Note: Descriptions are shown in the official language in which they were submitted.
CA 02203876 1997-04-28
1
SPECIFICATION
Propylene-Ethylene Copolymer Composition
and Process for Producing the Same
TECHNICAL FIELD
The present invention relates to a propylene-ethylene
copolymer composition and a process for producing the
composition. More specifically, the present invention relates
to a propylene-ethylene copolymer composition having a good
moldability and a superior balance of rigidity, toughness, and
impact-strength, and relates to a process for producing the
composition.
BACKGROUND ART
Since polypropylene resins are comparatively cheap and have
various superior characteristics, they have been used in
diversified fields. However, improvement in the impact-
strength, particularly impact-strength at low temperatures has
been required of the resins. Many processes for solving the
above problem have been proposed so far. In general, a process
for producing a propylene block copolymer wherein a propylene
homopolymer component is first formed and then a component of an
ethylene-propylene random copolymer is introduced thereto has
been used. vdhereas the propylene block copolymer has an
improved impact-strength as compared with propylene
homopolymers, it has a lowered rigidity, hardness and heat-
resistance. As the mean for improving the demerits, a method
has been proposed in Laid-open Japanese Patent Publication No.
.~ .
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Hei 5-117342 wherein the ratio of the melt flow rate of the
polymer obtained in the first stage to that obtained in the
second stage are specified, and they have been broadly employed
in various industrial fields such as automobiles and household
appliances.
In recent years, thinning and lightening of injection-molded
products or extrusion-molded products have been required from
the viewpoints of saving resources and energy. However,
polymers having a superior moldability while satisfying
characteristics such as rigidity, hardness, heat-resistance, and
impact-strength have not yet been provided. In order to obtain
thinned and lightened injection-molded products or extrusion-
molded products, it is necessary to increase the melt-flow rate
of propylene block copolymers. However, when the melt-flow rate
was increased, such a problem was raised that the rigidity,
toughness and impact-strength were reduced, while the
moldability was improved. Even in the case of the Laid-open
Japanese Patent Publication No. Hei 5-117342 mentioned above,
improvement in this respect is insufficient. For instance, when
MFR (i) exceeded 50 g/10 minutes, Izod impact strength was
extremely lowered. It is evident that in order to increase the
melt flow rate of propylene block copolymers, it is sufficient
to use propylene polymers having a low molecular weight.
However, the subject of keeping the copolymers, at the same
time, from causing the decrease in rigidity, toughness, and
impact-strength has not yet been solved.
On the other hand, a polypropylene resin containing a
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propylene polymer having a position of main dissolution peak (T
max) according to a temperature-rise fractionation method of 117
°C or 118 °C or higher, and a half-value width (6) of the peak
of 3.4 degree or 4.0 degree or lower has been proposed in Laid-
open Japanese Patent Publication Nos. Hei 5-5010, Hei 5-9228,
Hei 5-9219, and Hei 5-32723 with a purpose of improving the
rigidity and heat resistance of polypropylene, and also it has
been described therein that a nucleator (nucleating agent) may
be blended in the resin, if necessary. However, it was unable
to regard the impact-strength, toughness, and rigidity of the
resulting polypropylene resin as sufficient.
The subject of the present invention is to provide
propylene-ethylene copolymer compositions which have a high
rigidity, a high toughness, and a high impact strength, and are
superior in moldability, and to provide a process for producing
such compositions.
DISCLOSURE OF THE INVENTION
In view of the problems described above, an extensive
research was conducted by the present inventors to improve the
balance of the rigidity, toughness, impact-strength, and
moldability of propylene-ethylene copolymers. As a result, it
has been found that propylene-ethylene copolymer compositions
having a high rigidity, high toughness, high impact-strength,
and superior moldability can be obtained by producing the
propylene-ethylene copolymer compositions through two stage
polymerizations wherein a polypropylene having a high melt-flow
rate and excellent performances is produced in a first stage of
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polymerization, and then an ethylene-propylene copolymer is
produced, in a second stage, around the polypropylene produced
in the first stage; and further it has been found that more
superior polymer compositions can be obtained by adding a
specific nucleator to the compositions, to achieve the present
invention.
The aspects of the invention claimed by the present
application are as follows:
(1) A propylene-ethylene copolymer composition having a melt
flow rate of 10 to 300 g/10 minutes and obtained by
producing 60 to 95 ~ by weight, based on the weight of
whole polymer, of a propylene polymer having a melt flow
rate (ASTM D-1238, hereinafter refer to the same meaning) in
the range of 100 to 1,000 g/10 minutes and having a ratio
(Cf) of integrated values of the propylene polymer dissolved
in o-dichlorobenzene at a temperature of lower than 112°C,
and a temperature of 112°C or higher, respectively, which is
an index of the stereoregurality in molecules and molecular
weight distribution, when the amounts of the propylene
polymer dissolved therein at each of the temperatures were
determined by raising the temperature of the o-dichloro-
benzene continuously or stepwise, of 0.5 or less, by
conducting polymerization of propylene in the presence of a
highly stereoregular catalyst and hydrogen in a first stage
(polymerization step (I)), and then
producing 5 to 40 ~ by weight, based on the weight of
whole polymer, of an ethylene-propylene copolymer by feeding
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ethylene and propylene to the product produced in the first
stage so that the content of ethylene becomes 30 to 80 o by
weight, in a second stage (polymerization step (II)).
(2) The propylene-ethylene copolymer composition recited in
5 (1) above wherein a value of common logarithm of the ratio
of the melt flow rate of the propylene polymer obtained in
the polymerization step (I) (MFR (i)) to the melt flow rate
of the ethylene-propylene copolymer obtained in the
polymerization step (II) (MFR (ii)}, (MFR (i)/MFR (ii)), is
4 to 9.
(3) The propylene-ethylene copolymer composition recited in
(1) above wherein a value of common logarithm of the ratio
of the melt flow rate of the propylene polymer obtained in
the polymerization step (I) (MFR (i)) to the melt flow rate
of the ethylene-propylene copolymer obtained in the
polymerization step (II) (MFR (ii}), (MFR (i)/MFR (ii)}, is
5.05 to 9.
(4) The propylene-ethylene copolymer composition recited in
(1) above wherein the melt flow rate is 55 to 110 g/10
minutes.
(5) The propylene-ethylene copolymer composition recited in
(1) above wherein the melt flow rate is 210 to 300 g/10
minutes.
(6) A propylene-ethylene copolymer composition comprising 100
parts by weight of the propylene-ethylene copolymer
composition recited in (1) above and 0.0002 to 1 part by
weight of an cx-crystal nucleator blended therewith.
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(7) The propylene-ethylene copolymer composition recited in
(6) above wherein the oc-crystal nucleator is at least one
compound selected from the group consisting of talc, metal
salts of aromatic carboxylic acids, dibenzylidene sorbitol
compounds, metal salts of aromatic phosphoric acids, poly-3-
methyl-1-butene, polyvinyl cyclohexanes, and
polyallyltrimethylsilanes.
(8) A propylene-ethylene copolymer composition comprising 100
parts by weight of the propylene-ethylene copolymer
composition recited in (1) above and 0.0001 to 1 part by
weight of a /3-crystal nucleator blended therewith.
(9) The propylene-ethylene copolymer composition recited in
(8) above wherein the ~3-crystal nucleator is y-quinacridone;
an amide compound expressed by any one of the followings (1)
to (3); a mixture of a cyclic phosphorus compound. expressed
by the following general formula (1) with at least one
magnesium compound selected from the group consisting of the
followings (4) to (8); a mixture of a cyclic phosphorus
compound expressed by the following general formula (4) with
at least one magnesium compound selected from the group
consisting of the followings (8) and (9); or a mixture of
the foregoings:
( 1 ) R3 - ( R2 ) NCO-R1-CON ( Rq ) -R5
(2) R7-CONH-R6-CONH-R8
(3 ) R1o-CONH-R9-NHCO-R11
(4) Magnesium salt of aliphatic acids
(5) Magnesium salt of aliphatic phosphoric acids
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(6) Magnesium oxide, magnesium hydroxide, or magnesium
carbonate
(7) Magnesium salt of cyclic phosphorus compounds expressed
by the following general formula (2)
(8) Magnesium phosphinate compounds expressed by the
following general formula (3)
(9) Magnesium sulfate or talc
General formula (1)
Arl - O
Ar2 - P - OH
O
General formula (2)
Ar3 - O
I
Ar4 - P - OMgl~2
If
O
General formula (3)
Ar5 - OH
Ar _ P / OMgii2
I) \ H
O
General formula (4)
Ar7 - O
I
Ar8 - P - H
I I
O
In the above formulas,
when R1 represents a residual group of aromatic
dicarboxylic acids except for saturated or unsaturated
aliphatic groups or alicyclic groups of 1 to 28 carbon
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atoms, or 3,9- bis(phenyl-4-yl)-2,4,8,10-
tetraoxaspiro[5.5]undecane, then R2 and R4 represent
hydrogen, and each of R3 and R5 represents the same or
different cycloalkyl group or cycloalkenyl group of 3 to 18
carbon atoms, phenyl group, alkylphenyl group, alkenylphenyl
group, cycloalkylphenyl group, biphenyl group,
alkylcyclohexyl group, alkenylcyclohexyl group,
cycloalkylcyclohexyl group, or phenylcyclohexyl group of 7
to 18 carbon atoms, or phenylalkyl group or cyclohexylalkyl
group of 7 to 10 carbon atoms, and
when RI represents 3,9-bis(phenyl-4-yl)-2,4,8,10-
tetraoxaspiro[5.5]undecane, then R2 to R5 represent the same
or different hydrogen, alkyl group, cycloalkyl group, or aryl
group; or each of R2 and R3, and R4 and R5 jointly form an
alkylene group by bonding to each other at the respective
ends,
R6 represents a residual group of saturated or
unsaturated aliphatic, alicyclic, or aromatic amino acids of
1 to 28 carbon atoms,
R~ and R8 represent the same or different cycloalkyl
group or cycloalkenyl group of 3 to 18 carbon atoms, phenyl
group, alkylphenyl group, alkenylphenyl group,
cycloalkylphenyl group, biphenyl group, alkylcyclohexyl
group, alkenylcyclohexyl group, cycloalkylcyclohexyl group,
or phenylcyclohexyl group of 7 to 18 carbon atoms, or
phenylalkyl group or cyclohexylalkyl group of 7 to 10 carbon
atoms.
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R9 represents a residual group of aliphatic diamines, a
residual group of alicyclic diamines, or a residual group of
aromatic diamines of 1 to 24 carbon atoms (except for
xylylenediamine residual group),
Rlo and R11 represent the same or different cycloalkyl
group or cycloalkenyl group of 3 to 14 carbon atoms, phenyl
group, alkylphenyl group or alkenylphenyl group of 7 to 10
carbon atoms, or phenylalkyl group or cyclohexylalkyl group
of 7 to 9 carbon atoms, and
Arl to Ara represent arylene group, alkylarylene group,
cycloalkylarylene group, arylarylene group, or aralarylene
group, respectively.
(10) A process for producing a propylene-ethylene copolymer
composition having a melt flow rate of 10 to 300 g/10
minutes, which comprises carrying out the polymerization of
propylene by using a highly stereoregular catalyst in the
presence of hydrogen in a first stage (polymerization step
(I)) to produce 60 to 95 $ by weight, based on the weight of
whole polymer, of a propylene polymer having a melt flow
rate in the range of 100 to 1,000 g/10 minutes and having a
ratio (Cf) of integrated values of the propylene polymer
dissolved in o-dichlorobenzene at a temperature of lower
than 112°C, and a temperature of 112°C or higher,
respectively, which is an index of the stereoregurality in
molecules and molecular weight distribution, when the
amounts of the propylene polymer dissolved therein at each
of the temperatures were determined by raising the
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temperature of the o-dichlorobenzene continuously or
stepwise, of 0.5 or less, and then
producing 5 to 40 ~ by weight, based on the weight of
the whole polymer, of an ethylene-propylene copolymer by
5 feeding ethylene and propylene to the product obtained in
the first stage so that the content of ethylene becomes 30
to 80 ~ by weight, in a second stage (polymerization step
(II)).
(11) A propylene polymer composed of repetition units
10 expressed by the following general formula (5}
-(CH-CH2)-
CH3
and having a number-average molecular weight of 10,000 to
60,000, a density of 0.90 to 0.92 g/cm3, and a ratio (Cf) of
integrated values of the propylene polymer dissolved in o-
dichlorobenzene at a temperature of lower than 112°C, and a
temperature of 112°C or higher, respectively, which is an
index of the stereoregurality in molecules and molecular
weight distribution, when the amounts of the propylene
polymer dissolved therein at each of the temperatures were
determined by raising the temperature of the o-
dichlorobenzene continuously or stepwise, of 0.5 or less.
The range of melt flow rate of the propylene polymer of the
polymerization step (I) is 100 to 1,000 g/10 minutes, preferably
100 to 500 g/10 minutes, and most desirably 150 to 350 g/10
minutes. Polymerization is carried out so as to give a value of
the Cf, which is an index of the stereoregularity in molecules
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and the molecular weight distribution of the propylene polymer,
of 0.5 or less, preferably 0.1 to 0.4. The smaller the Cf
value, the higher the stereoregularity and the narrower the
molecular weight distribution.
Then the Cf value of the polymer of the polymerization step
(I) exceeds 0.5, toughness of the molded product lowers.
Further, when the melt flow rate is less than 100 g/10 minutes,
fluidity of the polymer lowers, and when it exceeds 1,000 g/10
minutes, toughness of the polymer notably lowers.
The portion of the ethylene-propylene copolymer of the
polymerization step (II) is formed by copolymerization of
propylene with ethylene, and the content of ethylene in the
copolymer is 30 to 80~ by weight and more preferably 35 to 55~
by weight. When the copolymer has a content of ethylene outside
the range mentioned above, impact-strength unpreferably lowers.
Propylene-ethylene copolymer compositions of the present
invention comprise a propylene polymer of the polymerization
step (I) and an ethylene-propylene copolymer of the
polymerization step (II) mentioned above, and the proportion of
the propylene polymer of the polymerization step (I) is 60 to
95~ by weight and the proportion of the copolymer of the
polymerization step (II) is 5 to 40~ by weight. Vdhen the
proportion of the propylene polymer of the polymerization step
(I) is less than 60~ by weight, rigidity of the product lowers,
and when it exceeds 95~ by weight, improvement in impact
strength at low temperatures is insufficient.
Melt flow rate (which refers to an amount of a melted resin
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extruded for 10 minutes at 230 °C when a load of 21.18N is
applied; hereinafter abbreviated as MFR) of the propylene-
ethylene copolymer compositions of the present invention is 20
to 300 g/10 minutes and preferably 20 to 150 g/10 minutes. The
range wherein the moldability and physical properties are most
balanced is 55 to 110 g/10 minutes. However, for the
applications wherein the moldability is considered to be
important, the range of 210 to 300 g/20 minutes is preferable.
Propylene-ethylene copolymer compositions of the present
invention are superior in the balance of mechanical strengths,
particularly in the balance between rigidity and toughness, and
impact-resistance, and at the same time, are superior in the
moldability. Thus, the compositions are suitable as resins for
thinned or lightened injection molded or extrusion molded
articles, and are useful as resources- or energy-saving
materials.
As examples of the catalyst used in the polymerization steps
(I) and (II) for producing the propylene-ethylene copolymer
compositions of the present invention, highly stereoregular
catalysts comprising a solid catalyst component containing
magnesium, titanium, halogen, and a polycarboxylic acid ester,
an organoaluminum compound, and an electron donor (Laid-open-
Japanese Patent Publication Nos. Hei 3-220207, Hei 4-103604, and
others), and highly stereoregular catalysts such as the
metallocene compounds mentioned below (Laid-open Japanese Patent
Publication Nos. Hei 3-12406, Hei 7-136425, and others) can be
used, but the catalysts are not limited to these ones.
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As the metallocene compounds, for example, compounds
consisting of chiral, transition metal compounds represented by
the following general formula:
Q(CSHq_n,Rlm) (CSHq_nR2n)~
wherein (C5H4_mRlm) and (C5H4_nR2n) represent a SubStltuted
cyclopentadienyl group; m and n are an integer of 1 to 3; R1 and
R2 may be the same or different, and each of them represents a
hydrocarbon group, a silicon-containing hydrocarbon group, or a
hydrocarbon group forming one or more hydrocarbon rings which
may be bonded to two carbon atoms on the cyclopentadienyl ring
and substituted by a hydrocarbon, of 1 to 20 carbon atoms; Q
represents a divalent hydrocarbon group, un-substituted silylene
group, or a hydrocarbon-substituted silylene group all of which
may cross-link (C5H4_mRlm) and (C5H4_nR2n) ; M represents a
transition metal selected from the group consisting of titanium,
zirconium, and hafnium; and X and Y may be the same or
different, and each of which represents hydrogen, halogen, or
hydrocarbon; and aluminoxane compounds can be mentioned.
Metallocene compounds expressed by such a general formula
specifically include rac-dimethylsilylene-bis(2-methyl-4,5,6,7-
tetrahydroindenyl)zirconium dichloride, rac-dimethylsilylene-
bis(2-methyl-4,5,6,7-tetrahydroindenyl)zirconium dimethyl, rac-
ethylene-bis(2-methyl-4,5,6,7-tetrahydroindenyl)hafnium
dichloride, rac-dimethylsilylene-bis(2-methyl-4-
phenylindenyl)zirconium dichloride, rac-
dimethylsilylene-bis(2-methyl-4-phenylindenyl)zirconium
dimethyl, rac-dimethylsilylene-bis(2-methyl-4-
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phenylindenyl)hafnium dichloride,
dimethylsilylene(2,4-dimethylcyclopentadienyl)(3',5'-
dimethylcyclopentadienyl)titanium dichloride, dimethyl-
silylene(2,4-dimethylcyclopentadienyl)(3',5'-dimethyl-
cyclopentadienyl)zirconium chloride, dimethylsilylene(2,4-
dimethylcyclopentadienyl)(3',5'-dimethylcyclopentadienyl)-
zirconium dimethyl, dimethylsilylene(2,4-dimethylcyclo-
pentadienyl)(3',5'-dimethylcyclopentadienyl)hafnium chloride,
dimethylsilylene(2,4-dimethylcyclopentadienyl)(3',5'-
dimethylcyclopentadienyl)hafnium dimethyl, dimethyl-
silylene(2,3,5-trimethylcyclopentadienyl)(2',4',5'-
trimethylcyclopentadienyl)titanium dichloride, dimethyl-
silylene(2,3,5-trimethylcyclopentadienyl)(2',4',5'-
trimethylcyclopentadienyl)zirconium dichloride, dimethyl-
silylene(2,3,5-trimethylcyclopentadienyl)(2',4',5'-
trimethylcyclopentadienyl)zirconium dimethyl, dimethyl
silylene(2,3,5-trimethylcyclopentadienyl)(2',4',5'-
trimethylcyclopentadienyl)hafnium dichloride, and dimethyl-
silylene(2,3,5-trimethylcyclopentadienyl)-(2',4',5'-
trimethylcyclopentadienyl)hafnium dimethyl.
Particularly preferable compounds among those are
halogenated hafnium compounds and halogenated zirconium
compounds, and most preferable ones are halogenated hafnium
compounds.
A representative method for synthesizing such metallocene
compounds is described, taking dimethylsilylene(2,4-
dimethylcyclopentadienyl)(3_.',5'-dimethylcyclopentadienyl)-
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hafnium dichloride as example, as follows:
Dichlorodimethylsilane is reacted with (2,4-dimethyl-
cyclopentadienyl)(3',5'-dimethylcyclopentadienyl)sodium to
obtain dimethyl(2,4-dimethylcyclopentadienyl)(3',5'-
5 dimethylcyclopentadienyl)silane, which is reacted with
butyllithium to obtain lithium dimethylsilylene(2,4-
dimethylcyclopentadienyl}(3',5'-dimethylcyclopentadienyl), which
is reacted in turn with hafnium tetrachloride to obtain
dimethylsilylene(2,4-dimethylcyclopentadienyl)(3',5'-
10 dimethylcyclopentadienyl)hafnium dichloride.
Starting materials used for producing the propylene-ethylene
copolymer compositions of the present invention are propylene
and ethylene, but it is also possible to use other a-olefins,
non-conjugated dienes, and others, if necessary, in an extent in
15 which achievement of the objects of the present invention is not
disturbed.
The polymerization step (I) is one to produce a highly
crystalline propylene homopolymer having a high melt flow rate,
and the polymerization step (II) is one to produce a propylene-
ethylene copolymer having a low melt flow rate. The
polymerizations may be either continuous or batch-wise. That
is, the polymerization steps (I) and (II) may be carried out
successively in the same system, or after a polypropylene
produced in the polymerization step (I) was separated,
polymerization step (II) may be carried out by feeding ethylene
and propylene to the polypropylene, with or without adding the
catalyst again, to react with the polypropylene mentioned above.
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In the polymerization step (I), a slurry polymerization wherein
polymerization of propylene is carried out in a hydrocarbon
solvent such as n-hexane, n-heptane, n-octane, benzene; and
toluene, a bulk polymerization which is carried out in liquefied
propylene, or a gas phase polymerization can be adopted. In the
case of the slurry polymerization in the polymerization step
(I), polymerization temperature is 20 to 90 °C, preferably 50 to
80 °C, and polymerization pressure is 0 to 5 MPa. In the case
of the gas phase polymerization, the polymerization temperature
is 20 to 150 °C, and the polymerization pressure is 0.2 to 5
MPa. Polymerization step (II) is carried out at a
polymerization temperature of 20 to 80 °C, preferably 40 to 70
°C and under a polymerization pressure of 0 to 5 MPa in the case
of either the slurry polymerization or the gas phase
polymerization. For controlling molecular weight, hydrogen gas
is used. In the polymerization step (I), it is preferable for
obtaining a polymer having a high melt flow rate to increase the
concentration of hydrogen, for example, up to 0.15 or more of
the ratio of hydrogen concentration/propylene concentration
(molar ratio). In the polymerization step (II), it is
preferable for obtaining a copolymer having a low melt flow rate
to suppress the concentration of hydrogen gas down to an
extremely low value, for example, lower than 1 mol ~, or to
bring the concentration of hydrogen gas into zero.
The logarithmic value of the ratio of the melt flow rate of
the polymer obtained in the polymerization step (I) (MFR(i)) to
the melt flow rate of the polymer obtained in the polymerization
CA 02203876 1997-04-28
17
step (II) (MFR(ii)), (MFR(i)/MFR(ii}},-is preferably 4 to 9. In
order to obtain preferable toughness, flexural modulus, and Izod
impact strength, this value is preferably 4 or more, while in
order to stably carry out a production of the product, the value
is preferably 9 or less. This value is more preferably 5.05 to
9_ When the value is 5.05 or more, still more excellent
toughness, flexural modulus, and Izod impact strength can be
obtained. The value is most preferably 5.05 to 8. When it is 8
or less, further stable production conditions can be obtained.
Further, it is possible to blend the following polymers with
the propylene-ethylene copolymer compositions of the present
invention within the range where the achievement of effect of
the present invention is not disturbed:
conventional crystalline propylene polymers, that is,
crystalline propylene homopolymers outside the scope of the
present invention, low-crystalline or crystalline random
copolymer, or crystalline block copolymer of propylene with one
or more cx-olefin such as ethylene, butene-1, pentene-2, 4-
methyl-pentene-l, hexene-1, and octene-1 containing 70 ~ by
weight or more of propylene component, copolymers of propylene
with vinyl acetate or acrylic acid ester, or saponified products
of the copolymers, copolymers of propylene with an unsaturated
silane compound, copolymers of propylene with an unsaturated
carboxylic acid or its anhydride, reaction products of the
copolymer mentioned just above with a metallic ion compound,
modified propylene polymers obtained by modifying crystalline
propylene polymers with an unsaturated carboxylic acid or its
CA 02203876 1997-04-28
18
derivative, and modified propylene polymers modified with an
unsaturated silane compound.
It is also possible to blend the following substances:
various kind of elastomers (for example, non-crystalline
ethylene-propylene random copolymers, non-crystalline ethylene-
propylene-non-conjugated dime terpolymers, low crystalline
ethylene-butene-1 random copolymers, low crystalline propylene-
butene-1 random copolymers, low crystalline ethylene-hexene-1
random copolymers, low crystalline ethylene-octene-1 random
copolymers, polybutadienes, polyisoprenes, polychloroprenes,
chlorinated polyethy~enes, chlorinated polypropylenes,
fluorinated rubbers, styrene-butadiene rubbers, acrylonitrile-
butadiene rubbers, styrene-butadiene-styrene block copolymers,
styrene-isoprene-styrene block copolymers, styrene-ethylene-
butylene-styrene block copolymers, styrene-propylene-butylene-
styrene block copolymers, ethylene-ethylene-butylene-ethylene
block copolymers, and ethylene-propylene-butylene-ethylene block
copolymers), and thermoplastic synthetic resins (for example,
ultra-low density polyethylenes, low density polyethylenes,
linear low density polyethylenes, medium density polyethylenes,
high density polyethylenes, ultra-high molecular weight
polyethylenes, non-crystalline ethylene-cyclic alkene copolymers
(such as non-crystalline ethylene-tetracyclododecene
copolymers), polyolefins excluding crystalline propylene
polymers such as polybutenes and poly-4-methylpentenes, atactic
polystyrenes, syndiotactic polystyrenes, styrene-acrylonitrile
copolymers, acrylonitrile-butadiene-styrene copolymers,
CA 02203876 1997-04-28
19
methacryl-butadiene-styrene copolymers, polyamides, polyethylene
terephthalates, polybutylene terephthalates, polyethylene
naphthalates, polybutylene naphthalates, polycarbonates,
polyvinyl chlorides, fluorine resins, petroleum resins (such as
CS petroleum resins, hydrogenated C5 petroleum resins, C9
petroleum resins, hydrogenated C9 petroleum resins, C5-Cg
copolymerized petroleum resins, hydrogenated C~-C9 copolymerized
petroleum resins, and acid-modified C9 petroleum resins each
having a softening point of 80 to 200°C), and DCPD resins (such
as cyclopentadiene petroleum resins, hydrogenated
cyclopentadiene petroleum resins, cyclopentadiene-C5
copolymerized petroleum resins, hydrogenated cyclopentadiene-C5
copolymerized petroleum resins, cyclopentadiene-C9 copolymerized
petroleum resins, hydrogenated cyclopentadiene-C9 copolymerized
petroleum resins, cyclopentadiene-C5-C9 copolymerized petroleum
resins, and hydrogenated cyclopentadiene-C5-C9 copolymerized
petroleum resins each having a softening point of 80 to 200°C).
When the following cx-crystal nucleator and/or ~3-crystal
nucleator is added to the propylene-ethylene copolymer
compositions of the present invention, toughness, rigidity, and
impact strength of the compositions as formed into molded
articles can further be improved.
In the present specification, cx-crystal nucleator or i(i-
crystal nucleator means an agent which makes it possible to
obtain a crystal of polypropylene in cx-form or ~i-form when a
melt-crystallization of the polypropylene is conducted in the
presence of the crystal nucleator (Polymer, pp 3443-3448, Vol.
CA 02203876 1997-04-28
35, No. 16, 1994).
As the (x-crystal nucleator used in the present invention,
the followings can be mentioned as example.
inorganic compounds such as talc, alum, silica, titanium
5 oxide, calcium oxide, magnesium oxide, carbon black, and clay
minerals,
carboxylic acids excluding aliphatic monocarboxylic acids
such as malonic acid, succinic acid, adipic acid, malefic acid,
azelaic acid, sebacic acid, dodecanoic diacid, citric acid,
10 butanetricarboxylic acid, butanetetracarboxylic acid, naphthenic
acid, cyclopentanecarboxylic acid, 1-methylcyclopentane-
carboxylic acid, 2-methylcyclopentanecarboxylic acid,
cyclopentenecarboxylic acid, cyclohexanecarboxylic acid, 1-
methylcyclohexanecarboxylic acid, 4-methylcyclohexanecarboxylic
15 acid, 3,5-dimethylcyclohexanecarboxylic acid, 4-
butylcyclohexanecarboxylic acid, 4-octylcyclohexanecarboxylic
acid, cyclohexenecarboxylic acid, 4-cyclohexene-1,2-dicarboxylic
acid, benzoic acid, toluic acid, xylyl acid, ethyl benzoate, 4-
t-butyl benzoate, salicylic acid, phthalic acid, trimellitic
20 acid, and pyromellitic acid,
normal salts or basic salts of lithium, sodium, potassium,
magnesium, calcium, strontium, barium, zinc, or aluminum of the
carboxylic acids mentioned above,
dibenzylidene sorbitol compounds such as
1-3, 2 -4-dibenzylidenesorbitol,
1'3-benzylidene- 2-4-p-methylbenzylidenesorbitol,
1-3-benzylidene- 2 -4-p-ethylbenzylidenesorbitol,
CA 02203876 1997-04-28
2I
1'3-p-methylbenzylidene- 2-4-benzylidenesorbitol,
1-3-p-ethylbenzylidene- 2 -4-benzylidenesorbitol,
1'3-p-methylbenzylidene- 2'4-p-ethylbenzylidenesorbitol,
1-3-p-ethylbenzylidene- 2'4-p-methylbenzylidenesorbitol,
1-3,2 '4-bis(p-methylbenzylidene)sorbitol,
1'3,2-4-bis(p-ethylbenzylidene)sorbitol,
1-3,2-4-bis(p-n-propylbenzylidene)sorbitol,
13,2 -4-bis(p-i-propylbenzylidene)sorbitol,
1'3,2 '4-bis(p-n-butylbenzylidene)sorbitol,
1'3,2 -4-bis(p-s-butylbenzylidene)sorbitol,
1'3,2 -4-bis(p-t-butylbenzylidene)sorbitol,
1'3-(2',4'-dimethylbenzylidene)-2 '4-benzylidenesorbitol,
1-3-benzylidene-2 '4-(2',4'-dimethylbenzylidene)sorbitol,
1'3,2 -4-bis(2',4'-dimethylbenzylidene)sorbitol,
1'3,2 '4-bis(3',4'-dimethylbenzylidene)sorbitol,
1'3,2-4-bis(p-methoxybenzylidene)sorbitol,
1-3,2 '4-bis(p-ethoxybenzylidene)sorbitol,
1'3-benzylidene-2'4-p-chlorobenzylidenesorbitol,
1'3-p-chlorobenzylidene-2 '4-benzylidenesorbitol,
1-3-p-chlorobenzylidene-2'4-p-methylbenzylidenesorbitol,
1-3-p-chlorobenzylidene-2'4-p-ethylbenzylidenesorbitol,
1'3-p-methylbenzylidene-2'4-p-chlorobenzylidenesorbitol,
1-3-p-ethylbenzylidene-2-4-p-chlorobenzylidenesorbitol, and
1-3,2 '4-bis(p-chlorobenzylidene)sorbitol,
arylphosphate compounds such as
lithium-bis(4-t-butylphenyl)phosphate,
sodium-bis(4-t-butylphenyl)phosphate,
CA 02203876 1997-04-28
22
lithium-bis(4-cumylphenyl)phosphate,
sodium-bis(4-cumylphenyl)phosphate,
potassium-bis(4-t-butylphenyl)phosphate,
calcium-mono(4-t-butylphenyl)phosphate,
calcium-bis(4-t-butylphenyl)phosphate,
magnesium-mono(4-t-butylphenyl)phosphate,
magnesium-bis(4-t-butylphenyl)phosphate,
zinc-mono(4-t-butylphenyl)phosphate,
zinc-bis(4-t-butylphenyl)phosphate,
aluminumdihydroxy-(4-t-butylphenyl)phosphate,
aluminumhydroxy-bis(4-t-butylphenyl)phosphate,
aluminum-tris(4-t-butylphenyl)phosphate,
sodium-2,2'-methylene-bis(4,6-di-t-butylphenyl)phosphate,
sodium-2,2'-ethylidene-bis(4,6-di-t-butylphenyl)phosphate,
sodium-2,2'-methylene-bis(4-cumyl-6-t-butylphenyl)phosphate,
lithium-2,2'-methylene-bis(4,6-di-t-butylphenyl)phosphate,
lithium-2,2'-ethylidene-bis(4,6-di-t-butylphenyl)phosphate,
lithium-2,2'-methylene-bis(4-cumyl-6-t-butylphenyl) phosphate,
sodium-2,2'-ethylidene-bis(4-i-propyl-6-t-butylphenyl)
phosphate,
lithium-2,2'-methylene-bis(4-methyl-6-t-butylphenyl) phosphate,
lithium-2,2'-methylene-bis(4-ethyl-6-t-butylphenyl) phosphate,
sodium-2,2'-butylidene-bis(4,6-di-methylphenyl)phosphate,
sodium-2,2'-butylidene-bis(4,6-di-t-butylphenyl)phosphate,
sodium-2,2'-t-octylmethylene-bis(4,6-di-methylphenyl) phosphate,
sodium-2,2'-t-octylmethylene-bis(4,6-di-t-butylphenyl)
phosphate,
CA 02203876 1997-04-28
23
sodium-2,2'-methylene-bis(4-methyl-6-t-butylphenyl) phosphate,
sodium-2,2'-methylene-bis(4-ethyl-6-t-butylphenyl) phosphate,
sodium-(4,4'-dimethyl-6,6'-di-t-butyl-2,2'-biphenyl) phosphate,
sodium-2,2'-ethylidene-bis(4-s-butyl-6-t-butylphenyl) phosphate,
sodium-2,2'-methylene-bis'(4,6-di-methylphenyl)phosphate,
sodium-2,2'-methylene-bis'(4,6-di-ethylphenyl)phosphate,
potassium-2,2'-ethylidene-bis(4,6-di-t-butylphenyl) phosphate,
calcium-bis[2,2'-methylene-bis(4,6-di-t-butylphenyl) phosphate],
magnesium-bis[2,2'-methylene-bis(4,6-di-t-butylphenyl)
phosphate],
zinc-bis[2,2'-methylene-bis(4,6-di-t-butylphenyl) phosphate],
aluminum-tris[2,2'-methylene-bis(4,6-di-t-butylphenyl)
phosphate],
calcium-bis[2,2'-methylene-bis(4-methyl-6-t-butylphenyl)
phosphate],
calcium-bis[2,2'-ethylidene-bis(4,6-di-t-butylphenyl)
phosphate],
calcium-bis[2,2'-thiobis(4-methyl-6-t-butylphenyl) phosphate],
calcium-bis[2,2'-thiobis(4-ethyl-6-t-butylphenyl) phosphate],
calcium-bis[2,2'-thiobis(4,6-di-t-butylphenyl) phosphate],
magnesium-bis[2,2'-thiobis(4,6-di-t-butylphenyl) phosphate],
magnesium-bis[2,2'-thiobis(4-t-octylphenyl) phosphate],
barium-bis[2,2'-methylene-bis(4,6-di-t-butylphenyl) phosphate],
calcium-bis[(4,4'-dimethyl-6,6'-di-t-butyl-2,2'-biphenyl)
phosphate],
magnesium-bis[2,2'-ethylidene-bis(4,6-di-t-butylphenyl)
phosphate],
CA 02203876 1997-04-28
24
barium-bis[2,2'-ethylidene-bis(4,6-di-t-butylphenyl) phosphate],
aluminum-tris[2,2'-ethylidene-bis(4,6-di-t-butylphenyl)
phosphate],
aluminumdihydorxy-2,2'-methylene-bis(4,6-di-t-butylphenyl)
phosphate,
aluminumdihydorxy-2,2'-methylene-bis(4-cumyl-6-t-
butylphenyl)phosphate,
aluminumhydorxy-bis[2,2'-methylene-bis(4,6-di-t-
butylphenyl)phosphateJ,
aluminumhydorxy-bis[2,2'-methylene-bis(4-cumyl-6-t-
butylphenyl)phosphate),
titaniumdihydorxy-bis[2,2'-methylene-bis(4,6-di-t-
butylphenyl)phosphate],
tindihydroxy-bis[2,2'-methylene-bis(4,6-di-t-butylphenyl)
phosphate],
zirconiumoxy-bis[2,2'-methylene-bis(4,6-di-t-butylphenyl)
phosphate],
aluminumdihydroxy-2,2'-methylene-bis(4-methyl-6-t-
butylphenyl)phosphate,
aluminumhydroxy-bis[2,2'-methylene-bis(4-methyl-6-t-
butylphenyl)phosphate],
aluminumdihydroxy-2,2'-ethylidene-bis(4,6-di-t-butylphenyl)
phosphate, and
aluminumhydroxy-bis[2,2'-ethylidene-bis(4,6-di-t-
butylphenyl)phosphate],
mixtures of a cyclic, multi-valent metal arylphosphate
compound among the aryl phosphate compounds mentioned above with
CA 02203876 1997-04-28
an alkali metal salt of aliphatic monocarboxylic acids (lithium,
sodium, or potassium salt of aliphatic monocarboxylic acids such
as acetic acid, lactic acid, propionic acid, acrylic acid,
octylic acid, isooctylic acid, nonanoic acid, decanoic acid,
5 lauric acid, myristic acid, palmitic acid, stearic acid, oleic
acid, linolic acid, linoleic acid, 12-hydroxystearic acid,
ricinolic acid, behenic acid, erucic acid, montanic acid,
melissic acid, stearoyl lactic acid, /3-dodecylmercaptoacetic
acid, /3-dodecylmercaptopropionic acid, /3-N-lauroyl
10 aminopropionic acid, and /3-N-methyl-N-lauryl aminopropionic
acid) or a mixture with basic aluminum'lithium'hydroxy'
carbonate-hydrate, and
high molecular weight compounds such as poly 3-methyl-1-
butene, poly 3-methyl-1-pentene, poly 3-ethyl-1-pentene, poly 4-
15 methyl-1-pentene, poly 4-methyl-1-hexene, poly 4,4-dimethyl-1-
pentene, poly 4,4-dimethyl-1-hexene, poly 4-ethyl-1-hexene, poly
3-ethyl-1-hexene, polyallylnaphthalene, polyallylnorbornane,
atactic polystyrene, syndiotactic polystyrene,
polydimethylstyrene, polyvinylnaphthalene, polyallylbenzene,
20 polyallyltoluene, polyvinylcyclopentane, polyvinylcyclohexane,
polyvinylcycloheptane, polyvinyltrimethylsilane, and
polyallyltrimethylsilane.
Among the compounds mentioned above, followings are
particularly preferable:
25 talc, aluminumhydroxy-bis(4-t-butylbenzoate),
1-3,2-4-dibenzylidenesorbitol,
1'3,2 -4-bis(p-methylbenzylidene)sorbitol,
CA 02203876 1997-04-28
26
1~3,2~4-bis(p-ethylbenzylidene)sorbitol,
1~3,2 ~4-bis(2',4'-dimethylbenzylidene)sorbitol,
1-3,2 ~4-bis(3',4'-dimethylbenzylidene)sorbitol,
1~3-p-chlorobenzylidene-,2~4-p-methylbenzylidenesorbitol,
1~3,2 ~4-bis(p-chlorobenzylidene)sorbitol,
sodium-bis(4-t-butylphenyl)phosphate,
sodium-2,2'-methylene-bis(4,6-di-t-butylphenyl)phosphate,
mixtures of a cyclic polyvalent metal arylphosphate such as
calcium-2,2'-methylene-bis(4,6-di-t-butylphenyl)phosphate,
aluminum-2,2'-methylene-bis(4,6-di-t-butylphenyl)phosphate,
aluminumdihydroxy-2,2'-methylene-bis(4,6-di-t-
butylphenyl)phosphate, or aluminumhydroxy-bis[2,2'-methylene-
bis(4,6-di-t-butylphenyl)phosphate] with an alkali metal salt of
aliphatic monocarboxylic acids; poly 3-methyl-1-butene,
polyvinylchlcohexane, and polyallyltrimethylsilane.
Amide compounds expressed by the (1) R3-(R2)NCO-R1-CON(R4)-R5
mentioned above and used in the present invention as /3-crystal
nucleator can readily be prepared by amidating a prescribed
aliphatic, alicyclic, or aromatic dicarboxylic acid and
prescribed ammonia, or an aliphatic, alicyclic, or aromatic
monoamine.
As the aliphatic dicarboxylic acid, malonic acid,
diphenylmalonic acid, succinic acid, phenylsuccinic acid,
diphenylsuccinic acid, glutaric acid, 3,3-dimethylglutaric acid,
adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic
acid, 1,12-dodecanoic diacid, 1,14-tetradecanoic diacid, and
1,18-octadecanoic diacid are specifically mentioned as examples.
CA 02203876 1997-04-28
27
As the alicyclic dicarboxylic acids, 1,2-
cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid,
and 1,4-cyclohexanediacetic acid are specifically mentioned as
examples.
As the aromatic dicarboxylic acid, p-phenylene diacetic
acid, p-phenylene diethanoic acid, phthalic acid, 4-t-
butylphthalic acid, isophthalic acid, 5-t-butylisophthalic acid,
terephthalic acid, 1,8-naphthalic acid, 1,4-
naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid,
2,7-naphthalenedicarboxylic acid, diphenic acid, 3,3'-
biphenyldicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 4,4'-
binaphthyldicarboxylic acid, bis(3-carboxyphenyl)methane, bis(4-
carboxyphenyl)methane, 2,2-bis(3-carboxyphenyl)propane, 2,2-
bis(4-carboxyphenyl)propane, 3,3'-sulfonylbenzoic acid, 4,4'-
sulfonyldibenzoic acid, 3,3'-oxydibenzoic acid, 4,4'-
oxydibenzoic acid, 3,3'-carbonyldibenzoic acid, 4,4'-
carbonyldibenzoic acid, 3,3'-thiodibenzoic acid, 4,4'-
thiodibenzoic acid, 4,4'-(p-phenylenedioxy)dibenzoic acid, 4,4'-
isophthaloyldibenzoic acid, 4,4'-terephthaloyldibenzoic acid,
dithiosalicylic acid, and 3,9-bis(4-carboxyphenyl)-2,4,8,10-
tetraoxaspiro[5,5]undecane are specifically mentioned as
examples.
As the aliphatic monoamine, methylamine, ethylamine,
propylamine, butylamine, pentylamine, hexylamine, octylamine,
dodecylamine, octadecylamine, octacosylamine, N,N-
di(dodecyl}amine, and N,N-di(octadecyl)amine can specifically be
mentioned as examples.
CA 02203876 1997-04-28
28
As the alicyclic monoamine, cyclopropylamine,
cyclobutylamine, cyclopentylamine, cyclohexylamine, 2-
methylcyclohexylamine, 3-methylcyclohexylamine, 4-
methylcyclohexylamine, 2-ethylcyclohexylamine, 4-
ethylcyclohexylamine, 2-propylcyclohexylamine, 2-
isopropylcyclohexylamine, 4-propylcyclohexylamine, 4-
isopropylcyclohexylamine, 2-t-butylcyclohexylamine, 4-n-
butylcyclohexylamine, 4-i-butylcylohexylamine, 4-s-
butylcyclohexylamine, 4-t-butylcyclohexylamine, 2,4-di-t-
butylcyclohexylamine, 4-n-amylcyclohexylamine, 4-i-
amylcyclohexylamine, 4-s-amylcyclohexylamine, 4-t-
amylcyclohexylamine, 4-hexylcyclohexylamine, 4-
octylcyclohexylamine, 4-nonylcyclohexylamine, 4-
decylcyclohexylamine, 4-undecylcyclohexylamine, 4-
dodecylcyclohexylamine, 4-cyclohexylcyclohexylamine, 4-
phenylcyclohexylamine, cycloheptylamine, cyclododecylamine,
cyclohexylmethylamine, (x-cyclohexylethylamine, a-
cyclohexylethylamine, a-cyclohexylpropylamine, a-
cyclohexylpropylamine, 1'-cyclohexylpropylamine, 1-
adamantylamine, pyrrolidine, piperidine, hexamethyleneimine, N-
butyl-N-cyclohexylamine, and N,N-di(cyclohexyl)amine are
specifically mentioned as examples.
As the aromatic monoamine, aniline, o-toluidine, m
toluidine, p-toluidine, o-ethylaniline, m-ethylaniline, p
ethylaniline, o-propylaniline, m-propylaniline, p-propylaniline,
o-cumidine, m-cumidine, p-cumidine, o-t-butylaniline, p-n-
butylaniline, p-i-butylaniline, p-s-butylaniline, p-t-
CA 02203876 1997-04-28
29
butylaniline, 2,4-di-t-butylaniline, p-n-amylaniline, p-i-
amylaniline, p-s-amylaniline, p-i-amylaniline, p-hexylaniline,
p-heptylaniline, p-octylaniline, p-nonylaniline, p-decylaniline,
p-undecylaniline, p-dodecylaniline, p-cyclohexylaniline, o-
aminodiphenyl, m-aminodiphenyl, p-aminodiphenyl, p-aminostyrene,
benzylamine, a-phenylethylamine, /3-phenylethylamine, (x-
phenylpropylamine, ~i-phenylpropylamine, 1'-phenylpropylamine,
ot-naphthylamine, N-butyl-aniline, and N,N-diphenylamine are
specifically mentioned as examples.
Amide compounds expressed by the (2) R7-CONH-R6-CONH-R8
mentioned above and used in the present invention as /3-crystal
nucleator can readily be prepared by amidating a prescribed
aliphatic, alicyclic, or aromatic amino acid and an alicyclic or
aromatic monocarboxylic acid and monoamine.
As the aliphatic aminoacid, aminoacetic acid, a-
aminopropionic acid, ~i-aminopropionic acid,_a-aminoacrylic
acid, a-aminobutyric acid, (3-aminobutyric acid, 'r-aminobutyric
acid, a-amino-cx-methylbutyric acid, 1'-amino-a-methylbutyric
acid, a-amino-i-butyric acid, ~3-amino-i-butyric acid, U:-amino-
n-valeric acid, 8-amino-n-valeric acid, ~i-aminocrotonic acid,
ot-amino-a-methylvaleric acid, Cx-amino-i-valeric acid, 2-amino-
4-pentenoic acid, a-amino-n-caproic acid, 6-aminocaproic acid,
cx-amino-i-caproic acid, 7-aminoheptanoic acid, lx-amino-n-
caprylic acid, 8-aminocaprylic acid, 9-aminononanoic acid, 11-
aminoundecanoic acid, and 12-aminododecanoic acid can
specifically be mentioned as examples.
As the alicyclic amino acid, 1-aminocyclohexanecarboxylic
CA 02203876 1997-04-28
acid, 2-aminocyclohexanecarboxylic acid, 3-
aminocyclohexanecarboxylic acid, 4-aminocyclohexanecarboxylic
acid, p-aminomethylcyclohexanecarboxylic acid, and 2-amino-2-
norbornanecarboxylic acid are specifically mentioned as
5 examples.
As the aromatic amino acid, cx-aminophenylacetic acid, a-
amino-Q-phenylpropionic acid, 2-amino-2-phenylpropionic acid, 3-
amino-3-phenylpropionic acid, a-aminocinnamic acid, 2-amino-4-
phenylbutyric acid, 4-amino-3-phenylbutyric acid, anthranilic
10 acid, m-aminobenzoic acid, p-aminobenzoic acid, 2-amino-4-
methylbenzoic acid, 2-amino-6-methylbenzoic acid, 3-amino-4-
methylbenzoic acid, 2-amino-3-methylbenzoic acid, 2-amino-5-
methylbenzoic acid, 4-amino-2-methylbenzoic acid, 4-amino-3-
methylbenzoic acid, 2-amino-3-methoxybenzoic acid, 3-amino-4-
15 methoxybenzoic acid, 4-amino-2-methoxybenzoic acid, 4-amino-3-
methoxybenzoic acid, 2-amino-4,5-dimethoxybenzoic acid, o-
aminophenylacetic acid, m-aminophenylacetic acid, p-
aminophenylacetic acid, 4-(4-aminophenyl)butyric acid, 4-
aminomethylbenzoic acid, 4-aminomethylphenylacetic acid, o-
20 aminocinnamic acid, m-aminocinnamic acid, p-aminocinnamic acid,
p-aminohippric acid, 2-amino-1-naphthoic acid, 3-amino-1-
naphthoic acid, 4-amino-1-naphthoic acid, 5-amino-1-naphthoic
acid, 6-amino-1-naphthoic acid, 7-amino-1-naphthoic acid, 8-
amino-1-naphthoic acid, 1-amino-2-naphthoic acid, 3-amino-2-
25 naphthoic acid, 4-amino-2-naphthoic acid, 5-amino-2-naphthoic
acid, 6-amino-2-naphthoic acid, 7-amino-2-naphthoic acid, and 8-
amino-2-naphthoic acid are specifically mentioned as examples.
CA 02203876 1997-04-28
31
As the alicyclic monocarboxylic acid, cyclopropanecarboxylic
acid, cyclobutanecarboxylic acid, cyclopentanecarboxylic acid,
1-methylcyclopentanecarboxylic acid, 2-methylcyclopentane-
carboxylic acid, 3-methylcyclopentanecarboxylic acid, 1-
phenylcyclopentanecarboxylic acid, cyclopentenecarboxylic acid,
cyclohexanecarboxylic acid, 1-methylcyclohexanecarboxylic acid,
2-methylcyclohexanecarboxylic acid, 3-methylcyclohexane-
carboxylic acid, 4-methylcyclohexanecarboxylic acid, 4-
propylcyclohexanecarboxylic acid, 4-butylcyclohexanecarboxylic
acid, 4-pentylcyclohexanecarboxylic acid, 4-hexylcyclohexane-
carboxylic acid, 4-phenylcyclohexanecarboxylic acid, 1-
phenylcyclohexanecarboxylic acid, cyclohexenecarboxylic acid, 4-
butylcyclohexenecarboxylic acid, cycloheptanecarboxylic acid, 1-
cycloheptenecarboxylic acid, 1-methylcycloheptanecarboxylic
acid, 4-methylcycloheptanecarboxylic acid, and cyclohexylacetic
acid are specifically mentioned as examples.
As the aromatic monocarboxylic acid, benzoic acid, o-
methylbenzoic acid, m-methylbenzoic acid, p-methylbenzoic acid,
p-ethylbenzoic acid, p-propylbenzoic acid, p-n-butylbenzoic
acid, p-i-butylbenzoic acid, p-s-butylbenzoic acid, p-t-
butylbenzoic acid, p-n-amylbenzoic acid, p-i-amylbenzoic acid,
p-s-amylbenzoic acid, p-t-amylbenzoic acid, p-hexylbenzoic acid,
o-phenylbenzoic acid, p-phenylbenzoic acid, p-cyclohexylbenzoic
acid, phenylacetic acid, phenylpropionic acid, and phenylbutyric
acid are specifically mentioned as examples.
Monoamines which are starting materials for the amide
compounds expressed by the (2) mentioned above may be the same
CA 02203876 1997-04-28
32
as the monoamines which are the starting materials for the amide
compounds expressed by the (1) mentioned above.
Amide compounds expressed by the (3) Rlo-CONH-R9-NHCO-R11
mentioned above and used in the present invention as /3-crystal
nucleator can readily be prepared by amidating a prescribed
aliphatic diamine, alicyclic diamine, or aromatic diamine and a
prescribed monocarboxylic acid according to a conventional
method.
As the aliphatic diamine, saturated or unsaturated aliphatic
diamines of 1 to 24 carbon atoms are mentioned as examples.
Specifically, methylenediamine, ethylenediamine, 1,2-
diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,3-
diaminopentane, 1,5-diaminopentane, and 1,6-diamonohexane are
mentioned as examples.
As the alicyclic diamine, diaminocyclohexane,
bis(aminoalkyl)cyclohexanes of 8 to 12 carbon atoms, diamino-
dicyclohexylmethane, and diamino-dialkyldicyclohexylmethane of
15 to 21 carbon atoms such as 1,2-diaminocyclohexane, 1,4-
diaminocyclohexane, 4,4'-diaminodicyclohexylmethane, 4,4'-
diamino-3,3'-dimethyldicyclohexylmethane, 1,3-bis(aminomethyl)
cyclohexane, and 1,4-bis(aminomethyl)cyclohexane, as well as
alicyclic diamines such as isophoronediamine and menthendiamine
are mentioned as examples.
As the aromatic diamine, phenylenediamine,
naphthalenediamine, diaminodiphenylmethane, diaminodiphenyl
ether, diaminodipehnylsulfone, diaminodiphenylsulfide,
diaminodiphenyl ketone, and 2,2-bis(aminophenyl)propane are
CA 02203876 1997-04-28
33
mentioned as examples. More specifically, o-phenylenediamine,
m-phenylenediamine, p-phenylenediamine, 1,5-diaminonaphthalene,
4.4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, and
4,4'-diaminodiphenylsulfone are mentioned. However,
xylylenediamine can not achieve intended effects although it is
an aromatic diamine.
As the monocarboxylic acid mentioned above, phenylacetic
acid, cyclohexylacetic acid, cyclopropanecarboxylic acid,
cyclobutanecarboxylic acid, cyclopentanecarboxylic acid,
cyclohexanecarboxylic acid, 2-methylcyclohexanecarboxylic acid,
3-methylcyclohexanecarboxylic acid, 4-methylcyclohexane-
carboxylic acid, 4-t-butylcyclohexanecarboxylic acid, benzoic
acid, o-methylbenzoic acid, m-methylbenzoic acid, p-
methylbenzoic acid, p-ethylbenzoic acid, p-n-butylbenzoic acid,
p-i-butylbenzoic acid, p-s-butylbenzoic acid, and p-t-
butylbenzoic acid are mentioned as examples.
As the cyclic phosphorous compounds expressed by the general
formula (1) mentioned above and used in the present invention as
(3-crystal nucleator, the followings can be mentioned as
examples:
10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-
oxide,
1-methyl-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
2-methyl-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
6-methyl-10-hydroxy-9,10-dihydro-9-oxa-10-
CA 02203876 1997-04-28
34
phosphaphenanthrene-10-oxide,
7-methyl-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
8-methyl-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
6,8-dimethyl-20-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
2,6,8-trimethyl-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
2-ethyl-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
6-ethyl-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
8-ethyl-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
6,8-diethyl-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
2,6,8-triethyl-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
2-i-propyl-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
6-i-propyl-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
8-i-propyl-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
6,8-di-i-propyl-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
CA 02203876 1997-04-28
2,6,8-tri-i-propyl-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
2-s-butyl-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
5 6-s-butyl-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
8-s-butyl-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
1,8-di-s-butyl-10-hydroxy-9,10-dihydro-9-oxa-10-
10 phosphaphenanthrene-10-oxide,
2,6,8-tri-s-butyl-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
2-t-butyl-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
15 6-t-butyl-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
8-t-butyl-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
1,6-di-t-butyl-10-hydroxy-9,10-dihydro-9-oxa-10-
20 phosphaphenanthrene-10-oxide,
2,6-di-t-butyl-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
2,7-di-t-butyl-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
25 2,8-di-t-butyl-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
6,8-di-t-butyl-10-hydroxy-9,10-dihydro-9-oxa-10-
CA 02203876 1997-04-28
36
phosphaphenanthrene-10-oxide,
2,6,8-tri-t-butyl-10-hydroxy-9,10-dihydro-9-oxa-
phosphaphenanthrene-10-oxide,
2-t-amyl-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-20-oxide,
6-t-amyl-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
8-t-amyl-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
6,8-di-t-amyl-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
2,6,8-tri-t-amyl-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
2-t-octyl-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
6-t-octyl-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
8-t-octyl-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
6,8-di-t-octyl-10-hydroxy-9,10-dihydro-9-oxa-14-
phosphaphenanthrene-10-oxide,
2,6,8-tri-t-octyl-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
2-cyclohexyl-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
6-cyclohexyl-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
CA 02203876 1997-04-28
37
8-cyclohexyl-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
6,8-di-cyclohexyl-10-hydroxy-9,20-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
2,6,8-tri-cyclohexyl-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
6-phenyl-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
2-benzyl-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
6-benzyl-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
8-benzyl-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
6,8-di-benzyl-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
2,6,8-tri-benzyl-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
2-(a-methylbenzyl)-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
6-(a-methylbenzyl)-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
8-(a-methylbenzyl)-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
6,8-di(a-methylbenzyl)-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
2,6,8-tri(a-methylbenzyl)-10-hydroxy-9,10-dihydro-9-oxa-10-
CA 02203876 1997-04-28
38
phosphaphenanthrene-10-oxide,
2,6-di(~, ~-dimethylbenzyl)-10-hydroxy-9,10-dihydro-9-oxa-
10-phosphaphenanthrene-10-oxide,
6-t-butyl-8-methyl-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
6-benzyl-8-methyl-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
6-cyclohexyl-8-t-butyl-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
6-benzyl-8-t-butyl-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
6-(~-methylbenzyl)-8-t-butyl-10-hydroxy-9,10-dihydro-9-oxa-
10-phosphaphenanthrene-10-oxide,
6-t-butyl-8-cyclohexyl-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
6-benzyl-8-cyclohexyl-10-hydroxy-9,I0-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
6-t-butyl-8-benzyl-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
6-cyclohexyl-8-benzyl-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
2,6-di-t-butyl-8-benzyl-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide, and
2,6-dicyclohexyl-8-benzyl-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide.
These cyclic phosphorous compounds can, of course, be used
singly, but more than one of them can also be used in
CA 02203876 1997-04-28
39
combination.
As the magnesium compound expressed by one of the (4) to (8)
mentioned above and used in combination with the cyclic
phosphorous compounds which are expressed by the general formula
(1) mentioned above and used in the present invention as /3-
crystal nucleator, the followings can be mentioned as examples:
magnesium acetate, magnesium propionate, magnesium n-
butyrate, magnesium i-butyrate, magnesium n-valerate, magnesium
i-valerate, magnesium n-hexanoate, magnesium n-octanoate,
magnesium 2-ethylhexanoate, magnesium decanoate, magnesium
laurate, magnesium myristinate, magnesium myristoleate,
magnesium palmitate, magnesium palmitoleate, magnesium stearate,
magnesium oleate, magnesium linoleate, magnesium linolenate,
magnesium arachate, magnesium behenate, magnesium erucate,
magnesium lignocerate, magnesium cerotate, magnesium montanate,
magnesium melissinate, magnesium 12-hydroxyoctadecanate,
magnesium ricinoleate, magnesium cerebronate, magnesium (mono,
dimixed) hexylphosphate, magnesium (mono, dimixed)
octylphosphate, magnesium (mono, dimixed) 2-ethylhexylphosphate,
magnesium (mono, dimixed) decylphosphate, magnesium (mono,
dimixed) laurylphosphate, magnesium (mono, dimixed)
myristylphosphate, magnesium (mono, dimixed) palmitylphosphate,
magnesium (mono, dimixed) stearylphosphate, magnesium (mono,
dimixed) oleylphosphate, magnesium (mon, dimixed)
linolphosphate, magnesium (mono, dimixed) linolylphosphate,
magnesium (mono, dimixed) docosylphosphate, magnesium (mono,
dimixed) erucylphosphate, magnesium (mono, dimixed)
CA 02203876 1997-04-28
tetracosylphosphate, magnesium (mono, dimixed)
hexacosylphosphate, magnesium (mono, dimixed)
octacosylphosphate, magnesium oxide, magnesium hydroxide,
magnesium carbonate,
5 magnesium salts of cyclic phosphorous compounds such as
10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-
oxide,
1-methyl-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
10 2-methyl-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
6-methyl-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
7-methyl-10-hydroxy-9,10-dihydro-9-oxa-10-
15 phosphaphenanthrene-10-oxide,
8-methyl-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
6,8-dimethyl-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
20 2,6,8-trimethyl-20-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
2-ethyl-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
6-ethyl-10-hydroxy-9,10-dihydro-9-oxa-10-
25 phosphaphenanthrene-10-oxide,
8-ethyl-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
CA 02203876 1997-04-28
41
6,8-diethyl-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
2,6,8-triethyl-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-20-oxide,
2-i-propyl-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
6-i-propyl-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
8-i-propyl-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-20-oxide,
6,8-di-i-propyl-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
2,6,8-tri-i-propyl-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-20-oxide,
2-s-butyl-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
6-s-butyl-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-20-oxide,
8-s-butyl-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
2,8-di-s-butyl-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
2,6,8-tri-s-butyl-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
2-t-butyl-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
6-t-butyl-10-hydroxy-9,10-dihydro-9-oxa-10-
CA 02203876 1997-04-28
42
phosphaphenanthrene-10-oxide,
8-t-butyl-10-hydroxy-9,I0-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
1,6-di-t-butyl-10-hydroxy-9,10-dihydro-9-oxa-20-
phosphaphenanthrene-10-oxide,
2,6-di-t-butyl-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
2,7-di-t-butyl-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
2,8-di-t-butyl-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
6,8-di-t-butyl-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
2,6,8-tri-t-butyl-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
2-t-amyl-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
6-t-amyl-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
8-t-amyl-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
6,8-di-t-amyl-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
2,6,8-tri-t-amyl-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
2-t-octyl-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
CA 02203876 1997-04-28
43
6-t-octyl-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
8-t-octyl-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
6,8-di-t-octyl-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
2,6,8-tri-t-octyl-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
2-cyclohexyl-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
6-cyclohexyl-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
8-cyclohexyl-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
6,8-di-cyclohexyl-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
2,6,8-tri-cyclohexyl-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
6-phenyl-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
2-benzyl-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
6-benzyl-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
8-benzyl-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
6,8-di-benzyl-10-hydroxy-9,10-dihydro-9-oxa-10-
CA 02203876 1997-04-28
44
phosphaphenanthrene-10-oxide,
2,6,8-tri-benzyl-10-hydroxy-9,10-dihydra-9-oxa-20-
phosphaphenanthrene-10-oxide,
2-(a-methylbenzyl)-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
6-(a-methylbenzyl)-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
8-(a-methylbenzyl)-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
6,8-di(a-methylbenzyl)-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
2,6,8-tri(a-methylbenzyl)-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
2,6-di(a, ~-dimethylbenzyl)-10-hydroxy-9,10-dihydro-9-oxa-
10-phosphaphenanthrene-20-oxide,
6-t-butyl-8-methyl-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
6-benzyl-8-methyl-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
6-cyclohexyl-8-t-butyl-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
6-benzyl-8-t-butyl-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
6-(a-methylbenzyl)-8-t-butyl-10-hydroxy-9,10-dihydro-9-oxa-
10-phosphaphenanthrene-10-oxide,
6-t-butyl-8-cyclohexyl-20-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
CA 02203876 1997-04-28
6-benzyl-8-cyclohexyl-10-hydroxy-9,10-dihydro-9-oxa-20-
phosphaphenanthrene-10-oxide,
6-t-butyl-8-benzyl-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-20-oxide,
5 6-cyclohexyl-8-benzyl-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
2,6-di-t-butyl-8-benzyl-10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide, and
2,6-dicyclohexyl-8-benzyl-10-hydroxy-9,10-dihydro-9-oxa-10-
10 phosphaphenanthrene-10-oxide;
magnesium-bis(1'-hydroxy-2,2'-biphenylenephosphinate),
magnesium-bis(5-methyl-1'-hydroxy-2,2'-biphenylenephosphinate),
magnesium-bis(6-methyl-1'-hydroxy-2,2'-biphenylenephosphinate),
magnesium-bis(1'-hydroxy-4'-methyl-2,2'-biphenylenephosphinate),
15 magnesium-bis(1'-hydroxy-5'-methyl-2,2'-biphenylenephosphinate),
magnesium-bis(1'-hydroxy-6'-methyl-2,2'-biphenylenephosphinate),
magnesium-bis(1'-hydroxy-4',6'-dimethyl-2,2'-biphenylene-
phosphinate),
magnesium-bis(5,4'6'-trimethyl-1'-hydroxy-2,2'-biphenylene-
20 phosphinate),
magnesium-bis(5-ethyl-1'-hydroxy-2,2'-biphenylenephosphinate),
magnesium-bis(1'-hydroxy-4'-ethyl-2,2'-biphenylenephosphinate),
magnesium-bis(1'-hydroxy-6'-ethyl-2,2'-biphenylenephosphinate),
magnesium-bis(1'-hydroxy-4',6'-diethyl-2,2'-biphenylene-
25 phosphinate),
magnesium-bis(5,4',6'-triethyl-1'-hydroxy-2,2'-biphenylene-
phosphinate),
CA 02203876 1997-04-28
46
magnesium-bis(5-i-propyl-1'-hydroxy-2,2'-biphenylene-
phosphinate),
magnesium-bis(1'-hydroxy-4'-i-propyl-2,2'-biphenylene-
phosphinate),
magnesium-bis(1'-hydroxy-6'-i-propyl-2,2'-biphenylene-
phosphinate),
magnesium-bis(1'-hydroxy-4',6'-di-i-propyl-2,2'-biphenylene-
phosphinate),
magnesium-bis(5,4',6'-tri-i-propyl-1'-hydroxy-2,2'-biphenylene-
phosphinate),
magnesium-bis(5-s-butyl-1'-hydroxy-2,2'-biphenylenephosphinate),
magnesium-bis(1'-hydroxy-4'-s-butyl-2,2'-biphenylene-
phosphinate),
magnesium-bis(1'-hydroxy-6'-s-butyl-2,2'-biphenylene-
phosphinate),
magnesium-bis(6,6'-di-s-butyl-1'-hydroxy-2,2'-biphenylene-
phosphinate),
magnesium-bis(5,4',6'-tri-s-butyl-1'-hydroxy-2,2'-
biphenylenephosphinate),
magnesium-bis(5-t-butyl-1'-hydroxy-2,2'-biphenylene-
phosphinate),
magnesium-bis(1'-hydroxy-4'-t-butyl-2,2'-biphenylene-
phosphinate),
magnesium-bis(1'-hydroxy-6'-t-butyl-2,2'-biphenylene-
phosphinate),
magnesium-bis(5,6'-di-t-butyl-hydroxy-2,2'-biphenylene-
phosphinate),
CA 02203876 1997-04-28
47
magnesium-bis(5,4'-di-t-butyl-1'-hydroxy-2,2'-biphenylene-
phosphinate),
magnesium-bis(5,5'-di-t-butyl-1'-hydroxy-2,2'-biphenylene-
phosphinate),
magnesium-bis(6,4'-di-t-butyl-1'-hydroxy-2,2'-biphenylene-
phosphinate),
magnesium-bis(1'-hydroxy-4',6'-di-t-butyl-2,2'-biphenylene-
phosphinate),
magnesium-bis(5,4',6'-tri-t-butyl-1'-hydroxy-2,2'-biphenylene-
phosphinate), --
magnesium-bis(5-t-amyl-1'-hydroxy-2,2'-biphenylenephosphinate),
magnesium-bis(1'-hydroxy-4'-t-amyl-2,2'-biphenylene-
phosphinate),
magnesium-bis(1'-hydroxy-6'-t-amyl-2,2'-biphenylene-
phosphinate),
magnesium-bis(1'-hydroxy-4',6'-di-t-amyl-2,2'-biphenylene-
phosphinate),
magnesium-bis(5,4',6'-tri-t-amyl-1'-hydroxy-2,2'-
biphenylenephosphinate),-
magnesium-bis(5-t-octyl-1'-hydroxy-2,2'-biphenylene-
phosphinate),
magnesium-bis(1'-hydroxy-4'-t-octyl-2,2'-biphenylene-
phosphinate),
magnesium-bis(1'-hydroxy-6'-t-octyl-2,2'-biphenylene-
phosphinate),
magnesium-bis(1'-hydroxy-4',6'-di-t-octyl-2,2'-biphenylene-
phosphinate),
CA 02203876 1997-04-28
48
magnesium-bis(5,4',6'-tri-t-octyl-1'-hydroxy-2,2'-biphenylene-
phosphinate),
magnesium-bis(5-cyclohexyl-1'-hydroxy-2,2'-biphenylene-
phosphinate),
magnesium-bis(1'-hydroxy-4'-cyclohexyl-2,2'-biphenylene-
phosphinate),
magnesium-bis(1'-hydroxy-6'-cyclohexyl-2,2'-biphenylene-
phosphinate),
magnesium-bis(1'-hydroxy-4',6'-di-cyclohexyl-2,2'-biphenylene-
phosphinate),
magnesium-bis(5,4',6'-tri-cyclohexyl-1'-hydroxy-2,2'-
biphenylenephosphinate),
magnesium-bis(1'-hydroxy-4'-phenyl-2,2'-biphenylene-
phosphinate),
magnesium-bis(5-benzyl-1'-hydroxy-2,2'-biphenylenephosphinate),
magnesium-bis(1'-hydroxy-4'-benzyl-2,2'-biphenylene-
phosphinate),
magnesium-bis(1'-hydroxy-6'-benzyl-2,2'-biphenylene-
phosphinate),
magnesium-bis(1'-hydroxy-4',6'-di-benzyl-2,2'-biphenylene-
phosphinate),
magnesium-bis(5,4',6'-tri-benzyl-1'-hydroxy-2,2'-biphenylene-
phosphinate),
magnesium-bis[5-(cx-methylbenzyl)-1'-hydroxy-2,2'-biphenylene-
phosphinate),
magnesium-bis[1'-hydroxy-4'-((x-methylbenzyl)-2,2'-biphenylene-
phosphinate],
CA 02203876 1997-04-28
49
magnesium-bis[1'-hydroxy-6'-((x-methylbenzyl)-2,2'-biphenylene-
phosphinate],
magnesium-bis[1'-hydroxy-4',6'-di(cx-methylbenzyl)-2,2'-
biphenylenephosphinate],
magnesium-bis[5,4',6'-tri((x-methylbenzyl)-1'-hydroxy-2,2'-
biphenylenephosphinate],
magnesium-bis[5,4'-di(lx,cx-dimethylbenzyl}-1'-hydroxy-2,2'-
biphenylenephosphinate],
magnesium-bis(1'-hydroxy-4'-t-butyl-6'-methyl-2,2'-biphenylene-
phosphinate),
magnesium-bis(1'-hydroxy-4'-benzyl-6'-methyl-2,2'-biphenylene-
phosphinate),
magnesium-bis(1'-hydroxy-4'-cyclohexyl-6'-t-butyl-2,2'-
biphenylenephosphinate),
magnesium-bis(1'-hydroxy-4'-benzyl-6'-t-butyl-2,2'-biphenylene-
phosphinate),
magnesium-bis[1'-hydroxy-4'-(cx-methylbenzyl)-6'-t-butyl-2,2'-
biphenylenephosphinate],
magnesium-bis(1'-hydroxy-4'-t-butyl-6'-cyclohexyl-2,2'-
biphenylenephosphinate),
magnesium-bis(1'-hydroxy-4'-benzyl-6'-cyclohexyl-2,2'-
biphenylenephosphinate),
magnesium-bis(1'-hydroxy-4'-t-butyl-6'-benzyl-2,2'-
biphenylenephosphinate),
magnesium-bis(1'-hydroxy-4'-cyclohexyl-6'-benzyl-2,2'-
biphenylenephosphinate),
magnesium-bis(5,4'-di-t-butyl-6'-benzyl-2'-hydroxy-2,2'-
CA 02203876 1997-04-28
biphenylenephosphinate), and
magnesium-bis(5,4'-dicyclohexyl-6'-benzyl-1'-hydroxy-2,2'-
biphenylenephosphinate).
These magnesium compounds can, of course, be used singly,
5 but more than one of them can also be used in combination.
Weight proportion of the mixture of these cyclic phosphorous
compound with these magnesium compounds is not particularly
restricted, but it is usually 0.01 to 100 parts by weight,
preferably 0.1 to 10 parts by weight of the magnesium compounds
10 per 1 part by weight of the cyclic phosphorous compounds.
As the cyclic phosphorous compounds expressed by the general
formula (4) mentioned above and used in the present invention as
a-crystal nucleator, the followings can be mentioned as
examples:
15 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide,
1-methyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide,
2-methyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide,
6-methyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide,
7-methyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-20-oxide,
20 8-methyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide,
6,8-dimethyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide,
2,6,8-trimethyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-
oxide,
2-ethyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide,
25 6-ethyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide,
8-ethyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide,
6,8-diethyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide,
CA 02203876 1997-04-28
51
2,6,8-triethyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-
oxide,
2-i-propyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide,
6-i-propyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide,
8-i-propyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide,
6,8-di-i-propyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-
oxide,
2,6,8-tri-i-propyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-
oxide,
2-s-butyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide,
6-s-butyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide,
8-s-butyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide,
1,8-di-s-butyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-
oxide,
2,6,8-tri-s-butyl-9,10-dihydro-9-oxa-IO-phosphaphenanthrene-10-
oxide,
2-t-butyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide,
6-t-butyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide,
8-t-butyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide,
1,6-di-t-butyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-
oxide,
2,6-di-t-butyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-
oxide,
2,7-di-t-butyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-
oxide,
2,8-di-t-butyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-
oxide,
CA 02203876 1997-04-28
52
6,8-di-t-butyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-
oxide,
2,6,8-tri-t-butyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-
oxide,
2-t-amyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide,
6-t-amyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide,
8-t-amyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide,
6,8-di-t-amyl-9,20-dihydro-9-oxa-10-phosphaphenanthrene-10-
oxide,
2,6,8-tri-t-amyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-
oxide,
2-t-octyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide,
6-t-octyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide,
8-t-octyl-9,10-dihydro-9-oxa-IO-phosphaphenanthrene-10-oxide,
6,8-di-t-octyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-20-
oxide,
2,6,8-tri-t-octyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-
oxide,
2-cyclohexyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide,
6-cyclohexyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide,
8-cyclohexyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-20-oxide,
6,8-di-cyclohexyl-9,10-dihydro-9-oxa-20-phosphaphenanthrene-10-
oxide,
2,6,8-tri-cyclohexyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-
10-oxide,
6-phenyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide,
2-benzyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide,
CA 02203876 1997-04-28
53
6-benzyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide,
8-benzyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-20-oxide,
6,8-di-benzyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-
oxide,
2,6,8-tri-benzyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-
oxide,
2-(a-methylbenzyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-
oxide,
6-(a-methylbenzyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-
oxide,
8-(~-methylbenzyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-
oxide,
6,8-di(a-methylbenzyl)-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
2,6,8-tri(~-methylbenzyl)-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
2,6-di(a, a-dimethylbenzyl)-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
6-t-butyl-8-methyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-
oxide,
6-benzyl-8-methyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-
oxide,
6-cyclohexyl-8-t-butyl-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
6-benzyl-8-t-butyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-
oxide,
6-(~-methylbenzyl)-8-t-butyl-9,10-dihydro-9-oxa-10-
CA 02203876 1997-04-28
54
phosphaphenanthrene-10-oxide,
6-t-butyl-8-cyclohexyl-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide,
6-benzyl-8-cyclohexyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-
10-oxide,
6-t-butyl-8-benzyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-20-
oxide,
6-cyclohexyl-8-benzyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-
10-oxide,
2,6-di-t-butyl-8-benzyl-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide, and
2,6-dicyclohexyl-8-benzyl-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide.
These cyclic phosphorous compounds can, of course, be used
singly, but more than one of them can also be used in
combination.
As the magnesium compounds expressed by the (8) to (9)
mentioned above which are used in combination with the cyclic
phosphorous compounds expressed by the general formula (4)
mentioned above and used in the present invention as (3-crystal
nucleator, various kind of the magnesium phosphinate compounds
mentioned above, magnesium sulfate, basic magnesium sulfate
(magnesium oxysulfate), and talc can be mentioned as examples.
These magnesium compounds can, of course, be used singly,
but more than one of them can also be used in combination.
Whereas the weight proportion of the mixture of these cyclic
phosphorous compounds and magnesium compounds is not
CA 02203876 1997-04-28
specifically restricted, it is usually 0.01 to 100 parts by
weight, preferably 0.1 to 10 parts by weight of the magnesium
compound per 1 part by weight of the cyclic phosphorous
compound.
5 As the ~i-crystal nucleator used in the present invention,
particularly the followings are preferable:
mixture of ?'-csuinacridone, adipic acid dianilide, suberic
acid dianilide, N,N'-dicyclohexylterephthalamide, N,N'-
dicyclohexyl-1,4-cyclohexanedicarboxyamide, N,N'-dicyclohexyl-
10 2,6-naphthalenedicarboxyamide, N,N'-dicyclohexyl-4,4'-
biphenyldicarboxyamide, N,N'-bis(p-methylphenyl)hexanediamide,
N,N'-bis(p-ethylphenyl)hexanediamide, N,N'-bis(4-
cyclohexylphenyl)hexanediamide, p-(N-cyclohexanecarbonylamino)
benzoic acid cyclohexylamide, 8-(N-benzoylamino)-n-valeric acid
15 anilide, 3,9-bis[4-(N-cyclohexylcarbamoyl)phenyl]-2,4,8,10-
tetraoxaspiro [5.5] undecane, N,N'-dicyclohexanecarbonyl-p-
phenylenediamine, N,N'-dibenzoyl-1,5-diaminonaphthalene, N,N'-
dibenzoyl-1,4-diaminocyclohexane, N,N'-dicyclohexanecarbonyl-
1,4-diaminocyclohexane, or 10-hydroxy-9,10-dihydro-9-oxa-10-
20 phosphaphenanthrene-10-oxide with magnesium stearate; mixture of
10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide
with (mono, dimixed) magnesium stearylphosphate; mixture of 10-
hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide with
magnesium (mono, dimixed) stearylphosphate; mixture of 10-
25 hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide with
magnesium oxide, mixture of 10-hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide with magnesium hydroxide; mixture
CA 02203876 1997-04-28
56
of 10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide
with magnesium carbonate; mixture of l0-hydroxy-9,10-dihydro-9-
oxa-10-phosphaphenanthrene-10-oxide with magnesium salt of 10-
hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide;
mixture of 10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-
10-oxide with magnesium-bis(1'-hydroxy-2,2'-
biphenylenephosphinate); mixture of 9,10-dihydro-9-oxa-10-
phosphapehnanthrene-10-oxide with magnesium sulfate; mixture of
9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide with talc:
and mixture of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-
oxide with magnesium-bis(1'-hydroxy-2,2'-biphenylene-
phosphinate).
These a-crystal or ~-crystal nucleators may, of course, be
used singly, and two or more kind thereof may also be used in
combination. Blending proportion of the nucleators is 0.0001 to
1 part by weight, preferably 0.01 to 0.5 part by weight, more
desirably 0.05 to 0.3 part by weight based on 100 parts by
weight of the propylene-ethylene copolymer. When the
proportion is far less than 0.0001 part by weight, effect of the
improvement on the rigidity, toughness, and impact-strength can
not fully be achieved, while when it is far greater than 1 part
by weight, more effect of the improvement on the rigidity,
toughness, and impact-strength can not be expected.
In the compositions of the present invention, various kind
of additives usually added to crystalline propylene polymers can
be used together within the range in which achievement of the
objects of present invention are not disturbed, examples of the
CA 02203876 1997-04-28
57
additives include antioxidants such as phenol-, thioether-, and
phosphorous-type antioxidants, light stabilizers, heavy metal
deactivators (copper deactivators), clarifiers, crystal-
nucleators other than those used in the present invention,
lubricants, antistatic agents, antifogging agents, antiblocking
agents, anti-fog-dropping agents, radical generators such as
organic peroxides, flame retardants, flame-retarding
auxiliaries, pigments, halogen-scavengers, dispersants or
neutralizing agents such as metal soaps, organic or inorganic
antifungus agents, inorganic fillers (such as mica,
wollastonite, zeolite, bentonite, perlite, diatomaceous earth,
asbestos, calcium carbonate, magnesium carbonate, magnesium
hydroxide, hydrotalcite, silicon dioxide, titanium dioxide, zinc
oxide, magnesium oxide, calcium oxide, zinc sulfide, barium
sulfate, magnesium sulfate, calcium silicate, aluminum silicate,
glass fibers, potassium silicate, carbon fibers, carbon blacks,
graphites, and metal fibers), the inorganic fillers mentioned
above and subjected to a surface treatment with surface treating
agents such as a coupling agent (for example, those of silane-,
titanate-, boron-, aluminate-, and zircoaluminate-type coupling
agent), and organic fillers (for example, wood flour, pulps,
used papers, synthetic fibers, and natural fibers).
Compositions of the present invention can be obtained, for
instance, blending a prescribed amount of the nucleator and the
various additives both mentioned above which are usually added
to conventional crystalline propylene polymers with a propylene-
ethylene copolymer used in the present invention by using a
CA 02203876 2003-08-06
58
conventional blending apparatus, for example, a Henschel~mixer
(trade name), super mixer, ribbon blender, or Banbury*mixer,
melting and kneading them at a melt-kneading temperature of 170
to 300 °C, preferably 200 to 270 °C by means of a conventional
S monoaxial extruder, biaxial extruder, Brabender~ or rollers, and
subjecting to a pelletizing. The compositions thus obtained can
be subjected to production of aimed molded products according to
one of various molding methods such as injection molding,
extrusion molding, and blow molding.
Now, the present invention will be described in more detail
with reference to Examples and Comparative Examples, and the
methods for determining the physical properties of the
compositions obtained are as follows:
(1) Melt flow rate:
Melt flow rate is determined according to ASTM D-1238 at a
measuring temperature of 230 °C.
(2) Determination of Cf value:
A fractionating column fabricated by filling glass beads
having a diameter of 0.1 mm in a stainless tube having a length
of 15 cm and an inner diameter of 0.46 cm over the whole length
of 15 cm of the tube is used. The fractionating column is kept
at 140 °C, and 0.5 ml of a sample prepared by dissolving a
polymer in o-dichlorobenzene at 140 °C to give a polymer
concentration of 2 mg/ml is fed and retained therein.
Subsequently, the temperature of the fractionating column is
lowered down to 0 °C at a temperature-lowering rate of 1
°C/minute to deposit the polymer in the sample on the surface of
*trade-mark
CA 02203876 2003-08-06
59
the glass beads in the column. Then, o-dichlorobenzene (0 °C)
is flown through the fractionating column at a flow rate of 1
ml/minute for 2 minutes, while keeping the temperature of the
fractionating column at 0 °C, to obtain the polymer soluble in
the solvent as extract. Then molecular weight distribution of
the polymer in the extracted solution is determined with an
infrared detector (wavelength: 3.42 ~1m). Subsequently
temperature is elevated in three steps, that is, each by 10 °C
in the range of 0 to 50 °C, each by 5 °C in the range of 50 to
9 0 °C , and each by 3 °C in the range of 9 0 to 14 0 °C
, the
procedure mentioned above are repeated, and the amount of the
polymer extracted at each of the temperatures is determined, and
thus the weight fraction and the molecular weight of the
respective fractions are determined. Cf value is obtained by
calculating A/B when the integrated values of the eluted amount
at a temperature lower than 112 °C and 112 °C or higher are
assumed to be A and B, respectively. Details of the
fractionation mentioned above is reported by J.B.P. Soares in
Polymer, Vol. 36, No. 8, pages 1639-1654, 1995.
(3) Determination of toughness:
(I) To 100 parts by weight of a virgin polymer are added 0.1
part by weight of IRGANOX 1010*(tetrakis[methylene-3-(3',5'-di-
butyl-4'-hydroxyphenyl)propionate]methane) (which is a phenol
type thermal stabilizer and produced by Ciba Geigy Corporation),
and 0.1 part by weight of calcium stearate. Then, they are
mixed at room temperature for 10 minutes by means of a high
speed agitating mixer (Henschel mixer (trade name)), and
*trade-mark
CA 02203876 2003-08-06
granulated by means of an extrusion granulator having a screw
diameter of 40 mm. The granules thus obtained are heated by
means of a pressing machine under conditions of a melted resin
temperature of 230 °C and 4 Mpa for 3 minutes, cooled under
5 conditions of 30 °C and 14.8 Mpa for 3 minutes, and then taken
out from the mold to obtain a compression-molded sheet of 0.5 mm
thick. A test piece of 50 mm long and 6 mm wide is punched from
the compressed sheet. The test piece is stretched in
longitudinal direction at 40 °C and at a displacement rate of 10
10 mm/minute by means of a Strograph*(trade name) manufactured by
Toyo Seiki Seisakusho Corporation, and the strength at the yield
point at that time is assumed to be Sy (unit: Mpa).
Subsequently, the stretched test piece used for the
determination of the strength of the yield point is cut off at a
15 narrowed, necked portion, and the central part of the test piece
is stretched again in longitudinal direction at 40 °C and at a
displacement rate of 10 mm/minute and the strength at which the
test piece is broken is assumed to be breaking strength Sb
(unit: MPa). Herein, (Sb-Sy) is regarded as a measure of
20 toughness. The larger the value, the higher the toughness.
(II) Using the pellets of the polymer composition obtained,
a sheet of 100 mm long, 100 mm wide and 0.7 mm thick is prepared
according to a method of injection molding, and the gate portion
of the sheet is punched in the flow direction of resin by means
25 of a punching machine to obtain a punched test piece of 100 mm
long and 10 mm wide. This punched test piece is stretched in
the longitudinal direction at 23 °C and at a displacement speed
*trade-mark
CA 02203876 1997-04-28
61
of 15 mm/min by means of a Strograph manufactured by Toyo Seiki
Seisakusho Corporation. The strength at the yield point at that
time is assumed to be Sy and the breaking strength at that time
is assumed to be Sb. Herein, (Sb-Sy) is regarded as a measure
of toughness.
(4) Ethylene content:
Copolymers having different reaction ratios of ethylene and
propylene are prepared in advance. Then, a calibration curve is
obtained by using the copolymers as standard samples according
to infrared absorption spectra, and the content is obtained by
employing the calibration curve according to infrared absorption
spectra.
(5) Determination of the ratio of polymerized amount in
polymerization step (I) to that in the polymerization step (II):
Ethylene content in the whole polymer is obtained by way of
the infrared absorption spectra mentioned above. Separately,
the ratio of the amount of reacted ethylene/propylene in the
polymerization step (II) is obtained, and the ratio captioned
above is calculated by using both of the values.
(6) Rigidity:
Rigidity is evaluated according to the following flexural
test:
Using the pellets of the copolymer composition obtained, a
test piece of 100 mm long, 10 mm wide and 4 mm thick is prepared
according to a method of injection molding, and flexural modulus
is determined by using the test piece according to JIS K 7203 to
evaluate its rigidity. A high rigidity material refers to a
CA 02203876 1997-04-28
62
material having a high flexural modulus.
(7) Impact-strength:
Impact-strength is evaluated according to the following Izod
impact-strength test:
Using the pellets of the copolymer composition obtained, a
notched test piece of 63.5 mm long, 13 mm wide and 3.5 mm thick
is prepared according to a method of injection molding. Using
the test piece, Izod impact strength thereof at -20 °C is
,determined according to JIS K 7110 to evaluate its impact-
strength. A material having a superior impact-strength refers
to a material having a high Izod strength.
BEST MODE FOR CARRYING OUT THE INVENTION
Example 1
a) Preparation of catalyst
Mixture of 230 g of magnesium ethoxide, 415 ml of 2-
ethylhexyl alcohol, and 1,650 ml of toluene was kept at 93 °C in
an atmosphere of carbon dioxide gas at 0.3 Mpa by using a
stainless steel autoclave of 3 Q, and agitated for 3 hours to
prepare a solution of magnesium carbonate.
Toluene in an amount of 300 ml, 15 ml of tributoxy borane,
and 19 ml of titanium tetrachloride were agitated at 30 °C for 5
minutes by using a four-necked flask of 1 l~, and 1150 ml of the
magnesium carbonate solution mentioned above was added thereto.
The mixed solution was further agitated for 10 minutes, and
2 ml of formic acid, 1 ml of 2-ethylhexylaldehyde, and 60 ml of
tetrahydrofuran were added thereto, and then the mixture was
agitated at 60 °C for one hour. After the agitation was stopped
CA 02203876 1997-04-28
63
and the supernatant was removed, the solids thus resulted were
washed with 200 ml of toluene. To the solids obtained were
added 200 ml of toluene and 100 ml of titanium tetrachloride,
and they were agitated at 135 °C for one hour.
After the agitation was stopped and the supernatant was
removed, 250 ml of toluene, 100 ml of titanium tetrachloride,
and 2.1 ml of di-n-butyl phthalate were added, and they were
agitated at 135 °C for 1 and half hours.
Further, after the agitation was stopped and the supernatant
was removed, 250 ml of toluene and 100 ml of titanium
tetrachloride were added, and they were agitated at 135 °C for
1.5 hour.
After the supernatant was removed, the solids were washed
successively with 200 ml of toluene and 200 ml of hexane to
obtain a solid catalyst product. This catalyst product had a
composition of 2.0 ~ by weight of titanium, 58.3 g by weight of
chlorine, 19 ~ by weight of magnesium, and 10.7 ~ by weight of
di-n-butyl phthalate.
b) Preparation of preactivated catalyst
A stainless steel reaction vessel having an internal volume
of 50 Q provided with slant blades was purged with nitrogen gas.
Subsequently, 40 ~ of n-hexane was charged, and 75 g of the
solid catalyst product mentioned above and 13 g triethylaluminum
were added at room temperature thereto, and then 100 g of
propylene was fed over 120 minutes. After the reaction was
finished, unreacted propylene and n-hexane were separated under
a reduced pressure to obtain 150 g of a preactivated catalyst.
CA 02203876 1997-04-28
64
c) Polymerization step (I)
n-Hexane in an amount of 250 ~ was fed into a stainless
steel polymerization vessel having an internal volume of 500 B,
provided with turbine type agitating blades, and purged with
nitrogen gas, 89 g of triethylaluminum and 69 g of di-i-
propyldimethoxysilane were fed, and then 15 g of the
preactivated catalyst mentioned was added. After the
temperature in the vessel was raised up to 70 °C, propylene and
hydrogen were fed, while keeping the total pressure at 0.8 Mpa
and the ratio of the concentration of hydrogen/propylene in the
gas phase part at 0.31, polymerization was carried out for 3
hours, and then feeding of propylene was stopped. After the
temperature in the vessel was cooled down to 30 °C, hydrogen and
unreacted propylene were discharged.
d) Polymerization step (II):
Following to the polymerization step (I), the temperature in
the vessel was elevated up to 60 °C, ethylene and propylene were
continuously fed for 2 hours so ws to give a feeding ratio of
ethylene of 40 ~. Total amount of the ethylene supplied was
4.5 Kg. During polymerization, hydrogen was fed so as to give a
hydrogen concentration in gas phase of 1~ by mol. Then, feeding
of ethylene and propylene was stopped, the temperature in the
vessel was cooled down to 30 °C, and unreacted ethylene and
propylene were discharged. Subsequently, 50 ~ of methanol was
fed into the vessel and the temperature in the vessel was raised
up to 60 °C. Thirty minutes after, 0.5 ~ of 20 weight $ of
aqueous solution of sodium hydroxide was further added, agitated
CA 02203876 1997-04-28
for 20 minutes, 100 L~ of deionized water was added, washed with
the water for 10 minutes, and the water phase was withdrawn.
After the water was withdrawn, 300 ~ of deionized water was
further added, agitated for 10 minutes, and the water phase was
5 withdrawn. Then the hexane slurry was withdrawn, subjected to a
filtration, and dried to obtain a propylene-ethylene copolymer
composition of the present invention.
The composition thus obtained was analyzed and the results
are shown in Table 1 below.
10 e) Production of injection-molded product
To 3.0 Kg of the powder product obtained by the procedures
described above were added 0.003 Kg of a phenolic thermal
stabilizer and 0.003 Kg of calcium stearate, and they were mixed
by means of a high speed stirring type mixer (Henschel Mixer
15 (trade name)) at room temperature for 10 minutes and the mixture
was granulated by using a screw type extrusion-granulator having
a screw diameter of 40 mm. Granulates thus obtained were molded
into a JIS test piece at a temperature of molten resin of 230 °C
and at a mold temperature of 50 °C by means of an injection
20 molding machine. The test piece was conditioned in the state
where it was kept for 72 hours in a chamber at a humidity of 50
and at room temperature of 23 °C to obtain a sample for
evaluating the physical properties thereof. The results of the
evaluation are shown in Table 2.
25 Example 2
Polymerization was carried out in the same manner as that in
Example 1 with the exception that two kind of organosilicon
CA 02203876 1997-04-28
66
compounds, i.e. dicyclopentyldimethoxysilane and
propyltriethoxysilane were used in place of di-i-propyldi-
methoxysilane in the catalyst system used in Example 1. The
results are shown in Tables 1 and 2.
Examples 3 to 9
Various polymer compositions were synthesized by using the
same catalyst and in the same polymerization process as those in
Example 1 with the exception that ethylene/propylene proportion
and hydrogen concentration were varied, and their physical
properties were measured. The results are shown in Tables 1 and
2.
Comparative example 1
Example 1 was repeated with the exception that the solid
catalyst component in the catalyst used in Example 1 was changed
to the reduction type catalyst described in Example 1 of Laid-
open Japanese Patent Publication No. Sho 58-201816;
triethylaluminum was changed to diethylaluminum chloride; and
di-i-propyldimethoxysilane was changed to methyl p-toluylate.
The results are shown in Tables 1 and 2.
Comparative examples 2 to 4
Example 1 was repeated with the exception that the
polymerization conditions in Example 1 were changed to those
shown in Table 1. The results are shown in Tables 1 and 2.
CA 02203876 1997-04-28
67
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CA 02203876 1997-04-28
68
Table 2
4Jhole polymer
composition
MFR Flexural Izod impact
(g/10 min) modulus strength
(MPa) (J/m,23C)
Example 1 59 2800 90
Example 2 58 1600 80
Example 3 58 1600 110
Example 4 29 1790 200
Example 5 110 1850 70
Example 6 220 1850 50
Example 7 79 1820 80
Example 8 56 1850 90
Example 9 59 1800 86
Comparative 59 1200 70
Example 1
Comparative 57 1500 30
Example 2
Comparative 57 1500 40
Example 3
Comparative 82 1550 78
Example 4
Evaluation of the results
4~lhen Examples 1 and 2 are compared with Comparative Example
1, the melt flow rate of propylene polymers are almost the same
but the toughness, flexural modulus, and Izod impact strength
notably decrease as the Cf value increases as apparent from
Tables 1 and 2. Wizen Examples 1 and 3 are compared with
Comparative Example 1, the toughness, flexural modulus, and Izod
impact strength in Comparative Example 1 are notably low as
apparent from Tables 1 and 2. These results show that the use of
CA 02203876 1997-04-28
69
a propylene polymer having a Cf value of 0.5 or less is
necessary for obtaining propylene-ethylene copolymer
compositions having a low melt flow, a high rigidity, a high
toughness, and a high impact strength.
When Examples 1, 3, 8 and 9 are compared with Comparative
Examples 2 and 3, it is apparent that the melt flow rate of the
propylene-ethylene copolymer compositions are almost the same,
but in the latter cases, there is a large difference in the
flexural modulus and the Izod impact strength since the reaction
ratios of propylene/ethylene in the polymerization step (II) are
outside the scope of the present invention. From the results,
it is clear that the propylene-ethylene copolymer compositions
of the present invention have a high rigidity, high toughness,
high impact-strength, and superior moldability. Further,
Examples 4 to 7 show that similar results are obtained in a
broad range of the melt flow rate.
When Examples 7 and 8 are compared with Comparative Example
4, it is understood that the polymerization proportions of
propylene and the melt flow rates of the propylene polymer in
the polymerization step (I) and the reaction ratios of
propylene/ethylene in the polymerization step (II) are almost
the same, but the value of common logarithm of the ratio of the
melt flow rate (MFR(i)) of the propylene polymer obtained in the
polymerization step (I) to the melt flow rate (MFR(ii)) of the
propylene-ethylene copolymer obtained in the polymerization step
(II) (MFR(i)/MFR(ii)) in Comparative Example ~ is small compared
with those in Examples 7 and 8; and the flexural modulus and
CA 02203876 1997-04-28
Izod impact strength in Comparative Example 4 are notably
inferior to those in Examples 7 and 8.
In the production process of the present invention, the
polymerization step (I) and the polymerization step (II) can
5 continuously be carried out; controls of ethylene content and
others are easy; and copolymer compositions having a small
quality variation can be provided.
Examples 10 to 17 and Control Examples 1 to 4
One hundred parts by weight of an unstabilized, powdery
10 propylene-ethylene copolymer having a MFR, Cf value and
ethylene-propylene composition at polymerization step (II)
described in Table 3 and the a-crystal nucleators and other
additives shown in [1) to [14] mentioned below were put in a
Henschel mixer (trade name) in a blending ratio described in
15 Table 3 below, mixed and agitated for 3 minutes, and then
subjected to a melt-kneading at 200 °C by means of a monoaxial
extruder having a die orifice diameter of 40 mm and converted
into pellets.
Further, as Control Examples 1 to 4, a prescribed amount of
20 the additives described in Table 3 were blended, respectively,
to 100 parts by weight of an unstabilized, powdery crystalline
propylene-ethylene copolymer having a MFR, Cf value, and
propylene-ethylene copolymer composition described in Table 3,
and subjected to a melt-kneading in the same manner as in
25 Examples 10 to 17 to obtain pellets.
Test pieces used for evaluating the toughness were prepared
by subjecting the pellets obtained to an injection molding at a
CA 02203876 1997-04-28
71
resin temperature of 250 °C and at a mold temperature of 50 °C,
and punching the molded article. Further, test pieces used for
evaluating the rigidity and impact-strength were prepared by
subjecting the pellets obtained to an injection molding at a
resin temperature of 250 °C and at a mold temperature of 50°C.
Using the test pieces thus obtained and according to the
test methods mentioned above, the toughness, rigidity, and
impact-strength were evaluated. The results are shown in Table
3.
The oc-crystal nucleators and additives of the present
invention and shown in Table 3 are as follows:
oc-crystal nucleator [1]: talc
ditto [2]: aluminum hydroxy-bis(4-t-butylbenzoate)
ditto [3]: 1-3,2-4-dibenzylidene sorbitol
ditto [4]: 1-3,2-4-bis(p-methylbenzylidene)sorbitol
ditto [5]: 1-3,2-4-bis(p-ethylbenzylidene}sorbitol
ditto [6]: 1-3,2-4-bis(2',4'-dimethylbenzylidene)
sorbitol
ditto [7]: 1-3,2-4-bis(3',4'-dimethylbenzylidene)
sorbitol
ditto [8]: 1-3-p-chlorobenzylidene-2-4-p-methylbenzyl-
idene sorbitol
ditto [9]: sodium-bis(4-t-butylphenyl)phosphate
ditto [10]: sodium-2,2'-methylene-bis(4,6-di-t-butyl-
phenyl)phosphate
ditto [11]: a mixture of aluminumdihydroxy-2,2'-
methylene-bis(4,6-di-t-butylphenyl}-
CA 02203876 1997-04-28
72
phosphate, aluminum hydroxy-bis[2,2'-
methylene-bis(4,6-di-t-butylphenyl)
phosphate], and lithium stearate (1:1:1
(weight ratio))
ditto [12]: poly 3-methyl-1-butene
ditto [13]: polyvinylcyclohexane
ditto [14]: polyallyltrimethylsilane
Phenolic antioxidant: tetrakis[methylene-3-(3',5'-di-t-
butyl-4'-hydroxyphenyl)propionate]methane
Phosphoric antioxidant: bis(2,4-di-t-butylphenyl)penta-
erythritol-diphosphite
Ca-St . calcium stearate
CA 02203876 1997-04-28
73
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CA 02203876 1997-04-28
74
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CA 02203876 1997-04-28
It is seen from Table 3 that the copolymer compositions of
Examples 10 to 17 having an a-crystal nucleator blended therein
are remarkably superior in rigidity and impact strength as
compared with Control Examples wherein no nucleator was added.
5 Examples 28 to 45 and Control Examples 5 to 8
One hundred parts by weight of an unstabilized, powdery,
propylene-ethylene copolymer having a MFR, Cf value, and
ethylene-propylene composition at the polymerization step (II)
described in Table 4 below, and ~-crystal nucleators and other
10 additives described in Table 4 were put in a Henschel mixer
(trade name) in a blending ratio described in Table 4, mixed and
agitated for 3 minutes, and then subjected to a melt-kneading at
200 °C by means of a monoaxial extruder having a die orifice
diameter of 40 mm and converted into pellets.
15 Further, as Control Examples 5 to 8, a prescribed amount of
an additive described in Table 4 below was blended to 100 parts
by weight of an unstabilized, powdery ethylene-propylene
copolymer having a MFR,.Cf value, and ethylene-propylene
composition described in Table 4, and subjected to a melt-
20 kneading in the same manner as in Examples 28 to 45 to obtain
pellets.
Test pieces used for evaluating toughness were prepared by
subjecting the pellets obtained to an injection molding at a
resin temperature of 250 °C and at a mold temperature of 50 °C,
25 and punching the molded article.
Using the test pieces thus obtained, the toughness was
evaluated according to the test method mentioned above. The
CA 02203876 1997-04-28
76
results are shown in Table 4.
Examples 46 to 63 and Control Examples 9 to 12
One hundred parts by weight of an unstabilized, powdery
propylene-ethylene copolymer having a MFR, Cf value, and
ethylene-propylene composition at the polymerization step (II)
described in Table 5 below and a prescribed amount of (3-crystal
nucleators and other additives were put in a Henschel mixer
(trade name) in a blending ratio described in Table 5, mixed and
agitated for 3 minutes, and then subjected to a melt-kneading by
means of a monoaxial extruder having a die orifice diameter of a
40 mm at 200 °C and converted into pellets.
Further, as Control Examples 9 to 12, a prescribed amount of
the additives described in Table 5 below were blended to 100
parts by weight of an unstabilized, powdery propylene-ethylene
copolymer having a MFR, Cf value, and ethylene-propylene
composition described in Table 5 below, and subjected to a melt-
kneading in the same manner as in Examples 28 to 45 to obtain
pellets.
The test pieces used for evaluating the toughness were
prepared by subjecting the pellets obtained to an injection
molding at a resin temperature of 250 °C and at a mold
temperature of 50 °C, and punching the molded article.
Using the test pieces obtained and according to the test
method mentioned above, the toughness was evaluated. The
results are shown in Table 5.
The ~-crystal nucleators and the additives shown in Tables 4
and 5 are as follows:
CA 02203876 1997-04-28
77
~i-crystal nucleator [1]:'y-quinacridone
ditto [2]: adipic acid dianilide
ditto [3]: suberic acid dianilide
ditto [4]: N,N'-dicyclohexyl terephthalamide
ditto [5]: N,N'-dicyclohexyl-1,4-cyclohexane dicarboxy-
amide
ditto [6]: N,N'-dicyclohexyl-2,6-naphthalene dicarboxy-
amide
ditto [7]: N,N'-dicyclohexyl-4,4'-biphenyl dicarboxy-
amide
ditto [8]: N,N'-bis(p-methylphenyl)hexanediamide
ditto [9]: N,N'-bis(p-ethylphenyl)hexanediamide
ditto [10]: N,N'-bis(4-cyclohexylphenyl)hexanediamide
ditto [11J: p-(N-cyclohexanecarbonylamino)benzoic acid
cyclohexylamide
ditto [12): b-(N-benzoylamino)-n-valeric acid anilide
ditto [13]: 3,9-bis[4-(N-cyclohexylcarbamoyl)phenyl]-
2,4,8,10-tetraoxaspiro[5.5]undecane
ditto [14]: N,N'-dicyclohexanecarbonyl-p-phenylene-
diamine
ditto [15]: N,N'-dibenzoyl-1,5-diaminonaphthalene
ditto [16]: N,N'-dibenzoyl-1,4-diaminocyclohexane
ditto [17]: N,N'-dicyclohexanecarbonyl-1,4-diamino-
cyclohexane
ditto [18]: a mixture of 50 ~ by weight of 10-hydroxy-9,10-
dihydro-9-oxa-10-phosphaphenanthrene-10-oxide
with 50 ~ by weight of magnesium stearate
CA 02203876 1997-04-28
78
ditto [19]: a mixture of 50 ~ by weight of 10-hydroxy-9,10-
dihydro-9-oxa-10-phosphaphenanthrene-10-oxide
with 50 ~ by weight of (mono, dimixed)
magnesium stearyl phosphate
ditto [20]: mixture of 70 ~ by weight of 10-hydroxy-9,10-
dihydro-9-oxa-10-phosphaphenanthrene-10-oxide
with 30 ~ by weight of magnesium oxide
ditto [21): mixture of 70 ~ by weight of 10-hydroxy-9,10-
dihydro-9-oxa-10-phosphaphenanthrene-10-oxide
with 30 ~ by weight of magnesium hydroxide
ditto [22]: mixture of 70 ~ by weight of 10-hydroxy-9,10-
dihydro-9-oxa-10-phosphaphenanthrene-10-oxide
with 30 ~ by weight of magnesium carbonate
ditto [23): mixture of 50 ~ by weight of 10-hydroxy-9,10-
dihydro-9-oxa-10-phosphaphenanthrene-10-oxide
with 50 ~ by weight of magnesium salt of 10-
hydroxy-9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide
ditto [24]: mixture of 50 ~ by weight of 10-hydroxy-9,10-
dihydro-9-oxa-10-phosphaphenanthrene-10-oxide
with 50 ~ by weight of magnesium-bis(1'-
hydroxy-2,2'-biphenylenephosphinate)
ditto [25]: mixture of 70 ~ by weight of 9,10-dihydro-9-
oxa-10-phosphaphenanthrene-10-oxide with 30 ~
by weight of basic magnesium sulfate
ditto [26]: mixture of 70 o by weight of 9,10-dihydro-9-
oxa-10-phosphaphenanthrene-10-oxide with 30 ~
CA 02203876 1997-04-28
79
by weight of talc
ditto [27]: mixture of 50 ~ by weight of 9,10-dihydro-9-
oxa-10-phosphaphenanthrene-10-oxide with 50 ~
by weight of magnesium-bis(1'-hydroxy-2,2'-
biphenylenephosphinate
Phenolic antioxidant: tetrakis[methylene-3-(3',5'-t-butyl-4'-
hydroxyphenyl)propionate]methane
Phosphoric antioxidant: bis(2,4-di-t-butylphenyl)-
pentaerythritol-diphosphite
Ca-St: calcium stearate
CA 02203876 1997-04-28
d, wnu1ao
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Examples 28 to 45 described in Table 4 are directed to a
blend of a propylene-ethylene copolymer within the scope of the
present invention with (3-crystal nucleators, whereas Control
Examples 5 to 8 are directed to a blend of an ethylene-propylene
copolymer outside the scope of the present invention with ~i-
crystal nucleators. It is seen from Table 4 that the products
of Examples 28 to 45 are remarkably superior in toughness to
those of Control Example 5 to 8. Further, as to the propylene-
ethylene copolymer compositions shown in Table 5, an effect
similar to that mentioned above is observed_
INDUSTRIAL APPLICABILITY
Propylene-ethylene copolymer compositions having a superior
balance of rigidity, toughness, and impact-strength provided by
the present invention are used in various commercial fields as
starting materials for injection molded products and extrusion
molded products.
