THERMOPLASTIC POLYMER COMPOSITION, AND ARTICLE AND ELECTRIC WIRE
COMPRISING THE SAME
5
The present -invention relates to a flame-retardant polymer
composition comprising an ethylene/unsaturated ester copolymer,
10 a propylene-based polymer and a filler; an article comprising the
composition; and an electric wire and electric cable comprising
the composition. The present invention also relates to a
composition excellent in the balance among mechanical strength,
elongation at break, hardness, flexibility and heat resistance;
15 an article comprising the composition; and an electric wire and
electric cable having an insulator and/or a sheath compr ising the
composition.
20 [0002]
Propylene-based polymers are excellent in heat resistance,
mechanical strength and scratch resistance, and articles obtained
therefrom are used in a wide range of applications. Articles
obtained from general resin compositions composed of
SFw 2366
polypropylene and inorganicfillers are also excellent in heat
resistance and mechanical properties, but are poor in flexibility
and impact resistance. For this reason, ethylene copolymers are
primarily used in applications requiring properties such as
5 flexibility and impact resistance. However, articles obtained
from the ethylene copolymers are poor in scratch resistance and
heat resistance.
[0003]
To overcome this problem, an article composed of a
10 propylene-based polymer and an inorganic filler
(flame--retardant) is known as an electric wire and electric cable
or a wire and electric cable harness that requires scratch
resistance (Patent Literature 1)a
[0004]
15 It is also known that polypropylene is blended with a
propylene/butene copolymer, polyethylene and an inorganic filler
(Patent Literature 2).
[0005]
It is also known that a propylene-based polymer is blended
20 with an ethylene/a-olefin random copolymer elastomer or a styrene
elastomer together with an inorganic filler (Patent Literature
3).
[0006]
On the other hand, it is known that an ethylene/vinyl- acetate
SF-2366
copolymer is blended with polypropylene, a maleic acid--modified
polyethylene and a metal hydrate to form a composition (Patent
Literatures 4 to 8)4
[0007]
5 Various improvements have been made as described above for
thermoplastic polymer compositions using a propylene-based
polymer and an ethylene/vinyl acetate copolymer. Still, there
is demand for a composition further excellent in the balance among
mechanical properties, hardness, flexibility and heat resistance,
I0 an article comprising the composition, and an electric wire and
electric cable having an insulator and/or a sheath comprising the
composition.
CITATION LIST
15
[0008]
[Patent Literature 1] JP°A-2003--313377
[Patent Literature 2] JP-AG2008-97918
[Patent Literature 3] JP-A--2008-169257
20 [Patent Literature 4] JP--A---2008--94977
[Patent Literature 5] JP---A-2009---114230
[Patent Literature 6] JP-A-2009-54388
[Patent Literature 7] JP°-A---2009---19:L90
[Patent Literature 8] JP---A-2009---.216836
SF 2366
4
I OF THE INVENTION
?1&c W, , i r, r-i
[00091
5 It is an object of the present invention to provide a
thermoplastic polymer composition excellent in the balance among
mechanical strength, elongation at break, flexibility and heat
resistance. It is another object of the present invent-.ion to
provide an article comprising the composition, and an electric
10 wire and electric cable having an insulator and/or a sheath
comprising the composition.
SOLUTION TO PROBLEM
[00101
15 The present invention is based on the finding that the
combination of an ethylene/vinyl ester copolymer with a ;pecific
propylene-based polymer achieves good filler containability of
a filler, specifically, good dispersibility of an inorganic filler
in a thermoplastic polymer composition, and provides a
20 thermoplastic polymer composition excellent in the balance among
mechanical strength, elongation at break, flexibility and heat
resistance. Further, the present invention is based on the
finding that the use of such a specific thermoplastic polymer
composition provides an article excellent in the balance among
SF-2366
mechanical strength, elongation at break, flexibility and heat
resistance. The present invention has been completed based on
the findings.
[0011]
5 That is, the present invention relates to a thermoplastic
polymer composition comprising 1 to 350 parts by mass of a filler
(D) with respect to 100 parts by mass of polymer components that
comprise 50 to 90% by mass of an ethylene/unsaturated ester
copolymer (A) ; 1 to 40% by mass of a propylene--based polymer (B)
10 having a melting point as measured by differential scanning
calorimetry (DSC) of from 120 to 170°C; and 1 to 49% by mass of
a propylene-based polymer (C) having a melting point as measured
by differential scanning calorimetry (DSC) of lower than 120°C
or not being observed, provided that the total amount of (A), (B)
15 and (C) is 100% by mass.
[0012]
In a preferable embodiment of the present invention, the
propylene based polymers (C) are a propylene/ethylene random
copolymer (C-0), a ,propylene/C4-20 .-olefin random copolymer
20 (C-1) , and a propylene/ethylene/C4---20 a---olefin random copolymer
(C 2), and have (a) a molecular weight distribution (Mw/Mn) as
measured by gel permeation chromatography (GPC) of 1 to 3.
[001.3]
In a desirable embodiment of the present invention, the
SF--2366
6
propylene/C4-20 a----olefin random copolymer (C-1) satisfies the
following requirement (b)o
(b) the melting point Tm(°C) and the content M (mol%) of
a comonomer structural unit as determined by 13C-NMR spectrum
measurement satisfy the equation (I)-
(1) 146exp (-0 n 022M) > Tm > 125exp (°0 e 032M) ,
wherein Tm is lower than 120°C.
[0014]
In a desirable embodiment of the present invention, the
10 propylene/ethylene/C4--20 acolefi.n random copolymer (C-2)
satisfies the following requirement (n)-
(n) the propylene/ethylene/C4-20 a---olefin random copolymer
(C-2) contains 40 to 85 mol% of a structural unit derived from
propylene, 5 to 30 mol% of a structural unit derived from ethylene,
15 and 5 to 30 mol% of a structural unit derived from 04.20 a-olefi
provided that the total amount of the structural unit der ved from
propylene, the structural unit derived from ethylene and the
structural unit derived from C4-20 a-olefins is 100 mol%,
[0015]
20 In a desirable embodiment of the present invention, the
filler (D) is at least one filler selected from metal hydroxides,
metal carbonates and metal oxides.
[0016]
In a desirable embodiment of the present invention, the
SF-2366
7
filler (D) is selected from at least one filler selected from
organic phosphinic acid salts and polyphosphor salts.
[0017]
In a desirable embodiment of the present invention, the
5 ethylene/unsaturated ester copolymer (A) is a copolymer of
ethylene and a vinyl ester compound, more desirably a copolymer
of ethylene and vinyl acetate that has a vinyl acetate content
of from 25% by mass and up to 50% by mass.
[0018]
10 In a desirable embodiment of the present invention, the
ethylene/unsaturated ester copolymer (A) is a copolymer of
ethylene and a vinyl ester compound, more desirably a copolymer
of ethylene and vinyl acetate.
[0019]
15 In another embodiment of the present invention, these
thermoplastic polymer compositions further comprise a modified
olefin polymer (E), wherein the proportion of a vinyl compound
having a polar group according to the modification is 0.01 to 10
parts by mass based on 100 parts by mass of the total of (A) , (B) ,
20 (C) and (E)a
[0020]
The present invention further relates to an article
comprising the thermoplastic polymer composition, and the article
relates to an insulator of an electric wire and electric cable
SE-2366
8
or an electric wire and electric cable sheath.
ADVANTAGEOUS TS OF THE LJ 1i o; o
[0021]
5 The thermoplastic polymer composition of the present
invention provides performance excellent in the balance among
mechanical strength, elongation at break, flexibility and heat
resistance, and is widely applicable to articles, par-i.-icularly
suitable for electric wires and electric cables and the like.
10
[0022]
Hereinafter, the thermoplastic polymer composition of the
present invention is described.
15 Ethylene/unsaturated ester copolymer (A)_
An example of the ethylene/unsaturated ester copolymer (A)
used in the thermoplastic polymer composition of the present
invention is a copolymer of ethylene and a vinyl ester such as
vinyl acetate and vinyl propionate, or a copolymer of ethylene
20 and an alkyl ester having carbon atoms of about 20 or less of an
unsaturated carboxylic acid such as acrylic acid, methacrylic acid,
malefic acid, maleic anhydride, fumaric acid, itaconic acid and
itaconic anhydride. Specific examples of the copolymers include
copolymers of ethylene and unsaturated carboxylic acid esters such
SF-2:366
9
as methyl acrylate, ethyl acrylate, isopropyl acrylate, n -propyl
acrylate, i_sobutyl acrylate, n-butyl acrylate, 2-ethylhexyl
acrylate, methyl methacrylate, ethyl methacrylate, isobutyl
methacrylate, n-butyl methacrylate, glycidyl methacrylate,
5 dimethyl maleate and diethyl maleateo
[0025]
In addition to being the binary copolymers as described
above, the ethylene/unsaturated ester copolymer (A) may be a
multicomponent copolymer obtained by copolymerizing ethylene and
10 two or more kinds of compounds selected from the above unsaturated
ester compounds. Furthermore, as long as the properties of the
ethylene/unsaturated ester copolymer are not substantially
changed, other polar monomers may be copolymerized in a small
amount, such as acrylic acid, methacrylic acid, malefic acid,
15 itaconic acid, maleic anhydride, itaconic anhydride and carbon
monoxide.
[0024]
In the present invention, among these, a copolymer of
ethylene and a vinyl, ester compound is preferable, examples of
20 which include ethylene/vinyl acetate copolymer and
ethylene/vinyl propionate copolymer.
[0025]
In the present: invention, the proportion of the unsaturated
ester compound unit in the ethylene/unsaturated ester is usually
SF-2366
10
5 to 70% by mass, more preferably 15 to 60% by mass, still more
preferably 25 to 50% by mass. When the proportion of the
unsaturated ester compound is within these ranges, the balance
between mechanical strength and flame retardance is excellent.
5 If the proportion of the unsaturated ester compound is less than
15% by mass, flame retardance tends to be reduced. If the
proportion of the unsaturated ester compound is more than 60% by
mass, mechanical strength tends to be reduced.
[0026]
10 The ethylene/unsaturated ester copolymer (A) used in the
present invention preferably has a melt flow rate (190°C, 2160
g load: in accordance with JIS K7210-99) of 0.1 to 50 g/10 min,
particularly preferably 0.5 to 10 g/10 min, in view of properties,
processability and the like of the resulting composition.
15 [0027]
The ethylene/unsaturated ester copolymer (A) may be
obtained by performing radical copolymerization of ethylene and
an unsaturated ester compound at high temperature under high
pressure.
20 [0028]
For example, a copolymer with good random property produced
by high-pressure radical polymerization process using a common
autoclave method may be used,,
Propylene-based polymer (B)
SF--2366
11
An example of the propylene-based polymer (B) used in the
present invention is a propylene homopolymer or a copolymer of
propylene and at least one C2-20 u-olefin excluding propylene.
[0029]
Examples of the C2--20 a-olefin excluding propylene include
ethylene, 1-butene, 1-pentene, 1--hexene, 4-methyl-l--pentene,
l-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene,
l-octadecene and 1-eicosene. Preferred is ethylene or a C4-10
a--olefin. These asolefins may form a random copolymer or a block
10 copolymer with propylene.
[0030]
The structural unit derived from these a---olefins may be
contained in an amount of not more than 35 mol%, preferably not
more than 30 moi%, in all the structural units of the
15 propylene-based polymer
[0031]
The propylene-based polymer (B) usually has a melt flow rate
as measured at a temperature of 230 °C under a load of 2.16 kg in
accordance with ASTM D 1238 (MFR) of 0001 to 1000 g/10 min,
20 preferably 0.05 to 100 g/10 min, more preferably 0.1 to 50 g/10
min.
[0032]
The propylene---based polymer (B) used in the present
nven-C, i on has a meeleting point as measured by differ_ent_iial scanning
SF'---2366
12
calorimetry (DSC) of from 120 to 170°C, preferably 125 to 165°C..
[0033]
The propylene-based polymer (B) may have an isotactic
structure or a syndiotactic structure, but preferably has an
isotactic structure in terms of heat resistance and the like.
[0034]
As required, a plurality of propylene-based polymers (B)
may be used in combination.- for example, two or more kinds of
components differing in melting point and rigidity may be used.
10 [0035]
In order to obtain desired properties, the propylene-based
polymer (B) may be selected from.-
homopolypropylene excellent in heat resistance (usually,
a known polymer containing not more than 3 mol% of a
15 copolymerizable component other than propylene),
block polypropylene excellent in the balance between heat
resistance and impact resistance (usually, a known polymer
containing 3 to 30% by mass of a n-decane soluble component) , and
random polypropylene excellent in the balance between
20 flexibility and transparency (usually, a known polymer having a
melting peak temperature as measured by differential scanning
calorimetry (DSC) of not lower than 120°C, preferably 125°C to
150°C) These may be used in combination.
[0036]
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13
The propylene-based polymer (B) may be produced by
polymerizing propylene or by copolymerizing propylene and another
olefin for example with the use of a Ziegler catalyst system
comprising a solid catalyst component containing magnesium,
5 titanium, a halogen and an electron donor as an essential component,
an organoaluminum compound and an electron donor, or with the use
of a metallocene catalyst system using a metallocene compound as
a catalyst component.
Propylene-based polymer (C)
10 An example of the propylene-based polymer (C) used in the
present invention is a propylene homopolymer or a copolymer of
a propylene and at least one C2-20 olefin excluding propylene.
The C2-20 a-olefins excluding propylene may be similar to those
mentioned for the propylene-based polymer (B), and preferable
15 ranges thereof may be similar to those mentioned for the
propylene-based polymer (B) a These a-olefins may form a random
copolymer or a block copolymer with propylene.
[0037]
The propylene-based polymer (C) contains a structural unit
20 derived from propylene usually in an amount of 40 to 100 mol%,
preferably 40 to 99 mol%, more preferably 40 Lo 92 mol%, still
more preferably 50 to 90 mol%; and a structural unit derived from
C2-20 a---olefins excluding propylene used as a comonomer usually
in, an amount of 0 to 60 mol%, preferably 1 to 60 mol o, more
SF-2366
14
preferably 8 to 60 mol%, still more preferably 10 to 50 mol%,
provided that the total amount of propylene and the C2-20 a---olefin
is 100 mol%o
[0038]
5 The propylene-based polymer (C) used in the present
invention usually has a melt flow rate (MFR, ASTM D1238,
temperature 230'C, under a load of 2. 16 kg) of 0. 1 to 50 g/10 min
The propylene-basedpolymer (C) has a melting point as measured
by differential scanning calorimetry (DSC) of lower than 120°C,
10 more preferably from 40°C to lower than 110°C, still more
preferably 60°C to 100°C. In another embodiment, the
propylene--based polymer (C) preferably has a melting point that
is not observed.
[0039]
15 Here, the melting point not being observed means that the
crystal melting perik having a crystal, heat of fusion of not less
than 1 J/g is not observed in the range of from f-150 to 200°C.
Measurement conditions are as described in Examples.
[0040]
20 The propylene-based polymer (C) usually has an intrinsic
viscosity [g] as measured in decalin at 135 °C of 0.01 to 10 dl/g,
preferably 0005 to 10 dl/g. The propylene-based polymer (C)
preferably has a triad tacticity (mm fraction) as measured by
13C-°NMR of 85% or more, more preferably 85 to 97.5%, still more
SE'-2366
15
preferably 87 to 97%, particularly preferably 90 to 97%. When
the triad tacticity (mm fraction) is within these ranges, in
particular the balance between flexibility and mechanical
strength is excellent, and thus these ranges are preferred in the
present invention. The mm fraction can be measured by a method
described in page 21, line 7 to page 26, line 6 of WO 2004-087775.
[0041]
The propylene based polymer (C) may be produced by ^-i method
which is not particularly limited, but may be produced, for example,
10 by polymerizing propylene or by copolymerizing propylene and
another a--olefin in the presence of a known catalyst capable of
polymerizing u --olefins so as to have stereoregularity, i.e., an
isotactic structure or a syndiotactic structure, for example, a
catalyst containing a solid titanium component and an organic
15 metal compound as a main component, or a metallocene catalyst using
a metallocene compound as a catalyst component.. The
propylene--based polymer (C) may be produced by polymerizing
propylene or by copolymerizing propylene and another a-olefin in
the presence of a known catalyst capable of polymerizing olefins
20 so as to have an. atactic structure. The propylene=based polymer
(C) is preferably obtained by copolymerizing propylene and a C2°20
u-olefin excluding propylene in the presence of a metallocene
catalyst, as is described later.
[0042]
SF-2366
16
A specific example of the propylene-based polymer (C) having
features as described above is at least one selected from a
propylene/ethylene random copolymer (C---0), a propylene/C4-20
a-olefin random copolymer (C--1) and a propylene/ethylene/C4---20
a---olefin random copolymer (C-2)
[0043]
The use of the propylene/ethylene random copolymer (C--O)
or the propylene/C4-20 a-olefin random copolymer (C-_I.), for
example allows for exhibiting the compatibility with a
10 polypropylene crystalline component contained in the
propylene-based polymer (B), and leads to the provision of a
thermoplastic polymer composition further excellent in
mechanical strength, elongation at break, and scratch resistance.
[0044]
15 The propylene/ethylene/C4-20 a--.olefin random copolymer
(C-2) also has compatibility with a crystalline component of
polypropylene, as is the case with the propylene/C4-20 e-olefin
random copolymer (C-.1) The use of the propylene/ethylene/C4--20
a-olefin random copolymer (C-2) provides a thermoplastic polymer
20 resin composition further excellent in flexibility, elongation
at break and scratch resistance.
[0045]
The propylene/ethylene random copolymer (C-0), the
propylene/C4----20 a--olefin random copolymer (C----1) and
SF'--2366
1 '7
propylene/ethylene/C4--20 e olefin random copolymer (C--.2), each
of which is preferably used in the present invention, desirably
have (a) a molecular weight distribution (Mw/Mn) as measured by
gel permeation chromatography (GPC) of 1 to 3.
5 Propylene/ethylene random copolymer (C-0)
The propylene/ethylene random copolymer (CFO) preferably
used in the present invention is a random copolymer obtained by
randomly copolymerizing propylene and ethylene, and contains a
structural unit derived from propylene usually in an amount of
10 50 to 95 mol%, preferably 55 to 90 molt, more preferably 60 to
88 molt; arid a structural unit derived from ethylene used as a
comonomer usually in an amount of 5 to 50 molt, preferably 10 to
45 mol%, more preferably 12 to 40 molt, provided that the total
amount of propylene and ethylene is 100 molt.
15 Propylene/C4-20 a--olefin random copolymer (C-1)
An example of k:he propylene/C4-20 a-olefin random copolymer
(C-1) preferably used in the present invention is a copolymer of
propylene and at least one C4a-,20 a---olefin excluding propylene.
Examples of the C4:20 a-olefin excluding propylene include
20 1-,butene, 1-pentene, 1_-,hexene, 4-methyl---la--pentene, 1-ocLene,
1Gdecene, l-dodecene, l-tetradecene, 1-hexadecene, 1-octadecene
and l-eicosen.ea Among the propylene/C4-20 a--olefin random
copolymers (C -- 1) , a preferred propylene/C4---20 a--,olefin random
copolymer (C-1) satisfies the following requirement (b)-.
SF-2366
:1.8
(b) -the melting pointTm (°C) and the content M (mol%) of
a. comonomer structural unit as determined by 13C"NMR spectrum
measurement satisfy the equation (1)-
(1) 146exp(---00022M) ^ Tm > 125exp(-00032M), wherein I'm is
lower than 120°C, preferably not higher than 100°C.
[0046]
The melting point Tm of the propylene/C4-20 a-olefin random
copolymer (C-1) is measured by DSC as follows- a sample is put
in an aluminum pan, and heated at 100 °C/min to 200 °C, kept at 200 °C
10 for 5 minutes, and then cooled at 10°C /min to -150'C and thereafter
heated at 10°C/min to 200°C; a temperature of an endothermic peak
observed during the second heating is given as a melting point
Tma The propylene/C4---20 (Y-olefin random copolymer (C-l) usually
has a melting point 'I'm of lower than 12.0°C, preferably not higher
15 than 100°C, more preferably 40 to 95°C, still more preferably 50
to 90°C, When the melting point Tat is within these ranges, an
article excellent particularly in the balance between flexibility
and strength is obtained, and moreover, the resulting article has
a surface with suppressed tackiness, and thus the article
20 comprising the composition of the present invention is easy to
apply.
[0047]
in a preferable embodiment, the propylene/C4-20 a--olefin
random copolymer (C----1) further has a (c) crystallinity as measured
SF'---2366
19
by X-ray diffraction of not higher than 40%, more preferably not
higher than 35%.
[0048]
The propylene/C4-20 a-olefin random copolymer (C-1)
contains a structural unit derived from C4-20 a--olefins preferably
in an amount of 5 to 50 mol%, more preferably 10 to 35 mol o o In
particular, the C4-20 a'olefin is preferably l-butene.
[0049]
Such a propylene-based polymer may be obtained by a method
10 described in, for example, WO 2004/87775.
Propylene/ethylene/C4-20 a-olefin random copolymer (C--2)
An example of the propylene/ethylene/C4-20 u--olefin random
copolymer (C-2) preferably used in the present invention is a
copolymer of propylene, ethylene and at least one C4-20 a--olefin
15 excluding propylene. As the C4-20 a-olef in excluding propylene,
those mentioned for Lhepropylene/C4-20e olefin random copolymer
(C---1) can be mentioned.
[0050]
The propylene/ethylene/C4---20 a-olefin random copolymer
20 (C-2) suitably used in the present invention satisfies the
following requirement (n)W
(n) the propylene/ethylene /C4-20 a-olefin random copolymer
(C-2) contains 40 to 85 mol% of a structural unit derived from
propylene, 5 to 30 mol% of a structural unit derived fro-rri etthy l_ene,
SF---2366
20
5 to 30 m.ol% of a structural unit derived from C4-20 a--olefins,
provided that the total amount of the structural unit derived from
propylene, the structural unit derived from ethylene and the
structural unit derived from C4-20 a-olefins is 100 mol%o The
total amount of the structural unit derived from ethylene and the
structural unit derived from C4-20 asolefins is preferably 60 to
15 mol%A
[0051]
It is desirable that the propylene/ethylene/C4-20 a-olefin
10 random copolymer (C---2) further satisfies at least one of the
following requirements (o) and (p) , more preferably both of the
following requirements (o) and (p)a
(o) Shore A hardness is 30 to 90, preferably 35 to 60.
(p) The crystallinity as measured by X---ray diffraction is
15 not higher than 20%, preferably not higher than. 10%.
[0052]
The propylene/ethylene/C4 --20 a=olefin random copolymer
(C-2) desirably has a melting point Tm as measured by DSC of not
higher than 50°C or not being observed. The melting point not
20 being observed is more preferable. The melting point can be
measured in the same manner as described for the copolymer (C-1)
[0053]
The amount of the propylene component and the amount of the
other comonomer components are described in more detail as follow
SF-2366
21
It is desirable that the structural unit derived from propylene
is contained preferably in an amount of 60 to 82 mol%, more
preferably 61 to 75 mol%; the structural unit derived from ethylene
is contained preferably in an amount of 8 to 15 mol%, more
5 preferably 10 to 14 mol%; and the structural unit derived from
C4-20 a-olefins is contained preferably in an amount of 10 to 25
mol%, more preferably 15 to 25 mol%, provided that the total amount
of the structural unit derived from propylene, the structural unit
derived from ethylene and the structural unit derived from C4-20
10 a-olefins is 100 mol%o In particular, the C4-20 a---olefin is
preferably 1-butene.
[0054]
The propylene /ethylene /a49olefin random copolymer (C-2) may
be obtained by a method described in, for example, WO 2004/87775.
15 [0055]
In the present invention, the use ooof the
propylene/ethylene/C4-20 a---olefin random copolymer (C-2)
provides an article having further improved flexibility, larger
elongation at break and lower embrittlement--temperature in low
20 temperature environment. For example, in the case where this
article is an electric wire and electric cable, even when exposed
to low temperature, the electric wire and electric cable coating
hardly undergoes cracking.
[0056]
SF--2366
22
The propylene-based polymer (C), specific examples of which
include the propylene/ethylene random copolymer (C-0), the
propylene/C4-20 a-olefin random copolymer (C-1) and the
propylene/ethylene/C4-20 a--olefin random copolymer (C-2), may be
5 a polymer obtained by modifying part of or whole of the
propylene=based polymer (C) with a vinyl compound having a polar
group described later, as required.
[0057]
The vinyl compound having a polar group and the modification
10 method that are employable in this case may be a vinyl compound
having a polar group and a modification method that, are employed
for a modified olefin polymer (F) described later.
Filler (D)
The filler (D) used in the present invention is not
15 particularly limited, and may be various fillers including general
inorganic fillers and organic fillers that (,:rve as
flame-retardants, molding assistants, slip agent and the like.
[0058]
Among these, when inorganic fillers are used, at least one
20 inorganic filler selected from metal hydroxides, metal carbonates
and metal oxides is preferred.
[0059]
he metal hydroxides used in the present invention, which
are not particularly limited, include aluminum hydroxide,
SF 2366
23
magnesium hydroxide, calcium hydroxide, barium hydroxide,
manganese hydroxide, zinc hydroxide and hydrotalcite and mixtures
of these metal hydroxides. Preferable metal hydroxides include
magnesium hydroxide and a mixture of magnesium hydroxide and a
5 metal hydroxide other than magnesium hydroxide; and aluminum
hydroxide and a mixture of aluminum hydroxide and a metal hydroxide
other than aluminum hydroxide, e.g., a mixture of aluminum
hydroxide and magnesium hydroxide.
[0060]
10 The metal carbonates used in the present invention, which
are not particularly limite include calcium carbonate,
magnesium carbonate, zinc carbonate, barium carbonate and
mixtures of these metal carbonates.
[0061]
15 The metal oxides used in the present invention, which are
not particularly limited, include alumina, zinc oxide, Titanium
oxide, magnesium oxide, calcium oxide and mixtures of these metal
oxides.
[0062]
20 Among these, magnesium hydroxide, aluminum hydroxide, basic
magnesium carbonate and hydrotalcite are preferable, and the use
of magnesium hydroxide and/or aluminum hydroxide is preferable.
[0063]
As the inorganic fillers, those usually having an average
SF'-2366
24
particle diameter of about 0. 05 to 20 micrometer (pm) , preferably
about 0. "l to 5 micrometer (pm) are employable. In order to improve
the dispersibility with respect to the polymer components of the
composition, those having their surfaces treated with a
5 surface-treating agent are preferably used. Examples of the
surface-treating agent include alkali metal salts of higher fatty
acids such as sodium caprate, sodium laurate, sodium myristate,
sodium palmitate, sodium stearate, potassium stearate, sodium
oleate, potassium oleate and sodium linoleate; higher fatty acids
10 such as capric acid, lauric acid, myristic acid, palmitin, stearic
acid, oleic acid and linoleic acid; fatty acid amides; fatty acid
esters; higher aliphatic alcohols; titanium coupling agents such
as isopropyltriisostearoyl titanate,
isopropyltris(dioctylpyrophosphat.e)titanate and
15 tetra isopropylbis(dioctylphosphite)titanate; silane coupling
agents such as vinyl tri_ethoxysilane,
y-methacryloxyp.ropyltrimethoxysilane,
y-glycidoxypropyltrimethoxysilane; silicone oils; and various
phosphoric acid esters.
20 [0064]
Other examples of the filler (D) that are optionally used
in the present invention include organic and inorganic flame
retardance imparting agents (flame---retardants and
flame-retardant assistants)
SF-2366
[0065]
25
Usually, these organic and inorganic flame retardance
imparting agents (flame-retardants and flame-retardant
assistants) alone are used, independently of the filler (D)
5 including metal hydroxides, metal carbonates and metal oxides as
described above. However, as required, the filler (D) such as
metal hydroxides, metal carbonates and metal oxides may be used
in combination with the organic and inorganic flame retardance
imparting agents (flame--retardants and flame--retardant
10 assistants).
[0066]
The organic and inorganic flame retardance imparting agents
(flame-retardants and flame- retardant assistants) as other
examples of the filler (D) are described below.
15 [0067]
Examples of the flame retardance imparting agents that are
employed include bromine-based flame retardance imparting
agents; phosphorus-based flame retardance imparting agents such
as red phosphorus, phosphoric acid esters, phosphoric acid amides
20 and organic phosphine oxides; ammonium polyphosphate;
nitrogen=-based flame retardance imparting agents such as
phosphazene, triazine and melamine cyanurate; metal salt-based
flame retardance imparting agents such as alkali metal salts
polystyrene sulfonic acid; inorganic flame retardance imparting
SF-2366
26
agents such as zinc borate and zinc stannate; and silicone-based
flame retardance imparting agents such as silicone resins and
silicone oils.
[0068]
These flame retardance imparting agents may be used singly,
or two or more kinds thereof may be used in combination, as
required.
[0069]
Among these, the phosphorus-containing flame retardance
10 imparting agents are preferable, and examples thereof include
phosphorus-based flame retardance imparting agents including red
phosphorus, phosphoric acid esters, phosphoric acid amides and
organic phosphinic acid salts, and ammonium polyphosphate (APP)
as described above. Known phosphorus---containing flame
15 retardance imparting agents used as a flame-retardant are
employable. Specific examples thereof include ^immonium
phosphate, melamine pyrophosphate, ammonium polyphosphate and
melamine polyphosphate, with polyphosphoric acid compounds such
as melamine pyrophosphate and melamine polyphosphate being
20 preferable. These phosphorus-containing flame retardance
imparting agents include modified phosphoric acid compounds that
have their surfaces modified or coated with melamine, a melamine
resin, a fluoropolymer or the like; and melai-aine-cross linked
phosphoric acid compounds obtained by crosslinking with melamine
SF'-2366
27
These phosphorus-containing flame retardance imparting agents
may be used singly, two or more kinds thereof may be used in
combination.
[0070]
5 As the nitrogen-based flame retardance imparting agents,
compounds containing a triazine ring can be mentioned. Examples
thereof include compounds generally known as a flame-retardant,
such as melamine, ammeline, melam, benzogurniiamine,
acetoguanamine, phthalodiguanamine, melaminecyanurate, melamine
10 pyrophosphate, butylenediguanamine, norbornenediguanamine,
methylenedimelamine, ethylenedimelamine,
trimethylenedimelamine, tetramethylenedimelamine,
hexamethylenedimelamine and 1,3-hexylenedimelamine. Among
these, melaminecyanurate is preferable.
15 [0071]
The amount o:-- the flame retardance imparting agents such
as the compounds having a triazine ring may be the blending
proportion of the filler (D) as described above, but is 0.1 to
100 parts by mass, more preferably 0. 1 to 80 parts by mass, still
20 more preferably 5 to 60 parts by mass based on 100 parts by mass
of the total of the polymer components (A), (B) and (C) and
optionally (E) of the present invention. If the blending amount
is less than 0. 1 part by mass, the generation of a combustion inert
gas (nitrogen gas) from this compound tends to be insufficient,
SF-2366
28
and the synergistic effect with another flame retardance imparting
agent tends to be insufficient. On the other hand, even if the
amount is more than 100 parts by mass, there is not much difference
in flame retardance effect, and rather, such an amount may
adversely affect molding processability or mechanical properties
and the like of the resulting article, and thus is not desirable.
[0072]
In the embodiment using phosphorus-containing flame
retardance imparting agents, the amount of the
10 phosphorus-containing flame retardance imparting agent is 15 to
100 parts by mass, more preferably 30 to 90 parts by mass, still
more preferably 35 to 80 parts by mass, based on 100 parts by mass
of the total of the polymer components (A) , (B) and (C) , and
optionally (B) of the present invention.
15 [0073]
The inorganic flame retardance imparting agents include
antimony compounds such as antimony trioxide, antimony
pentaoxide and sodium antimonate; zinc compounds such as zinc
sulfate, zinc stannate, zinc h_ydroxystan.nate and zinc borate;
20 iron compounds such as ferrous hydroxyzincate and ferric oxide;
tin compounds such as metastannic acid, stannous oxide and
stannic oxide; and tungsten compounds such as metal salts of
tungstic acid, composite oxide acids of tungsten and a metalloid;
zirconium compounds; and hydrotalcites; these may be
SF-2366
29
surface-treated with a fatty acid, a silane coupling agent or
the like. Among these, zinc compounds, in particular at least
one zinc salt selected from zinc stannate, zinc hydroxystannate
and zinc borate, are preferable. The blending of these compounds
5 further improves flame retardance, and moreover increases a shell
formation rate during combustion and leads to more solid
formation of the shell. It is preferred that the zinc borate,
zinc hydroxystannate and zinc stannate each have an average
particle diameter of not more than 5 micrometer (pm), more
10 preferably not more than 3 micrometer (pm) e. Examples of the zinc
borate include ALCANEX FRC---500 (2 ZnO/3B203 e 3. 5H20) , ERC- 600
(product name, manufactured by MIZUSAWA INDUSTRIAL CHEMICALS,
LTD.). Examples of the zinc stannate (ZnSnO3) and zinc
hydroxystannate (ZnSn(OH)6) include ALCANEX ZS and ALCANEX ZHS
15 (product name, manufactured by MIZUSAWA INDUSTRIAL CHEMICALS,
LTD.).
[0074]
Examples of the silicone-based flame retardance imparting
agents include silicone resins and silicone oils. Examples of
20 the silicone resins include resins having three-dimensional.
netlike structure formed by combining structures of any of SiO2r
RSiO3/2, R2SiO and R3SiO1/2, wherein R is an alkyl group such as methyl
group, ethyl group and propyl group, or an aromatic group such
as phenyl group and benzyl group, or a substituent formed when
SF-2366
30
any of the above substituents has a vinyl group. Examples thereof
include silicone oils such as dimethyl silicone oil and
meLhylphenyl silicone oil; modified silicone oils such as
epoxy-modified silicone oil, alkyl-modified silicone oil,
5 amino----modified silicone oil, carboxyl-modified silicone oil,
alcohol-modified silicone oil and ether--modified silicone oil;
silicone rubbers such as dimethyl polysiloxane rubber and methyl
vinyl polysiloxane lubber; silicone resins such as methyl silicone
resin and ethyl silicone resin; and fine particulate silicone
10 powder (Si powder).
[0075]
The silicone powder (Si powder) and the like as described
above serve also as a molding assistant and a slip agent.
[0076]
15 In the embodiment using the silicone-based flame retardance
imparting agents of the present invention, the amount of the
silicone-based flame retardance imparting agent is 1 to 30 parts
by mass, more preferably 2 to 20 parts by mass, still more
preferably 2 to 15 parts by mass, based on 100 parts by mass of
20 the total of the polymer components (A), (B), (C) and optionally
(B) of the present invention.
[0077]
As described above, the fillers (B) used in the present
invention include organic fillers, inorganic fillers, various
SF--2366
flame retardance imparting agents, molding assistants and slip
agents, and at least one of these is used as required.
[0078]
The proportion of the filler (D) is preferably 1 to 350 parts
5 by mass, more preferably 100 to 300 parts by mass, based on 100
parts by mass of the total of (A), (B) and (C)o This allows the
thermoplastic polymer composition to achieve a balance among flame
retardance, mechanical properties and flexibility.
Modified olefin polymer (E)
10 In the present invention, a modified olefin polymer (E) is
preferably used together with the ethylene/unsaturated ester
copolymer (A), the propylene---based polymer. (B) and the
propylene-based polymer (C)v
[0079]
15 The modified olefin polymer (E) is a modified product of
a polymer other than the ethylene/unsaturated ester copolymer (A) ,
the propylene--based polymer (B) and the propylene.-based polymer
(C), with examples thereof including modified polyolefins such
as modified polyethylene, modified polypropylene, modified
20 polybutene, modified poly (4--methylllpentene) , modified
ethylene/a-olefin copolymers, e. g. , modified. ethylene/propylene
copolymer and modified ethylene/ 1-butene copolymer, modified
propylene/a-olefin copolymers, e.g., modified
propylene/ihutene copolymer, modified
SF-2366
32
propylene/ethylene/u--olefin copolymer wherein the a---olefin is
selected from C4-20 a-olefins, e e g a, modified
propylene /ethylene/i butene copolymer; and modified ethylene
unsaturated ester copolymer such as modified ethylene vinyl
acetate copolymer and modified ethylene acrylic acid ester
copolymers.
[0080]
These can be produced by graft modifying unmodified
polymers.
1 0 [0 0 81 ]
Examples of the vinyl compound having a polar group employed
for the modification include vinyl compounds that have an
oxygen-containing group such as an acid, an acid anhydride, an
ester, an alcohol, an epoxy and an ether; vinyl compounds that
15 have a nitrogen-containing group such as an isocyanate and an
amide; and vinyl compounds having a silicon-containing group such
as a vinylsilane.
[0082]
Among t.hese,. the vinyl compounds that have an
20 oxygen-containing group are preferable, and specifically
preferred are unsaturated epoxy monomers, unsaturated carboxylic
acids and derivatives thereof. Examples of the unsaturated epoxy
monomers include unsaturated glycidyl ethers and unsaturated
glycidyl esters (for example, glycidyl methacrylate)o Examples
SF-2366
33
of the unsaturated carboxylic acids include acrylic acid, maleic
acid, fumaric acid, tetrahydrophthalic acid, itaconic acid,
citraconic acid, crotonic acid, isocrotonic acid and nadic acid TM
(endo-cis-bicyclo [2, 2, 1] hept-5---ene2-2, 3-dicarboxylic acid).
[0083]
Examples of the derivatives of the unsaturated carboxylic
acids include acid halide compounds, amide compounds, imide
compounds, acid anhydrides and ester compounds of above
unsaturated carboxylic acids. Specific examples thereof include
1.0 malenyl chloride, maleimide, malefic anhydride, citraconic
anhydride, monomethyl, maleate, dimethyl maleate and glycidyl
maleate,
[00 81 ]
Among these, the unsaturated dicarboxylic acids and acid
15 anhydrides thereof are more preferable, and particularly
preferred are malefic acid, nadic acidTM and acid anhydrides
thereof.
[0085]
The graft position of the unsaturated carboxylic acids or
20 derivatives thereof to be grafted to the above unmodified olefin
polymers is not particularly limited, as long as the unsaturated
carboxylic acids or derivatives thereof are bonded to any carbon
atom of the olefin polymers.
[0086]
SF --2366
34
The modified olefin polymer (E) as described above may be
prepared by various known methods, for example, methods as
described below.
(1) a method in which the above unmodified olefin polymer
5 is molten with an extruder or the like, and an unsaturated
carboxylic acid or its derivative is added thereto, to thereby
perform graft copolymerization; and
(2), a method in which the above unmodified olefin polymer
is dissolved in a solvent, and an unsaturated. carboxylic acid or
10 its derivative is added thereto, to thereby perform graft
copolymerization.
[0087]
In any of the above methods, g: ft reaction is performed
preferably in the presence of a radical initiator for efficient
15 graft copolymerization of the above graft monomers such as
unsaturated carboxylic acids.
[0088]
Employable examples of the radical initiator include
organic peroxides and azo compounds. Examples of the organic
20 peroxides include benzoyl peroxide, dichlorobenzoyl peroxide,
and dicumyl peroxide. Examples of the azo compounds include
azobisisobutylnitrile and dimethyl azoisobutyratea
[0089]
Specific examples of the radical initiators that are
SF--2 3 6 6
35
preferably used include dialkyl peroxides such as dicumyl peroxide,
di-tert-butylperoxide,
2, 5-dimethyl-2, 5--di (tent--but.ylperoxy) hexine--.3, 2, 5"dimethyI...2,
5-di (tert--,butylperoxy) hexane
5 1, 4-bis (tert-butylperoxyisopropyl)benzene
[0090]
and
The radical initiator is used usually in an amount of 0. 001
to 1 part by mass, preferably 00003 to 005 part by mass, still
more preferably 0.05 to 0.3 part by mass, based on 100 parts by
10 mass of the unmodified olefin polymer.
[0091]
In the graft reaction employing the radical initiators, or
in the graft reaction not employing the radical initiators, the
reaction temperature is usually 60 to 350°C;, preferably 150 to
15 300°C.
[0092]
The graft amount of the vinyl compound having a polar group
in the modified olefin polymer (F) thus obtained is usually 0.01
to 10% by mass, preferably 0. 05 to 5% by mass, provided that the
20 mass of the modified olefin polymer is 100% by mass.
[0093]
In the present invention, the use of the modified olefin
polymer (L) as described above particularly increases the
interaction between the filler (D) and the polymer components,
SF- 2 3 66
36
resulting in the provision of a thermoplastic polymer composition
excellent in the balance among mechanical strength, elongation
at break, flexibility and heat resistance.
[0094]
5 Instead of adding the modified olefin polymer (E) or
together with the modified olefin polymer (E), at least part of
or whole of the polymers (A), (B) and (C) may be modified. In
this case, too, similar effects are obtained.
[0095]
10 In this case, the modification may be performed in
accordance with the description set forth for the olefin polymer
(E) as described above. In the present invention, the polymers
(A), (B) and (C) include a modified polymer (A), a modified polymer
(B) and a modified polymer (C) , respectively, which are obtained
15 by modifying part of or whole of the polymers (A), (B) and (C)
Thermoplastic polymer composition
The thermoplastic polymer composition of the present
invention comprises 1 to 350 parts by mass of the filler (D) with
respect to 100 parts by mass of the polymer components comprising
20 50 to 90% by mass of the ethylene/unsaturated ester copolymer (A)
1 to 40% by mass of the propylene-based polymer (B) having a melting
point as measured by differential scanning calorimetry (DSC) of
from 120 to 170°C; and 1 to 49% by mass of the propylene--based
polymer (C) having a melting point as measured by differential
SL-2366
37
scanning. calorimetry (DSC) of lower than 120°C or not being
observed, provided that the total amount of (A), (B) and (C) is
100% by mass.
[0096]
5 Among the thermoplastic polymer compositions of the present
invention, a thermoplastic polymer composition according to a
preferred embodiment comprises 100 to 300 parts by mass of the
filler (D) with respect to 100 parts by mass of the polymer
components comprising the ethylene/unsaturated ester copolymer
10 (A) in an amount of 52 to 90% by mass, more preferably 55 to 90%
by mass, still more preferably 55 to 85% by mass; the
propylene--based polymer (B) having a melting point as measured
by differential scanning calorimetry (DSC) of from 120 to 170°C
in an amount of 1 to 30% by mass, more preferably 1 to 20% by mass,
15 still more preferably 1 to 10% by mass; and the propylene-based
polymer (C) having a melting point as measured by diffor_ential
scanning calorimetry (DSC) of lower than 120°C or not being
observed in an amount of 5 to 49% by mass, more preferably 9 to
40% by mass, still more preferably 9 to 35% by mass, provided that
20 the total amount of (A), (B) and (C) is 100% by mass.
[0097]
The polymer components containing more than 40% by mass of
the propylene-based polymer (B) lead to reduced flexibility,
elongation at break and flame retardance. The polymer components
SF'--2366
3 8
containing more than 49% by mass of the propylene-based polymer
(C) lead to reduced flame retardancea
[0098]
When the modified olefin polymer (E) is used in combination,
5 it is desirable that the modified olefin polymer (E) is used in
such a manner that the proportion of the modified olefin polymer
(E) in the thermoplastic polymer composition is controlled such
that the proportion of the vinyl compound having a polar group
according to the modification is 0001 to 10 parts by mass based
10 on 100 parts by mass of the total of the ethylene/unsaturated ester
copolymer (A), the propylene--based polymer (B), the
propylene=based polymer (C) and the modified olefin polymer (E)
[0099]
When part of or whole of the polymers (A), (B) and (C) is
15 modified with the vinyl compound having a polar group, the amount
of the vinyl compound having a polar group contained in such
polymers is included in the above-mentioned graft amount.
[0100]
In general, a polymer other than the polymer components (A) ,
20 (B) and (C) is previously graft-modified with a vinyl compound
having a polar group, to give the modified olefin polymer (E).
In this case, the modified olefin polymer (E) in which the amount
of the vinyl compound having a polar group is 0. 01 to 10% by mass,
preferably 0. 05 to 5% by mass provided that the mass of the modified
SF-2366
39
olefin polymer is 100% by mass is incorporated in an amount of
2 to 30% by mass, preferably 3 to 20% by mass of the polymer
components comprising (A), (B), (C) and (E) of the thermoplastic
polymer composition of the present invention, provided that the
5 total amount of (A), (B), (C) and (E) is 100% by mass.
[0101]
When the polymer component (E) is not used and any of the
polymer components (A), (B) and (C) of the present invention is
partly or wholly graft--modified, the modification is performed
10 in such a manner that the proportion of the vinyl compound having
a polar group according to the modification is 0.01 to 10 parts
by mass based on 100 parts by mass of the total of the polymers
(A), (B) and (C)
[0102]
15 The ratios among (A), (B) and (C) in the embodiment using
the modified olefin copolymer (E) are similar to those in the
embodiment not using the modified olefin copolymer (E) e The
proportion of the amount of the filler (D) is 1 to 350 parts by
mass, more preferably 100 to 300 parts by mass, based on 100 parts
20 by mass of the total of (A), (B), (C) and (E).
[0103]
The thermoplastic polymer composition of the present
invention may optionally contain additives as long as they are
not detrimental to the object of the present invention, such as
SF-2366
40
other synthetic resins, other rubbers, antioxidants, heat
stabilizers, UV absorbents, weathering stabilizers, antistatic
agents, antislip agents, antiblocking agents, nucleating agents,
pigments, dyes, slip agents, hydrochloric acid absorbents and
copper inhibitors.
[0109]
The addition amounts of such other synthetic resins, other
rubbers, additives and the like are not particularly larnited as
long as not being detrimental to the object of the present
10 invention. The thermoplastic polymer composition in an exemplary
preferred embodiment contains the components (A), (B) , (C) , (D)
and (E) in a total amount of 60 to 100% by mass, preferably 80%
by mass to 100% by mass, and the rest in the thermoplastic polymer
composition is composed of the above other synthetic resins, other
15 rubbers, additives and like. Such. components include polyolefin
waxes such as polyethylene wax and polypropylene wax, low, density
polyethylene, middle-density polyethylene, low-density
polyethylene, LLDPE composed of a copolymer of ethylene and a C9m--10
a-olefin, ethylene elastomers and styrene elastomerso
20 [0105]
The thermoplastic polymer composition of the present
invention may be produced by a known method. For example, the
thermoplastic polymer composition may be obtained by
ultaneously or sequentially mixing the individual- components
SF-2366
41
placed in a Henschel mixer, aV--blender, a tumbler mixer, a ribbon
blender and the like and -then melt kneading the mixture with a
monoaxiial extruder, multiaxial extruder such as a biaxial
extruder, a kneader, a Banbury mixer and the like.
[0106]
Among these, the use of apparatus excellent in kneading
performance such as a multiaxial extruder, a kneader and a Banbury
mixer can provide a high quality thermoplastic polymer
composition in which each component is dispersed with more
10 uniformity. In any stage of the production described above,
other additives such as antioxidants may be added.
[0107]
The order of adding the individual components is not
particularly limited. When the modified olefin polymer (B) is
15 used in combination, a desirable order is such that the
propylene-based polymer (B) , the propylene-based polymer (C) and
the modified olefin polymer (B) are previously melt kneaded, and
the resultant product is melt kneaded together with the other
components, or such that part of these polymer components and the
20 whole of the filler (D) are melt kneaded to form master batches,
and these are melt kneaded. Thereby, a composition excellent in
the balance among mechanical strength, hardness, flexibility and
heat resistance can be obtained.
[0108]
SF-2366
42
Article
The article of the present invention comprises the
thermoplastic polymer composition as described above. The above
thermoplastic polymer composition can be melt-molded into various
5 forms by known melt molding methods. The known melt molding
methods include extrusion molding, rotating molding, calender
molding, injection molding, compression molding, transfer
molding, powder molding, blow molding and vacuum mold_7g. The
propylene resin composition according to an embodiment of the
10 present invention contains the filler at high proportion and is
excellent in the balance among mechanical strength, flexibility
and heat resistance. The thermoplastic polymer composition of
the present invention is widely applicable for articles having
flame retardance, such as electric wires and electric cables and
15 building materials.
[0109]
The article as described above may be a composite article
formed with an article composed of other materials, such as a
laminate.
20 [0110]
The article is excellent in the balance of properties, i.e. ,
maintaining mechanical strength and being excellent in
flexibility as well as in scratch resistance, and therefore can
be applied suitably for, e.g., the coating of electric wires and
SF-2366
43
electric cables including the use as an insulator of an electric
wire and electric cable and an electric wire and electric cable
sheath, typified by the coating of optical fibers. With the
article of the present invention, in particular, an article such
5 as a tubular electric wire and electric cable can have improved
scratch resistance. Thus, taking advantage of its flexibility
and its heat resistance, the article of the present invention is
suited for an electric wire and electric cable sheath and an
electric wire and electric cable coating for consumer and
10 household devices such as a power cord.
[0111]
The coating layers such as an insulator of an electric wire
and electric cable and an. electric wire and electric cable sheath
as described above are formed around electric wires and electric
15 cables by a known method e.g., extrusion molding.
[0112]
Hereinafter, the present invention is described in greater
detail based on Examples without limiting the present invention.
20
[0113]
Components (A) to (H)
Ethylene/unsaturated ester copolymer (A)
Ethylene/vinyl acetate copolymer (EVA--1)
S F- 2366
44
EVAF'LEX EV40LX (product name, manufactured by DuPont-Mitsui
Polychemicals Co., Ltd.), vinyl acetate content: 41% by mass,
MFR (measured in accordance with JIS K 7210-=99, at 190°C, under
a load of 2016 kg) : 2 g/10 min
5 Ethylene/vinyl acetate copolymer (EVA-2)
EVAFLEX EV270 (product name, manufactured by DuPont-Mitsui
Polychemicals Co., Ltd.), vinyl acetate content: 28% by mass,
(measured in accordance with JIS K 721099, at 190 (,C, under a load
of 2.16 kg) : 1 g/10 min
10 Propylene-based polymer (B)
As an isotactic homopolypropylene (hereinafter,
abbreviated ash-PP), a propylene/ethylene copolymer (Tm: 160°C,
melt flow rate (temperature 230°C, load: 2.16 kg): 3 g/10 min)
was used.
15 [0114]
Propylene-based polymer (C)
(C-1) Propylene/1-butene copolymer (PBR)
A propylene/1-butene copolymer (MER (temperature 230'C)-
V g/10 min, Tm: 75'C, 1--butene content: 26 mol%, Mw/Mn: 2i,
20 crystallinity (WARD method) : 28%) produced by a method described.
in WO 2004/87775 was used.
(C°2) Propylene/ethylene/1-butene copolymer (PEER)
A propylene/ethylene/1--butene random copolymer (MFR
(temperature 230°C): 6.0 g/10 min, Tm: not observed, Ethylene
SF--2366
45
content: 16 mol%, 1-wbutene content: 6 mol% , Mw/Mn : 20, Shore A
hardness: 75, crystallinity (WARD method): not higher than 5%,
mm value: 90%) produced by a method described in. WO 2004/87775
was used.
5 (C-3) Propylene/ethylene copolymer (PER)
A propylene/ethylene copolymer (MFR (temperature 230°C):
3.0 g/10 min, Tm: 46'C and 109'C, Ethylene content: 22 mol%, Mw/Mn:
2„1, Shore A hardness: 67) was used.
[0 115]
:1.0 Filler
(D---1) Magnesium hydroxide (Mg(OH)2)
Magnifin I15IV (product name, (Mg (OF-I) 2) manufactured by
Albemarle Corporation) was used. Average particle diameter d50
= 106 to 200 micrometer (pm)
15 (D-2) Organic phosphinic acid salt
Exolit OP1230 (product name, organic phosphinic acid salt
manufactured by Clariant) was used.
(D-3) Ammonium polyphosphate (APP)
Exolit AP462 (product name, ammonium polyphosphate (APP)
20 manufactured by Clariant) was used.
(Dm4) Si powder
DC4-7081 (product name, Si powder manufactured by Dow
Corning Toray Co., Ltd.) was used.
[0116]
SF--2366
46
Si powder serves as a flame retardance imparting agent and
as a molding assistant (slip agent).
[0117]
Modified olefin polymer (E)
5 Using the following ethylene/1 -_butene copolymer (E-1)
produced with a metallocene catalyst, a maleic anhydride
graft-modified ethylene/1-butene copolymer (E-2) was produced.
[0118]
(E-1) Ethylene/1butene copolymer (EBR)
10 An ethylene/ 1-butene copolymer (density. 870 kg/m3, MFR
(190°C): 0.5 g/10 min, Mw/Mn4 201)
(E---2) Graft-modified ethylene/1=butene copolymer (acid-modified
EBR)
10 kg of the ethylene/ 1-butene copolymer (E---l) and a
15 solution obtained by dissolving 50 g of maleic anhydride and 3
g of di-tent-butyl peroxide in 50 g of acetone were b.lended in
a Henschel mixer.
[0119]
The resultant blended product was introduced into a hopper
20 of a monoaxial extruder having a screw diameter of 40 min and L/D
of 26, and was extruded into a strand at a resin temperature of
260°C and an extruded amount of 6 kg/h. The strand was water---coold
and pelletized to provide a :maleic anhydride graft---modified
ethylene/1-butene copolymer (E-2)
SF--2366
[0120]
4'7
From the resultant acid-modified ethylene/1--butene
copolymer (E-2), unreacted malefic anhydride was extracted with
acetone to measure a malefic anhydride graft amount in this
5 copolymer. As a result, the graft amount was found to be 0.43%
by mass.
Measurement methods of property values
Property values were measured as follows.
[0121]
10 (1) Comonomer (ethylene and 1-butene) contents and rmrunm
(stereoregularity pentad _sotacticity)
Comonomer contents arid mmmm were determined by 13C-NMR
spectrum analysis.
[0122]
15 (2) Melt flow rate (MFR)
Melt flow rate of the ethylene /unsaturated ester copolymer
(A) was measured at 190°C under a load of 2.16 kg in accordance
with JIS K 721099
[0123]
20 Melt flow rate for the other polymers was measured at a
temperature of 190'C or 230'C under a load of 2.16 kg in accordance
with ASTM D-1238
[0124]
(3) Melting point (Tm)
SF- 2 3 66
48
DSC exothermic and endothermic curves were determined, and
a temperature at a top of the melting peak that had AH in heating
of not less than 1 J/g was defined as Tm. This measurement was
performed such that a sample was put in an aluminum pan and was
5 heated at 100°C/min to200°C, kept at 200°C for 5 minutes, and
then cooled at 10'C/min to -150'C and thereafter heated at 10°C/mm n
to 200°C; the exothermic and endothermic curves obtained at this
time was used for the measurement.
[0125]
10 (4) Molecular weight distribution (Mw/Mn)
Molecular weight distribution (Mw/Mn) was measured by GPC
(gel permeation chromatography) The measurement was performed
with the use of an orthodichlorobenzene solvent at a temperature
140°C,
15 [0126]
(5) Density
Density was measured in accordance with a method described
in .ATM D 1505 .
[0127]
20 (6) Crystallinity
Crystallinity was determined by analysis of wide-angle
X-ray profile obtained from a measurement using RINT2500
(manufactured by Rigaku Corporation) as a measurement apparatus,
and CuKa as an X-ray source
SF-2366
49
[0128]
(7) Intrinsic viscosity [T1]
An Ubbelohde viscometer was used. A polymer sample was
dissolved in decalin and a viscosity of the solution was measured
a temperature of 135°C. From a value thus measured, an
intrinsic viscosity was determined.
[0129]
(8) Tensile strength at break, Elongation at break, Initial
tensile modulus (Young's modulus)
10 In accordance with ASTM D638, a sheet of 2 mm in thickness
was prepared with a press molding machine and this sheet was tested
to measure breaking strength (TS) , elongation at break (EL) and
initial tensile modulus.
[0130]
15 (9) Shore A hardness
In accordance with ASTM D2240, a sheet of 2 mm in thickness
was prepared with a press molding machine, and this sheet was
tested with an A-type measurement device and a scale was read
immediately after the contact of an indenter.
20 [0131]
(10) Shore D hardness
In accordance with ASTM D2240, a sheet of 2 mm in thickness
was prepared with a press molding machine, and this sheet was
tested with a D--,type measurement device and a scale was read 5
SF-2366
50
seconds after the contact of an indenter.
[0132]
(11) Limiting oxygen index (LOI)
In accordance with JIS K7201--2, a sheet of 2 an in thickness
5 was prepared with a press molding machine, and this sheet was
tested to measure limiting oxygen index. Limiting oxygen index
was used as an indicator of flame retardance.
[0133]
(12) Thermal deformation
10 In accordance with JIS C3005, a sheet of 2 mm in thickness
was prepared with a press molding, machine, and this sheet was was
used for measurement performed under predetermined conditions
(90°C, 30 min). Thermal deformation rato was used as an indicator
of heat resistance.
15 [0134]
(13) TMA softening temperature
A pressure of 2 kg/cm2 was applied to a planar indentor of
1. 8 mm in diameter with heating at a heating rate of 5'C/min,
measure a displacement (penetration depth) A temperature at the
20 time when the penetration depth reached 500 pm was defined as a
softening temperature. The softening temperature was used as an
indicator of heat resistance.
[0135]
(14) Vertical flame test (UL VWt1 test)
SF-2366
51,
In accordance with UL 1580 standard, an article in the shape
of an electric wire and electric cable was subjected to a vertical
flame test (UL VW-r1. test) The test result was used as an indicator
of flame retardanceo
5 [01361
Examples 1 to 12 and Comparative Examples 1 to 7
A composition with a formulation indicated in Table 1 was
kneaded with a Labo Plastomill manufactured by TOYO SE-1KI Co.,
Ltd.
10 [01371
This was formed into a sheet of 2 in thickness with a
press molding machine (heating: a temperature of 190°C, and 7 min,
cooling: a temperature of 15°C, 4 min, cooling rate: about
40°C/min). This sheet was evaluated in terms of elongation at
15 break (EL), initial tensile modulus (Young modulus) , Shore D
hardness, heating deformation, TMA softening tempera i- tire and
limiting oxygen index. The results are set forth in Table 1-1,
Table 1-2 and Table 1-3.
[0138]
20 [Table 1-11
SF-2366
Table 1-1
52
Comp. Comp . Comp. Comp.
Item Unit Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 i
Ex. 1 Ex. 2 Ex. 3 Ex. 4
EVA-1 wto 100 95 75 80 85 _ 75 55 75 75
h-PP wt% 20 100 2 2 5 10 ^0
PEE^R w to
^
-
_ _ _
,
9 18
10 _
- - ---
P^^
--
wt%
-
-- - -
-
-
- -------
- - - - -- - - --- ! 1 - -
u
_ --
Acid-modified EER wt%o 5 5
-5
5 5 5 5
Magnesium hydroxide phr 200 200 200 200 200 200 200 200 200 200
il
Elongation at break o 340 310 190 20 250 290 280 260 230 220
Tens e
t
Ini tial tensile
al tn
tes MP 40 40 110 4700 60 50 60 70 70 80
modulus
a
Shore D hardness ( 5 sec after ) - 33 34 45 72 37 36 37 40 41 43
Heating deformation o 18 1 4 1 11 10 8 5 5 5
(90°C330 mi=n)
Limiting oxygen index % 48 44 36 29 37 42 37 33 36 37
SF-2366
1391
T le 1-21
Table 1-2
53
Unit
Comp. Comp. Comp.
Ex.. 7 . 8 Ex. 9 Ex. 10
Ex. 5 . 6 Ex. 7
EVA-2 wt% 100 95 75 80 75 55 75
°
--------
h-PP
---
wt%
------------
- - - ------
20
------
2
---
2
----
5
------ 10
------------- -------- -
PEER
--
wt%
- ---
-- --- - --
18
-
18 3 5
------ --------
O PBR wto
-
o
--- -
Acid-modified EER
-
wt%
-- - ---
5
------- --
5
---- -
5
- - -
5
- -----
5
U Magnesium hydroxide phr 200 200 200 200 200 200 200
Elongation at break % 160 190 110 130 150 150 150
Tensile
test
Initial tensile
MPa 200 170 330 200 180 190 220
moduli-is
Shore D hardness ( 5 sec after ) - 53 53 58 54 52 52 54
Limiting oxygen index % 49 45 37 39 37 34 37
TMiA softening temperature °C 117 130 163 128 139 152 154
SF-2366
[0140]
[Table 1-3]
Table 1-3
54
Item Unit Ex. 11 Ex, 12
EVA-2 wto 80 75
h°-PP wt % 2 2
-------------------------------------
PBR
----------------
wto
-----------------------
18
----------------------
18
o
f
--------------------- ------------------------------
Acid-modified EBR
-----------------
wt %
--------
0
---------
5
U Magnesium hydroxide pYr 200 200
i
Elongation at break %
Tens le
Initial tensile
test MPa
modulus
Shore D hardness (5 sec after) - 53 50
Limiting oxygen index % -- e
TMA softening temperature °C 120 126
5 [0141]
In the embodiments using EVA having a vinyl acetate content
of 41% but not using h-PP and PBER or PBR in combination as a polymer
component (Comparative Example 1 and Comparative Example 2), the
thickness loss ratio in heating deformation is high and thus heat
10 resistance is insufficient. In the embodiment not using PBER or
PBR in combination (Comparative Example 3) and in the embodiment
not using EVA in combination (Comparative Example 4), flexibility
and elongation at break are insufficient. By contrast, in the
embodiments using EVA, h-PP and PBER in combination (Examples 1
15 to 6), articles excellent in the balance among flexibility,
mechanical strength, elongation at break, heat resistance and
flame retardance can be obtained.
[0142]
In the embodiments using EVA having a vinyl acetate content
2366
55
of vinyl acetate content of 28% by mass but not using h -PP and
PBER, PER or PBRas a polymer component in combination (Comparative
Example 5 and Comparative Example 6), heat resistance is
insufficient. In the embodiment not using PBER, PER or PBR in
5 combination (Comparative Example 7), flexibility and elongation
at break are insufficient. By contrast, in the embodiments using
EVA, h-PP and PBER or PER in combination (Examples 7 to 12),
articles excellent in the balance among flexibility, mechanical
strength, elongation at break, heat resistance and flame
10 retardance can be obtained.
Examples 13 to 16 and Comparative Examples 8 and 9
A composition with a formulation indicated in Table 2 was
melt kneaded with a biaxial extruder having a screw diameter of
32 mm, L/D of 42) to give a corresponding resin compound. At this
15 time, attention was paid to make sure that the resin temperature
was not higher than 230°C.
[0143]
Using an electric wire and electric cable coater, a copper
core wire and cable (manufactured by Musashikinsen, 0018 mm in
20 diameter, 30-ply, pitch: 13, right--handed twining, outer
diameter: 1... 2 mm) was coated with the compound obtained, to provide
an electric wire and electric cable (outer diameter: 400 mm).
[0144]
The results of the property value measurement are set forth
5F-2566
56
in Table 2. The electric wires and electric cables of Examples
14 and 15 passed the UL VW-1 test.
[01.45]
[Table 2]
SF-2366
able 2
57
PHOS-10 PHOS-11 PHOS-12 PHOS-13 PHOS-14 PHOS-12-2
I tem Comp . Comp .
unit Ex. 13 Ex. 14 Ex. 15 Ex. 16
Ex.8 Ex.9
EVA-2 wt% 100 80 80 80 80 80
h-PP wt% 20 11 11 11 11
PBER wt% 9 9 9 9
Composition Organic phosphinic r 40 40 20 40 60
acid salt .OP1230 -
Armonium
phr 20
polyphosphate AP462
Si powder DC4-7081 phr 5 5 5 5 5 5
Tensile strenggth at MPa 13 8.8 1 15 12 8.9 16
break
Tensile
test Elongation at break % 710 420 640 580 510 680
Initial tensile
MPa 42 120 48 81 110 37
modulus
SF--2366
[0146]
58
The thermoplastic polymer composition of the present
invention is also capable of containing fillers at a high
5 proportion, and is excellent in the balance among mechanical
strength, flexibility and heat resistance. Further, the
thermoplastic polymer composition of the present invention is
widely applicable for flame-,retardant articles such as electric
wires and electric cables and building materials.
10 [01471
When the thermoplastic polymer composition according to the
present invention is applied for an insulating layer of all electric
wire and electric cable sheath and for an electric wire and
electric cable coating, the article according to the present
15 invention is an electric wire and electric cable sheath and/or
a coating layer. The electric wire and electric cable sheath and
the coating layer are formed around electric wires and electric
cables by a known method such as extrusion molding method.
[0148]
20 The present invention can provide a thermoplastic polymer
composition that is both highly flame-retardant and is flexible,
and can provide articles thereof.
[0149]
The thermoplastic polymer composition according to the
SF---2366
59
present invention has advantageous effects as described above,
and thus are suited for various articles such as electric wire
and electric cable coating, tapes, films, f lame-retardant sheets,
pipes, blow-molded articles, flame-retardant wall paper,
5 particularly suited for an electric wire and electric cable
sheath and an insulator of an electric wire and electric cable
and an electric wire and electric cable coating. In particular,
taking advantage of its flexibility and its heat resistance, the
thermoplastic polymer composition according to the present
10 invention. is used suitably for an electric wire and electric cable
sheath and an electric wire and electric cable coating for consumer
and household devices such as a power cord.
SF-2366
60

Claims
1. A thermoplastic polymer composition comprising 1 to
350 parts by mass of a filler (D) with respect to 100 parts by
5 mass of polymer components that comprise 50 to 90% by mass of an
ethylene/unsaturated ester copolymer (A); 1 to 40% by mass of a
propylene polymer (B) having a melting point as measured by
differential scanning calorimetry (DSC) of from 120 to 110°C; and
1 to 49% by mass of a propylene-based polymer (C) having a melting
10 point as measured by differential scanning calorimetry (DSC) of
lower than 120°C or not being observed, provided that the total
amount of (A), (B) and (C) is 100% by mass.
2. The thermoplastic polymer composition according to
15 Claim 1, wherein the propylene-based polymer (C) is at least one
polymer selected from apropylene/ethylene random copolymer (C'0),
a propylene/C4---20 a-olefin random copolymer (C-'1) and a
propylene/ethylene/C4-20 (x.-olefin random copolymer (C-2), and
has (a) a molecular weight distribution (Mw/Mn) as measured by
20 gel permeation chromatography (GPC) of 1 to 3.
3. The thermoplastic polymer composition according to
Claim 1 or 2, wherein the propylene--based polymer (C)
propylene/C4---20 u--olefin :random copolymer (C---1) satisfying the
SF--2 366
following requirement (b)o
61
(b) the melting point Tm (°C) and the content M (mol%) of
a comonomer structural unit as determined by 13C-NMR spectrum
measurement satisfy the equation (1)n
(1) 146exp(-Oo022M) ? Tm ? 125exp(-0. 032M), wherein Tm is
lower than 120°C.
4. The thermoplastic polymer composition according to
Claim 1 or 2, wherein, the propylene-based polymer (C) is a
10 propylene/ethylene/C4---20 olefin random copolymer (C-2)
satisfying the following requirement (n)e
(n) the propylene/ethylene/C4-20 u--olefin random copolymer
(CP-2) contains 40 to 85 mol% of a structural unit derived from
propylene, 5 to 30 mol% of a structural unit derived from ethylene,
15 and 5 to 30 mol% of a structural unit derived from C4ry20 a-olefins,
provided that the tonal amount of the structural unit der'i ved from
propylene, the structural unit derived from ethylene and the
structural unit derived from C4-20 a -olefins is 100 mol%.
20 5. The thermoplastic polymer composition according to
any one of Claims 1 to 4, wherein the filler (0) is at least one
filler selected from metal hydroxides, metal carbonates and metal
oxides.
SF-2366
62
60: The thermoplastic polymer composition according to
any one of Claims I to 4, wherein the filler (D) is selected from
at least one filler selected from organic phosphinic acid salts
and polyphosphor salts.
7. The thermoplastic polymer composition according to
any one of Claims 1 to 6, wherein the ethylene/unsaturated ester
copolymer (A) is a copolymer of ethylene and a vinyl, ester
compound.
10
8. The thermoplastic polymer composition according to
Claim 7, wherein the ethylene/unsaturated ester copolymer (A) is
a copolymer of ethylene and vinyl acetate that has a vinyl acetate
content of from 25% by mass and up to 50% by mass.
15
9. The thermoplastic polymer composition according -to
any one of Claims "1 to 8, which further comprises a modified olefin
polymer (B) wherein the proportion of a vinyl compound having a
polar group according to the modification is 0.01 to 10 parts by
20 mass based on 100 parts by mass of the total of (A) , (B) , (C) and
(B).
10. An article comprising the thermoplastic polymer
composition according to any one of Claims I to 9.
SF-2366
63
11. The article according to Claim 10, which is an
insulator of an electric wire and electric cable or an electric
wire and electric cable sheath.