JPH11269327A - Polypropylene resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition having suppressed crystallization rate, exhibiting excellent processability, capable of selecting the polymer characteristics of both components in harmonized state and useful for protect film, etc., by compounding a specific propylene polymer with an ethylene propylene copolymer. SOLUTION: This composition is composed of (A) 100 pts.wt. of a propylene polymer having an isotactic pentad chain (mmmm) fraction (an index of stereoregularity) of >=97%, an Mw/Mn ratio (Q value) (an index of molecular weight distribution) of <=4 (Mw and Mn are weight-average molecular weight and number-average molecular weight, respectively) and Mw of 1,000-500,000 and (B) 20-1,000 pts.wt. of an ethylene propylene copolymer having a propylene content of 30-95 mold, a variation from the average composition of <=10% in the molecular weight dependency of the composition, a Q value of <=4 and an Mw of 1,000-1,000,000. The Kai value defined by formula (m1 and m2 are the weight-average polymerization degrees of the component A and the component B, respectively) is adjusted to >=0.01.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a polypropylene resin composition comprising a propylene polymer and an ethylene-propylene copolymer. More specifically, the present invention relates to a polypropylene resin composition having a good compatibility between a propylene polymer and an ethylene-propylene copolymer, which are constituent components, and having a suppressed crystallization rate.

[0002]

2. Description of the Related Art A polypropylene resin composition comprising a propylene polymer and an ethylene-propylene copolymer is useful as an industrial material having excellent physical properties, especially impact resistance. Such a polypropylene resin composition,
It is known that the properties of the composition change depending on the type of the ethylene-propylene copolymer mixed therein, and many techniques are known as to the optimum compounding technique according to the purpose.

[0003] One of the causes of the change in the properties of such a polypropylene resin composition is that the composition depends on the affinity between the propylene polymer and the ethylene-propylene copolymer, that is, the compatibility at the molecular level. It is thought that this is due to the change in the dispersion structure or state of dispersion. The crystallization properties, which are important physical properties of the propylene polymer,
It has been reported that the degree of crystallization may change depending on the blending of the ethylene-propylene copolymer, and that the blending of the ethylene-propylene copolymer changes the degree of crystallinity or lowers the crystallization rate (Martuscelli E., POLYMER, 1982, Volume 23,
229). It is considered that these changes in the crystallization characteristics also depend on the affinity (or compatibility) between the propylene polymer and the ethylene-propylene copolymer.

The affinity (or compatibility) between the propylene polymer and the ethylene-propylene copolymer has been studied intensively in addition to the above. For example, neutron scattering studies (Lohse, DJ ,; Polymer Engineering Sci.
ence 26, 1500 (1986)), morphological observation (Coppola, F. et.al; P
olymer 28, 47 (1987)), NMR (Nirabella FMet.al .;
Polymer 37,931 (1996)), all of which are propylene polymers and ethylene propylene copolymers.
It is concluded that they are incompatible in the solid phase and even in the molten state under heating. These studies have been conducted on ethylene propylene copolymers having a wide composition distribution. Detailed structure of the ethylene propylene copolymer, for example, molecular weight distribution, copolymer composition of propylene and ethylene, furthermore, such as the steric structure of the propylene chain,
There is no discussion of the change in compatibility when is controlled.

[0005] Even when an intimate mixture obtained by pouring a homogeneous mixture of a propylene polymer and an ethylene-propylene copolymer dissolved in a solvent into a non-solvent is melted under heating, demixing ( Phase separation),
It has been reported that the degree of demixing changes the crystal structure when solidified (Hashimoto T. Macromolecule)
s, 19, 1690 (1986)). The propylene polymer and ethylene-propylene copolymer used in this study have a large molecular weight and a wide molecular weight distribution for both components.

An amorphous continuous phase formed from a part of an ethylene-propylene copolymer dissolved in an amorphous part of polypropylene and a three-dimensional pseudo-network-like ethylene-propylene copolymer phase In addition, a composition in which a crystalline lamella of polypropylene is present as a dispersed phase is also known (42,3932 (1993), Proc. Of the Symposium on Polymer Science), but the composition still forms a sea / island structure. ing.
As described above, when the affinity (or compatibility) between the propylene polymer and the ethylene-propylene copolymer is not sufficient, it is difficult to mix both polymers intimately at the molecular level, and it is difficult to mix both polymers. A so-called sea / island structure in which the dispersed phase is dispersed to some extent in the other polymer phase may be observed with an optical microscope. In this document, the degree of dissolution is examined by lowering the mechanical dispersion temperature, but there is no suggestion of compatibility in terms of molecular size.

[0007]

[Summary of the Invention] <Summary> The present invention consists of a propylene polymer and an ethylene propylene copolymer, which have a stable crystallization rate, that is, have a low crystallization rate. It is intended to provide a polypropylene resin composition.

[0008]

Accordingly, the polypropylene resin composition according to the present invention comprises the following component (A) 10
It is characterized by comprising 0 parts by weight and 20 to 1000 parts by weight of the component (B), wherein the Kai calculated by the following formula [I] is 0.01 or more.

Component (A) : a propylene polymer satisfying the following conditions (a) to (c). Condition (a): The fraction of isotactic pentad chains (mmmm), which is an index of stereoregularity, is 97% or more. Condition (b): Weight average molecular weight (Mw) and number average molecular weight (Mn) Mw which is an index of the molecular weight distribution calculated from
/ Mn (Q value) is 4 or less, Condition (c): Weight average molecular weight (Mw) is 1000 to 50
0000.

Component (B) : an ethylene propylene copolymer satisfying the following conditions (d) to (g). Condition (d): Propylene content is 30 to 95 mol%. Condition (e): Variation from average composition in molecular weight dependence of composition is 10% or less. Condition (f): Weight average Mw which is an index of the molecular weight distribution calculated from the molecular weight (Mw) and the number average molecular weight (Mn)
/ Mn (Q value) is 4 or less, Condition (g): Weight average molecular weight (Mw) is 1000 to 10
00000.

Formula [I] :

(Equation 2) [In the formula, m ₁ represents a weight average polymerization degree of the component (A), and m _1
2 indicates the weight average polymerization degree of the component (B). <Effect> The polypropylene resin composition according to the present invention has good compatibility between the polypropylene polymer and the ethylene-propylene copolymer, and the crystallization rate of the polypropylene polymer is sufficiently suppressed. Under various processing conditions such as molding, adhesion, and adhesion to a thermoplastic resin, a stable soft molded product can be obtained. For example, a propylene polymer characteristic and an ethylene propylene copolymer characteristic can be selected harmoniously according to the necessity of softness, transparency, heat resistance and the like in a protection film or the like.

[0012]

DESCRIPTION OF THE PREFERRED EMBODIMENTS <Component (A)> The component (A) of the polypropylene resin composition according to the present invention is a propylene polymer satisfying the following conditions (a) to (c) (hereinafter referred to as the propylene polymer). Is sometimes referred to as “PP”), preferably a propylene homopolymer. Condition (a): The fraction of isotactic pentad chains (mmmm), which is an index of stereoregularity, is 97% or more. Condition (b): Weight average molecular weight (Mw) and number average molecular weight (Mn) Mw which is an index of the molecular weight distribution calculated from
/ Mn (Q value) is 4 or less, Condition (c): Weight average molecular weight (Mw) is 1000 to 50
0000.

Here, the condition (a) is, specifically, ¹³ C
-Conventional method by NMR spectrum analysis (for example, Randall J.
C., J. Polymer Sci., 12 , 703 (1974)), the fraction of isotactic pentad chains (mmmm), which is an index of stereoregularity, is 97% or more, preferably 98% or more. , Is the condition. If the stereoregularity is low, the melting point of the target polypropylene resin composition decreases, and the heat resistance decreases. The component (A) in the present invention
Preferably, the atactic polymer component content is low, and the atactic polymer component defined by the boiling heptane soluble matter is 5% or less, preferably 3% or less, particularly preferably 1% or less.

The condition (b) is that Mw / Mn (Q value), which is an index of the molecular weight distribution calculated from the weight average molecular weight (Mw) and the number average molecular weight (Mn), is 4 or less. is there. Here, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are all measured by GPC (the specific measuring method will be described later), and the component (A) in the present invention Has an Mw / Mn (Q value) of 4 or less, preferably 3.5 or less, particularly preferably 3.0 or less.
It is as follows. When Mw / Mn exceeds 4, the existence of a high molecular weight component having reduced compatibility cannot be ignored, and the critical kai (described later in detail) fluctuates, and even if other conditions are within the scope of the present invention, the compatibility is reduced. As a result, crystallization may not be sufficiently suppressed.

The condition (c) is a condition relating to the weight average molecular weight of the component (A). The component (A) in the present invention satisfies the condition that the weight average molecular weight (Mw) is 1,000 to 500,000. Here, the weight average molecular weight (Mw) is also based on GPC measurement. When the weight average molecular weight (Mw) is less than 1000, the compatibility with the ethylene propylene copolymer (component (B)) is improved, but it is difficult to sufficiently increase mechanical properties such as impact strength and elongation at break. Therefore, the composition obtained is not suitable as a molding material. On the other hand, the weight average molecular weight (Mw) is 500
If it exceeds 000, the fluidity at the time of thermoplastic molding decreases, and it is not suitable as a general molding material. The preferred weight average molecular weight (Mw) is 10,000 to 400,000.

The component (A) in the present invention satisfies the above-mentioned conditions (a) to (c). In the present invention, the component (A) which satisfies the following conditions (condition (h)) with respect to the melting point. Is particularly preferred. The condition (h) is that the melting point is 150 ° C.
Above, preferably 155 ° C. or higher. If the melting point is less than 150 ° C., the heat resistance of the molded product is not sufficient, the rigidity in the daily use temperature range has a large temperature dependency, and the application of the adhesive material may be limited.

Such a component (A) can be produced by a known method. Specifically, a known stereoregular polymerization catalyst (preferably, a catalyst obtained by combining a tetravalent titanium compound supported on magnesium chloride with an organic metal component such as triethylaluminum (for example, JP-A-1-202
04, JP-A-1-24806, JP-A-2-7741
No. 3, the catalyst described in JP-A-2-107610, etc.) and the molecular weight distribution (Q = Mw / Mn) of the produced polymer is adjusted to the range used in the present invention by an operation such as Soxhlet extraction. Or a stereoregular polymerization catalyst such as a metallocene catalyst for producing an isotactic polymer, for example, (r) -dimethylsilylenebis (2
Metallocene compounds described in JP-A-8-208733, such as -ethyl-4-phenylindenyl) zirconium dichloride and (r) -dimethylsilylenebis (2-methyl-4,5-benzoindenyl) zirconium dichloride; r) -dimethylsilylenebis (2,4-
Metallocene compounds described in JP-A-6-239914, such as dimethyl-4-hydroazulenyl) zirconium dichloride, and (r) -ethylenebis (4,4-dimethyl-4,5,6,7-tetrahydro-4-silindenyl) JP-A-6-2399 such as zirconium dichloride
It can be produced using a metallocene compound described in JP-A No. 15-No.

The promoter component for activating the metallocene transition metal compound is not particularly limited, and a combination of an organometallic compound such as triethylaluminum and triisobutylaluminum and an ion-exchange layered silicate compound such as montmorillonite, methylalumoxane And oxyaluminum compounds such as methylisobutylalumoxane, and metallocene complexes activated with boron compounds such as (tetraphenylborate) tetrahydrofuran.

The polymerization method employed for producing the component (A) is not limited to a batch system, a continuous system, a semi-batch system or the like, and uses an inert hydrocarbon medium such as pentane, hexane, toluene and cyclohexane. Any of a polymerization method, a polymerization method using a monomer to be used as a medium itself, and a method of performing polymerization in a gas phase without using a medium or substantially in the absence of a medium may be used. The polymerization temperature is usually from about 0 to 280 ° C., the polymerization pressure is usually from 1 to 2000 kg / cm ² , and it can be produced by controlling the molecular weight using a molecular weight modifier such as hydrogen. <Component (B)> The component (B) of the polypropylene resin composition according to the present invention is an ethylene propylene copolymer satisfying the following conditions (d) to (g) (hereinafter, this ethylene propylene polymer is referred to as “EPR”). May be indicated). Condition (d): Propylene content is 30 to 95 mol%. Condition (e): Variation from average composition in molecular weight dependence of composition is 10% or less. Condition (f): Weight average Mw which is an index of the molecular weight distribution calculated from the molecular weight (Mw) and the number average molecular weight (Mn)
/ Mn (Q value) is 4 or less, Condition (g): Weight average molecular weight (Mw) is 1000 to 10
00000. Condition (d) relates to the propylene content of component (B). The propylene content of the component (B) is from 30 to
It is 95 mol%, preferably 50 to 90 mol%, particularly preferably 50 to 75 mol%. Propylene content of 3
If the amount is less than 0 mol%, the compatibility with the component (A) is reduced, and the effect of suppressing the crystallization rate is not obtained or is extremely small. Further, the affinity of the interface between the propylene polymer (component (A)) and the ethylene propylene copolymer (component (B)) decreases, and the mechanical properties of the composition, such as tensile elongation,
Impact strength etc. decrease. If the propylene content exceeds 95 mol%, the compatibility with the propylene polymer of the component (A) increases, but the glass transition temperature increases, so that the low-temperature impact strength of the composition decreases and the embrittlement temperature decreases. Of ethylene propylene copolymer (component (B))
Is less advantageous.

The condition (e) relates to the dependence of the composition on the molecular weight. Generally, depending on the copolymerization mechanism, the propylene content in the copolymer may be non-uniform with respect to the molecular weight. In the case where the molecular weight distribution is relatively wide, if there is a component having a higher propylene content than the average composition in the high molecular weight section, the compatibility is reduced. For the molecular weight dependency, the propylene content of each section classified by GPC is evaluated (the method will be described later). Component (B) in the present invention has a variation from the average composition of 10% or less, preferably 5% or less,
More preferably, it is at most 3%.

The condition (f) is that Mw / Mn (Q value), which is an index of the molecular weight distribution calculated from the weight average molecular weight (Mw) and the number average molecular weight (Mn), is 4 or less. is there. Here, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are all measured by GPC as in the case of the component (A), and the component (A) in the present invention is , Mw / Mn (Q value) is 4 or less,
It is preferably at most 3.5, particularly preferably at most 3.0. When Mw / Mn exceeds 4, the compatibility is reduced, and as a result, the crystallization suppressing effect is reduced.

The condition (g) is a condition relating to the weight average molecular weight (Mw) of the component (B). Component (B) in the present invention
Has a weight average molecular weight (Mw) of 1,000 to 100,000
0 is satisfied. Here, the weight average molecular weight (Mw) is also based on GPC measurement. When the weight average molecular weight (Mw) is less than 1,000,
It is not practical because mechanical properties such as elongation at break are low.
On the other hand, when the weight average molecular weight (Mw) is more than 1,000,000, the fluidity when the composition is thermoplastically molded is reduced. Preferably, the weight average molecular weight (Mw) is 10,000
８００800,000 ethylene propylene copolymer is used.

The ethylene propylene copolymer used as the component (B) in the present invention can be produced by a known method. In the present invention, a stereoregular polymerization catalyst,
For example, those produced using a metallocene catalyst are preferred. Preferred specific examples of metallocene-based catalysts for producing such an isotactic polymer can be found, for example, in the above-mentioned known documents concerning the production of the propylene polymer of the component (A).

The promoter component for activating the metallocene transition metal compound is not particularly limited, and a combination of an organometallic compound such as triethylaluminum and triisobutylaluminum and an ion-exchange layered silicate compound such as montmorillonite, methylalumoxane And oxyaluminum compounds such as methylisobutylalumoxane, and metallocene complexes activated with boron compounds such as (tetraphenylborate) tetrahydrofuran.

As in the case of the above-mentioned component (A), the polymerization method used for producing the component (B) is not limited, such as a batch system, a continuous system, or a semi-batch system. A polymerization method using an inert hydrocarbon medium such as toluene or cyclohexane, a polymerization method using a monomer to be used as a medium, a method of performing polymerization in a gas phase without using a medium or in the substantial absence thereof. And so on. The polymerization temperature is usually about 0 to 280 ° C, and the polymerization pressure is usually 1 to 2000 kg.
/ Cm ² and can be produced by controlling the molecular weight using a molecular weight modifier such as hydrogen. <Polypropylene resin composition> The polypropylene resin composition according to the present invention comprises 100 parts by weight of the above component (A) and 20 to 1000 parts by weight of the component (B). If the amount of the component (B) is large, the rigidity of the composition tends to decrease. If the amount of the component (B) exceeds 1,000 parts by weight, the component (A) such as high-temperature rigidity retention and non-adhesion can be obtained.
The effect of the formulation is lost. If the compounding amount of the component (B) is less than 20 parts by weight, effects suitable for the purpose of the compounding of the component (B), such as low-temperature impact strength and reduction in critical temperature, cannot be obtained. The amount of component (B) is based on 100 parts by weight of component (A).
Preferably it is 40 to 100 parts by weight.

Mixing of components (A) and (B) can be carried out by any suitable method. For example,
After dissolving both components in a common solvent of both components (preferably, for example, hot xylene, hot toluene, etc.), a mixture of both components is recovered using a precipitant (preferably, for example, methanol, ethanol, and acetone). Alternatively, in a method of distilling a solvent, for example, a method of melting and mixing both components with an extruder, a Banbury mixer, and various thermoplastic molding methods (preferably, for example, injection molding and extrusion molding), mixing both components with a molding machine. There is a method to put in. In the present invention, the polymerization is carried out in two stages, and in the presence of a first-stage polymerization product (for example, component (A)),
Subsequently, a second stage polymerization (eg, formation of component (B)) is performed to obtain a mixture of polymerization products in both stages.
A method of a so-called polymerization blend can also be adopted.

Further, the polypropylene resin composition according to the present invention is characterized in that, in addition to satisfying the above requirements, kai calculated by the following formula [I] is 0.01 or more.

[0028]

(Equation 3) [In the formula, m ₁ represents a weight average polymerization degree of the component (A), and m _1
2 indicates the weight average polymerization degree of the component (B). This formula [I] is widely known as a formula that gives an interaction parameter of a limit of compatibility of a polymer / polymer equivalent binary system derived from a thermodynamic theory derived by Scott (Akiyama et al.) , "Polymer Blend", page 18, CMC (1981)). When the type of the polymer to be used is determined, there are specific interaction parameters kai and c (= critical value of kai: detailed later). In this system, when the degree of polymerization of the two polymers used is determined, the interaction parameter value (kai) of the two polymers used can be calculated by the formula [I]. Then, the ka obtained when two kinds of polymers to be used are selected is determined.
When i is larger than kai, c, the two components are compatible in a molten state.

Hereinafter, the polypropylene resin composition according to the present invention and the requirements for defining the components (A) and (B) will be described in more detail with respect to Production Examples 1 to 4 described below. (1) The weight average molecular weight (Mw) and the number average molecular weight (Mn) are measured by GPC. In each case, after calibration with standard polystyrene, the viscosity formula, η =
KM ^α where Log [K] = − 3.407, α =
0.733, and NM in ethylene propylene copolymer
Using the ethylene mole fraction (φ _C2 ) determined by R, η = KM
^α where Log [K] = φ _C2 (-3.616) +
This value is obtained by multiplying the value calculated by the universal calibration method by 0.5 using (1−φ _C2 ) (−3.407) and α = 0.733. Measurement is made by WATERS
ALC-GPC1500 was used, and Shodex AD801MS was used as a column. 0.2cc of orthodichlorobenzene, 140 ° C, 2mg / ml was injected, and 1c
Flow at c / min and detection at 3420 cm ^-1 in the infrared. (2) The degree of polymerization is defined as a value obtained by dividing the weight average molecular weight (Mw) or number average molecular weight (Mn) obtained by GPC by the average molecular weight of the repeating unit. That is,
If it is a propylene polymer, it is Mw / 42, and if it is an ethylene propylene copolymer containing 50 mol% of ethylene, the weight average molecular weight (Mw) is 28 × 0.5 + 4.
It is a value obtained by dividing by 2 × 0.5. (3) The fraction of the isotactic pentad chain (mmmm) of the propylene polymer of the component (A) was determined by dissolving the polymer in 2 ml of orthodichlorobenzene using JNM GSX270 manufactured by JEOL Ltd. Of deuterated benzene as a locking solvent was measured at 130 ° C. In order to improve the S / N ratio, integration was performed 10,000 times. The analysis is described in J.A. C. A method already proposed by Randall (Jounal of polymer science 1
2, 703, (1974)), [mmmm] was estimated. (4) The propylene content of the component (B) was determined by using JNM GSX270 manufactured by JEOL Ltd. to dissolve the polymer in 2 ml of orthodichlorobenzene, and then adding 0.5 ml of deuterated benzene as a locking solvent to 130 ° C. Was measured. In order to obtain a sufficient S / N ratio, integration was performed 10,000 times. The analysis is in H. N. The method already proposed by Cheng et al. (Macromolecules 1984, Vol 17, P19
50) was used. (5) The molecular weight dependence of the ethylene composition in the component (B) was detected by using GPC manufactured by waters, using Shodex 806MS as the column, and using Zero-Dead, vol, cl, manufactured by BARNES as the flow cell. An IR made by Nicole Co. was used for the vessel. Chloroform 4mg /
200 ml of the prepared component (B) solution was flowed at room temperature at a flow rate of 1 ml, and the measurement was performed. The resolution at this time is 4
cm ⁻¹ . In the analysis, the intensity at 2950 cm ^{-1 and} the intensity at 2180 cm ^-1 were measured using analysis software manufactured by OMLOCK. The ratio of this intensity at each elution time (I
2950 / I 2180) is proportional to the ethylene fraction. A composition variation rate of 10% or less indicates that the intensity ratio at each molecular weight is within ± 5% of the average intensity ratio. (6) Kai and c were determined as follows.

The proportions of the propylene polymer (component (A)) and the ethylene-propylene copolymer (component (B)) were changed respectively, and the total amount of the components (A) and (B) was xylene. A xylene solution at 135 ° C. was prepared so that the concentration of the solution was 0.2% by weight. A small amount of IRGANOX 1010 manufactured by Ciba was added. After the xylene solution was kept at a constant temperature for 10 minutes under stirring, it was poured into a 10-fold amount of a dry ice methanol solution. After filtering the obtained precipitate, it was vacuum-dried at room temperature to obtain a mixed sample.

[0031] In later Production Example 4, deuterated ethylene propylene copolymer by the same polymerization procedure but varying the _C 2 _{H 2} during polymerization of ethylene-propylene copolymer _{C 2 D 2 (D-EPR50} ) I got This D-EPR
50 was subjected to GPC fractionation, and sample D-EPR5 shown in Table 2 was sampled.
OE and D-EPR50I were obtained. PP1, PP2 and EPR50 obtained in Production Examples 1, 2 and 4 were used in combination.

The measurement was carried out using a neutron scattering apparatus SANS-U owned by the Institute of Physical Properties, The University of Tokyo, based on the method described in Polymer Experimental Science (Kyoritsu Shuppan, Polymer Solid Structure 1). The degree of polymerization of the propylene polymer (component (A)) was determined by dissolving the propylene polymer in a mixed solution (1.0 / 1.6 [g / g]) of an orthodichlorobenzene / deuterated xylene solution, and having a solution concentration of 1 to 1. Measurements were taken at 129 ° C. for four different concentrations of 5%, and Zimm plotted,
Polymer 19, 739 (1978)), the absolute molecular weight and the radius of gyration at a propylene concentration of Zero were determined with reference to Maconnachie A. at.

The above D-EPR50I and EPR50I isometric volume blend sample, and D-EPR50E and E
PR50E volume fraction blend sample (matched
-Pair) was prepared. Neutron scattering measurements were performed at 160 ° C, Graessly, WW Mocromolecules 26, 1137 (1993).
And the conventional radius and absolute molecular weight of the ethylene propylene copolymer were determined. At this time, the interaction between proton and deuterium was set to a parameter of 4 × 10 ⁻⁴ . The measurement of the above blend was performed by weighing each of the deuterated ethylene propylene copolymer and the ethylene propylene copolymer, dissolving them in chloroform, mixing them, and then suction-drying the chloroform.

PP1, P obtained by the above-described method
Using the degree of polymerization and the radius of gyration of each of P2 and the deuterated ethylene-propylene copolymer (Table 2), the interaction parameters kai and c for the propylene polymer and the ethylene-propylene copolymer are described in the literature (Peter A. Weimann, et. .al.Mac
romolecules, 30, 3650 (1997)) and according to RPA theory (de-Gennes, P, G Scalling concepts in polymer).
physics, Conell University press: New york, 1979).

In the measurement of the blended sample, a propylene polymer and an ethylene-propylene copolymer are dissolved in heated toluene, then thrown into methanol, and the precipitated component is filtered and dried. Kai and c were determined by scattering. As shown in Table 3, kai, c was 0.01. (7) Determination of spherulite growth rate The crystallization rate was evaluated by keeping the blend sample heated to 230 ° C. under a nitrogen atmosphere for 7 minutes, and at a rate of 135 ° C. at 70 ° C./min.
℃, and the isothermal crystallization process was performed using Olympus BH2
Observation was performed using a polarizing microscope. For observation, TC-600PH manufactured by Linkham 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. A value G (μm / μm / g) obtained by determining an average value from the growth rates of 30 spherulites.
Table 4 shows s) as the crystallization rate.

[0036]

EXAMPLES The propylene polymer (component (A)) and ethylene propylene copolymer (component (B)) used in the following examples and comparative examples were produced according to the following production examples. It is. <Production Example 1> [Production of component (A) (PP1)] Production of solid catalyst component 200 ml of dehydrated and deoxygenated n-heptane was introduced into a flask sufficiently purged with nitrogen.
Cl ₂ 0.4 mole and _{Ti (O-n-C 4} H 9) 4
Was introduced thereinto and reacted at 95 ° C. for 2 hours. After the 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 completion of the reaction, the reaction product was washed with n-heptane. Then n-
Phthalic acid chloride 0.0 in 25 ml of heptane
24 moles were mixed, introduced into the flask at 70 ° C. for 30 minutes, and reacted at 90 ° C. for 1 hour. After the completion of the reaction, the resultant was washed with n-heptane. Subsequently, 0.4 mol of SiCl ₄ was introduced and reacted at 80 ° 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. Then, a sufficiently nitrogen-purged flask, a n- heptane purified in the same manner as above was introduced 50 ml, the synthesized solid component in the five grams _{introduced, (t-C 4 H 9} ) (CH 3) Si (O
CH ₃ ) ₂ 1.2 ml, (C ₅ H ₉ ) ₂ Si
(OCH ₃ ) ₂ 1.2 ml and Al (C ₂ H
₆ ) ₃ 1.7 grams were contacted at 30 ° C for 2 hours. After the completion of the contact, the solid was sufficiently washed with n-heptane to obtain a solid catalyst component mainly composed of magnesium chloride. Its titanium content was 1.1% by weight.

Propylene Polymerization In a 1.5 liter stainless steel autoclave having a stirring and temperature control device, 500 ml of sufficiently dehydrated and deoxygenated n-heptane and 100 mg of triethylaluminum were prepared as described above. 15 milligrams of solid catalyst component and then 20
Introduce 00 ml, raise temperature and pressure, polymerization pressure = 5k
Propylene was polymerized under the conditions of g / cm ² G, a polymerization temperature of 75 ° C., and a polymerization time of 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 had an MFR of 500 (g / g).
10 minutes), polymer bulk density = 0.48 (g / cc), polymer density = 0.9083 (g / cc), and ¹³ C-
Isotactic pentad fraction by NMR [mmm
m] = 98.3 (mol%). The obtained propylene polymer was subjected to Soxhlet extraction with boiling heptane, the soluble component was poured into methanol, filtered and dried to obtain a propylene polymer (PP1) (Table 2).

<Production Example 2> [Production of Component (A) (PP2)] In the course of the polymerization of propylene under the above-mentioned production conditions of PP1, the hydrogen amount was 1800 m.
The polymerization operation was carried out under the same conditions except that
A propylene polymer of R = 400 (g / 10 minutes) was obtained.
This was subjected to extraction filtration under the same conditions as for PP1, to obtain a propylene polymer (PP2). This is [mmm
m] was 98% (Table 2).

<Production Example 3> [Production of component (A) (PP3)] A polymerization operation was carried out under the same conditions except that the amount of hydrogen was changed to 1600 ml during the polymerization of propylene under the above-mentioned conditions of PP1.
A 300 (g / 10 min) propylene polymer was obtained and used as a sample without extraction. Its [mmmm] was 98% (Table 1).

<Production Example 4> [Production of component (B) (EPR50A, B, D, F, I, and J)] EPR50 (ethylene / propylene = 50/50)
Synthesis of polymer ethylene-propylene-hydrogen (volume ratio 49.6: 49.
6: 0.8), into a stirred autoclave having an internal temperature of 65 ° C. and an internal volume of 1 L replaced with a mixed gas of 500 mL of heptane, further adding the above-mentioned mixed gas and adding an internal pressure of 0 kg / c.
m ² G. 5.0 mmol of methyl isobutylalumoxane in terms of A1 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 49.2: 49.2: volume) is adjusted so that the internal pressure becomes 0.2 kg / cm ² G.
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. Number average molecular weight (M
n) is 1500 and the weight average molecular weight (Mw) is 3620
0, molecular weight distribution (Mw / Mn) was 2.41. The ethylene propylene copolymer (E
PR1) has a total ethylene content of 47 mol%,
The composition variation was 2%. Mw / Mn is 2.0
Met. The obtained ethylene-propylene copolymer was converted into a 5% solution of chloroform by Nippon Kagaku Kogyo Co., Ltd.
Separation was performed for each molecular weight shown in Tables 1 and 2 using C908 graded GPC and column AJ3H manufactured by the company. EPR50 from ethylene propylene copolymer with preparative ethylene content of 50%
J, EPR50I, EPR50F, EPR50D, EP
R50B and EPR50A were obtained (Tables 1 and 2).

<Production Example 5> [Component (B) (EPR25A, D and EPR25W)
Of EPR25 (ethylene / propylene = 75/25)
Synthesis of polymer 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, which was replaced with a mixed gas of 2.2), and the above mixed gas was added thereto to further add an internal pressure of 0 kg / c.
m ² G. In this autoclave, 5.0 mmol of methylisobutylalumoxane in terms of Al atom was added, and dimethylsilylene (2-methyl-4,5-benzoindenyl) was used.
5.0 μmol of zirconium dichloride was introduced, and then ethylene was added so that the internal pressure became 0.2 kg / cm ² G.
Propylene-hydrogen (volume ratio 18.6: 79.2: 2.
The polymerization operation was carried out for 72 minutes while additionally introducing the mixed gas of 2). Heptane was distilled off from a heptane solution of the produced polymer to obtain 10 g of a polymer. The ethylene propylene copolymer (EPR25) thus obtained had an ethylene content of 25 mol% and a composition variation of 1%. Mw / Mn was 2.1. Further, after dissolving EPR25 in chloroform, filtration was performed to remove the catalyst residue, and the mixture was dried and solidified to obtain EPR25W. The ethylene propylene copolymer (EPR2
About 5), as a 5% chloroform solution, LC908 fractionated GPC manufactured by Nippon Kagaku Kogyo Co., Ltd., column AJ3H manufactured by the company.
Was separated for each molecular weight shown in Table 1. EPR from ethylene propylene copolymer with 50% preparative ethylene content
25A and EPR25D were obtained (Table 1).

<Example 1> The above PP1 (density 0.91)
g / cm ³ ) and EPR50D (density 0.86 g / c)
m ³ ) was added to 20% by volume, and an antioxidant was added at 0.1% by weight based on the whole polymer. This is 13
A 2% solution of hot xylene at 5 ° C. was stirred at a constant temperature for 15 minutes to obtain a homogeneous solution. A hot xylene solution was poured into 10 times the amount of xylene in dry ice / methanol, and the precipitate was filtered and dried in vacuo at room temperature. The obtained sample was placed on a glass slide and the growth rate G of spherulite was observed at 135 ° C.

<Examples 2 to 6> As shown in Table 4,
About the resin composition (Examples 2-6) obtained by mix | blending a component (A) and a component (B), 13 like Example 1
The spherulite growth rate G was observed at 5 ° C.

Comparative Example 1 0.1% by weight of an antioxidant IRGANOX1010 was added to the above PP1.
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. The hot xylene solution was poured into 10 times the amount of xylene in dry ice / methanol, and the precipitate was filtered and dried in vacuo at room temperature. The obtained sample was placed on a glass slide and the spherulite growth rate G was measured at 135 ° C.
Was observed.

<Comparative Examples 2 and 3> P as the component (A)
The spherulite growth rate G was observed at 135 ° C. in the same manner as in Comparative Example 1 except that P2 or PP3 was used.

<Comparative Example 4> EPR50 was added to the above PP1.
A in an amount of 20% by weight, and an antioxidant Irg
Anox 1010 was added at 0.1% by weight based on the total polymer. This was converted into a hot xylene 2% solution at 135 ° C.
The mixture was stirred at a constant temperature for 5 minutes to obtain a uniform solution. Xylene 10
The hot xylene solution was poured into twice the amount of dry ice / methanol, and the precipitate was filtered and then dried in vacuum at room temperature. The obtained sample was placed on a glass slide and the growth rate G of spherulite was observed at 135 ° C.

<Comparative Examples 5 and 6> As shown in Table 4, the resin compositions obtained by blending the respective components (Comparative Examples 5 to 6)
For 6), the spherulite growth rate G was observed as in Comparative Example 4.

<Comparative Example 7> EPR50 was added to the above PP2.
B in an amount of 40% by volume, and an antioxidant Irga
Nox1010 was added in an amount of 0.1% by weight based on the entire polymer. This was converted into a hot xylene 2% solution at 135 ° C.
The mixture was stirred at a constant temperature for minutes to obtain a homogeneous solution. The hot xylene solution was poured into 10 times the amount of xylene in dry ice / methanol, and the precipitate was filtered and dried in vacuo at room temperature. The obtained sample was placed on a glass slide and the growth rate G of spherulite was observed at 135 ° C.

Comparative Example 8 An EPR50 was added to the above PP3.
B in an amount of 20% by volume, and an antioxidant Irga
Nox1010 was added in an amount of 0.1% by weight based on the entire polymer. This was converted into a hot xylene 2% solution at 135 ° C.
The mixture was stirred at a constant temperature for minutes to obtain a homogeneous solution. The hot xylene solution was poured into 10 times the amount of xylene in dry ice / methanol, and the precipitate was filtered and dried in vacuo at room temperature. The obtained sample was placed on a glass slide and the growth rate G of spherulite was observed at 135 ° C.

[0051]

[Table 1]

[0052]

[Table 2]

[0053]

[Table 3]

[0054]

[Table 4]

[0055]

The polypropylene resin composition according to the present invention has good compatibility between the polypropylene polymer and the ethylene-propylene copolymer, and the crystallization rate of the polypropylene polymer is sufficiently suppressed. Under various processing conditions such as molding and adhesion or adhesion to a thermoplastic resin such as molding, a stable soft molded product can be obtained. For example, it is possible to select the propylene polymer characteristics and the ethylene propylene copolymer characteristics in harmony with the need for softness, transparency, heat resistance, etc. with a protective film, etc., as described in the Summary of the Invention. Has been described above.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Hiroyuki Nakano 1 Tohocho, Yokkaichi-shi, Mie, Mitsubishi Chemical Corporation Yokkaichi Office

Claims (1)

[Claims] 1. A composition comprising 100 parts by weight of the following component (A) and 20 to 1000 parts by weight of the component (B):
Wherein the kai calculated by the formula is not less than 0.01. Component (A) : a propylene polymer satisfying the following conditions (a) to (c). Condition (a): The fraction of isotactic pentad chains (mmmm), which is an index of stereoregularity, is 97% or more. Condition (b): Weight average molecular weight (Mw) and number average molecular weight (Mn) Mw which is an index of the molecular weight distribution calculated from
/ Mn (Q value) is 4 or less, Condition (c): Weight average molecular weight (Mw) is 1000 to 50
0000. Component (B) : an ethylene propylene copolymer satisfying the following conditions (d) to (g). Condition (d): Propylene content is 30 to 95 mol%. Condition (e): Variation from average composition in molecular weight dependence of composition is 10% or less. Condition (f): Weight average Mw which is an index of the molecular weight distribution calculated from the molecular weight (Mw) and the number average molecular weight (Mn)
/ Mn (Q value) is 4 or less, Condition (g): Weight average molecular weight (Mw) is 1000 to 10
00000. Formula [I] : [In the formula, m ₁ represents a weight average polymerization degree of the component (A), and m _1
2 indicates the weight average polymerization degree of the component (B). ]