JP2000309669A - Polypropylene resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polypropylene resin composition, which depends on forming and crystallization conditions to a lesser extent, is solidified at a stably fast rate, and has good formability. SOLUTION: This polypropylene resin composition contains 100 pts.wt. of a component A and 2 to 100 pts.wt. of a component B, wherein the component A is a propylene polymer(PP) satisfying the following conditions (1) and (2): (1) steric regularity of 97% or more, and (2) weight-average molecular weight of 10,000 to 1,000,000, and the component B is an ethylene/propylene copolymer(EPR) satisfying the following conditions (3) to (6): (3) propylene content of 20 to 80 mol%, (4) uniform compositional distribution with molecular weight, biasing 10% or less from the average composition, (5) weight-average molecular weight of 10,000 to 1,000,000, and (6) the component having a molecular weight of 10,000 or less accounting for 10% or less.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a propylene resin composition having a small decrease in crystallization rate, in other words, a small decrease in crystallinity, and hence a small decrease in rigidity as a composition.

[0002]

2. Description of the Related Art Ethylene propylene copolymer (EPR)
The propylene resin (PP) resin composition reinforced with is an industrial material having excellent physical properties, especially impact resistance.
In general, since the properties of the composition change depending on the type of EPR mixed with PP, many inventions have been disclosed with respect to a suitable compounding technique according to the purpose.

For example, a blend of a polymer (PP and EPR) polymerized using a metallocene catalyst (Japanese Patent Laid-Open No. 10-1573),
A multi-stage polymerization comprising producing PP in the first stage polymerization and then performing a second stage polymerization in which EPR is formed in the co-presence of the PP (JP-A-5-202152 and JP-A-5-202152)
-206921) and the formation of a polymer using a Ziegler catalyst [a multi-stage polymerization method in which PP is formed in the first step and EPR is formed in the second step] (JP-A-58-8).
Many technologies are known, such as a blend of PP and EPR obtained using a Ziegler catalyst.

[0004] Incidentally, it is considered that one of the causes of the change in the properties of the composition is that the dispersion structure of the composition changes depending on the affinity (compatibility at the molecular level) between PP and EPR. I have. In addition, crystallization properties, which are important physical properties of PP, may change depending on the composition of EPR, and it has been reported that the degree of crystallinity changes or the crystallization rate decreases depending on the composition of EPR. (POLYME
R, 1982, 23, 229). It is believed that the performance changes of these compositions also depend on the affinity of PP and EPR.

The affinity (compatibility) between PP and EPR has been studied intensively in addition to the above. For example, neutron scattering studies (Lohse, DJ:
Polymer Engineering Science
e 26.1500 (1986)), morphological observations (Co
ppola, F .; et. al; Polymer 28,
47 (1987)), NMR (Nirabella)
F. M. et. al. Polymer 37,931;
(1996)), all of which are PP / EP
It is concluded that R is incompatible in the solid phase and also in the molten state under heating. Although these studies have been conducted on EPR having a broad composition distribution, EP
No studies have been found on the detailed structure of R, for example, the copolymer composition and composition distribution of propylene and ethylene, and further, the steric structure of the propylene chain. Also, when the intimate mixture obtained by throwing a homogeneous PP / EPR mixture dissolved in a solvent into a non-solvent is heated to be in a molten state, the demixing (phase separation) proceeds and the degree of demixing increases. Has also been shown to change the crystal structure upon solidification (Hashimoto T. Macromole).
cules, 19, 1690 (1986)). Both PP and EPR used in this study had a large molecular weight and a broad molecular weight distribution.

[0006] Further, a crystalline lamella of PP is dispersed as a dispersed phase in an amorphous phase in which a part of EPR is dissolved in an amorphous part of PP and in an amorphous continuous phase formed from an EPR phase which is three-dimensionally pseudo-meshed. Compositions present are also disclosed (PolyPr
e. 42, 3932 (1993)), the composition still has insufficient compatibility of the amphoteric components and forms a sea / island structure. Although the degree of dissolution has been studied by lowering the mechanical dispersion temperature, there is no suggestion as to the compatibility of molecular size.

[0007]

DISCLOSURE OF THE INVENTION The present invention relates to a method for blending E
An object of the present invention is to provide a resin composition comprising PP and EPR, which has little crystallization inhibition by PR, that is, has a small decrease in crystallization rate.

[0008]

Accordingly, the polypropylene resin composition according to the present invention comprises the following component (A) 10
0 parts by weight and 2 to 100 parts by weight of the component (B). Component (A) Propylene polymer (PP) satisfying the following (1) and (2) (1) Stereoregularity (mmmm) is 97% or more;
(2) Ethylene propylene copolymer (EPR) satisfying the following (3) to (6), having a weight average molecular weight of 10,000 to 1,000,000, and (3) a propylene content of 20 to 80 mol%. (4) having a uniform composition distribution in which the variation from the average composition in the molecular weight dependence of the composition is 10% or less;
(5) the weight average molecular weight is 10,000 to 1,000,000;
(6) The ratio of components having a molecular weight of 10,000 or less is 10% or less.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION <Component (A)> (1) The PP used as the component (A) in the present invention is:
A homopolymer of propylene, C ¹³ -NMR spectrum analysis than a conventional method, for example, the fraction of which is an index of stereoregularity is determined by the method described isotactic pentad (chain (mmmm) is 97% Above, preferably 98
% Or more. If the stereoregularity is low, the melting point decreases, and the heat resistance decreases. Depending on the production method, a small amount of the atactic polymer component may be present even if the average value (mmmm) is a high value. Because the presence of such an atactic polymer component is not preferred,
The component (A) in the present invention has an atactic polymer component defined by a boiling heptane-soluble component of 5% or less, preferably 3% or less, and more preferably 1% or less.

(2) The component (A) used in the present invention is a ratio Mw / Mn which is a measure of the molecular weight distribution calculated from the weight average molecular weight Mw and the number average molecular weight Mn measured by gel permeation chromatography (GPC). (Hereinafter Q
The value is 15 or less, preferably 7 or less, and more preferably 5 or less. Mw /
When Mn exceeds 7, the presence of a low molecular weight component having good compatibility in the component (A) cannot be ignored, and the critical Kai
(PP / EPR interaction parameter kai) fluctuates, and within the scope of the present invention, component (B), that is, EPR,
As a result, the crystallization of the composition of the present invention, that is, the component (A) + the component (B) may be suppressed. The component (A) of the present invention has a weight average molecular weight Mw.
Is 10,000 or more and 1,000,000 or less. If the Mw is less than 10,000, the component (A), and eventually the component (A) + the component (B), is unsuitable as a structural material due to reduced mechanical strength such as impact resistance and tensile rupture. In addition, as a result of the improved compatibility with the component (B), that is, EPR, in the present invention, the effect of avoiding the suppression of the crystallization rate referred to in the present invention becomes insignificant.
If the Mw exceeds 1,000,000, the fluidity of the composition of the present invention at the time of thermoplastic molding decreases, and it is not suitable as a general molding material. Therefore, component (A) preferably has a Mw of 2
10,000 to 800,000, more preferably 100,000 to 500,000,
PP.

The component (A) has a melting point of 150 ° C. or higher,
Those having a temperature of preferably 155 ° C. or higher are also suitable. If the melting point is low, the heat resistance of a molded article made from the composition of the present invention is reduced, and the molded article is not suitable for a wide range of applications utilizing the properties of PP.

[0012] In the present invention, optionally ethylene or other α- olefins, for example C ₄ ~ _10, in particular 1-
Use of PP in which one or two or more of butene, 1-hexene, 1-octene, and the like are copolymerized in a small amount in a range where the above-mentioned compatibility, melting point range and molecular weight are not substantially changed in the determination of the molecular weight. Can be. Such copolymerized PP specifically contains ethylene up to 5 mol%, preferably 2 mol%.
Up to and including random or block copolymerized PP.

<Component (B)> (3) EPR used as component (B) in the present invention
A propylene (C ₃₎ content of 20 to 80 mol%, preferably 30 to 75 mol%, of. If the C ₃ content is less than 20 mol%, the compatibility will be too low and PP
The affinity of the interface between EPR and EPR may be extremely reduced, and the mechanical properties may be reduced due to the separation of the interface. If the C ₃ content exceeds 80 mol%, not only the compatibility with PP increases, but also the dispersion of EPR becomes too fine, and the stress concentration on the EPR dispersed phase, which is the main toughness development mechanism. Is not effective, and the glass transition temperature of the EPR rises, lowering the low-temperature impact strength and raising the embrittlement temperature, lowering the advantages of EPR blending.

(4) The C ₂ / C ₃ composition in the component (B) may have a molecular weight dependency. If the composition distribution is non-uniform when the molecular weight distribution is relatively wide, there may be a component having a high compatibility with a higher C ₃ content than the average composition in the low molecular weight section, and the compatibility increases, Crystallization is inhibited. The EPR used in the present invention preferably shows a uniform composition in a substantially entire molecular weight range, and the variation from the average composition in the molecular weight dependence of the composition is 10% or less, preferably 5% or less.

(5) The EPR used as the component (B) in the present invention has a weight average molecular weight Mw measured by GPC of 10,000 to 1,000,000. If it exceeds 1,000,000, the fluidity of the composition of the present invention, that is, the component (A) + the component (B) at the time of thermoplastic molding is reduced, and the appearance of a molded article is reduced. Preferably, those having Mw of 30,000 to 800,000 are used.

(6) Further, the component (B) is such that the proportion of components having a molecular weight of 10,000 or less in the molecular weight distribution determined by GPC is 10% or less, preferably 5% or less. If a low molecular weight component in an amount exceeding 10% is present, the degree of polymerization may be in a range of good compatibility, and crystallization may be inhibited by the effect of the component. GPC
In order to determine the molecular weight distribution from the measurement, the molecular weight distribution is calculated from the molecular weight distribution in terms of PS using a known standard polystyrene (PS).
Using the ethylene mole fraction (φc2) determined by MP, the viscosity equation η = KMα, where Log [k] = φc2 (−
3.616) + (1−φc2) × (−3.407), α
= 0.733 and is calculated by the universal calibration method. If it contains other small amounts of copolymer components,
It can be approximately calculated by the above equation using the ethylene mole fraction.

In the work leading up to the present invention, PP and EP
For the combination of R, the previously unknown interaction parameters kai, c were determined, revealing the interrelation of the limit weight-average degree of polymerization with respect to compatibility in principle considerations. The value of kai, c specific to the system of PP and EPR is 0.01. Therefore, the mutual relationship between the weight average polymerization degrees is expressed by the weight average polymerization degree m ^{1 of} PP, E
When the weight average degree of polymerization m ^{2 of} PR is

[0018]

(Equation 1) If the kai calculated in is less than 0.01, the system is considered incompatible.

The above equation is widely known as an equation that gives the interaction parameter of the limit of compatibility of a polymer / polymer equivalent binary system derived from the thermodynamic theory derived by Scott (Akiyama et al.). "Polymer blend"
Page 18, CMC (1981)).

For example, the PP used as the component (A) in the present invention has a weight average molecular weight of Mw1 due to the requirement of mechanical strength when the composition of the present invention is used as a structural material.
In the case where the molecular weight is not less than 10,000, the Mw of incompatible EPR in the above (formula) is about 5,700 with respect to 10,000 of Mw of PP. Similarly, for Mw 100,000 of PP, it is about 2300. (Formula) is an ideal one that does not consider the influence of molecular weight distribution and composition distribution.
Since the ratio changes when the EPR ratio is apart from the equivalent amount, the ratio is not strict and a practical range needs to be experimentally determined.

Specific Description (a) Mw and Mn Mw and Mn are measured by GPC. Measurement is WATE
ALC-GPC150C manufactured by RS was used, and Shortex AD801MS was used as a column. 0.2 cc of orthodichlorobenzene, 140 ° C., 2 mg / ml was injected, and flowed at 1 cc / min, and infrared was detected at 3420 cm ⁻¹ .

(B) Degree of polymerization The degree of polymerization was determined by the weight average molecular weight Mw obtained by GPC.
Alternatively, it is defined as a value obtained by dividing the number average molecular weight Mn by the average molecular weight of the repeating unit. That is, if it is PP, Mw /
42, which is a value obtained by dividing the aforementioned Mw by (28 × 0.5 + 42 × 0.5) in the case of EPR containing 50 mol% of ethylene.

(C) Ratio of isotactic pentad chain (mmmm) of PP The ratio of stereoregularity (mmmm) is determined by JNM manufactured by JEOL Ltd.
After dissolving the polymer in 2 ml of orthodichlorobenzene using GSX270, 0.5 ml of deuterated benzene was added as a locking solvent, and the measurement was performed at 130 degrees.
In order to improve the S / N, integration was performed 10,000 times. The analysis is described in J.A. C. Using the method already proposed by Randall (Journal of Polymer)
r Science 12, 703, (1974)),
[Mmmm] was estimated.

(D) Propylene content of EPR The propylene content of EPR was measured by JNM manufactured by JEOL Ltd.
Using GSX270, the polymer was dissolved in 2 ml of orthodichlorobenzene, and 0.5 ml of deuterated benzene was added as a locking solvent, and the measurement was performed at 130 ° C. In order to obtain a sufficient S / N, integration was performed 10,000 times. The analysis is in H. N. The method already proposed by Cheng et al. Was used (Macromolecules 1984).
Year, Vol. 117, P1950).

(E) Dependence of C ₂ composition in EPR on molecular weight This physical property was determined by using GPC manufactured by Waters Inc. with Shodex 806MS in the column and BARN in the flow cell.
ES-Zero-Dead. vol. cl,
The measurement was performed using an IR made by Nicole as the detector.
EPR solution 2 prepared to 4 mg / ml chloroform
The measurement was carried out by flowing 00 ml at a normal temperature at a flow rate of 1 ml.
The resolution at this time was 4 cm ^-1 . Analysis were measured intensity I of intensity and 2180 cm ^-1 in 2950 cm ^-1 was performed using analysis software Omurokku Corporation. The ratio of this intensity at each elution time (I 2950 / I 218)
0) is proportional to the C ₂ fraction. A composition variation of 10% or less means that the intensity ratio at each molecular weight is within ± 5% of the average intensity ratio.

(F) Determination of kai, c The determination of kai, c was performed as follows. Therefore, it was implemented.

First, PP and EPR are weighed at 0.2 wt.
%, A 135 degree xylene solution was prepared. At this time, as an antioxidant, IRGANOX1010 manufactured by Ciba
Was added in small amounts. Here, the xylene solution is added under stirring with 1
After constant temperature for 0 minutes, the mixture was thrown into a 10-fold amount of a dry ice methanol solution. The resulting precipitate was vacuum-dried at room temperature after filtration to obtain a mixed sample.

In Production Example 4, C ₂ H ₂ was added during EPR polymerization.
Deuterated E by the same polymerization except for changing the the C ₂ D ₂
PR and D-EPR50 were obtained. Samples D-EPR50E and D-EPR5 shown in Table 2 were sampled by GPC fractionation of D-EPR.
0I was obtained. PP1, PP2 and EPR50 shown in Production Examples 1, 2, and 4 were used together.

Using a neutron scattering apparatus SANS-U owned by the Institute of Solid State Physics, the University of Tokyo, the measurement was carried out according to the method described in Experimental Polymer Science (Kyoritsu Shuppan, Polymer Solid Structure 1).
The degree of polymerization of PP is determined by adding a mixed solution of orthodichlorobenzene / deuterated xylene solution (1.0 / 1.6 [g / g]) to P.
P was dissolved, and measured at 129 ° C. for four different concentrations of 1 to 5%, and Zimm plotted.
Maconnachie A. et. al. : Poly
The absolute molecular weight and the radius of gyration at the PP concentration of Zero were determined with reference to mer 19, 739 (1978).

The above D-EPR50I and EPR50I volume fraction blend samples, and D-EPR50E and EP
R50E volume fraction blend sample (matched-
pair) was prepared. Neutron scattering measurements were taken at 160 degrees and Graessly. W. W. : Mocromol
ecules 26, 1137 (1993)), the radius of gyration and absolute molecular weight of EPR were determined. At this time, the interaction between proton and deuterium is 4 × 10 ^-4
And In the above blend, deuterated EPR and EPR were each weighed, dissolved in chloroform and mixed, and then suction-dried of chloroform.

PP1 obtained by the method described above,
Using the degree of polymerization and the radius of gyration of each of PP2 and deuterated EPR (Table 2), the interaction parameters kai, c in PP and EPR blends were described in the literature (Peter A.W.).
eimann, et. al. Macromolecul
es, 30, 3650 (1997)) and RP
A theory (de-Genenes, PG Sc.
alling: Concepts in Polym
er Physics Cornell Univer
(city Press, New York, 1979)
The temperature was determined at 160 to 220 degrees.

The blend sample was made of PP and E at the time of measurement.
PR was dissolved in heated toluene, then poured into methanol, and the precipitated component was filtered and dried. A sample obtained was packed in a quartz cell and subjected to neutron scattering to carry out kai. c was determined. As shown in Table 3, kai. c is 0.01
It is.

<Composition and Production Thereof> In the polypropylene resin composition according to the present invention, the composition ratio of component (A) PP to component (B) EPR is such that component (A) is 100 parts by weight and component (B) 2 100 parts by weight. Component (B)
When the amount of (EPR) is increased, the impact resistance of the composition tends to increase and the rigidity tends to decrease. When the EPR exceeds 100 parts by weight, the impact strength of the composition is increased, but the rigidity is greatly reduced, and such a composition is not suitable for a wide range of applications utilizing the crystallinity of PP. Preferably, component (B) is from 5 to 50 parts by weight.

Production Example 1 used in Examples and Comparative Examples of the present invention
The molecular structures of PP and EPR are as shown in Table 1.

The propylene homopolymer and ethylene-propylene copolymer constituting the composition of the present invention can be produced by known methods. Specifically, a propylene homopolymer is produced by a known stereoregular polymerization catalyst (for example, a catalyst obtained by combining magnesium chloride-supported titanium tetrachloride and an organic metal component such as triethylaluminum (for example, JP-A-1-202004). No. 1-24806
Nos. 2-77413, 2-107610, and 3
-39302, 3-234707, 4-293
No. 910, No. 4-296304), and the like. Polymerization of propylene is performed, and the molecular weight distribution (Q = Mw / Mn) of the resulting polymer is determined by an operation such as Soxhlet extraction. A metallocene-based catalyst for producing an isotactic polymer as a stereoregular polymerization catalyst, for example, (r) -dimethylsilylenebis (2-ethyl-4-phenylindenyl) zirconium dichloride (Japanese Unexamined Patent Application Publication No. 2-208733
JP-A-8-208733, such as (r) -dimethylsilylenebis (2-methyl-4,5-benzoindenyl) zirconium dichloride, and (r) -dimethylsilylenebis (2 Metallocene compounds described in JP-A-6-239914, such as (4,4-dimethyl-4-hydroazulenyl) zirconium dichloride, and (r) -ethylenebis (4,4-dimethyl-).
4,5,6,7-tetrahydro-4-sylinedenyl)
A propylene polymer produced using a metallocene compound described in JP-A-6-239915 such as zirconium dichloride can be exemplified.

As the ethylene-propylene copolymer, those produced using a metallocene-based catalyst for producing an isotactic polymer are suitable, and specific examples of such a catalyst are, for example, those described above. Can be found in

The cocatalyst component which should constitute the catalyst system by activating the metallocene transition metal compound is not particularly limited, and tri-lower alkyl aluminum such as triethylaluminum and triisobutylaluminum (in this specification, "lower alkyl" is means C ₁ -C ₄ alkyl), lower alkyl halides, other organometallic compounds and combination of ion-exchange layered silicate such as montmorillonite, methylalumoxane, lower alkyl substituted oxy aluminum and methyl isobutyl alumoxane Examples include the use of a compound or the like, and the use as a metallocene complex activated with a boron compound such as (tetraphenyl borate) tetrahydrofuran.

The polymerization may be carried out in batch, continuous, semi-batch, etc., without any limitation, and includes pentane, hexane, heptane, toluene,
A polymerization method using an inert hydrocarbon medium such as cyclohexane, a polymerization method using a monomer itself as a medium,
Those produced without limitation, such as a method in which polymerization is carried out in a gas phase without using a medium or in the substantial absence thereof, can be used.

The polymerization temperature is usually about 0 to 280 ° C., the polymerization pressure is usually 1 to 2000 kg / cm ² , and the molecular weight is controlled by using a molecular weight modifier such as hydrogen. May be.

The composition may be prepared by any mixing method. A method in which both components are dissolved in a common solvent such as hot xylene and then coprecipitated using a precipitant to recover or remove the solvent, a method of melting and mixing with an extruder, Banbury mixer, etc., injection molding, extrusion molding For example, in various thermoplastic molding methods, there is a method of directly mixing and feeding into a molding machine.

The component (A) and the component (B) are usually produced by polymerizing the corresponding monomers, respectively.
A method for performing the other step in the presence of the product of the production step (and usually in a state where the catalyst used in the step still has a reaction activity), in other words, a so-called “chemical blend” or a method of block copolymerization. , Can also be. For example, a composition of the present invention can be manufactured "in situ" by producing PP in a first stage polymerization followed by forming an EPR in a second stage polymerization.

The following components can be added to the composition of the present invention, if necessary. As long as the decrease in crystallization rate does not decrease to 70% or less of the uncombined composition corresponding to the present invention, 50 parts by weight or less of rubber or elastomer, for example, a component having a molecular weight of 10,000 or less per 10 parts by weight of PP is added. % or more comprising an ethylene propylene copolymer, copolymers of ethylene and C ₃ -C ₂₀ 2 or more monomers selected from α- olefins, styrene-butadiene diblock, triblock or radial block copolymers,
And those in which aliphatic unsaturated bonds have been hydrogenated, low-density polyethylene, and linear low-density polyethylene. Also, aluminum hydroxy dipara-
Known nucleating agents such as t-butyl benzoate, dibenzylidene sorbitol (DBS), substituted DBS such as methylated DBS, and 2,2-methylenebis (4,6-di-t-butylphenyl) sodium phosphate are known. % Or less can be used. These nucleating agents have the same effect in improving transparency and rigidity even when incorporated in the composition of the present invention. Other inorganic fillers such as calcium carbonate, talc, mica and glass fiber are PP10
50 parts by weight or less can be blended with respect to 0 parts by weight.

<Determination of spherulite growth rate> The crystallization rate was evaluated by keeping the blend sample heated to 230 ° C at a constant temperature for 7 minutes in a nitrogen atmosphere, cooling to 135 ° C at 70 ° C / min, and isothermal crystallization process. Was observed using an Olympus BH2 polarizing microscope. For observation, TC-600PH manufactured by Linkham Inc. was used as a heat stage. The crystallization rate is determined from the observed growth rate of the spherulite as an increase in radius (μm) per time (second) and from the slope of the proportional part of the time-temperature relationship. The value G (μm / s) obtained by calculating the average value from the growth rates of 30 spherulites is shown in Table 4 as the crystallization rate.

[Production Example] <Production Example 1> (Production of PP1) Production of solid catalyst component 200 ml of dehydrated and deoxygenated n-heptane was introduced into a flask sufficiently purged with nitrogen.
0.4 mol of Cl ₂ and 0.8 mol of Ti (On-C ₄ H ₉ ) ₄ were introduced and reacted at 95 ° C. for 2 hours. After completion of the reaction, the temperature was lowered to 40 ° C., and then 48 ml of methylhydropolysiloxane (of 20 centistokes) was introduced and reacted for 3 hours. The resulting solid component was washed with n-heptane.

Next, into a flask sufficiently purged with nitrogen,
50 ml of n-heptane purified in the same manner as above was introduced, and the solid component synthesized as above was added in an amount of 0.1 g in terms of Mg atom.
24 moles were introduced. Next, 0.4 mol of SiCl ₄ was mixed with 25 ml of n-heptane, introduced into the flask at 30 ° C. for 30 minutes, and reacted at 70 ° C. for 3 hours. After the completion of the reaction, the resultant was washed with n-heptane. Next, 0.024 mol of phthalic acid chloride was mixed with 25 ml of n-heptane, and the mixture was introduced into the flask at 70 ° C. for 30 minutes.
The reaction was performed at 0 ° C. for 1 hour. After the completion of the reaction, the resultant was washed with n-heptane. Then, 0.4 mol of SiCl ₄ was introduced to
The reaction was performed at 0 ° C. for 6 hours. After the completion of the reaction, the solid was sufficiently washed with n-heptane to obtain a solid component. This had a titanium content of 1.3% by weight. Next, 50 flasks of n-heptane purified in the same manner as above were placed in a flask sufficiently purged with nitrogen.
Ml was introduced, the synthesized solid component in the five grams _{introduced, (t-C 4 H 3} ) (CH 3) Si (OCH
₃ ) ₂ 1.2 ml, (C ₅ H ₉ ) ₂ Si (OC
H ₃ ) ₂ 1.2 ml, Al (C ₂ H ₅ ) ₃ 1.
7 grams were contacted at 30 ° C. for 2 hours. After the end of contact, n
Washing thoroughly with heptane to obtain a solid catalyst component mainly composed of magnesium chloride; The titanium content of this is
1.1% by weight.

In a 1.5 liter stainless steel autoclave having a propylene polymerization stirring and temperature control device, 500 ml of sufficiently dehydrated and deoxygenated n-heptane, 100 mg of triethylaluminum as a promoter component and 100 mg of triethylaluminum were added. 15 mg of the solid catalyst component produced above,
Then, 2000 ml of hydrogen was introduced, the temperature was raised and the pressure was increased, polymerization pressure = 5 kg / cm ² G, polymerization temperature = 75 ° C.,
Propylene was polymerized under the condition of polymerization time = 2 hours. After completion of the polymerization, the obtained polymer slurry was separated by filtration, and the polymer was dried. As a result, 190.6 g of a polymer was obtained. The filtrate yielded 0.6 grams of polymer. The obtained polymer is MF
R = 500 (g / 10 min), polymer bulk density = 0.48
(G / cc), polymer density = 0.9083 (g / c)
a c), it was isotactic pentad fraction by ^{13 C-NMR [mmmm] =} 98.3 (mol%).

The obtained PP was subjected to Soxhlet extraction with boiling heptane, the soluble component was poured into methanol, filtered, and dried to obtain PP1 (Table 1).

<Production Example 2> (Production of PP2) Polymerization was carried out under the same conditions except that the amount of hydrogen was changed to 1800 ml during the polymerization of PP under the conditions of PP1 to obtain a polymer having an MFR of 400 (g / 10 minutes). I got Extraction filtration was performed under the same conditions as for PP1, to obtain PP2. Its [mmmm] was 98% (Table 1).

<Production Example 3> (Production of PP3) Polymerization was carried out under the same conditions except that the amount of hydrogen was changed to 1600 ml during the polymerization of PP under the conditions of PP1 to obtain MFR = 300 (g / 10 min). This was used as a sample without extracting it. [Mmmm] was 98% (Table 1).

<Production Example 4> (Production of EPR50B, D, E, F, I, J) Synthesis of copolymer of EPR50 (ethylene / propylene = 50/50) Ethylene-propylene-hydrogen (volume ratio: 49.6: 49.
6: 0.8) 500 mL of heptane was charged into a stirred autoclave having an internal temperature of 65 ° C. and an internal volume of 1 L replaced with a mixed gas of 0: 6 kg / c.
m ² G. 5.0 mmol of methylisobutylaluminoxane in terms of Al atom and 5.0 μmol of dimethylsilylene (2-methyl-4,5-benzoindenyl) zirconium dichloride were introduced into this autoclave,
Thereafter, ethylene so that the inside pressure becomes 0.2 kg / cm ² G - propylene - hydrogen (volume ratio 49.2: 49.2:
The polymerization operation was carried out for 83 minutes while additionally introducing the mixed gas of 1.6). Heptane was distilled off from a heptane solution of the produced polymer to obtain 24 g of a polymer. The number average molecular weight (Mn) of this polymer was 1500 and the weight average molecular weight (M
w) is 36,200 molecular weight distribution (Mw / Mn) is 2.41
Met.

The EPR1 thus obtained had a total ethylene content of 47 mol% and a composition variation of 2%. Mw / Mn was 2.0.

The obtained EPR was collected as a 5% solution in chloroform using LC908 graded GPC manufactured by Nippon Kagaku Kogyo Co., Ltd., and column AJ3H manufactured by Nippon Kagaku Kogyo Co., Ltd. for each molecular weight. From EPR with 50% preparative ethylene content, EPR50J, EPR
50I, EPR50F, EPR50D, EPR50B,
EPR50E was obtained.

<Production Example 5> (Production of EPR25A, D) Production of EPR25 Synthesis of copolymer of ethylene / propylene = 75/25 Ethylene-propylene-hydrogen (volume ratio 18.6: 79.
2: 2.2) 500 mL of heptane was charged into a stirred autoclave having an internal temperature of 65 ° C. and an internal volume of 1 L replaced with a mixed gas of 2.2), and the above-mentioned mixed gas was further added.
m ² G. 5.0 mmol of methylisobutylaluminoxane in terms of Al atom and 5.0 μmol of dimethylsilylene (2-methyl-4,5-benzoindenyl) zirconium dichloride were introduced into this autoclave,
Thereafter, ethylene-propylene-hydrogen (volume ratio 18.6: 79.2: volume) is adjusted so that the internal pressure becomes 0.2 kg / cm ² G.
The polymerization operation was carried out for 72 minutes while additionally introducing the mixed gas of 2.2). Heptane was distilled off from a heptane solution of the produced polymer to obtain 10 g of a polymer. The number average molecular weight (Mn) of this polymer is 9670, and the weight average molecular weight (M
w) is 20300 and the molecular weight distribution (Mw / Mn) is 2.0
Nine.

The thus obtained EPR25 had an ethylene content of 25 mol% in total and a composition variation of 1%. Mw / Mn was 2.0.

The above-obtained EPR25 was converted to a chloroform 5% solution as LC908 grade G (manufactured by Nippon Kagaku Kogyo Co., Ltd.).
Using a PC and a column AJ3H manufactured by the same company, fractions were collected at each molecular weight. EPR25 from EPR with 50% preparative ethylene content
A, EPR25D was obtained.

[0056]

EXAMPLES The crystallization rates of the compositions obtained from the samples of Tables 1 and 2 are as shown in Table 4.

<Example 1> The density of PP was 0.91 g / c.
m ^3, the density of EPR as 0.85 g / cm ³ PP3
Is weighed so that EPR50B becomes 20 vol%,
An antioxidant was added in an amount of 0.1 wt% based on all the polymers. This was stirred at a constant temperature for 15 minutes as a 2% solution of hot xylene at 135 ° to obtain a uniform solution. This hot xylene solution was poured into 10 times the amount of xylene used in dry ice / methanol, and the resulting precipitate was filtered and vacuum dried at room temperature to obtain a polypropylene resin composition. The obtained sample was placed on a glass slide, and the growth rate G
Was observed.

<Example 2> With the composition shown in Table 4, the growth rate G of spherulite was observed at 135 ° C in the same manner as in Example 1.

Comparative Example 1 Antioxidant I against PP3
0.1% by weight of RGANOX1010 was added. This was stirred at a constant temperature for 15 minutes as a 2% solution of hot xylene at 135 ° C. to obtain a uniform solution. This hot xylene solution was poured into 10 times the amount of xylene used in dry ice / methanol, and the resulting precipitate was filtered and vacuum dried at room temperature.

Place the obtained sample on a glass slide,
The spherulite growth rate G was observed at 135 ° C.

<Comparative Examples 2 to 5> The growth rate G at 135 ° C. was observed with the compositions shown in Table 4 as in Example 1.

<Comparative Example 4> EPR50D was added to PP1 for 20
vol%, and the antioxidant IRGANOX
1010 was added in an amount of 0.1% by weight based on the whole polymer.
This was stirred at a constant temperature for 15 minutes as a 2% solution of hot xylene at 135 ° C. to obtain a uniform solution. This hot xylene solution was poured into 10 times the amount of xylene used in dry ice / methanol, and the resulting precipitate was filtered and vacuum dried at room temperature.

Place the obtained sample on a glass slide
The spherulite growth rate G was observed at 35 ° C.

<Reference Examples 1 and 2> Except that PP1 and PP2 were used as PP, P at 135 ° C.
The growth rate G of the spherulite in the case of only P was confirmed. The results are shown together in (Table 4).

[0065]

[Table 1]

[0066]

[Table 2]

[0067]

[Table 3]

[0068]

[Table 4] <Example 3> (Production of PP-4) (1) Preparation of catalyst component Dimethylsilylenebis [1,1 '-{2-methyl-4-
(4-chlorophenyl) -4-hydroazulenyl}] c
Synthesis of funium dichloride (a) Synthesis of racemic / meso mixture 1.8 ml of 1-bromo-4-chlorobenzene (15.3
1 mmol of a pentane solution (1.64 M) of t-butyllithium in a solution of 2 mmol) of normal hexane (20 ml) and diethyl ether (20 ml) at -78 ° C.
(30.65 mmol) was added dropwise. The resulting solution is
After stirring at 5 ° C. for 1 hour, 1.96 g (13.79 mmol) of 2-methylazulene was added to the solution to carry out a reaction. While gradually returning the reaction solution to room temperature,
Stir for 5 hours. Thereafter, the reaction solution was cooled to 0 ° C., tetrahydrofuran (20 mL) and 30 μl (0.38 mmol) of 1-methylimidazole were added, and 0.84 ml (6.9 mmol) of dichlorodimethylsilane was further added. After stirring the reaction solution at room temperature for 1.5 hours, dilute hydrochloric acid was added to stop the reaction, the separated organic phase was concentrated under reduced pressure, dichloromethane was added, and the mixture was dried over magnesium sulfate. After distilling off the solvent under reduced pressure, an amorphous crude product was obtained.

Next, the above reaction product was dissolved in 20 ml of dry diethyl ether, and 8.6 ml of an n-hexane solution (1.6 M) of n-butyllithium was added at −78 ° C.
(13.8 mmol) was added dropwise. After completion of the dropwise addition, the reaction solution was stirred for 12 hours while gradually returning to room temperature. After distilling off the solvent under reduced pressure, 15 ml of a mixed solvent of toluene and diethyl ether (40: 1) was added and the mixture was cooled to −78 ° C., and 2.2 g of hafnium tetrachloride (6.9 mmol) was added thereto.
l) was added. Thereafter, the temperature was immediately returned to room temperature, and the reaction was performed with stirring for 5 hours. The obtained reaction solution was filtered on celite, and the solid separated by filtration was mixed with 5 ml of toluene and 4 ml of hexane.
Washed with ml and collected. The collected solid was extracted with 40 ml of dichloromethane, the solvent was distilled off from the extract, and dimethylsilylenebis [1,1 ′-{2-methyl-4- (3-
Chlorophenyl) -4-hydroazulenyl {] hafnium dichloride racemic / meso mixture (571 mg, yield 1)
0%).

(B) Purification of the racemic form Further, 571 mg of the above-mentioned racemic-meso mixture was dissolved in 15 ml of dichloromethane, and a high-pressure mercury lamp of 100 W was used for 15 minutes.
The content of the racemate was increased by irradiating the solution for 1 minute, then the insoluble matter was filtered off, and the collected filtrate was concentrated to dryness. Next, the obtained solid component was stirred with 5 ml of toluene, and filtered with a frit. The remaining solid component is dissolved in toluene 3
The residue was washed with 4 ml of hexane and 4 ml of hexane, and dried under reduced pressure to obtain 290 mg of dimethylsilylenebis [1,1 '-{2-methyl-4- (3-chlorophenyl) -4-hydroazulenyl}] hafnium dichloride.

The chemical shift of ¹ H-NMR of the above racemate was as follows. 300 MHz, CDCl ₃
(Ppm) δ 0.95 (s, 6H, SiMe ₂ );
21 (s, 6H, 2-Me), 4.92 to 4.96 (b
rd, 2H), 5.70 to 6.15 (m, 8H),
6.78 (d, 2H), 7.28 (s, 8H, aro)
m) Production of organic aluminum component 135 ml of demineralized water and 16 g of magnesium sulfate were collected in a 500 ml round bottom flask and dissolved with stirring. Montmorillonite (Kunipia F, manufactured by Kunimine Industries) is added to this solution.
22.2 g was added, and the mixture was heated and treated at 80 ° C. for 1 hour. Next, 300 ml of demineralized water was added, and the solid was recovered by filtration.

To this, 46 ml of demineralized water and 23.
After adding 4 g and 29.2 g of magnesium sulfate, the mixture was heated and treated under reflux for 2 hours. Demineralized water 200m after treatment
1 and filtered. Further, 400 ml of demineralized water was added and the mixture was filtered, and this operation was repeated twice. Next, the resultant was dried at 100 ° C. to obtain a chemically treated montmorillonite.

In a 100 ml round bottom flask, 1.05 g of the above chemically treated montmorillonite was collected and placed under reduced pressure at 200 ° C.
For 2 hours. To this, a toluene solution of triethylaluminum (0.5 mmol / ml) under purified nitrogen
Was added and reacted at room temperature for 1 hour, followed by washing twice with 30 ml of toluene to obtain an organoaluminum component as a toluene slurry.

(2) Propylene Prepolymerization Into the above slurry, 0.6 ml of a toluene solution of triisobutylaluminum (0.5 mmol / ml) was added to dimethylsilylenebis {1,1′-
19.1 ml of a toluene solution (1.5 μmol / ml) of (2-methyl-4- (3-chlorophenyl) -4-hydroazulenyl)｝ hafnium dichloride ceramide was added, and the mixture was contacted at room temperature for 10 minutes.

Into a 2 L induction-stirring autoclave, 40 ml of toluene and the whole amount of the above contact substance were introduced under purified nitrogen. Propylene was introduced under stirring at a total polymerization pressure of 0.6 MPa at room temperature for 3 minutes. Next, unreacted propylene was purged and the pressure was replaced by purified nitrogen, and then the prepolymerized catalyst was taken out. It contained 2.20 g of polymer per gram of organoaluminum component.

(3) Polymerization of Propylene 2.0 ml of a toluene solution (0.2 mmol / ml) of triisobutylaluminum (0.2 mmol / ml) and 136 Nml of hydrogen gas were added to an autoclave having a stirrer having an internal volume of 3 L and substituted with purified nitrogen. And 750 g of liquefied propylene. Thereafter, 30 mg of the prepolymerized catalyst obtained in Example 2 (2) was injected as a solid catalyst component, and after the temperature was increased, 75 mg was added.
The polymerization was carried out at a temperature of 1 hour. As a result, as shown in Table 5, 2
83 g of polypropylene were obtained.

Production of EPR1 (1) Preparation of Catalyst Component Dimethylsilylenebis (2-methylbenzoindenyl)
Racemic zirconium dichloride is described in the literature (Organ
Omatolics, 1994, 13, 964).

(2) Propylene Prepolymerization In a glass reactor having an inner volume of 0.5 L and equipped with a stirring blade, W was added.
2.4 g (20.7 m) of MAO _on SiO ₂ manufactured by ITCO
mol-Al), and 50 ml of n-heptane was introduced. 20.0 ml of a racemic solution of dimethylsilylenebis (2-methylbenzoindenyl) zirconium dichloride previously diluted in toluene (0.637 mmol)
l), followed by triisobutylaluminum (Ti
BA) n-heptane solution 4.14 ml (3.03 mm
ol). Thereafter, the reaction was carried out at room temperature for 2 hours, and propylene was flowed to carry out prepolymerization to obtain a solid catalyst component.

(3) Preparation of Ethylene-Propylene Copolymer 1.5 L of dehydrated and deoxygenated n-heptane was introduced into an autoclave having a stirrer having an internal volume of 3 L, which had been replaced with purified nitrogen. Aluminum 1
00 mg was added to bring the temperature to 65 ° C. Here, the prepolymerized catalyst obtained above was used as a solid catalyst component in 150 parts.
mg, and mixed in another gas regulating tank.
A mixed gas of ethylene (C ₂ concentration in the mixed gas = 30% by weight) was introduced at a pressure of 5 kg / cm ² · G,
The polymerization was carried out while maintaining the pressure and temperature for 3 hours. As a result, 163 g of an ethylene-propylene copolymer (EPR1) as shown in Table 5 was obtained.

The crystallization rate was measured by the following method.

That is, 1.6 g of PP4 and 0.4 g of EPR1 obtained were weighed (weight ratio 80/20),
100 ml of xylene was added and dissolved by heating at 135 ° C. for 15 minutes.
This was thrown into methanol, and the resulting precipitate was collected by filtration. The material dried under vacuum at room temperature for 48 hours is placed on a slide glass, and the spherulite growth rate in a 135 ° C. atmosphere is observed under a polarizing microscope, and video recording is performed. The average spherulite growth rate was determined from the time change of the increase in the radius of the ten spherulites in a certain direction, and was defined as the crystallization rate.

Example 4 Method for Producing PP-5 and EPR-2 (1) Preparation of Catalyst Component (Dimethylsilylenebis {1,1 ′-(2-methyl-4)
-Phenyl-4-hydroazulenyl) ニ ル hafnium dik
The following reactions were all carried out under an inert gas atmosphere, and the reaction solvent used was previously dried.

(A) Synthesis of racemic-meso mixture 3.22 g of 2-methylazulene was dissolved in 30 ml of hexane, and 21 ml (1.0 equivalent) of a solution of phenyllithium in cyclohexane-diethyl ether was added little by little at 0 ° C. After stirring the solution at room temperature for 1.5 hours,
After cooling to ℃, 30 ml of tetrahydrofuran was added. 45 μmol of 1-methylimidazole and 1.37 ml of dimethyldichlorosilane were added to this solution, and the mixture was returned to room temperature and 1
Stirred for hours. Thereafter, an aqueous solution of ammonium chloride was added thereto, and after liquid separation, the organic phase was dried over magnesium sulfate,
The solvent was distilled off under reduced pressure to obtain 5.84 g of a crude product of bis {1,1 '-(2-methyl-4-phenyl-1,4-dihydroazulenyl)} dimethylsilane.

The crude product of bis {1,1 ′-(2-methyl-4-phenyl-1,4-dihydroazulenyl)} dimethylsilane obtained above was dissolved in 30 ml of diethyl ether. -Butyl lithium hexane solution 1
4.2 ml (1.6 mol / L) was added dropwise, and the mixture was gradually returned to room temperature and stirred for 12 hours. After evaporating the solvent under reduced pressure, toluene / diethyl ether (40: 1) 80 ml
, 3.3 g of hafnium tetrachloride is added at -60 ° C,
The mixture was gradually returned to room temperature and stirred for 4 hours. The obtained solution is concentrated under reduced pressure, and the obtained solid is washed with toluene, extracted with dichloromethane, and dimethylsilylenebis ｛1,
1.74 g of a racemic / meso mixture of 1 '-(2-methyl-4-phenyl-4-hydroazulenyl) hafnium dichloride was obtained.

(B) Purification of the racemic form 1.74 g of a racemic-meso mixture obtained by repeating the above reaction was dissolved in 30 ml of dichloromethane, and
It was introduced into a Pyrex glass container having a W high pressure mercury lamp. The solution was irradiated with light under normal pressure for 40 minutes while stirring to increase the ratio of the racemate, and then dichloromethane was distilled off under reduced pressure. 10 ml of toluene was added to the obtained yellow solid.
Was added and stirred, followed by filtration. The filtered solid was washed with 8 ml of toluene and 4 ml of hexane to give dimethylsilylenebis {1,1 '-(2-methyl-4-phenyl-4-).
917 mg of a racemic form of (hydroazulenyl) hafnium dichloride was obtained.

Preparation of Organic Aluminum Component 135 ml of demineralized water and 16 g of magnesium sulfate were collected in a 500 ml round bottom flask and dissolved with stirring. Montmorillonite (Kunipia F, manufactured by Kunimine Industries) is added to this solution.
22.2 g was added, and the mixture was heated and treated at 80 ° C. for 1 hour. Next, 300 ml of demineralized water was added, followed by filtration to collect a solid content.

To this, 46 ml of demineralized water and 23.
After adding 4 g and 29.2 g of magnesium sulfate, the mixture was heated and treated under reflux for 2 hours. After treatment, demineralized water 20
0 ml was added and filtered. Further, 400 ml of demineralized water was added and the mixture was filtered, and this operation was repeated twice. Then 100 ° C
To obtain a chemically treated montmorillonite.

In a 100 ml round bottom flask, 1.05 g of the above chemically treated montmorillonite was collected and placed under reduced pressure at 200 ° C.
For 2 hours. To this, a toluene solution of triethylaluminum (0.5 mmol / ml) under purified nitrogen
Was added and reacted at room temperature for 1 hour, followed by washing twice with 30 ml of toluene to obtain an organoaluminum component as a toluene slurry.

(2) Propylene Prepolymerization The above slurry was mixed with 0.6 ml of a toluene solution of triisobutylaluminum (0.5 mmol / ml) and dimethylsilylenebis {1,1 ′ synthesized in Example 3 (1).
19.1 ml of a toluene solution (1.5 μmol / ml) of-(2-methyl-4-phenyl-4-hydroazulenyl) hafnium dichloridracemate was added thereto, and contacted at room temperature for 10 minutes.

Into a 2 L induction-stirring autoclave, 40 ml of toluene and the entire amount of the above contact substance were introduced under purified nitrogen. Propylene was introduced under stirring at a total polymerization pressure of 0.6 MPa at room temperature for 3 minutes. Next, unreacted propylene was purged and the pressure was replaced with purified nitrogen, and then the prepolymerized catalyst was taken out. This contained 2.98 g of polymer per gram of organoaluminum component.

(3) Propylene block copolymerization 2 L having a built-in irrigated stirring blade replaced with purified nitrogen
Into an induction-stirring autoclave, a toluene solution of triisobutylaluminum (0.5 mmol / ml)
After adding 13 ml of hydrogen gas and charging 13 KPa of hydrogen gas, 700 g of liquefied propylene was charged. Then, Example 3 (2)
37.5 as a solid catalyst component using the prepolymerized catalyst obtained in
mg, and polymerization was carried out at 70 ° C. for 20 minutes after the temperature was raised. The propylene and hydrogen were then purged to terminate the first stage polymerization reaction.

When the polymer yield in the first step was weighed, 257 g of polypropylene was obtained. After 35 g of the polymer was withdrawn under a flow of purified nitrogen, the temperature was raised to 50 ° C. with stirring and mixing, and after the temperature was increased, propylene gas and ethylene gas were charged so that the total polymerization pressure became 1.96 MPa. The polymerization of the stage was started. The total polymerization pressure is 1.96 MPa
The polymerization reaction was carried out at 50 ° C. for 85 minutes while supplying a mixed gas of propylene and ethylene so as to be constant. Here, the propylene / (propylene + ethylene) ratio is 3 on average.
8.2 mol%. Thereafter, propylene and ethylene were purged to obtain 276 g of a white powdery propylene block copolymer.

The crystallization rate was measured in the same manner as in Example 3.

The analysis of the polymer composition was performed as follows. That is, at 135 ° C., orthodichlorobenzene (O
DCB) When the solution is cooled to 5 ° C., the soluble components dissolved therein are converted into EPR components (EPR2), and the insoluble components are converted into PP.
It was separated as a (PP6) component. The molecular weight measurement by gel permeation chromatography (GPC) of fractionation and fractionation is carried out by using commercially available cross-fractionation chromatography (CFC T manufactured by Diamond Instruments).
150B).

<Example 5> Method for producing PP-6 (1) Preparation of catalyst component Example 1, component (A) of JP-A-3-234707
A solid catalyst component was obtained according to the method described in (1). (2) Polymerization of propylene After sufficiently replacing the stirred autoclave having an inner volume of 100 L with propylene, 25 L of purified n-heptane was introduced, and a solution of triethylaluminum in n-heptane (0.
(1 mol / L) and 3.2 g of the solid catalyst component synthesized in (1) were introduced at 65 ° C. in a propylene atmosphere. Further, the propylene was fed at a temperature of 75 ° C. at a feed rate of 4.5 kg / hour for 213 minutes while maintaining the hydrogen concentration in the gas phase at 0.5% by volume, and then polymerization was continued for another 40 minutes.

Thereafter, the catalyst was decomposed with butanol,
The product was filtered and dried to obtain 11.9 kg of a polymer as shown in Table 5. The same crystallization rate as in Example 1 was evaluated using the same EPR1 as in Example 3 as the component (B).

Comparative Example 6 The crystallization rate of PP4 of Example 3 containing no EPR was evaluated.

Comparative Example 7 The crystallization speed of PP6 containing no EPR in Example 5 was evaluated.

Comparative Example 8 Evaluation was made in the same manner as in Example 3 except that the EPR was changed to the following EPR. Preparation of EPR4 Dehydrated and deoxygenated n-heptane 1.5 in an autoclave having a stirrer having a volume of 3 L and replaced with purified nitrogen.
L was introduced, then 160 mg of diethylaluminum dichloride was added to bring the temperature to 65 ° C. here,
40 mg of a titanium trichloride catalyst (01 catalyst) manufactured by M & S Catalysts Co., Ltd. was injected and mixed in another gas conditioning tank. A propylene / ethylene mixed gas (C ₂ concentration in the mixed gas = 25% by weight) was introduced at a pressure of 5 kg / cm ² · G, and polymerization was carried out while maintaining the pressure and temperature for 3 hours.
As a result, 181 g of an ethylene-propylene copolymer as shown in Table 5 was obtained.

[0100]

[Table 5]

[0101]

According to the present invention, in various moldings for thermoplastic resins such as injection molding and extrusion molding, it is possible to provide a material which is less dependent on molding conditions and crystallization conditions, has a stable and fast solidification rate, and has good moldability. Can be.

Continued on the front page (72) Inventor Koichiro Ishii 1 Tohocho, Yokkaichi-shi, Mie Japan Process Development Center, Japan (72) Inventor Hiroyuki Nakano 1 Tohocho, Yokkaichi-shi, Mie Japan Nippon Polychem Co., Ltd. In-house Process Development Center (72) Inventor Satoshi Yamamoto 1 Toho-cho, Yokkaichi-shi, Mie F-term in Yokkaichi Office of Mitsubishi Chemical Corporation (reference) 4J002 BB12W BB15X FD010

Claims (1)

[Claims] 1. A polypropylene resin composition comprising 100 parts by weight of the following component (A) and 2 to 100 parts by weight of component (B). Component (A) (1) below
Propylene polymer (PP) satisfying (2): (1) stereoregularity (mmmm) is 97% or more; (2) weight average molecular weight is 10,000 to 1,000,000; component (B) (3) Ethylene propylene copolymer (EPR) satisfying (6) (3) The propylene content is 20 to 80 mol%, (4) The variation from the average composition in the molecular weight dependence of the composition is 10%. (5) The weight average molecular weight is 10,000 to 1,000,000, and (6) The proportion of components having a molecular weight of 10,000 or less is 10% or less.