodiment, the diaphragm disposed in the speaker member forming mold is formed by
injection molding a material for forming the diaphragm in the speaker member forming mold. It
is preferable to further include the step of obtaining. Such a manufacturing method, a so-called
two-color molding method (continuous two-color molding method), is a manufacturing method in
which the molding time is short and the productivity is high. According to such a two-color
molding method, since it is not necessary to manufacture the diaphragm in a separate step in
advance, there is an advantage that the process can be simplified even in comparison with the
above-mentioned insert molding method. is there. Specifically, in the two-color molding method,
one speaker member forming mold in which two molding machines and two injection molding
machines are connected is prepared, and first, vibration is performed by the first molding
machine. The plate can be molded, and then the second molding machine can be used to mold
the edge member in the same mold (speaker member forming mold).
[0125]
The speaker member forming mold used in the method for manufacturing a speaker member
according to the present embodiment is not particularly limited as long as the diaphragm can be
disposed therein, and conventionally known ones can be appropriately selected and used. .
[0126]
As materials for forming the diaphragm, conventionally known materials (for example,
polyethylene, polypropylene and the like) can be appropriately selected and used.
[0127]
The conditions for injection molding the thermoplastic elastomer composition are not
particularly limited, and can be carried out by a conventionally known method.
For example, injection molding can be performed under conditions of a cylinder temperature of
180 to 280 ° C., a mold temperature of 20 to 80 ° C., and an injection speed of 10 to 2000
mm / sec.
[0128]
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EXAMPLES Hereinafter, the present invention will be specifically described based on examples,
but the present invention is not limited to these examples.
In the examples and comparative examples, "parts" and "%" are based on mass unless otherwise
specified. Moreover, the various measurement in an Example and a comparative example was
performed by the following method.
[0129]
[Intrinsic viscosity [η]]: Intrinsic viscosity [η] is measured using a Ubbelohde viscometer in a
decalin solvent at 135 ° C. Specifically, the thermoplastic elastomer composition is dissolved in
decalin solvent to prepare a sample solution. The sample solution is measured in a 135 ° C.
constant temperature oil bath using a Ubbelohde viscometer.
[0130]
[Loss tangent (tan δ)]: A pellet of the thermoplastic elastomer composition produced in the
following examples and comparative examples is prepared, and the pellet is used as an injection
molding machine (model number "J-110AD", manufactured by Japan Steel Works, Ltd.) Using
injection molding, a sheet-like molded article having a length of 120 mm, a width of 120 mm and
a thickness of 2 mm is obtained. The resulting molded product is punched out with a dumbbell to
obtain a 38 mm × 3 mm rectangular test piece, ie, a 38 mm × 3 mm × 2 mm test piece. For
this test piece, using a dynamic viscoelasticity measuring device ("RSAII" manufactured by TA
Instruments Co., Ltd.), in a tensile mode, measure "tan δ" under the conditions of a temperature
of 25 ° C and a frequency of 1.0 Hz. Do.
[0131]
[Melt flow rate (MFR)]: Pellets of the thermoplastic elastomer composition produced in the
following examples and comparative examples are prepared, and the pellets are in accordance
with JIS K 7210, a load of 2.16 kg and a temperature of 230 ° C. Measure with
[0132]
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[Hardness]: Using a 120 mm × 120 mm × 2 mm sheet-like molded article produced by the
above [loss tangent (tan δ)], the Duro A hardness at 5 seconds after the start of measurement is
measured according to JIS K6253.
[0133]
[Tension test]: A molded film with a length of 120 mm, a width of 120 mm and a thickness of 2
mm is obtained by injection molding under the conditions of an injection molding machine
cylinder temperature of 250 ° C, a mold temperature of 50 ° C and an injection speed of 50
mm / sec. The punched film obtained is punched into a dumbbell shape No. 3 shape in
accordance with JIS-K6251 to prepare a test piece, and the tensile break strength (TB) of the test
piece in the flow direction and the direction perpendicular to the flow And measure the tensile
elongation at break (EB).
[0134]
[Anisotropy of tensile elongation at break]: Using the tensile elongation at break (EB (%) in the
direction perpendicular to the flow direction and the flow obtained by the above [Tensile test]),
Calculate the value of the tensile elongation at break (EB) in the direction perpendicular to the
flow).
The evaluation of the anisotropy of the tensile elongation at break can be judged that the
anisotropy of the tensile elongation at break is small when the calculated value satisfies the
following expression, and when the expression below is not satisfied, the tensile expression is
tensile. It can be judged that the anisotropy of the breaking elongation is large.
Formula: {Tension elongation at break (EB) in flow direction / Tension elongation at break
perpendicular to flow (EB)} ≦ 1.
5
[0135]
[Compression set (%)]: Using a 120 mm × 120 mm × 2 mm sheet-like molded article produced
by the above [loss tangent (tan δ)], in accordance with JIS K6262, at a temperature of 70 ° C.
for 22 hours taking measurement.
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[0136]
[Oil bleed property]: A 120 mm × 120 mm × 2 mm sheet-like molded article produced in the
above [Loss tangent (tan δ)] was put into a gear oven heated to 60 ° C. and was heated for 168
hours.
After 168 hours, observe whether liquid bleed out occurs on the surface of the molded article.
When a liquid bleed out was observed, (D) the second mineral oil-based softener, that is, the oil
was bled out and appearance defects occurred, so the oil bleed property was evaluated as poor
× . When no bleed-out was observed, (D) the second mineral oil-based softener, that is, the
oil had not bled out and maintained a good appearance, so the oil bleed property was good. It is
evaluated as "o".
[0137]
[Recycling Properties]: A 120 mm × 120 mm × 2 mm sheet-like molded article produced by the
above [loss tangent (tan δ)] is punched into a dumbbell-like No. 3 shape in accordance with JISK6251 to produce a test piece. The test piece is set to a temperature of 160 to 250 ° C. which is
a temperature used when recycling the thermoplastic elastomer composition, and the presence
or absence of the plastic deformation property is observed. When the plastic deformation
characteristic is recognized, that is, when the test specimen is melted and deformed, it is
evaluated that the recycling characteristic is good "o", and when the plastic deformation
characteristic is not recognized, that is, the molten deformation of the specimen is not observed
The case was evaluated as having a recycling property of "bad".
[0138]
Synthesis Example 1 [(A) Preparation of Oil-Extended Ethylene-Based Copolymer]: Using a 10liter stainless steel autoclave equipped with a stirrer, which is previously purged with nitrogen,
and co-flowed continuously under a pressure of 1 MPa. The polymerization reaction was carried
out. While continuously supplying hexane as a polymerization solvent at a rate of 65 L / hr from
the feed port at the lower part of the above-mentioned autoclave, ethylene, propylene and 5ethylidene-2-norbornene are each 0.80 Nm <3>, 2 / hr. The solution was continuously fed at a
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rate of 0.1 L and 0.1 L. At the same time, the catalyst ethylaluminum sesquichloride and
vanadium trichloride are continuously supplied at a rate of 13.85 g / hr and 0.384 g / hr,
respectively, and hydrogen as a molecular weight modifier is a velocity of 0.4 NL / hr. Supply
continuously. The polymerization temperature in the autoclave was kept at 22 ° C. for
copolymerization. After termination of the reaction, the polymer (ethylene-based copolymer)
obtained by the copolymerization reaction was transferred into another storage machine. To 100
parts of this copolymer, 120 parts of "Diana Process PW 90" (trade name) manufactured by
Idemitsu Kosan Co., Ltd. is added as a first mineral oil-based softener, and the mixture is stirred
to obtain a copolymer rubber by steam stripping. Were deposited to prepare an oil-extended
ethylene-based copolymer (a-1) as the (A) oil-extended ethylene-based copolymer.
[0139]
With respect to the ethylene-based copolymer contained in the produced oil-extended ethylenebased copolymer (a-1), the above-mentioned intrinsic viscosity [極限], the ratio of weight average
molecular weight (Mw) to number average molecular weight (Mn) (Mw / Each evaluation of the
value of Mn) and the area ratio of the area ¦ region of 100,000 or less molecular weight
converted into polystyrene was performed. As the evaluation result, the intrinsic viscosity [η] is
6.7, the value of the ratio (Mw / Mn) of weight average molecular weight (Mw) to number
average molecular weight (Mn) is 2.4, and it is converted to polystyrene The area ratio of the
area having a molecular weight of 100,000 or less was 0.5%. Moreover, the ethylene-based
copolymer contained in the oil-extended ethylene-based copolymer (a-1) is a structural unit
derived from ethylene (shown as "ethylene" in Table 1), a structural unit derived from propylene
(Table Structural units derived from propylene in 1 and 5-ethylidene-2-norbornene
(indicated as 5-ethylidene-2-norbornene in Table 1) are each 100% of all structural units
Against 67%, 26.5% and 6.5%.
[0140]
(Synthesis Examples 2, 4 and 5) The amounts of ethylene, propylene, 5-ethylidene-2-norbornene,
ethylaluminum sesquichloride, vanadium trichloride, hydrogen supplied, and polymerization
temperature were adjusted so as to obtain the formulation shown in Table 1. Oil-extended
ethylene copolymers (a-2), (a-4) and (a-5) were prepared in the same manner as in Synthesis
Example 1.
[0141]
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[0142]
Synthesis Example 3 Continuous supply of ethylene, propylene and 5-ethylidene-2-norbornene at
a rate of 0.75 Nm <3>, 1.4 L and 0.10 L / hr, respectively, as a catalyst Continuously feeding
vanadium chloride at a rate of 1.216 g / hr, continuously feeding hydrogen at a rate of 0.06 NL /
hr, copolymerizing while maintaining the polymerization temperature at 30 ° C., An oil-extended
ethylene-based copolymer (a-3) was produced in the same manner as in Synthesis Example 1
except that the amount of the first mineral oil-based softener added was 100 parts.
[0143]
The ethylene-based copolymer contained in the produced oil-extended ethylene-based copolymer
(a-3) has an intrinsic viscosity [η] of 4.7, and a weight average molecular weight (Mw) and a
number average molecular weight (Mn) The ratio of (Mw / Mn) was 3.7, and the area ratio of the
region having a molecular weight of 100,000 or less converted to polystyrene was 3.2%.
[0144]
Said each evaluation was performed about the produced oil-extended ethylene-type copolymer
(a-1)-(a-5).
The evaluation results are shown in Table 1.
[0145]
(B) α-olefin-based thermoplastic resin (that is, α-olefin-based crystalline thermoplastic resin
(b1) and α-olefin-based amorphous thermoplastic resin) used in the following examples and
comparative examples (B2)), (C) crosslinking agent, crosslinking aid, (D) first mineral oil softener,
(E-1) ethylene / α-olefin copolymer rubber, (E-2) isobutylene-isoprene The copolymer rubber, (E3) styrenic thermoplastic elastomer, and (F) anti-aging agent will be described below.
[0146]
As the α-olefin crystalline thermoplastic resin (b1), a propylene / ethylene random copolymer
(trade name Prime Polypro B 241 manufactured by Prime Polymer Co., density 0.91 g / cm
<3>, MFR (temperature 230) ° C, load 2.16 kg) 0.5 g / 10 min, shown in Table 2 as b-1-1 ),
propylene / ethylene copolymer (trade name Novatec PP BC 08 AHA, manufactured by Japan
Polypropylene Corp., density 0.90 g / cm <3>, MFR (temperature 230 [deg.] C., load 2.16 kg) 80
g / 10 min., Indicated in Table 2 as "b-1-2" are used.
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[0147]
As the α-olefin type amorphous thermoplastic resin (b2), a propylene / 1-butene amorphous
copolymer (trade name REXTAC RT2780 , manufactured by Huntsman, density 0.87 g / cm
<3>, 190 Melt viscosity of 8000 mPa · s, indicated in Table 2 as "b-2") is used.
[0148]
As the crosslinking agent (C-1), a mixture of 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3 and
silica (trade name "Perhexin 25B-40", manufactured by Nippon Oil and Fats Co., Ltd. , C-1 in
Table 2) is used.
[0149]
As the cross-linking coagent (C-2), divinylbenzene (trade name "divinylbenzene (81%)",
manufactured by Nippon Steel Chemical Co., Ltd., shown as "c-2" in Table 2) is used.
[0150]
A trade name "Diana Process Oil PW90" manufactured by Idemitsu Kosan Co., Ltd. is used as the
first mineral oil-based softener and the second mineral oil-based softener.
[0151]
(E-1) As ethylene / α-olefin copolymer rubber, ethylene / α-olefin copolymer rubber: EPDM, 66
mass% of constituent units derived from ethylene, derived from 5-ethylidene-2-norbornene The
intrinsic viscosity of 1.9 dl / g measured in a decalin solvent having a constituent unit of 4.5% by
mass and 135 ° C. is used.
It shows as "E-1" in Table 2.
[0152]
(E-2) As an isobutylene-isoprene copolymer rubber, butyl rubber (trade name Butyl 268
manufactured by JSR, ratio of structural units derived from isoprene = 1.5 mol%, Mooney
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,
viscosity ML1 + 8 (125 ° C.) = 5 Use).
It shows as "E-2" in Table 2.
[0153]
(E-3) As a styrene-based thermoplastic elastomer, styrene-isoprene copolymer (trade name
"HYBRAR 5127" manufactured by Kuraray Co., Ltd., styrene content 20%, MFR (load at 190 ° C
2.16 kg) = 5 g / 10 min , Soft segment uses vinyl-polyisoprene).
It shows as "E-3" in Table 2.
[0154]
(F) As anti-aging agent, pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate]
(trade name "Irganox 1010", manufactured by Ciba Specialty Chemicals) Use
It shows as "F" in Table 2.
[0155]
(Example 1) (a-1) 60 parts of an oil-extended ethylene copolymer, (b-1-1) α-olefin, in a pressure
type kneader (volume: 10 liters, manufactured by Moriyama Co., Ltd.) heated to 150 ° C. -Based
crystalline thermoplastic resin 7 parts, (b-1-2) α-olefin based crystalline thermoplastic resin 6
parts, (b-2) α-olefin based amorphous thermoplastic resin 7 parts, first mineral 10 parts of oilbased softener, 10 parts of (E-1) ethylene / α-olefin copolymer rubber, and 0.1 part of (F) antiaging agent were added.
[0156]
Thereafter, the mixture is kneaded for 15 minutes at 40 rpm (shear rate 200 / sec) until the (b)
α-olefin thermoplastic resin melts and the components added to the above kneader are
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uniformly dispersed, and kneading in the molten state Thing (raw material composition) was
obtained.
The obtained melt-kneaded product was pelletized using a feeder ruder (manufactured by
Moriyama Co., Ltd.).
[0157]
100 parts of the pelletized kneaded product, 1 part of the (C-1) crosslinking agent, and 0.9 parts
of the (C-2) crosslinking aid were charged into a Henschel mixer and mixed for 30 seconds.
Thereafter, using a twin-screw extruder (co-directional complete meshing screw, L / D = 33.5,
manufactured by Ikegai Co., Ltd.), residence time: 1 minute 30 seconds, 300 rpm, (shear speed
400 / second) Dynamic heat treatment was carried out under the conditions of 2.) to obtain a
pellet-like thermoplastic elastomer composition.
[0158]
The above evaluation results for the thermoplastic elastomer composition of this example are:
loss tangent (tan δ) 0.13, melt flow rate (MFR) 25 g / 10 min, hardness 61, tensile breaking
strength in the flow direction ( TB) 5.3MPa, tensile elongation at break (EB) in the flow direction
500%, tensile rupture strength perpendicular to the flow (TB) 5.6MPa, tensile elongation at break
perpendicular to the flow (EB) ), The anisotropy of tensile elongation at break is 1.1, the
compression set is 31%, the evaluation of the oil bleeding property is o , and the evaluation of
the recycling property is o .
[0159]
(Examples 2 to 4 and Comparative Examples 1 to 7) Thermoplastic elastomer compositions (II) to
(X) were obtained in the same manner as in Example 1 except that the formulation was made as
shown in Table 2.
Said each evaluation was performed about obtained thermoplastic elastomer composition (II)-(X).
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The evaluation results are shown in Table 3.
[0160]
[0161]
[0162]
As is clear from Table 3, the thermoplastic elastomer compositions (I) to (IV) of Examples 1 to 4
are different from the thermoplastic elastomer compositions (V) to (X) of Comparative Examples
1 to 7, respectively. Since the loss tangent (tan δ) was good, it was confirmed to have excellent
vibrational absorptivity, small anisotropy in tensile elongation at break, and good oil bleedability,
mechanical properties and recycling characteristics.
[0163]
On the other hand, Comparative Example 1 thermoplastic elastomer composition (V) has an
intrinsic viscosity [η] value of an ethylene copolymer contained in an oil-extended ethylene
copolymer, and a Mw / Mn value of Since it is out of the range, the mechanical properties and
the oil bleeding property are inferior to those of the thermoplastic elastomer composition (III) of
Example 3.
In the thermoplastic elastomer composition (VI) of Comparative Example 2, the Mw / Mn value of
the ethylene-based copolymer contained in the oil-extended ethylene-based copolymer is outside
the range of the present invention. Compared to the thermoplastic elastomer composition (III), it
has inferior oil bleeding properties.
In the thermoplastic elastomer composition (VII) of Comparative Example 3, the value of the
intrinsic viscosity [η] of the ethylene-based copolymer contained in the oil-extended ethylenebased copolymer is outside the scope of the present invention, so Example 3 Compared with the
thermoplastic elastomer composition (III) of the above, it has inferior vibration absorption,
mechanical properties, and oil bleedability.
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In the thermoplastic elastomer composition of Comparative Example 4, the content of the αolefin-based thermoplastic resin was out of the range of the present invention, so it was
impossible to produce the thermoplastic elastomer composition.
In the thermoplastic elastomer composition (VIII) of Comparative Example 5, the content of the
α-olefin thermoplastic resin is out of the range of the present invention, and thus, the
thermoplastic elastomer composition (VIII) of Comparative Example 5 is compared with the
thermoplastic elastomer composition (III) of Example 3. Poor in vibration absorption.
The thermoplastic elastomer composition (IX) of Comparative Example 6 is compared with the
thermoplastic elastomer composition (III) of Example 3 because the content of the (E) damping
property-imparting material is out of the range of the present invention. Poor in vibration
absorption.
The thermoplastic elastomer composition (X) of Comparative Example 7 is compared with the
thermoplastic elastomer composition (III) of Example 3 because the content of the (E) damping
material is outside the range of the present invention. Poor in oil bleeding.
[0164]
The thermoplastic elastomer composition of the present invention can be suitably used, for
example, as a material of a thin-walled molded article such as an edge member of a speaker.
[0165]
It is a figure which shows the chromatogram obtained by analyzing an ethylene-type copolymer
by gel permeation chromatography.
It is a top view showing one embodiment of the speaker member manufactured by the
manufacturing method of the speaker member of the present invention.
Explanation of sign
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[0166]
1: Elution curve, T1: Time for elution of a component with a molecular weight of 100,000
converted to polystyrene, S1: Area of a portion detected after the elution time T1, ST: Total area
surrounded by the elution curve 1 and the horizontal axis, 10: speaker member, 11: diaphragm,
12: edge member, d: width.
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