US 6,005,034 AGrant

Propylene-Ethylene Copolymer Composition and Process for Producing the Same

Issue Date:1999-12-21

•8 Claims

Abstract

A propylene-ethylene copolymer composition is obtained which has good moldability and an excellent balance of rigidity, toughness, and impact-strength. The composition has a melt flow rate of 10 to 300 g/10 minutes and is 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 D1238) 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.degree. C., and a temperature of 112.degree. C. or higher, respectively, of 0.5 or less, by carrying out polymerization of propylene in the presence of a highly stereoregular catalyst and hydrogen in a 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 ethylene and propylene to the propylene polymer to react so that the content of ethylene becomes 30 to 80% by weight. Also provided is a propylene-ethylene copolymer composition comprising the composition mentioned above and a .alpha.-crystal and/or .beta.-crystal nucleator added therewith.

Metadata

Assignees

Chisso Corpoation
Toyota Jidosha Kabushiki Kaisha

Inventors

Teruaki Hayashida
Shinei Gima
Kouichi Hatada
Osamu Kojima
Ken Shimizu
Hirokazu Nakajima
Takao Nomura
Yoshihiro Kanome
Takeyoshi Nishio

Application Information

Application Number:US 817850&

Filing Date:1997-04-30

Priority Date:1995-08-31

Art Unit:173

Classifications

IPC:

C08L 2312C08F 1006C08F21006

Field of Search:

524525139;148;378;394;417;451;117;90;141;229;372;396240;247;270;322;106;216;323

Patent Drawings

This patent does not have any drawings.

Description

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. Whereas 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. 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 propylene polymer having a position of main dissolution peak (T max) according to a temperature-rise fractionation method of 117.degree. C. or 118.degree. C. or higher, and a half-value width (.sigma.) 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 5-9218, 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 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.degree. C., and a temperature of 112.degree. C. or higher, respectively, which is an index of the stereoregularity 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, 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 ethylene and propylene to the product produced in the first stage so that the content of ethylene becomes 30 to 80% by weight, in a second stage (polymerization step (II)).

(2) 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 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 0.0001 to 1 part by weight of an .alpha.-crystal nucleator blended therewith.

(7) The propylene-ethylene copolymer composition recited in (6) above wherein the .alpha.-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 .beta.-crystal nucleator blended therewith.

(9) The propylene-ethylene copolymer composition recited in (8) above wherein the .beta.-crystal nucleator is .gamma.-quinacridone; an amide compound expressed by any one of the following (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 following (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 following (8) and (9); or a mixture of the foregoing:

(1) R.sub.3 --(R.sub.2)NCO--R.sub.1 --CON(R.sub.4)--R.sub.5

(2) R.sub.7 --CONH--R.sub.6 --CONH--R.sub.8

(3) R.sub.10 --CONH--R.sub.9 --NHCO--R.sub.11

(4) Magnesium salt of aliphatic acids

(5) Magnesium salt of aliphatic phosphoric acids

(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 ##STR1## wherein the above formulas, when R.sub.1 represents a residual group of aromatic dicarboxylic acids except for saturated or unsaturated aliphatic groups or alicyclic groups of 1 to 28 carbon atoms, or 3,9-bis(phenyl-4-yl)-2,4,8,10-tetraoxaspiro[5.5]undecane, then R.sub.2 and R.sub.4 represent hydrogen, and each of R.sub.3 and R.sub.5 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 R.sub.1 represents 3,9-bis(phenyl-4-yl)-2,4,8,10-tetraoxaspiro[5.5]undecane, then R.sub.2 to R.sub.5 represent the same or different hydrogen, alkyl group, cycloalkyl group, or aryl group; or each of R.sub.2 and R.sub.3, and R.sub.4 and R.sub.5 jointly form an alkylene group by bonding to each other at the respective .omega.-ends,

R.sub.6 represents a residual group of saturated or unsaturated aliphatic, alicyclic, or aromatic amino acids of 1 to 28 carbon atoms,

R.sub.7 and R.sub.8 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,

R.sub.9 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),

R.sub.10 and R.sub.11 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

Ar.sub.1 to Ar.sub.8 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.degree. C., and a temperature of 112.degree. C. or higher, respectively, which is an index of the stereoregularity 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, and then

producing 5 to 40% by weight, based on the weight of the whole polymer, of an ethylene-propylene copolymer by 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 expressed by the following general formula (5) ##STR2## and having a number-average molecular weight of 10,000 to 60,000, a density of 0.90 to 0.92 g/cm.sup.3, and a ratio (Cf) of integrated values of the propylene polymer dissolved in o-dichlorobenzene at a temperature of lower than 112.degree. C., and a temperature of 112.degree. C. or higher, respectively, which is an index of the stereoregularity 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 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.

When 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. When 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 extruded for 10 minutes at 230.degree. C. when a load of 21.18 N is applied; hereinafter abbreviated as MFR) of the propylene-ethylene copolymer compositions of the present invention is 10 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/10 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 No. Hei 3-12406, Japanese Patent Application No. Hei 7-136425, and others) can be used, but the catalysts are not limited to these ones.

As the metallocene compounds, for example, compounds consisting of chiral, transition metal compounds represented by the following general formula:

wherein (C.sub.5 H.sub.4-m R.sup.1.sub.m) and (C.sub.5 H.sub.4-n R.sup.2.sub.n) represent a substituted cyclopentadienyl group; m and n are an integer of 1 to 3; R.sup.1 and R.sup.2 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 (C.sub.5 H.sub.4-m R.sup.1.sub.m) and (C.sub.5 H.sub.4-n R.sup.2.sub.n) ; 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-phenylindenyl)hafnium dichloride, dimethylsilylene(2,4-dimethylcyclopentadienyl)(3',5'-dimethylcyclopentadie nyl)titanium dichloride, dimethylsilylene(2,4-dimethylcyclopentadienyl)(3',5'-dimethylcyclopentadie nyl)zirconium chloride, dimethylsilylene(2,4-dimethylcyclopentadienyl)(3',5'-dimethylcyclopentadie nyl)zirconium dimethyl, dimethylsilylene(2,4-dimethylcyclopentadienyl)(3',5'-dimethylcyclopentadie nyl)hafnium chloride, dimethylsilylene(2,4-dimethylcyclopentadienyl)(3',5'-dimethylcyclopentadie nyl)hafnium dimethyl, dimethylsilylene(2,3,5-trimethylcyclopentadienyl)(2',4',5'-trimethylcyclop entadienyl)titanium dichloride, dimethylsilylene(2,3,5-trimethylcyclopentadienyl)(2',4',5'-trimethylcyclop entadienyl)zirconium dichloride, dimethylsilylene(2,3,5-trimethylcyclopentadienyl)(2',4',5'-trimethylcyclop entadienyl)zirconium dimethyl, dimethylsilylene(2,3,5-trimethylcyclopentadienyl)(2',4',5'-trimethylcyclop entadienyl)hafnium dichloride, and dimethylsilylene(2,3,5-trimethylcyclopentadienyl)-(2',4',5'-trimethylcyclo pentadienyl)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'-dimethylcyclopentadie nyl)hafnium dichloride as example, as follows:

Dichlorodimethylsilane is reacted with (2,4-dimethylcyclopentadienyl) (3',5'-dimethylcyclopentadienyl)sodium to obtain dimethyl(2,4-dimethylcyclopentadienyl)(3',5'-dimethylcyclopentadienyl)sila ne, which is reacted with butyllithium to obtain lithium dimethylsilylene(2,4-dimethylcyclopentadienyl)(3',5'-dimethylcyclopentadie nyl), which is reacted in turn with hafnium tetrachloride to obtain dimethylsilylene(2,4-dimethylcyclopentadienyl)(3',5'-dimethylcyclopentadie nyl)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 .alpha.-olefins, non-conjugated dienes, and others, if necessary, in an extent in 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. 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.degree. C., preferably 50 to 80.degree. C., and polymerization pressure is 0 to 5 MPa. In the case of the gas phase polymerization, the polymerization temperature is 20 to 150.degree. 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.degree. C., preferably 40 to 70.degree. 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 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 .alpha.-olefin such as ethylene, butene-1, pentene-1, 4-methyl-pentene-1, 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 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 diene 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 polyethylenes, 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, methacryl-butadiene-styrene copolymers, polyamides, polyethylene terephthalates, polybutylene terephthalates, polyethylene naphthalates, polybutylene naphthalates, polycarbonates, polyvinyl chlorides, fluorine resins, petroleum resins (such as C.sub.5 petroleum resins, hydrogenated C.sub.5 petroleum resins, C.sub.9 petroleum resins, hydrogenated C.sub.9 petroleum resins, C.sub.5 -C.sub.9 copolymerized petroleum resins, hydrogenated C.sub.5 -C.sub.9 copolymerized petroleum resins, and acid-modified C.sub.9 petroleum resins each having a softening point of 80 to 200.degree. C.), and DCPD resins (such as cyclopentadiene petroleum resins, hydrogenated cyclopentadiene petroleum resins, cyclopentadiene-C.sub.5 copolymerized petroleum resins, hydrogenated cyclopentadiene-C.sub.5 copolymerized petroleum resins, cyclopentadiene-C.sub.9 copolymerized petroleum resins, hydrogenated cyclopentadiene-C.sub.9 copolymerized petroleum resins, cyclopentadiene-C.sub.5 -C.sub.9 copolymerized petroleum resins, and hydrogenated cyclopentadiene-C.sub.5 -C.sub.9 copolymerized petroleum resins each having a softening point of 80 to 200.degree. C.).

When the following .alpha.-crystal nucleator and/or .beta.-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, .alpha.-crystal nucleator or .beta.-crystal nucleator means an agent which makes it possible to obtain a crystal of polypropylene in .alpha.-form or .beta.-form when a melt-crystallization of the polypropylene is conducted in the presence of the crystal nucleator (Polymer, pp 3443-3448, Vol. 35, No. 16, 1994).

As the .alpha.-crystal nucleator used in the present invention, the followings can be mentioned as example:

inorganic compounds such as talc, alum, silica, titanium oxide, calcium oxide, magnesium oxide, carbon black, and clay minerals,

carboxylic acids excluding aliphatic monocarboxylic acids such as malonic acid, succinic acid, adipic acid, maleic acid, azelaic acid, sebacic acid, dodecanoic diacid, citric acid, butanetricarboxylic acid, butanetetracarboxylic acid, naphthenic acid, cyclopentanecarboxylic acid, 1-methylcyclopentanecarboxylic acid, 2-methylcyclopentanecarboxylic acid, cyclopentenecarboxylic acid, cyclohexanecarboxylic acid, 1-methylcyclohexanecarboxylic acid, 4-methylcyclohexanecarboxylic 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 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,

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,

1.3,2.4-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,

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,

aluminumihydroxy-bi(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,

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],

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)phosphate],

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 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, 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, .beta.-dodecylmercaptoacetic acid, .beta.-dodecylmercaptopropionic acid, .beta.-N-lauroyl aminopropionic acid, and .beta.-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-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, polyallyltoluene, polyvinylcyclopentane, polyvinylcyclohexane, polyvinylcycloheptane, polyvinyltrimethylsilane, and polyallyltrimethylsilane.

Among the compounds mentioned above, followings are particularly preferable:

talc, aluminumhydroxy-bis(4-t-butylbenzoate), 1.3,2.4-dibenzylidenesorbitol, 1.3,2.4-bis(p-methylbenzylidene)sorbitol, 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) R.sub.3 --(R.sub.2)NCO--R.sub.1 --CON(R.sub.4)--R.sub.5 mentioned above and used in the present invention as .beta.-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.

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.

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, .alpha.-cyclohexylethylamine, .beta.-cyclohexylethylamine, .alpha.-cyclohexylpropylamine, .beta.-cyclohexylpropylamine, .gamma.-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-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, .alpha.-phenylethylamine, .beta.-phenylethylamine, .alpha.-phenylpropylamine, .beta.-phenylpropylamine, .gamma.-phenylpropylamine, .alpha.-naphthylamine, N-butyl-aniline, and N,N-diphenylamine are specifically mentioned as examples.

Amide compounds expressed by the (2) R.sub.7 --CONH--R.sub.6 --CONH--R.sub.8 mentioned above and used in the present invention as .beta.-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, .alpha.-aminopropionic acid, .beta.-aminopropionic acid, .alpha.-aminoacrylic acid, .alpha.-aminobutyric acid, .beta.-aminobutyric acid, .gamma.-aminobutyric acid, .alpha.-amino-.alpha.-methylbutyric acid, .gamma.-amino-.alpha.-methylbutyric acid, .alpha.-amino-i-butyric acid, .beta.-amino-i-butyric acid, .alpha.-amino-n-valeric acid, .delta.-amino-n-valeric acid, .beta.-aminocrotonic acid, .alpha.-amino-.beta.-methylvaleric acid, .alpha.-amino-i-valeric acid, 2-amino-4-pentenoic acid, .alpha.-amino-n-caproic acid, 6-aminocaproic acid, .alpha.-amino-i-caproic acid, 7-aminoheptanoic acid, .alpha.-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 acid, 2-aminocyclohexanecarboxylic acid, 3-aminocyclohexanecarboxylic acid, 4-aminocyclohexanecarboxylic acid, p-aminomethylcyclohexanecarboxylic acid, and 2-amino-2-norbornanecarboxylic acid are specifically mentioned as examples.

As the aromatic amino acid, .alpha.-aminophenylacetic acid, .alpha.-amino-.beta.-phenylpropionic acid, 2-amino-2-phenylpropionic acid, 3-amino-3-phenylpropionic acid, .alpha.-aminocinnamic acid, 2-amino-4-phenylbutyric acid, 4-amino-3-phenylbutyric acid, anthranilic 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-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-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-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.

As the alicyclic monocarboxylic acid, cyclopropanecarboxylic acid, cyclobutanecarboxylic acid, cyclopentanecarboxylic acid, 1-methylcyclopentanecarboxylic acid, 2-methylcyclopentanecarboxylic acid, 3-methylcyclopentanecarboxylic acid, 1-phenylcyclopentanecarboxylic acid, cyclopentenecarboxylic acid, cyclohexanecarboxylic acid, 1-methylcyclohexanecarboxylic acid, 2-methylcyclohexanecarboxylic acid, 3-methylcyclohexanecarboxylic acid, 4-methylcyclohexanecarboxylic acid, 4-propylcyclohexanecarboxylic acid, 4-butylcyclohexanecarboxylic acid, 4-pentylcyclohexanecarboxylic acid, 4-hexylcyclohexanecarboxylic 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 as the monoamines which are the starting materials for the amide compounds expressed by the (1) mentioned above.

Amide compounds expressed by the (3) R.sub.10 --CONH--R.sub.9 --NHCO--R.sub.11 mentioned above and used in the present invention as .beta.-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 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-methylcyclohexanecarboxylic 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 .beta.-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-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-10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide,

2,6,8-trimethyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxi de,

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-oxid e,

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-oxi de,

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,

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-phosphaphenanthrene-10-oxid e,

2,6,8-tri-s-butyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-o xide,

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-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-phosphaphenanthrene-10-oxid e,

2,6-di-t-butyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxid e,

2,7-di-t-butyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxid e,

2,8-di-t-butyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxid e,

6,8-di-t-butyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxid e,

2,6,8-tri-t-butyl-10-hydroxy-9,10-dihydro-9-oxa-phosphaphenanthrene-10-oxid e,

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-ox ide,

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-10-phosphaphenanthrene-10-oxid e,

2,6,8-tri-t-octyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-o xide,

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-o xide,

2,6,8-tri-cyclohexyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-1 0-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-ox ide,

2-(.alpha.-methylbenzyl)-10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthre ne-10-oxide,

6-(.alpha.-methylbenzyl)-10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthre ne-10-oxide,

8-(.alpha.-methylbenzyl)-10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthre ne-10-oxide,

6,8-di(.alpha.-methylbenzyl)-10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenan threne-10-oxide,

2,6,8-tri(.alpha.-methylbenzyl)-10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphe nanthrene-10-oxide,

2,6-di(.alpha.,.alpha.-dimethylbenzyl)-10-hydroxy-9,10-dihydro-9-oxa-10-pho sphaphenanthrene-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-o xide,

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-(.alpha.-methylbenzyl)-8-t-butyl-10-hydroxy-9,10-dihydro-9-oxa-10-phospha phenanthrene-10-oxide,

6-t-butyl-8-cyclohexyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene -10-oxide,

6-benzyl-8-cyclohexyl-10-hydroxy-9,10-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-phosphaphenanthren e-10-oxide, and

2,6-dicyclohexyl-8-benzyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthr ene-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 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 .beta.-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) tetracosylphosphate, magnesium (mono, dimixed) hexacosylphosphate, magnesium (mono, dimixed) octacosylphosphate, magnesium oxide, magnesium hydroxide, magnesium carbonate, magnesium salts of cyclic phosphorous compounds such as