JP2018002770A - Polypropylene resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polypropylene resin composition excellent in impact resistance, rigidity, transparency, and formability.SOLUTION: A polypropylene resin composition is made of 100 pts.wt. of a polypropylene resin composition (X) and 1 to 10 pts.wt. of and a polypropylene resin (Y), where the polypropylene resin composition (X) contains 83 to 88 wt.% of a propylene-ethylene block copolymer component (1) containing 75 to 85 wt.% of a propylene-based homopolymer (A) having a melt flow rate (MFR) according to JIS K 7210 (230°C and load of 2.16 kg) of 3.5 to 300 g/10 min and 15 to 25 wt.% of a propylene-ethylene copolymer (B) satisfying (B1) to (B2) (provided that total of propylene-based homopolymer (A) and propylene-ethylene copolymer (B) is 100 wt.%), and 12 to 17 wt.% of an ethylenic polymer (C) satisfying (C1) to (C3) (provided that total of propylene-ethylene block copolymer component (1) and ethylenic polymer (C) is 100 wt.%); the polypropylene resin composition (X) has an MFR according to JIS K 7210 (230°C and load of 2.16 kg) of 5 to 100 g/10 min; and the polypropylene resin (Y) is a polypropylene resin having (Y1) to (Y4) characteristics and a long-chain branch structure.SELECTED DRAWING: None

Description

  The present invention relates to a polypropylene resin composition, and more particularly to a polypropylene resin composition excellent in impact resistance, rigidity, transparency and moldability.

  Polypropylene is lightweight and excellent in mechanical strength and the like, and in particular, propylene-ethylene block copolymer is inferior in transparency but excellent in balance between impact resistance and rigidity. Widely used in various fields such as food packaging containers.

Propylene-ethylene random copolymers are inferior in impact resistance, but are excellent in transparency and heat sealability, and are used in dessert cups and films.
In recent years, there has been a demand for polypropylene having both rigidity, impact resistance, and transparency. JP 2006-161033 A (Patent Document 1) describes polypropylene and ethylene-α-olefin copolymer for retort food packaging. A composition using a combination is described.

JP 2006-161033 A

  An object (problem) of the present invention relates to a polypropylene resin composition, and more specifically, to provide a polypropylene resin composition excellent in impact resistance, rigidity, transparency and moldability.

As a result of intensive studies to solve the above problems, the present inventor has obtained a polypropylene resin composition comprising a specific propylene-ethylene block copolymer and an ethylene polymer, and a polypropylene resin containing a specific polypropylene resin. By using the composition, it was found that a polypropylene resin composition excellent in the balance of rigidity, impact resistance, transparency and moldability was obtained, and the present invention was completed.
The present invention provides the following polypropylene resin composition.

That is, according to the first invention of the present invention, a polypropylene resin composition comprising 100 parts by weight of a polypropylene resin composition (X) and 1 to 10 parts by weight of a polypropylene resin (Y),
The polypropylene resin composition (X) is
75-85 wt% of a propylene-based homopolymer (A) having a melt flow rate (MFR) of 3.5 to 300 g / 10 min based on JIS K7210 (230 ° C., 2.16 kg load), and the following (B1) To 15 to 25 wt% of propylene-ethylene copolymer (B) satisfying (B2) (provided that the total of propylene-based homopolymer (A) and propylene-ethylene copolymer (B) is 100 wt%) Propylene-ethylene block copolymer component (A) 83-88 wt%; and ethylene-based polymer (C) satisfying the following (C1)-(C3) 12-17 wt% (provided that the propylene-ethylene block copolymer Component (a) and the ethylene polymer (C) is 100 wt% in total);
(B1) The ethylene content is 20 to 35 wt% (based on 100 wt% of the total weight of the propylene-ethylene copolymer B).
(B2) The intrinsic viscosity [η] B measured in 135 ° C. o-dichlorobenzene is 2.0 to 3.0 dl / g.
(C1) The density is 0.905 to 0.920 g / cm ³ .
(C2) The melting point is 100 ° C. or higher.
(C3) MFR based on JIS K6922-2 (190 degreeC, 2.16kg load) is 10-50 g / 10min.
The polypropylene resin composition (X) has an MFR in accordance with JIS K7210 (230 ° C., 2.16 kg load) of 5 to 100 g / 10 minutes; and the polypropylene resin (Y) has the following (Y1) to It is a polypropylene resin having the characteristics of (Y4) and having a long-chain branched structure. (Y1): MFR is 0.1 to 30 g / 10 min.
(Y2): GPC molecular weight distribution (Mw / Mn) is 3.0 to 10, and Mz / Mw is 2.5 to 10.
(Y3): Melt tension (MT) (unit: g) is
log (MT) ≧ −0.9 × log (MFR) +0.7 or MT ≧ 15
Satisfy one of the following.
(Y4): 25 degreeC paraxylene soluble component amount (CXS) is less than 5.0 weight% with respect to polypropylene resin (X) whole quantity.
This polypropylene resin composition is provided.

According to a second aspect of the present invention, there is provided the polypropylene resin composition according to the first aspect, wherein the polypropylene resin (Y) further has the following property (Y5). .
(Y5): The branching index g ′ when the absolute molecular weight (Mabs) is 1,000,000 is 0.30 or more and less than 1.00.

Further, according to the third invention of the present invention, the polypropylene resin composition (Y) further has the following property (Y6): provide.
(Y6): The mm fraction of three propylene units by ¹³ C-NMR is 95% or more.

  Furthermore, according to the fourth invention of the present invention, the polypropylene resin composition according to any one of the first to third inventions, wherein the HAZE having a molded body thickness of 1 mmt in accordance with JIS K7136 (ISO14782) is 30% or less. Offer things.

Furthermore, according to a fifth invention of the present invention, the polypropylene according to any one of the first to fourth inventions, wherein the Charpy impact strength at 0 ° C. based on JIS K7111 (ISO179) is 2.5 kJ / m ² or more. A resin composition is provided.

  Furthermore, according to the sixth aspect of the present invention, there is provided the polypropylene resin composition according to any one of the first to fifth aspects, wherein the flexural modulus according to JIS K7171 (ISO178) is 950 MPa or more.

  In another aspect, according to a seventh aspect of the present invention, there is provided an injection molded article comprising the polypropylene resin composition according to any one of the first to sixth aspects.

  The polypropylene resin composition of the present invention is excellent in the balance between rigidity, impact resistance, transparency and moldability.

  Embodiments of the present invention will be described in detail below. However, the description of the constituent elements described below is an example of the embodiments of the present invention, and the present invention is not limited to these contents.

The polypropylene resin composition of the present invention is a polypropylene resin composition comprising 100 parts by weight of a polypropylene resin composition (X) and 1 to 10 parts by weight of a polypropylene resin (Y), and is characterized by the following. is there.
The polypropylene resin composition (X) is
75-85 wt% of a propylene-based homopolymer (A) having a melt flow rate (MFR) of 3.5 to 300 g / 10 min based on JIS K7210 (230 ° C., 2.16 kg load), and the following (B1) To 15 to 25 wt% of propylene-ethylene copolymer (B) satisfying (B2) (provided that the total of propylene-based homopolymer (A) and propylene-ethylene copolymer (B) is 100 wt%) Propylene-ethylene block copolymer component (A) 83-88 wt%; and ethylene-based polymer (C) satisfying the following (C1)-(C3) 12-17 wt% (provided that the propylene-ethylene block copolymer Component (a) and the ethylene polymer (C) is 100 wt% in total);
(B1) The ethylene content is 20 to 35 wt% (based on 100 wt% of the total weight of the propylene-ethylene copolymer B).
(B2) The intrinsic viscosity [η] B measured in 135 ° C. o-dichlorobenzene is 2.0 to 3.0 dl / g.
(C1) The density is 0.905 to 0.920 g / cm ³ .
(C2) The melting point is 100 ° C. or higher.
(C3) MFR based on JIS K6922-2 (190 degreeC, 2.16kg load) is 10-50 g / 10min.
The polypropylene resin composition (X) has an MFR in accordance with JIS K7210 (230 ° C., 2.16 kg load) of 5 to 100 g / 10 minutes; and the polypropylene resin (Y) has the following (Y1) to It is a polypropylene resin having the characteristics of (Y4) and having a long-chain branched structure. (Y1): MFR is 0.1 to 30 g / 10 min.
(Y2): GPC molecular weight distribution (Mw / Mn) is 3.0 to 10, and Mz / Mw is 2.5 to 10.
(Y3): Melt tension (MT) (unit: g) is
log (MT) ≧ −0.9 × log (MFR) +0.7 or MT ≧ 15
Satisfy one of the following.
(Y4): 25 degreeC paraxylene soluble component amount (CXS) is less than 5.0 weight% with respect to polypropylene resin (X) whole quantity.

  Hereinafter, each component in the polypropylene resin composition of the present invention will be described in detail.

  The polypropylene resin composition (X) used in the present invention contains a propylene-ethylene block copolymer component (a) and an ethylene polymer (C). And the said propylene-ethylene block copolymer component (a) contains a propylene-type homopolymer (A) and a propylene-ethylene copolymer (B).

[Propylene-ethylene block copolymer component (a)]
The propylene-ethylene block copolymer component (a) used in the present invention is a propylene-based homopolymer (A) described later of 75 to 85 wt%, and a propylene-ethylene copolymer (B) described later of 15 to 25 wt%. (However, the total of the propylene homopolymer (A) and the propylene-ethylene copolymer (B) is 100 wt%).
In addition, the propylene-ethylene block copolymer component (a) needs to be in the range of 83 to 88 wt%, preferably 83 to 87 wt%, in 100 wt% of the polypropylene resin composition (X). Preferably it is 83-86 wt%.

1. [Propylene-based homopolymer (A)]
The propylene homopolymer (A) used in the present invention has a melt flow rate (MFR) in the range of 3.5 to 300 g / 10 minutes in accordance with JIS K7210 (230 ° C., 2.16 kg load). Necessary, preferably 10 to 200 g / 10 min, more preferably 30 to 100 g / 10 min. If MRF is 3.5 g / 10 min or more, the fluidity at the time of injection molding can be sufficiently ensured, and a desired injection-molded product can be obtained. On the other hand, if the MRF is 300 g / 10 min or less, sufficient impact resistance can be obtained. The propylene homopolymer (A) is in the range of 75 to 85 wt%, preferably 77 to 84 wt%, more preferably 78 to 83 wt%, in 100 wt% of the propylene-ethylene block copolymer component (a). It is.

2. [Propylene-ethylene copolymer (B)]
The propylene-ethylene copolymer (B) used in the present invention needs to be in the range of 15 to 25 wt% in 100 wt% of the propylene-ethylene block copolymer component (a), preferably 16 to It is 23 wt%, more preferably 17-22 wt%. If the content of the propylene-ethylene copolymer (B) is 15 wt% or more, sufficient impact resistance can be obtained. On the other hand, if the content of the propylene-ethylene copolymer (B) is 25 wt% or less, sufficient rigidity and transparency can be obtained.

In addition, the propylene-ethylene copolymer (B) satisfies the following characteristics (B1) to (B2) as described above.
(B1): The ethylene content in the propylene-ethylene copolymer (B) needs to be in the range of 20 to 35 wt% when the total weight of the propylene-ethylene copolymer (B) is 100 wt%. , Preferably 22-33 wt%, more preferably 25-30 wt%. If the ethylene content is 20 wt% or more, sufficient impact resistance can be obtained. On the other hand, if it is 35 wt% or less, sufficient transparency can be obtained.
(B2): Further, for the propylene-ethylene copolymer (B), the intrinsic viscosity [η] B measured in orthodichlorobenzene (o-dichlorobenzene) at 135 ° C. is 2.0 to 3.0 dl / g. The range is preferably 2.0 to 2.8 dl / g, more preferably 2.2 to 2.8 dl / g. If the intrinsic viscosity [η] B is 2.0 dl / g or more, sufficient impact resistance can be obtained. On the other hand, if it is 3.0 dl / g or less, sufficient transparency is obtained.
The intrinsic viscosity [η] B is obtained by dissolving the propylene-ethylene block copolymer component (a) in p-xylene at 130 ° C. to give a solution, and then leaving the polymer separated by filtration at 25 ° C. for 12 hours. Then, after evaporating p-xylene from the filtrate to obtain the propylene-ethylene copolymer (B), it can be measured using an Ubbelohde viscometer at a temperature of 135 ° C. using orthodichlorobenzene as a solvent.

3. [Ethylene polymer (C)]
The ethylene-based polymer (C) used in the present invention needs to be contained in the range of 12 to 17 wt%, preferably 13 to 17 wt%, more preferably 14 in 100 wt% of the polypropylene resin composition (X). ˜17 wt%. If the content of the ethylene polymer (C) is 12 wt% or more, sufficient impact resistance and transparency can be obtained. On the other hand, if it is 17 wt% or less, sufficient moldability can be obtained.

In addition, the ethylene polymer (C) satisfies the following characteristics (C1) to (C3).
(C1): The density of the ethylene-based polymer (C) needs to be 0.905 to 0.920 g / cm ³ , preferably 0.907 to 0.920 g / cm 3, and more preferably 0.910. ˜0.918 g / cm ³ . If the density of the ethylene polymer (C) is within this range, sufficient transparency can be obtained. The density is a value measured by the D method (density rib tube method) according to JIS K7112.
(C2): The melting point of the ethylene polymer (C) needs to be in the range of 100 ° C. or higher, preferably 102 ° C. or higher, more preferably 105 ° C. or higher. When the melting point of the ethylene polymer (C) is 100 ° C. or higher, the mold release property at the time of injection molding is ensured and the continuous moldability is excellent. The upper limit of the melting point of the ethylene polymer (C) is not particularly limited, but is usually preferably 125 ° C. or lower.
Here, the specific measurement of melting | fusing point uses a differential scanning calorimeter (DSC), took 5 mg of sample amount, hold | maintained at 200 degreeC for 5 minute (s), and crystallized to 40 degreeC at the temperature-fall rate of 10 degree-C / min, Further, the peak position of a curve drawn when the film is melted at a temperature rising rate of 10 ° C./min is defined as a melting peak temperature (melting point) Tm (° C.).
(C3): Further, for the ethylene polymer (C), the MFR based on JIS K6922-2 (190 ° C., 2.16 kg load) needs to be in the range of 10 to 50 g / 10 min, preferably 15 It is -45g / 10min, More preferably, it is 17-40g / 10min. When the MFR of the ethylene polymer (C) is 10 g / 10 min or more, the fluidity at the time of injection moldability can be sufficiently ensured. On the other hand, if it is 50 g / 10 minutes or less, bleeding out on the surface of the molded product can be suppressed, and transparency is improved.

Examples of the ethylene polymer (C) used in the polypropylene resin composition of the present invention include an ethylene homopolymer and an ethylene-α-olefin random copolymer, and an ethylene elastomer is preferable. Those ethylene-based elastomers can be used singly or in combination of two or more, as long as the effects of the present invention are not impaired. Here, as α-olefins other than ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 4-methyl-pentene-1, 4-methyl-hexene-1, 4,4-dimethylpentene-1 and the like can be mentioned. In the case of a copolymer of ethylene and another α-olefin, the amount of ethylene units is preferably 70 to 99% by weight.
Such ethylene-α-olefin random copolymers are commercially available, such as Novatec LL series, Harmolex series, Kernel series, Mitsui Chemicals Tuffmer P series and Tuffmer A series manufactured by Nippon Polyethylene Corporation. Examples include the Evolue series manufactured by Prime Polymer Co., Ltd., Sumikasen E, EP series, and Excellen GMH series manufactured by Sumitomo Chemical Co., Ltd.

4). [Polypropylene resin composition (X)]
The polypropylene resin composition (X) used in the present invention needs to have a melt flow rate (MFR) in the range of 5 to 100 g / 10 min in accordance with JIS K7210 (230 ° C., 2.16 kg load). Yes, preferably 10 to 90 g / 10 min, more preferably 20 to 80 g / 10 min. If MFR is 5 g / 10 minutes or more, the fluidity at the time of injection molding can be sufficiently ensured, and a desired injection-molded product can be obtained. On the other hand, if it is 100 g / 10 min or less, sufficient impact resistance can be obtained.

  The ratio of the propylene homopolymer (A) and the propylene-ethylene copolymer (B) and the ethylene content are measured by the CFC-IR method. The method is as follows.

(I) Analytical apparatus to be used (a) Cross fractionation apparatus CFC T-100 (abbreviated as CFC) manufactured by Dia Instruments Co., Ltd.
(A) Fourier transform type infrared absorption spectrum analysis FT-IR, manufactured by PerkinElmer 1760X
The fixed wavelength infrared spectrophotometer attached as a CFC detector is removed, and an FT-IR is connected instead, and this FT-IR is used as a detector.
The transfer line from the outlet of the solution eluted from the CFC to the FT-IR is 1 m long and maintained at a temperature of 140 ° C. throughout the measurement. The flow cell attached to the FT-IR has an optical path length of 1 mm and an optical path width of 5 mmφ, and is maintained at a temperature of 140 ° C. throughout the measurement.
(C) Gel permeation chromatography (GPC)
The GPC column in the latter part of the CFC is used by connecting three AD806MS manufactured by Showa Denko KK in series.

(Ii) CFC measurement conditions (a) Solvent: orthodichlorobenzene (ODCB)
(A) Sample concentration: 4 mg / ml
(U) Injection volume: 0.4ml
(D) Crystallization: The temperature is lowered from 140 ° C. to 40 ° C. over about 40 minutes.
(E) Classification method:
The fractionation temperature at the time of temperature rising elution fractionation is 40 ° C., 100 ° C., and 140 ° C., and the fractions are separated into a total of three fractions.
In addition, the elution ratio (unit:% by weight) of the component eluting at 40 ° C. or lower (fraction 1), the component eluting at 40 to 100 ° C. (fraction 2), and the component eluting at 100 to 140 ° C. (fraction 3), respectively It is defined as W40, W100, and W140. W40 + W100 + W140 = 100. Moreover, each fractionated fraction is automatically transported to the FT-IR analyzer as it is.
(F) Solvent flow rate during elution: 1 ml / min

(Iii) Measurement conditions for FT-IR After elution of the sample solution from the GPC at the latter stage of the CFC starts, FT-IR measurement is performed under the following conditions, and GPC-IR data is collected for each of the above-described fractions 1 to 3. .
(A) Detector: MCT
(A) Resolution: 8 cm ^-1
(C) Measurement interval: 0.2 minutes (12 seconds)
(D) Number of integrations per measurement: 15 times

(Iv) Post-treatment and analysis of measurement results The elution amount and molecular weight distribution of the components eluted at each temperature are determined using the absorbance at 2945 cm ⁻¹ obtained by FT-IR as a chromatogram. The elution amount is normalized so that the total elution amount of each elution component is 100%. Conversion from the retention volume to the molecular weight is performed using a calibration curve prepared in advance with standard polystyrene.
Standard polystyrenes used are the following brands manufactured by Tosoh Corporation.
F380, F288, F128, F80, F40, F20, F10, F4, F1, A5000, A2500, A1000.
A calibration curve is prepared by injecting 0.4 ml of a solution dissolved in ODCB (containing 0.5 mg / ml BHT) so that each is 0.5 mg / ml. The calibration curve uses a cubic equation obtained by approximation by the least square method.
Conversion to molecular weight uses a general-purpose calibration curve with reference to “Size Exclusion Chromatography” written by Sadao Mori (Kyoritsu Shuppan). The following numerical values are used for the viscosity equation ([η] = K × M ^α ) used at that time.
(A) When creating a calibration curve using standard polystyrene K = 0.000138, α = 0.70
(A) When measuring a sample of a propylene-based block copolymer K = 0.000103, α = 0.78
The molecular weight of each elution portion subjected to the elution fractionation is defined as Mw (40), Mw (100), and Mw (140). The total molecular weight distribution was calculated by summing up the data obtained by three fractions. Accordingly, the content (% by weight) of a component having a weight average molecular weight of 3,000 or less, which will be described later, is obtained by integration.
The ethylene content distribution (distribution of ethylene content along the molecular weight axis) of each elution component is a ratio of the absorbance at 2956 cm ⁻¹ and the absorbance at 2927 cm ⁻¹ obtained by FT-IR, and is obtained by using polyethylene, polypropylene, or ¹³ Using ethylene-propylene-rubber (EPR) whose ethylene content is known by C-NMR measurement, etc., and mixtures thereof, converted into ethylene content (% by weight) using a calibration curve prepared in advance. Ask.

The ratio (Wc) of the propylene-ethylene copolymer (B) part in the propylene-ethylene block copolymer component (a) in the present invention is calculated by the following formula (I) using the result measured by the above method. The above is defined and determined by the following procedure.
Wc (weight%) = W40 × A40 / B40 + W100 × A100 / B100 (I)

In the formula (I), W40 and W100 are the elution ratios (unit: weight%) in each of the above-mentioned fractions, and A40 and A100 are the average ethylene contents (actually measured in each fraction corresponding to W40 and W100 ( B40 and B100 are the ethylene content (unit: wt%) of (B) contained in each fraction. A method for obtaining A40, A100, B40, and B100 will be described later.
The meaning of the formula (I) is as follows. That is, the first term on the right side of formula (I) is a term for calculating the amount of (A) contained in fraction 1 (portion soluble at 40 ° C.). When fraction 1 contains only (B) and does not contain (A), W40 directly contributes to the content of (B) derived from fraction 1 in the whole, but fraction 1 contains (B) Since a small amount of the component derived from (A) (component having an extremely low molecular weight) is included in addition to the component derived from it, it is necessary to correct that portion. Therefore, by multiplying W40 by A40 / B40, the amount derived from the component (B) in the fraction 1 is calculated. For example, when the average ethylene content (A40) of fraction 1 is 15% by weight and the ethylene content (B40) of (B) contained in fraction 1 is 20% by weight, 15/20 of fraction 1 = 3/4 (Ie 75% by weight) is derived from (B), and 1/4 is derived from (A). Thus, the operation of multiplying A40 / B40 by the first term on the right side means that the contribution of (B) is calculated from the weight% (W40) of fraction 1.

Here, the calculation is performed in consideration of the following conditions.
(A) As described above, the average ethylene contents corresponding to fractions 1 and 2 obtained by CFC measurement are A40 and A100, respectively (the unit is weight%). A method for obtaining the average ethylene content will be described later.
(A) The ethylene content corresponding to the peak position in the differential molecular weight distribution curve of fraction 1 is defined as B40 (unit is% by weight).
Fraction 2 is considered to be substantially B100 = 100 in the present invention because it is considered that the rubber part is completely eluted at 40 ° C. and cannot be defined with the same definition.
B40 and B100 are the ethylene content of (B) contained in each fraction, but it is practically impossible to obtain this value analytically. The reason is that there is no means for completely separating and sorting (A) and (B) mixed in the fraction. As a result of studies using various model samples, B40 can explain the effect of improving the material physical properties well by using the ethylene content corresponding to the peak position of the differential molecular weight distribution curve of fraction 1. That is, B40 is the ethylene content corresponding to the peak position of the differential molecular weight distribution curve of fraction 1. In addition, B100 has two points that it has crystallinity derived from an ethylene chain and that the amount of (A) contained in these fractions is relatively smaller than the amount of (A) contained in fraction 1. For this reason, the approximation to 100 is closer to the actual situation and hardly causes an error in calculation. Therefore, the analysis is performed with B100 = 100.

(C) For the above reason, the ratio (Wc) is obtained according to the following formula (II).
Wc (weight%) = W40 × A40 / B40 + W100 × A100 / 100 (II)
In other words, W40 × A40 / B40, which is the first term on the right side of the formula (II), indicates (B) content (% by weight) having no crystallinity, and W100 × A100 / 100, which is the second term, is a crystal. (A) content (weight%) which has property is shown.
Here, the average ethylene contents A40 and A100 of the fractions 1 and 2 obtained by B40 and CFC measurement are obtained as follows.
The ethylene content corresponding to the peak position of the differential molecular weight distribution curve is defined as B40. Further, the sum of the products of the weight ratio for each data point and the ethylene content for each data point, which is taken in as data points during measurement, is defined as the average ethylene content A40 of fraction 1. The average ethylene content A100 of fraction 2 is determined in the same manner.

The significance of setting the three types of fractionation temperatures is as follows.
In the CFC analysis of the present invention, 40 ° C. is necessary and sufficient for fractionating only polymers having no crystallinity (for example, most of (B) or extremely low molecular weight components in (A)). It has the meaning that it is a moderate temperature condition. 100 ° C. is a component that is insoluble at 40 ° C. but becomes soluble at 100 ° C. (for example, in (B), a component having crystallinity due to the chain of ethylene and / or propylene, and low crystallinity (A)) is a temperature necessary and sufficient to elute only. 140 ° C. is a component that is insoluble at 100 ° C. but becomes soluble at 140 ° C. (for example, (A) a particularly highly crystalline component, and (B) extremely high molecular weight and extremely high ethylene The temperature is necessary and sufficient for eluting only the component having crystallinity and recovering the total amount of the propylene-ethylene block copolymer component (a) used in the analysis.
In addition, W140 does not contain the component (B) at all, or even if it is present, it is extremely small and can be substantially ignored. Therefore, it is excluded from the calculation of the ratio of (B) and the ethylene content of (B). To do.

5. [Polypropylene resin (Y)]
The polypropylene resin (Y) used in the present invention is a polypropylene resin having a branched structure and needs to be in the range of 1 to 10 parts by weight based on 100 parts by weight of the polypropylene resin composition (X). The amount is preferably 2 to 10 parts by weight. When the content of the polypropylene resin (Y) is 1 part by weight or more, sufficient transparency can be obtained. On the other hand, when it is 10 parts by weight or less, sufficient impact resistance can be obtained.

Further, the polypropylene resin (Y) satisfies the properties (Y1) to (Y4) as described above.
(1) Characteristic (Y1): MFR
The melt flow rate (MFR) of the polypropylene resin (Y) used in the present invention needs to be in the range of 0.1 to 30 g / 10 minutes, preferably 0.3 to 20 g / 10 minutes, more preferably 0.5 to 10 g / 10 min.
If MFR is 0.1 g / 10 min or more, sufficient fluidity can be ensured, and the problem of poor extrusion during injection molding does not occur. On the other hand, if it is 30 g / 10 min or less, high rigidity, high impact resistance, and high transparency are exhibited.
The method for controlling the MFR value is well known, and by adjusting the temperature and pressure which are the polymerization conditions of the polypropylene resin (Y), or by controlling the amount of hydrogen added in the method of adding a chain transfer agent such as hydrogen during the polymerization, Adjustments can be made easily.

  In the present invention, the MFR of the propylene-based resin is JIS K7210: 1999 “Method of plastic-thermoplastic melt mass flow rate (MFR) and test method for melt volume flow rate (MVR)”, condition M (230 ° C, 2.16 kg load), and the unit is g / 10 minutes.

(2) Characteristic (Y2): Molecular weight distribution by GPC Further, the polypropylene resin (Y) needs to have a relatively wide molecular weight distribution, and the molecular weight distribution Mw / Mn (obtained by gel permeation chromatography (GPC)). Here, it is necessary that Mw is a weight average molecular weight and Mn is a number average molecular weight) of 3.0 or more and 10 or less. Further, the molecular weight distribution Mw / Mn of the polypropylene resin (Y) is preferably in the range of 3.5 to 8.0, more preferably 4.1 to 6.0.
Further, it is necessary that Mz / Mw (where Mz is the Z average molecular weight), which is a parameter that more significantly represents the breadth of the molecular weight distribution, is 2.5 or more and 10 or less. The preferable range of Mz / Mw is 2.8 to 8.0, more preferably 3.0 to 6.0.
As the molecular weight distribution is wider, the moldability is improved, but when Mw / Mn and Mz / Mw are in this range, the moldability is particularly excellent.

The definitions of Mn, Mw and Mz are described in “Basics of Polymer Chemistry” (edited by Polymer Society, Tokyo Kagaku Dojin, 1978) and can be calculated from molecular weight distribution curves by GPC.
And the specific measuring method of GPC is as follows.
Apparatus: Waters GPC (ALC / GPC 150C)
Detector: MIRAN 1A IR detector manufactured by FOXBORO (measurement wavelength: 3.42 μm)
Column: AD806M / S (3 pieces) manufactured by Showa Denko KK
Mobile phase solvent: orthodichlorobenzene (ODCB)
Measurement temperature: 140 ° C
Flow rate: 1.0 ml / min
Injection volume: 0.2ml
Sample preparation: Prepare a 1 mg / mL solution using ODCB (containing 0.5 mg / mL BHT) and dissolve at 140 ° C. for about 1 hour.

Conversion from the retention capacity obtained by GPC measurement to the molecular weight is performed using a calibration curve prepared in advance by standard polystyrene (PS). The standard polystyrenes used are all the following brands manufactured by Tosoh Corporation.
F380, F288, F128, F80, F40, F20, F10, F4, F1, A5000, A2500, A1000
A calibration curve is created by injecting 0.2 mL of a solution dissolved in ODCB (containing 0.5 mg / mL BHT) so that each is 0.5 mg / mL. The calibration curve uses a cubic equation obtained by approximation by the least square method.
In addition, the following numerical value is used for the viscosity formula [η] = K × M ^α used for conversion to molecular weight.
PS: K = 1.38 × 10 ⁻⁴ , α = 0.7
PP: K = 1.03 × 10 ⁻⁴ , α = 0.78

In order to adjust Mw / Mn to 3.0 to 10 and Mz / Mw to 2.5 to 10, the temperature and pressure conditions of propylene polymerization are changed, or the most common technique is hydrogen or the like The chain transfer agent can be easily adjusted by adding the chain transfer agent during propylene polymerization.
Furthermore, when using 2 or more types of the metallocene catalyst mentioned later and a catalyst, it can control by changing the quantity ratio.

(3) Characteristic (Y3): Melt tension (MT)
Furthermore, the polypropylene resin (Y) used in the present invention has the following relationship between melt tension (MT) and MFR:
log (MT) ≧ −0.9 × log (MFR) +0.7 or MT ≧ 15
You need to meet one of the following:

  Here, MT is Capillograph 1B manufactured by Toyo Seiki Seisakusho Co., Ltd. Capillary: 2.0 mm in diameter, 40 mm in length, cylinder diameter: 9.55 mm, cylinder extrusion speed: 20 mm / min, take-off speed: 4. The melt tension when measured under the conditions of 0 m / min and temperature: 230 ° C. is expressed in grams. However, when the MT of the polypropylene resin (Y) is extremely high, the resin may be broken at a take-up speed of 4.0 m / min. In such a case, the take-up speed can be lowered to take off the resin. Let MT be the tension at the highest speed. The measurement conditions and units of MFR are as described above.

This regulation on melt tension is an index for the polypropylene resin (Y) having a branched structure to have sufficient melt tension to exhibit high rigidity and high impact resistance. Generally, MT correlates with MFR. Therefore, it is defined by the relational expression with MFR.
Thus, the method of defining the melt tension MT by the relational expression with MFR is a normal method for those skilled in the art. The following relational expression has been proposed.
log (MS)> − 0.61 × log (MFR) +0.82
(Here, MS is synonymous with MT.)
Japanese Unexamined Patent Application Publication No. 2003-64193 proposes the following relational expression as a definition of polypropylene having a high melt tension.
11.32 × MFR−0.7854 ≦ MT
Furthermore, Japanese Patent Laid-Open No. 2003-94504 proposes the following relational expression as a definition of polypropylene having a high melt tension.
MT ≧ 7.52 × MFR−0.576

In the present invention, the polypropylene resin (Y) having a branched structure is represented by the relational formula:
log (MT) ≧ −0.9 × log (MFR) +0.7 or MT ≧ 15
If either of these is satisfied, it can be said that the resin has a sufficiently high melt tension, and is useful for developing high rigidity and high impact resistance.
The polypropylene resin (Y) has the following relational expression:
log (MT) ≧ −0.9 × log (MFR) +0.9 or MT ≧ 15
It is more preferable to satisfy | fill, and it is still more preferable to satisfy | fill the following relational expressions.
log (MT) ≧ −0.9 × log (MFR) +1.1 or MT ≧ 15

  Although it is not necessary to provide the upper limit value of MT in particular, when MT exceeds 40 g, the take-up speed is remarkably slowed by the measurement method described above, and measurement becomes difficult. In such a case, since it is considered that the spreadability of the resin is also deteriorated, it is preferably 40 g or less, more preferably 35 g or less, and most preferably 30 g or less.

  In order to satisfy the relational expression of MT and MFR described above, the long chain branching amount of the polypropylene resin (Y) may be increased to increase the melt tension. Selection of a preferable metallocene catalyst described later and a combination thereof, and This can be achieved by controlling the amount ratio and prepolymerization conditions and introducing many long-chain branches.

(4) Characteristic (Y4): 25 ° C. paraxylene soluble component amount (CXS)
It is preferable that the polypropylene resin (Y) used in the present invention has high stereoregularity and has a small amount of low crystallinity components that cause stickiness and bleed out of a molded product. This low crystalline component is evaluated by the amount of xylene soluble component (CXS) at 25 ° C., and in the present invention, it is necessary to be less than 5.0% by weight based on the total amount of the polypropylene resin (Y). Preferably it is 3.0 weight% or less, More preferably, it is 1.0 weight% or less, More preferably, it is 0.5 weight% or less. The lower limit is not particularly limited, but is usually 0.01% by weight or more, preferably 0.03% by weight or more.

In addition, the detail of the measuring method of 25 degreeC xylene soluble component amount (CXS) is as follows.
A 2 g sample (polypropylene resin (Y)) is dissolved in 300 ml of p-xylene (containing 0.5 mg / ml BHT) at 130 ° C. to form a solution, and then left at 25 ° C. for 12 hours. Thereafter, the precipitated polymer is separated by filtration, p-xylene is evaporated from the filtrate, and further dried under reduced pressure at 100 ° C. for 12 hours to recover xylene-soluble components at room temperature. The ratio (% by weight) of the weight of the recovered component to the charged sample weight is defined as CXS.

  In order to make CXS less than 5% by weight, it can be produced by using a metallocene catalyst, as will be described later. It is necessary that the reaction conditions are not extremely high and that the amount ratio of the organoaluminum compound to the metallocene complex is not increased too much.

  The polypropylene resin (Y) used in the present invention preferably satisfies the following properties (Y5) to (Y7) in addition to the properties (Y1) to (Y4).

(5) Characteristic (Y5): Branching index g ′
As a direct indicator that the polypropylene resin (Y) used in the present invention has long-chain branching, a branching index g ′ can be mentioned.
The branching index g ′ is determined by the ratio of the intrinsic viscosity [η] lin of the linear polymer having the same molecular weight as the intrinsic viscosity [η] br of the polymer having a long chain branched structure, that is, [η] br / [η] lin. Given a long chain branching structure, it takes a value less than one.
The definition is described in, for example, “Developments in Polymer Characterization-4” (JV Dawkins ed. Applied Science Publishers, 1983), and is an index well known to those skilled in the art.
The branching index g ′ can be obtained as a function of the absolute molecular weight Mabs by using, for example, a GPC equipped with a light scatterometer and a viscometer as described below.

  The polypropylene resin (Y) used in the present invention preferably has a branching index g ′ of 0.30 or more and less than 1.00 when the absolute molecular weight Mabs determined by light scattering is 1,000,000, more preferably 0.00. It is 55 or more and 0.98 or less, more preferably 0.75 or more and 0.96 or less, and particularly preferably 0.78 or more and 0.95 or less.

  The polypropylene resin (Y) used in the present invention is preferably considered to have a comb-shaped chain as a molecular structure. When the branching index g ′ is less than 0.30, the main chain is few and the side chain is The ratio is extremely large. In such a case, the melt tension may not be improved or a gel may be generated, which is not preferable. On the other hand, when it is 1.00 or more, this means that there is no long chain branching, and high rigidity, high impact resistance and high transparency are not exhibited.

The lower limit of the branching index g ′ is preferably the above value for the following reason.
According to the document “Encyclopedia of Polymer Science and Engineering vol. 2” (John Wiley & Sons 1985 p. 485), the g ′ value of the comb polymer is represented by the following formula.

Here, g is a branching index defined by the rotation radius ratio of the polymer, and ε is a constant determined by the shape of the branched chain and the solvent. According to Table 3 of 487, a value of about 0.7 to 1.0 is reported for the comb chain in a good solvent. λ is the ratio of the main chain in the comb chain, and p is the average number of branches.
According to this equation, the number of branches is extremely large for a comb chain, that is, p is infinite, and g ′ = g ^ε = λ ^ε , which is not less than the value of λ ^ε. In general, there will be a lower limit.

  On the other hand, a conventionally known random branched chain formula that is considered to occur in the case of electron beam irradiation or peroxide degradation is given by the formula (19) on page 485 in the same document. In the branched chain, as the number of branch points increases, g ′ and g value monotonously decrease without any lower limit value. That is, in the present invention, the fact that the g ′ value has a lower limit means that the polypropylene resin (Y) having a long chain branched structure used in the present invention has a structure close to a comb chain. Therefore, the distinction from the random branched chain generated by conventional electron beam irradiation or peroxide degradation becomes clearer.

  Moreover, in the branched polymer having a structure close to the comb chain having the branching index g ′ in the above range, the degree of decrease in melt tension when repeated kneading is small, and it is industrially subjected to re-molding as a recycled material. At this time, the deterioration of physical properties and moldability is reduced.

A specific method for calculating the branching index g ′ is as follows.
Waters Alliance GPCV2000 is used as a GPC apparatus equipped with a differential refractometer (RI) and a viscosity detector (Viscometer). As the light scattering detector, a DAWN-E manufactured by Wyatt Technology, a multi-angle laser light scattering detector (MALLS) is used. The detectors are connected in the order of MALLS, RI, and Viscometer. The mobile phase solvent is 1,2,4-trichlorobenzene (an antioxidant “Irganox 1076” manufactured by BASF Japan Ltd. is added at a concentration of 0.5 mg / mL).
The flow rate is 1 mL / min, and two columns of Tosoh Corporation GMHHR-H (S) HT are connected and used. The temperature of the column, sample injection section, and each detector is 140 ° C. The sample concentration is 1 mg / mL and the injection volume (sample loop volume) is 0.2175 mL.

In order to obtain the absolute molecular weight (Mabs) obtained from MALLS, the mean square inertia radius (Rg), and the intrinsic viscosity ([η]) obtained from Viscometer, the data processing software ASTRA (version 4.73.04) attached to MALLS is used. The calculation is performed with reference to the following documents.
1. "Developments in Polymer Characterization-4" (JV Dawkins ed. Applied Science Publishers, 1983. Chapter 1.)
2. Polymer, 45, 6495-6505 (2004).
3. Macromolecules, 33, 2424-2436 (2000).
4). Macromolecules, 33, 6945-6925 (2000).

  The branching index g ′ is a ratio of the intrinsic viscosity ([η] br) obtained by measuring a sample with the above Viscometer and the intrinsic viscosity ([η] lin) obtained separately by measuring a linear polymer ([[ η] br / [η] lin).

When a long-chain branched structure is introduced into a polymer molecule, the radius of inertia becomes smaller than that of a linear polymer molecule having the same molecular weight. Since the intrinsic viscosity becomes smaller as the radius of inertia becomes smaller, the intrinsic viscosity ([η] br) of the branched polymer with respect to the intrinsic viscosity ([η] lin) of the linear polymer having the same molecular weight as the long chain branched structure is introduced. ) Ratio ([η] br / [η] lin) becomes smaller.
Therefore, when the branch index (g ′ = [η] br / [η] lin) is a value smaller than 1, it means that a branch is introduced. Here, as a linear polymer for obtaining [η] lin, a commercially available homopolypropylene (“Novatec PP (registered trademark)” manufactured by Nippon Polypro Co., Ltd., grade name: FY6) is used. The fact that the logarithm of [η] lin of a linear polymer has a linear relationship with the logarithm of molecular weight is known as the Mark-Houwink-Sakurada equation, so [η] lin is appropriately set on the low molecular weight side or the high molecular weight side. Extrapolation can yield numerical values.

  In order to make the branching index g ′ 0.30 or more and less than 1.00, it is achieved by introducing many long-chain branches, selection of preferred metallocene catalysts described later, a combination thereof, a quantitative ratio thereof, and prepolymerization This can be achieved by controlling the conditions for polymerization.

(6) Characteristic (Y6): mm fraction of propylene unit 3 chain by ¹³ C-NMR The polypropylene resin (Y) used in the present invention is characterized by high stereoregularity.
Stereoregularity of the ^height 13 that can be evaluated by ^{C-NMR, 13 C-NMR} mm fraction of the propylene unit triad sequences obtained by it is preferably 95% or more.
As for the mm fraction, the upper limit of the ratio of three propylene unit chains in which the direction of methyl branching in each propylene unit is the same in any three propylene unit chains composed of head-to-tail bonds in the polymer chain is 100%. This mm fraction is a value indicating that the steric structure of the methyl group in the polypropylene molecular chain is controlled isotactically, and the higher the value, the higher the degree of control. If the mm fraction is smaller than this value, the mechanical properties tend to decrease.
Accordingly, the mm fraction is preferably 95% or more, more preferably 96% or more, and still more preferably 97% or more.

In addition, the detail of the measuring method of mm fraction of the propylene unit 3 chain | strand by ¹³ C-NMR is as follows.
A sample of 375 mg is completely dissolved in 2.5 ml of deuterated 1,1,2,2-tetrachloroethane in an NMR sample tube (10φ), and then measured at 125 ° C. by a proton complete decoupling method. The chemical shift sets the central peak of the three peaks of deuterated 1,1,2,2-tetrachloroethane to 74.2 ppm. The chemical shift of other carbon peaks is based on this.
Flip angle: 90 degrees Pulse interval: 10 seconds Resonance frequency: 100 MHz or more Integration frequency: 10,000 times or more Observation range: -20 ppm to 179 ppm
Number of data points: 32768

The analysis of the mm fraction is performed using the measured ¹³ C-NMR spectrum.
The spectrum is assigned with reference to Macromolecules, (1975) 8 pp. 687 and Polymer, 30, vol. 1, 1350 (1989).
Note that a more specific method for determining the mm fraction is described in detail in paragraphs [0053] to [0065] of Japanese Patent Laid-Open No. 2009-275207, and the present invention is performed according to this method. .

  The mm fraction can be 95% or more by using a polymerization catalyst that achieves a highly crystalline polymer, and by using a preferred metallocene catalyst described later for polymerization.

(7) Characteristic (Y7): Strain hardening degree (λmax)
As a further additional feature of the polypropylene resin (Y) having a branched structure according to the present invention, the strain hardening degree (λmax (0.1)) in the measurement of elongational viscosity at a strain rate of 0.1 s ⁻¹ is 6.0. It is mentioned above.
The strain hardening degree (λmax (0.1)) is an index representing the strength at the time of melting, and when this value is large, there is an effect of improving the melt tension. As a result, there is an effect of finely dispersing rubber during injection molding, and the impact resistance of the injection molded product is improved. The strain hardening degree is preferably 6.0 or more, and more preferably 8.0 or more.

Details of the calculation method of λmax (0.1) are as follows.
The elongational viscosity at a temperature of 180 ° C. and a strain rate = 0.1 s ⁻¹ is plotted on a logarithmic graph with the horizontal axis representing time t (seconds) and the vertical axis representing elongational viscosity ηE (Pa · seconds). On the log-log graph, the viscosity immediately before strain hardening is approximated by a straight line.
Specifically, first, the slope at each time when the extensional viscosity is plotted against time is obtained. In this case, considering that the measurement data of the extensional viscosity is discrete, various averaging methods are used. Is used. For example, there is a method of obtaining the slope of adjacent data and taking a moving average of several surrounding points.

  The elongational viscosity is a simple increasing function in the low strain region, gradually approaches a constant value, and if there is no strain hardening, it agrees with the Truton viscosity after a sufficient amount of time. From about 1 strain amount (= strain rate × time), the extensional viscosity starts to increase with time. That is, the slope tends to decrease with time in the low strain region, but tends to increase from about 1 strain, and there is an inflection point on the curve when the extensional viscosity is plotted against time. . Therefore, a point where the slope of each time obtained above takes the minimum value in the range of the distortion amount of about 0.1 to 2.5 is obtained, and a tangent line is drawn at the point, and the straight line has a distortion amount of 4.0. Extrapolate until The maximum value (ηmax) of the extensional viscosity ηE until the strain amount becomes 4.0 is obtained, and the viscosity on the approximate straight line up to that time is ηlin. ηmax / ηlin is defined as λmax (0.1).

6). Method for Producing Branched Polypropylene Resin (Y) The polypropylene resin (Y) having a branched structure is not particularly limited as long as it satisfies the above-mentioned characteristics, but as described above, it has low low crystallinity. A preferred production method for satisfying all the conditions of component amount, high stereoregularity, relatively wide molecular weight distribution, range of branching index g ′, and high melt tension is a macromer copolymerization method using a combination of metallocene catalysts. This method is used. As an example of such a method, for example, a method disclosed in Japanese Patent Application Laid-Open No. 2009-57542 can be given.
This method produces a polypropylene having a long-chain branched structure using a catalyst in which a catalyst component having a specific structure having macromer-producing ability and a catalyst component having a specific structure having high molecular weight and macromer copolymerization ability are combined. According to this method, industrially effective methods such as a bulk polymerization method and a gas phase polymerization method are used, particularly in a single-stage polymerization under a practical pressure temperature condition, and further, hydrogen as a molecular weight regulator is removed. It is possible to produce a polypropylene resin having a long-chain branched structure having the desired physical properties.

In the past, it was necessary to increase the branching efficiency by lowering the crystallinity by using a polypropylene component having a low stereoregularity. However, in the above method, a polypropylene component having a sufficiently high stereoregularity is required. It can be introduced into the side chain by a simple method, and is preferable as the polypropylene resin (Y) used in the present invention. It is suitable for satisfying the characteristics regarding the ratio and the amount of paraxylene soluble component (CXS).
In addition, by using the above-mentioned method, it is possible to broaden the molecular weight distribution by using two types of catalysts having greatly different polymerization characteristics, and simultaneously satisfy the characteristics relating to the melt tension, the molecular weight distribution Mw / Mn, and the branching index g ′. It is preferable.

Therefore, a preferable method for producing a polypropylene resin (Y) having a branched structure used in the present invention will be described in detail below.
As a preferred method for producing a polypropylene resin (Y) having a branched structure, a method for producing a propylene polymer using the following catalyst components (A), (B) and (C) as a propylene polymerization catalyst may be mentioned.
(A): at least one from component [A-1] which is a compound represented by the following general formula (a1) and at least from component [A-2] which is a compound represented by the following general formula (a2) One or more transition metal compounds of Group 4 of the periodic table.
(B): Ion exchange layered silicate (C): Organoaluminum compound

Hereinafter, the catalyst components (A), (B), and (C) will be described in detail.
(1) Catalyst component (A)
(I) Component [A-1]: Compound represented by the following general formula (a1)

[In General Formula (a1), R ¹¹ and R ¹² each independently represent a heterocyclic group containing nitrogen, oxygen or sulfur having 4 to 16 carbon atoms. R ¹³ and R ¹⁴ each independently contain halogen, silicon, oxygen, sulfur, nitrogen, boron, phosphorus, or a plurality of heteroelements selected from these, having 6 to 16 carbon atoms An aryl group, a heterocyclic group containing 6 to 16 carbon atoms, nitrogen, oxygen or sulfur. X ¹¹ and Y ¹¹ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 20 carbon atoms, or a halogenated group having 1 to 20 carbon atoms. Represents a hydrocarbon group, an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, an amino group, or a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms, Q ¹¹ is a divalent hydrocarbon group having 1 to 20 carbon atoms, It represents a silylene group or a germylene group which may have a hydrocarbon group having 1 to 20 carbon atoms. ]

The heterocyclic group containing nitrogen, oxygen or sulfur having 4 to 16 carbon atoms of R ¹¹ and R ¹² is preferably a 2-furyl group, a substituted 2-furyl group, a substituted 2-thienyl group, It is a substituted 2-furfuryl group, and more preferably a substituted 2-furyl group.
Moreover, as a substituted 2-furyl group, a substituted 2-thienyl group, and a substituted 2-furfuryl group, an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, and a propyl group, Examples include halogen atoms such as fluorine atom and chlorine atom, alkoxy groups having 1 to 6 carbon atoms such as methoxy group and ethoxy group, and trialkylsilyl groups. Of these, a methyl group and a trimethylsilyl group are preferable, and a methyl group is particularly preferable.
Further, R ¹¹ and R ¹² are particularly preferably a 2- (5-methyl) -furyl group. R ¹¹ and R ¹² are preferably the same as each other.

Carbon atoms 6 to 16 of the R ¹³ and R ^14, halogen, silicon, oxygen, sulfur, nitrogen, boron, phosphorus, or may contain a plurality of hetero elements selected from these, the aryl group In the range of 6 to 16 carbon atoms, one or more hydrocarbon group having 1 to 6 carbon atoms, silicon-containing hydrocarbon group having 1 to 6 carbon atoms, 1 to 6 carbon atoms on the aryl cyclic skeleton It may have a halogen-containing hydrocarbon group as a substituent.
At least one of R ¹³ and R ¹⁴ is preferably a phenyl group, a 4-methylphenyl group, a 4-i-propylphenyl group, a 4-t-butylphenyl group, a 4-trimethylsilylphenyl group, or 2,3-dimethyl. A phenyl group, 3,5-di-t-butylphenyl group, 4-phenyl-phenyl group, chlorophenyl group, naphthyl group, or phenanthryl group, more preferably a phenyl group, 4-i-propylphenyl group, 4- t-butylphenyl group, 4-trimethylsilylphenyl group, 4-chlorophenyl group. Further, it is preferable that R ¹³ and R ¹⁴ are the same.

In the general formula (a1), X ¹¹ and Y ¹¹ are auxiliary ligands and react with the catalyst component (B) to generate an active metallocene having olefin polymerization ability. Therefore, as long as this object is achieved, X ¹¹ and Y ¹¹ are not limited in the type of ligand, and are independently a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms. A C1-C20 silicon-containing hydrocarbon group, a C1-C20 halogenated hydrocarbon group, a C1-C20 oxygen-containing hydrocarbon group, an amino group, or a C1-C20 nitrogen-containing hydrocarbon Indicates a group.

In the general formula (a1), Q ¹¹ is a silylene that may have a divalent hydrocarbon group having 1 to 20 carbon atoms and a hydrocarbon group having 1 to 20 carbon atoms that connects two five-membered rings. Represents either a group or a germylene group. When two hydrocarbon groups are present on the silylene group or the germylene group, they may be bonded to each other to form a ring structure.
Specific examples of Q ¹¹ include alkylene groups such as methylene, methylmethylene, dimethylmethylene and 1,2-ethylene; arylalkylene groups such as diphenylmethylene; silylene groups; methylsilylene, dimethylsilylene, diethylsilylene, di ( n-propyl) silylene, di (i-propyl) silylene, alkylsilylene groups such as di (cyclohexyl) silylene, (alkyl) (aryl) silylene groups such as methyl (phenyl) silylene; arylsilylene groups such as diphenylsilylene; tetra An alkyl oligosilylene group such as methyldisilylene; a germylene group; an alkylgermylene group in which the silicon of the above-mentioned divalent hydrocarbon group having 1 to 20 carbon atoms is replaced with germanium; (alkyl) (aryl) germylene Group; arylgermylene group And so on. In these, the silylene group which has a C1-C20 hydrocarbon group, or the germylene group which has a C1-C20 hydrocarbon group is preferable, and an alkylsilylene group and an alkylgermylene group are especially preferable.

Of the compounds represented by the general formula (a1), preferred compounds are specifically exemplified below.
Dichloro [1,1′-dimethylsilylenebis {2- (2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (2-thienyl) -4-phenyl -Indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-diphenylsilylenebis {2 -(5-Methyl-2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethylgermylenebis {2- (5-methyl-2-furyl) -4-phenyl-indenyl} ] Hafnium, dichloro [1,1'-dimethylgermylenebis {2- (5-methyl-2-thienyl) -4-phenyl-indenyl}] hafnium, dic B [1,1′-dimethylsilylenebis {2- (5-t-butyl-2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5- Trimethylsilyl-2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-phenyl-2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [ 1,1′-dimethylsilylenebis {2- (4,5-dimethyl-2-furyl) -4-phenyl-indenyl}] hafnium dichloride, dichloro [1,1′-dimethylsilylenebis {2- (2-benzofuryl) ) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- ( -Methylphenyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-ipropylphenyl) -indenyl}] hafnium, dichloro [ 1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-trimethylsilylphenyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (2 -Furfuryl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-chlorophenyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-fluorophenyl) -indenyl}] Hough , Dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-trifluoromethylphenyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylene Bis {2- (5-methyl-2-furyl) -4- (4-t-butylphenyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (2-furyl) -4 -(1-Naphtyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (2-furyl) -4- (2-naphthyl) -indenyl}] hafnium, dichloro [1,1 ′ -Dimethylsilylenebis {2- (2-furyl) -4- (2-phenanthryl) -indenyl}] hafnium, dichloro [1,1'-dimethylsilylenebis {2- (2-furyl) -4- (9-phenanthryl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (1-naphthyl) -indenyl}] hafnium, Dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (2-naphthyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- ( 5-methyl-2-furyl) -4- (2-phenanthryl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (9- Phenanthryl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-t-butyl-2-furyl) -4- (1-naphthyl) -indenyl}] ha Nitrogen, dichloro [1,1′-dimethylsilylenebis {2- (5-tert-butyl-2-furyl) -4- (2-naphthyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-t-butyl-2-furyl) -4- (2-phenanthryl) -indenyl}] hafnium, dichloro [1,1'-dimethylsilylenebis {2- (5-t-butyl-2- Furyl) -4- (9-phenanthryl) -indenyl}] hafnium.

  Of these, more preferred are dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylene. Bis {2- (5-methyl-2-furyl) -4- (4-methylphenyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-ipropylphenyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-trimethylsilylphenyl) -indenyl} ] Hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-chlorophenyl) -indenyl}] hafni Dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (2-naphthyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2 -(5-Methyl-2-furyl) -4- (4-t-butylphenyl) -indenyl}] hafnium.

  Particularly preferred is dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis { 2- (5-Methyl-2-furyl) -4- (4-ipropylphenyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl)- 4- (4-Trimethylsilylphenyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-t-butylphenyl) -indenyl} ] Hafnium.

(Ii) Component [A-2]: Compound represented by general formula (a2)

[In General Formula (a2), R ²¹ and R ²² are each independently a hydrocarbon group having 1 to 6 carbon atoms, and R ²³ and R ²⁴ are each independently halogen, silicon, oxygen, It is a C6-C16 aryl group which may contain sulfur, nitrogen, boron, phosphorus, or a plurality of heteroelements selected from these. X ²¹ and Y ²¹ each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon having 1 to 20 carbon atoms. Group, an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, an amino group, or a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms, Q ²¹ is a divalent hydrocarbon group having 1 to 20 carbon atoms, carbon number It represents a silylene group or a germylene group which may have 1 to 20 hydrocarbon groups. M ²¹ is zirconium or hafnium. ]

R ²¹ and R ²² are each independently a hydrocarbon group having 1 to 6 carbon atoms, preferably an alkyl group, and more preferably an alkyl group having 1 to 4 carbon atoms. Specific examples include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, n-pentyl, i-pentyl, n-hexyl, and preferably methyl. , Ethyl, n-propyl.

R ²³ and R ²⁴ each independently contain a halogen having 6 to 16 carbon atoms, preferably 6 to 12 carbon atoms, halogen, silicon, or a plurality of hetero elements selected from these. It is a good aryl group. Preferable examples include phenyl, 3-chlorophenyl, 4-chlorophenyl, 3-fluorophenyl, 4-fluorophenyl, 4-methylphenyl, 4-i-propylphenyl, 4-t-butylphenyl, 4-trimethylsilylphenyl, 4 -(2-fluoro-4-biphenylyl), 4- (2-chloro-4-biphenylyl), 1-naphthyl, 2-naphthyl, 4-chloro-2-naphthyl, 3-methyl-4-trimethylsilylphenyl, 3, Examples include 5-dimethyl-4-t-butylphenyl, 3,5-dimethyl-4-trimethylsilylphenyl, 3,5-dichloro-4-trimethylsilylphenyl, and the like.

X ²¹ and Y ²¹ are auxiliary ligands, and react with the catalyst component (B) to produce active metallocene having olefin polymerization ability. Therefore, as long as this object is achieved, X ²¹ and Y ²¹ are not limited in the type of ligand, and are independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, C1-C20 silicon-containing hydrocarbon group, C1-C20 halogenated hydrocarbon group, C1-C20 oxygen-containing hydrocarbon group, amino group, or C1-C20 nitrogen-containing hydrocarbon group Indicates.

Q ²¹ is a binding group that bridges two conjugated five-membered ring ligands, and has a divalent hydrocarbon group having 1 to 20 carbon atoms and a hydrocarbon group having 1 to 20 carbon atoms. A silylene group or a germylene group having a hydrocarbon group having 1 to 20 carbon atoms, preferably a substituted silylene group or a substituted germylene group. The substituent bonded to silicon and germanium is preferably a hydrocarbon group having 1 to 12 carbon atoms, and two substituents may be linked.
Specific examples of Q ²¹ include methylene, dimethylmethylene, ethylene-1,2-diyl, dimethylsilylene, diethylsilylene, diphenylsilylene, methylphenylsilylene, 9-silafluorene-9,9-diyl, dimethylsilylene, Examples include diethylsilylene, diphenylsilylene, methylphenylsilylene, 9-silafluorene-9,9-diyl, dimethylgermylene, diethylgermylene, diphenylgermylene, methylphenylgermylene, and the like.

Further, M ²¹ is zirconium or hafnium, preferably hafnium.

As a non-limiting example of the metallocene compound represented by the general formula (a2), the following can be preferably exemplified.
However, in the following, only representative exemplary compounds are described avoiding many complicated examples, and the present invention is not construed as being limited to these compounds. Obviously, any ligand can be used. In the following, a compound in which the central metal is hafnium is described, but a compound substituted for zirconium is also treated as disclosed in the present specification.

  Dichloro {1,1′-dimethylsilylenebis (2-methyl-4-phenyl-4-hydroazurenyl)} hafnium, dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4 -Hydroazulenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-t-butylphenyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis { 2-methyl-4- (4-trimethylsilylphenyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (3-chloro-4-t-butylphenyl)- 4-hydroazulenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-methyl-4- ( -Methyl-4-t-butylphenyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (3-chloro-4-trimethylsilylphenyl) -4-hydroazurenyl} ] Hafnium, dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (3-methyl-4-trimethylsilylphenyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2 -Methyl-4- (1-naphthyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (2-naphthyl) -4-hydroazurenyl}] hafnium, dichloro [ 1,1′-dimethylsilylenebis {2-methyl-4- (4-chloro-2-naphthyl)- -Hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (2-fluoro-4-biphenylyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-Methyl-4- (2-chloro-4-biphenylyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (9-phenanthryl) -4-hydroazurenyl] }] Hafnium, dichloro [1,1′-dimethylsilylenebis {2-ethyl-4- (4-chlorophenyl) -4-hydroazulenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-n-propyl -4- (3-Chloro-4-trimethylsilylphenyl) -4-hydroazurenyl}] huff Nitrogen, dichloro [1,1′-dimethylsilylenebis {2-ethyl-4- (3-chloro-4-tert-butylphenyl) -4-hydroazulenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis { 2-ethyl-4- (3-methyl-4-trimethylsilylphenyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylgermylenebis {2-methyl-4- (2-fluoro-4-biphenylyl) ) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylgermylenebis {2-methyl-4- (4-t-butylphenyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′- (9-silafluorene-9,9-diyl) bis {2-ethyl-4- (4-chlorophenyl) -4-hydroazurenyl}] Funium, dichloro [1,1′-dimethylsilylenebis {2-ethyl-4- (4-chloro-2-naphthyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-ethyl -4- (2-fluoro-4-biphenylyl) -4-hydroazulenyl}] hafnium, dichloro [1,1 ′-(9-silafluorene-9,9-diyl) bis {2-ethyl-4- (3 5-dichloro-4-trimethylsilylphenyl) -4-hydroazurenyl}] hafnium and the like.

  Of these, dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- Methyl-4- (3-chloro-4-trimethylsilylphenyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-ethyl-4- (2-fluoro-4-biphenylyl) -4 -Hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-ethyl-4- (4-chloro-2-naphthyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-Ethyl-4- (3-methyl-4-trimethylsilylphenyl) -4-hydroazurenyl}] ha Dichloro, [1,1 ′-(9-silafluorene-9,9-diyl) bis {2-ethyl-4- (3,5-dichloro-4-trimethylsilylphenyl) -4-hydroazurenyl}] hafnium, is there.

  Particularly preferably, dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-ethyl -4- (2-Fluoro-4-biphenylyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-ethyl-4- (3-methyl-4-trimethylsilylphenyl) -4- Hydroazurenyl}] hafnium, dichloro [1,1 ′-(9-silafluorene-9,9-diyl) bis {2-ethyl-4- (3,5-dichloro-4-trimethylsilylphenyl) -4-hydroazurenyl}] Hafnium.

(2) Catalyst component (B)
The catalyst component (B) preferably used for producing the polypropylene resin (Y) is an ion-exchange layered silicate.
(I) Types of ion-exchanged layered silicates Ion-exchanged layered silicates (hereinafter sometimes simply referred to as silicates) are surfaces formed by ionic bonds or the like that are parallel to each other with a binding force. A silicate compound having a stacked crystal structure and containing exchangeable ions. Most silicates are mainly produced as a main component of clay minerals in nature, and therefore often contain impurities (quartz, cristobalite, etc.) other than ion-exchanged layered silicates. Good. Depending on the type, amount, particle size, crystallinity, and dispersion state of these impurities, it may be preferable to pure silicate, and such a complex is also included in the catalyst component (B).
The silicate to be used is not limited to a natural product, and may be an artificial synthetic product or may contain them.

Specific examples of the silicate include the following layered silicates described in Haruo Shiramizu “Clay Mineralogy” Asakura Shoten (1995).
That is, montmorillonite, sauconite, beidellite, nontronite, saponite, hectorite, stemite and other smectites, vermiculite and other vermiculites, mica, illite, sericite and sea chlorite and other mica, attapulgite, sepiolite and palygorskite , Bentonite, pyrophyllite, talc, chlorite group, etc.
The silicate is preferably a silicate in which the main component silicate has a 2: 1 type structure, more preferably a smectite group, and particularly preferably montmorillonite. The type of interlayer cation is not particularly limited, but a silicate containing an alkali metal or an alkaline earth metal as a main component of the interlayer cation is preferable from the viewpoint of being relatively easy and inexpensive to obtain as an industrial raw material.

(Ii) Chemical treatment of ion-exchangeable layered silicate The ion-exchangeable layered silicate of the catalyst component (B) can be used as it is without any particular treatment, but it is preferable to perform chemical treatment. Here, the chemical treatment of the ion-exchange layered silicate can be any of a surface treatment that removes impurities adhering to the surface and a treatment that affects the structure of the clay. Treatment, alkali treatment, salt treatment, organic matter treatment and the like.

<Acid treatment>:
In addition to removing impurities on the surface, the acid treatment can elute some or all of cations such as Al, Fe, Mg, etc. in the crystal structure.
The acid used in the acid treatment is preferably selected from hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid and oxalic acid.
Two or more salts (described in the next section) and acid may be used for the treatment. The treatment conditions with salts and acids are not particularly limited. Usually, the salt and acid concentrations are 0.1 to 50% by weight, the treatment temperature is room temperature to boiling point, and the treatment time is 5 minutes to 24 hours. It is preferable to carry out the process under the condition of selecting and eluting at least a part of the substance constituting at least one compound selected from the group consisting of ion-exchangeable layered silicates. In addition, salts and acids are generally used in an aqueous solution.

In addition, you may use what combined the following acids and salts as a processing agent. Moreover, the combination of these acids and salts may be sufficient.
<Salt treatment>:
Cations that are preferably 40% or more, more preferably 60% or more, of the exchangeable Group 1 metal cations contained in the ion-exchange layered silicate before being treated with salts, dissociated from the salts shown below. It is preferable to perform ion exchange.
The salt used in the salt treatment for the purpose of ion exchange is a group consisting of a cation containing at least one atom selected from the group consisting of group 1 to 14 atoms, a halogen atom, an inorganic acid, and an organic acid. A compound comprising at least one anion selected from the group consisting of at least one anion selected from the group consisting of group 2 to 14 atoms, Cl, Br, I, F, PO ₄ , SO ₄ , NO ₃ , CO ₃ , C ₂ O ₄ , ClO ₄ , OOCCH ₃ , CH ₃ COCHCOCH ₃ , OCl ₂ , O (NO ₃ ) ₂ , O (ClO ₄ ) ₂ , O (SO ₄ ) At least one anion selected from the group consisting of OH, O ₂ Cl ₂ , OCl ₃ , OOCH, OOCCH ₂ CH ₃ , C ₂ H ₄ O ₄ and C ₅ H ₅ O ₇ Is a compound consisting of

Preferred examples of such _{salts, LiF, LiCl, LiBr, LiI} , Li 2 SO 4, Li (CH 3 COO), LiCO 3, Li (C 6 H 5 O 7), LiCHO 2, LiC 2 O ₄ , LiClO ₄ , Li ₃ PO ₄ , CaCl ₂ , CaSO ₄ , CaC ₂ O ₄ , Ca (NO ₃ ) ₂ , Ca ₃ (C ₆ H ₅ O ₇ ) ₂ , MgCl ₂ , MgBr ₂ , MgSO ₄ , Mg (PO ₄ ) ₂ , Mg (ClO ₄ ) ₂ , MgC ₂ O ₄ , Mg (NO ₃ ) ₂ , Mg (OOCCH ₃ ) ₂ , MgC ₄ H ₄ O _{4 and the} like.
Further, Ti (OOCCH ₃ ) ₄ , Ti (CO ₃ ) ₂ , Ti (NO ₃ ) ₄ , Ti (SO ₄ ) ₂ , TiF ₄ , TiCl ₄ , Zr (OOCCH ₃ ) ₄ , Zr (CO ₃ ) ₂ , Zr (NO ₃ ) ₄ , Zr (SO ₄ ) ₂ , ZrF ₄ , ZrCl ₄ , ZrOCl ₂ , ZrO (NO ₃ ) ₂ , ZrO (ClO ₄ ) ₂ , ZrO (SO ₄ ), HF (OOCCH ₃ ) ₄ , HF (CO ₃ ) ₂ , HF (NO ₃ ) ₄ , HF (SO ₄ ) ₂ , HFOCl ₂ , HFF ₄ , HFCl ₄ , V (CH ₃ COCHCOCH ₃ ) ₃ , VOSO ₄ , VOCl ₃ , VCl ₃ , VCl ₄ , VBr _{3 and the} like.

Also, Cr (CH ₃ COCHCOCH ₃ ) ₃ , Cr (OOCCH ₃ ) ₂ OH, Cr (NO ₃ ) ₃ , Cr (ClO ₄ ) ₃ , CrPO ₄ , Cr ₂ (SO ₄ ) ₃ , CrO ₂ Cl ₂ , CrF ₃ , CrCl ₃ , CrBr ₃ , CrI ₃ , Mn (OOCCH ₃ ) ₂ , Mn (CH ₃ COCHCOCH ₃ ) ₂ , MnCO ₃ , Mn (NO ₃ ) ₂ , MnO, Mn (ClO ₄ ) ₂ , MnF ₂ , MnCl ₂ , Fe (OOCCH ₃ ) ₂ , Fe (CH ₃ COCHCOCH ₃ ) ₃ , FeCO ₃ , Fe (NO ₃ ) ₃ , Fe (ClO ₄ ) ₃ , FePO ₄ , FeSO ₄ , Fe ₂ (SO ₄ ) ₃ , FeF ₃ , FeCl ₃ , FeC ₆ H ₅ O _{7 and the} like.

In addition, Co (OOCCH ₃ ) ₂ , Co (CH ₃ COCHCOCH ₃ ) ₃ , CoCO ₃ , Co (NO ₃ ) ₂ , CoC ₂ O ₄ , Co (ClO ₄ ) ₂ , Co ₃ (PO ₄ ) ₂ , CoSO ₄ , CoF ₂ , CoCl ₂ , NiCO ₃ , Ni (NO ₃ ) ₂ , NiC ₂ O ₄ , Ni (ClO ₄ ) ₂ , NiSO ₄ , NiCl ₂ , NiBr _{2 and the} like.
Furthermore, Zn (OOCCH ₃ ) ₂ , Zn (CH ₃ COCHCOCH ₃ ) ₂ , ZnCO ₃ , Zn (NO ₃ ) ₂ , Zn (ClO ₄ ) ₂ , Zn ₃ (PO ₄ ) ₂ , ZnSO ₄ , ZnF ₂ , ZnCl ₂ , AlF ₃ , AlCl ₃ , AlBr ₃ , AlI ₃ , Al ₂ (SO ₄ ) ₃ , Al ₂ (C ₂ O ₄ ) ₃ , Al (CH ₃ COCHCOCH ₃ ) ₃ , Al (NO ₃ ) ₃ , AlPO ₄ , GeCl ₄ , GeBr ₄ , GeI _{4 and the} like.

<Alkali treatment>:
In addition to acid and salt treatment, the following alkali treatment or organic matter treatment may be performed as necessary. Examples of the treating agent used in the alkali treatment include LiOH, NaOH, KOH, Mg (OH) ₂ , Ca (OH) ₂ , Sr (OH) ₂ , Ba (OH) _{2 and the} like.

<Organic treatment>:
Examples of the organic treatment agent used for the organic treatment include trimethylammonium, triethylammonium, N, N-dimethylanilinium, triphenylphosphonium, and the like.
Examples of the anion constituting the organic treatment agent include hexafluorophosphate, tetrafluoroborate, and tetraphenylborate other than the anion exemplified as the anion constituting the salt treatment agent. However, it is not limited to these.

  Moreover, these processing agents may be used independently and may be used in combination of 2 or more types. These combinations may be used in combination for the treatment agent added at the start of the treatment, or may be used in combination for the treatment agent added during the treatment. The chemical treatment can be performed a plurality of times using the same or different treatment agents.

These ion-exchange layered silicates usually contain adsorbed water and interlayer water. In the present invention, it is preferable to remove these adsorbed water and interlayer water and use them as the catalyst component (B).
The heat treatment method of the ion-exchange layered silicate adsorbed water and interlayer water is not particularly limited, but it is necessary to select conditions so that interlayer water does not remain and structural destruction does not occur. The heating time is 0.5 hour or longer, preferably 1 hour or longer. At that time, the water content of the catalyst component (B) after the removal is 3% by weight or less when the water content when dehydrating for 2 hours under the conditions of a temperature of 200 ° C. and a pressure of 1 mmHg is 0% by weight, It is preferably 1% by weight or less.

As described above, particularly preferable as the catalyst component (B) is an ion-exchange layered silicate having a water content of 3% by weight or less, which is obtained by performing a salt treatment and / or an acid treatment.
The ion-exchange layered silicate can be treated with a catalyst component (C) of an organoaluminum compound, which will be described later, before formation of a catalyst or use as a catalyst, which is preferable. Although there is no restriction | limiting in the usage-amount of the catalyst component (C) with respect to 1g of ion-exchange layered silicate, Usually, 20 mmol or less, Preferably it is 0.5 mmol or more and 10 mmol or less. There is no limitation on the treatment temperature and time, the treatment temperature is usually 0 ° C. or more and 70 ° C. or less, and the treatment time is 10 minutes or more and 3 hours or less. It is possible and preferable to wash after the treatment. As the solvent, the same hydrocarbon solvent as that used in the prepolymerization or slurry polymerization method described later is used.

The catalyst component (B) is preferably spherical particles having an average particle size of 5 μm or more. If the particle shape is spherical, a natural product or a commercially available product may be used as it is, or a particle whose particle shape and particle size are controlled by granulation, sizing, fractionation, or the like may be used.
Examples of the granulation method used here include a stirring granulation method and a spray granulation method, but commercially available products can also be used.
Moreover, you may use organic substance, an inorganic solvent, inorganic salt, and various binders in the case of granulation.
The spherical particles obtained as described above desirably have a compressive fracture strength of 0.2 MPa or more, particularly preferably 0.5 MPa or more, in order to suppress crushing and generation of fine powder in the polymerization process. In the case of such particle strength, the effect of improving the particle properties is effectively exhibited particularly when prepolymerization is performed.

(3) Catalyst component (C)
The catalyst component (C) is an organoaluminum compound. Organic aluminum compounds used as the catalyst component (C) has the general ^{_{formula: (AlR 31 q Z 3-}} q) a compound represented by _p is suitable.
In this invention, it cannot be overemphasized that the compound represented by the said formula can be used individually, in mixture of multiple types or in combination.
In the above ^{formulas, R 31} represents a hydrocarbon group having 1 to 20 carbon atoms, Z is a halogen, hydrogen, an alkoxy group or an amino group. q represents an integer of 1 to 3, and p represents an integer of 1 to 2, respectively.
R ³¹ is preferably an alkyl group, and Z is a chlorine atom when it is halogen, a C 1-8 alkoxy group when it is an alkoxy group, and a carbon atom number 1 when it is an amino group. An amino group of ˜8 is preferred.

  Specific examples of the organoaluminum compound include trimethylaluminum, triethylaluminum, trinormalpropylaluminum, trinormalbutylaluminum, triisobutylaluminum, trinormalhexylaluminum, trinormaloctylaluminum, trinormaldecylaluminum, diethylaluminum chloride, diethylaluminum. Examples thereof include sesquichloride, diethylaluminum hydride, diethylaluminum ethoxide, diethylaluminum dimethylamide, diisobutylaluminum hydride, and diisobutylaluminum chloride.

Of these, trialkylaluminum and alkylaluminum hydride having p = 1 and q = 3 are preferable. More preferably, it is trialkylaluminum in which R ³¹ is an alkyl group having 1 to 8 carbon atoms.

(4) Formation of catalyst / preliminary polymerization The catalyst contacts each of the catalyst components (A) to (C) in the (preliminary) polymerization tank simultaneously or continuously, or once or multiple times. Can be formed.
The contacting of each component is usually performed in an aliphatic hydrocarbon or aromatic hydrocarbon solvent. Although a contact temperature is not specifically limited, It is preferable to carry out between -20 degreeC-+150 degreeC. As the contact order, any desired combination can be used, but particularly preferable ones for each component are as follows.

When the catalyst component (C) is used, the catalyst component (A), the catalyst component (B), or the catalyst component (A) and the catalyst are contacted before the catalyst component (A) and the catalyst component (B) are contacted. Contacting catalyst component (C) with both components (B), or contacting catalyst component (C) with catalyst component (A) and catalyst component (B), or catalyst component Although it is possible to contact the catalyst component (C) after bringing the catalyst component (B) into contact with (A), it is preferable that the catalyst component be brought into contact with the catalyst component (A) before contacting the catalyst component (B). It is a method of contacting any of the component (C).
Moreover, after making each component contact, it is possible to wash | clean with an aliphatic hydrocarbon or an aromatic hydrocarbon solvent.

The amount of catalyst components (A), (B) and (C) used is arbitrary. For example, the amount of the catalyst component (A) used relative to the catalyst component (B) is preferably in the range of 0.1 μmol to 1,000 μmol, particularly preferably 0.5 μmol to 500 μmol, relative to 1 g of the catalyst component (B). The amount of the catalyst component (C) relative to the catalyst component (A) is preferably a transition metal molar ratio of preferably 0.01 to 5 × 10 ⁶ , particularly preferably within a range of 0.1 to 1 × 10 ^4. .

  The component [A-1] (compound represented by the general formula (a1)) and the component [A-2] (compound represented by the general formula (a1)) are used in a proportion of the polypropylene resin (Y). The molar ratio of the transition metal of [A-1] to the total amount of the components [A-1] and [A-2] is preferably within a range satisfying the above characteristics, but is preferably 0.30 or more, 0.0. 99 or less.

  By changing this ratio, it is possible to adjust the balance between melt physical properties and catalyst activity. That is, from the component [A-1], a low molecular weight terminal vinyl macromer is produced, and from the component [A-2], a high molecular weight body obtained by copolymerizing a part of the macromer is produced. Therefore, by changing the ratio of the component [A-1], the average molecular weight, molecular weight distribution, bias of the molecular weight distribution toward the high molecular weight side, very high molecular weight component, branch (amount, length, Distribution) can be controlled, whereby the melt properties such as branching index g ′, strain hardening degree λmax, melt tension, and spreadability can be controlled.

In order to produce the polypropylene resin (Y), the molar ratio is preferably 0.30 or more, more preferably 0.40 or more, and further preferably 0.5 or more. Further, the upper limit is preferably 0.99 or less, and in order to obtain a polypropylene resin (Y) efficiently with high catalytic activity, it is preferably 0.95 or less, and more preferably 0.90 or less. It is.
In addition, by using component [A-1] within the above range, it is possible to adjust the balance between the average molecular weight and the catalytic activity with respect to the amount of hydrogen.

  The catalyst is preferably subjected to a prepolymerization treatment which consists of contacting it with an olefin and polymerizing it in a small amount. By performing the prepolymerization treatment, gel formation can be prevented when the main polymerization is performed. The reason is considered to be that long-chain branches can be uniformly distributed among the polymer particles when the main polymerization is performed, and the melt physical properties can be improved thereby.

  The olefin used in the prepolymerization is not particularly limited, but propylene, ethylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, 3-methyl-1-butene, vinylcycloalkane, Styrene and the like can be exemplified. The olefin feed method may be any method such as a feed method for maintaining the olefin at a constant rate or a constant pressure in the reaction tank, a combination thereof, or a stepwise change.

The prepolymerization temperature and time are not particularly limited, but are preferably in the range of −20 ° C. to + 100 ° C. and 5 minutes to 24 hours, respectively. The amount of prepolymerization is preferably 0.01 to 100, more preferably 0.1 to 50 in terms of a weight ratio with respect to the catalyst component (B). Moreover, a catalyst component (C) can also be added or added at the time of prepolymerization. It is also possible to wash after the prepolymerization.
In addition, a method of coexisting a polymer such as polyethylene or polypropylene, or a solid of an inorganic oxide such as silica or titania, at the time of contacting or after contacting each of the above components is also possible.

(5) Use of Catalyst / Propylene Polymerization Any polymerization mode can be used as long as the olefin polymerization catalyst including the catalyst component (A), the catalyst component (B), and the catalyst component (C) is in efficient contact with the monomer. Can be adopted.
Specifically, a slurry method using an inert solvent, a so-called bulk method, a solution polymerization method, or a substantially liquid solvent without using an inert solvent as a solvent. A gas phase method can be used. Moreover, the method of performing continuous polymerization and batch type polymerization is also applied. In addition to single-stage polymerization, it is possible to carry out multistage polymerization of two or more stages.
In the case of the slurry polymerization method, a saturated aliphatic or aromatic hydrocarbon such as hexane, heptane, pentane, cyclohexane, benzene, and toluene is used alone or as a mixture as a polymerization solvent.

The polymerization temperature is usually 0 ° C. or higher and 150 ° C. or lower. In particular, when a bulk polymerization method is used, it is preferably 40 ° C. or higher, more preferably 50 ° C. or higher. The upper limit is preferably 80 ° C. or lower, and more preferably 75 ° C. or lower.
Furthermore, when using a gas phase polymerization method, it is preferably 40 ° C. or higher, more preferably 50 ° C. or higher. The upper limit is preferably 100 ° C. or lower, more preferably 90 ° C. or lower.
The polymerization pressure is preferably 1.0 MPa or more and 5.0 MPa or less. In particular, when a bulk polymerization method is used, 1.5 MPa or more is preferable, and 2.0 MPa or more is more preferable. The upper limit is preferably 4.0 MPa or less, more preferably 3.5 MPa or less.
Furthermore, when using a gas phase polymerization method, 1.5 MPa or more is preferable, and 1.7 MPa or more is more preferable. Further, the upper limit is preferably 2.5 MPa or less, and more preferably 2.3 MPa or less.

Furthermore, as a molecular weight regulator and for an activity improving effect, hydrogen is supplementarily in a molar ratio with respect to propylene, preferably in the range of 1.0 × 10 ⁻⁶ or more and 1.0 × 10 ⁻² or less. Can be used.
Also, by changing the amount of hydrogen used, in addition to the average molecular weight of the polymer to be produced, the molecular weight distribution, the deviation of the molecular weight distribution toward the high molecular weight side, very high molecular weight components, branching (amount, length, Distribution) can be controlled, whereby the melt physical properties characterizing polypropylene having a long chain branching structure such as MFR, branching index, strain hardening degree, melt tension MT, and spreadability can be controlled.
Therefore, hydrogen should be used at a molar ratio to propylene of 1.0 × 10 ⁻⁶ or more, preferably 1.0 × 10 ⁻⁵ or more, more preferably 1.0 × 10 ⁻⁴ or more. Is good. Moreover, regarding an upper limit, it is good to use at 1.0 * 10 ^<-2> or less, Preferably it is 0.9 * 10 ^<-2> or less, More preferably, it is 0.8 * 10 ^<-2> or less.

  Moreover, you may perform the copolymerization which uses a C2-C20 alpha olefin comonomer except propylene, for example, ethylene and / or 1-butene as a comonomer other than a propylene monomer.

  Therefore, in order to obtain a polypropylene resin (Y) used in the present invention having a good balance between catalytic activity and melt properties, it is preferable to copolymerize ethylene and / or 1-butene. It is preferable to use it at 15 mol% or less with respect to propylene, more preferably 10 mol% or less, still more preferably 7 mol% or less.

  When propylene is polymerized using the catalyst and polymerization method exemplified here, one end of the polymer is mainly propenyl from the active species derived from the catalyst component [A-1] by a special chain transfer reaction generally called β-methyl elimination. The structure is shown and so-called macromers are produced. This macromer can generate a higher molecular weight and is taken into the active species derived from the catalyst component [A-2] having a better copolymerization property, and it is considered that the macromer copolymerization proceeds. Therefore, it is considered that the comb chain is the main branch structure of the polypropylene resin having a long chain branch structure to be generated.

7). Production method of propylene homopolymer (A) and propylene-ethylene copolymer (B) Used to obtain propylene homopolymer (A) and propylene-ethylene copolymer (B) used in the present invention. The catalyst is not particularly limited, and a known catalyst can be used.
For example, a so-called Ziegler-Natta catalyst or metallocene catalyst (for example, described in JP-A-5-295022) in which a titanium compound and organoaluminum are combined can be used.
In the present invention, since a propylene block copolymer having a good balance between rigidity and impact resistance is particularly preferable, a Ziegler-Natta catalyst having high stereoregularity is generally more preferable.

With respect to the process for producing the propylene homopolymer (A) and the propylene-ethylene copolymer (B), any process may be used as long as the above-mentioned properties are satisfied. The process is preferred, and among them, it is more preferred to produce by a process having a horizontal reactor having a stirrer that rotates about a horizontal axis in a form that removes the heat of polymerization using the latent heat of vaporization of liquefied propylene.
Further, the mixing of the propylene homopolymer (A) and the propylene-ethylene copolymer (B) may be produced by any method as long as the above-mentioned characteristics are satisfied. By adopting, the dispersion of the propylene-ethylene copolymer (B) with respect to the propylene homopolymer (A) becomes good, and the transparency is further improved.
These propylene homopolymers (A) and propylene-ethylene copolymers (B) may be used alone or in combination of two or more.

[Nucleating agent]
By containing a nucleating agent in the polypropylene resin composition of the present invention, a molded product with better transparency can be obtained.
As the nucleating agent, an organic phosphate metal salt, an organic monocarboxylic acid metal salt, an organic dicarboxylic acid metal salt, a polymer nucleating agent, dibenzylidene sorbitol or a derivative thereof, a metal salt of diterpenic acid, or the like is used.

  Examples of the organic phosphate metal salt include sodium-2,2′-methylene-bis (4,6-di-t-butylphenyl) phosphate, sodium-2,2′-ethylidene-bis (4,6 -Di-t-butylphenyl) phosphate, lithium-2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate, lithium-2,2'-ethylidene-bis (4,6 -Di-t-butylphenyl) phosphate, sodium-2,2'-ethylidene-bis (4-i-propyl-6-t-butylphenyl) phosphate, lithium-2,2'-methylene-bis (4 -Methyl-6-t-butylphenyl) phosphate, lithium-2,2'-methylene-bis (4-ethyl-6-t-butylphenyl) phosphate, nato Um-2,2′-butylidene-bis (4,6-di-methylphenyl) phosphate, sodium-2,2′-butylidene-bis (4,6-di-t-butylphenyl) phosphate, sodium 2,2′-t-octylmethylene-bis (4,6-di-methylphenyl) phosphate, sodium-2,2′-t-octylmethylene-bis (4,6-di-t-butylphenyl) phosphate Fate, calcium-bis [(2,2′-methylene-bis (4,6-di-t-butylphenyl) phosphate], magnesium-bis [2,2′-methylene-bis (4,6-di-) t-butylphenyl) phosphate], barium-bis [2,2′-methylene-bis (4,6-di-t-butylphenyl) phosphate], sodium-2,2′- Tylene-bis (4-methyl-6-tert-butylphenyl) phosphate, sodium-2,2′-methylene-bis (4-ethyl-6-tert-butylphenyl) phosphate, sodium-2,2′- Ethylidene-bis (4-s-butyl-6-tert-butylphenyl) phosphate, sodium-2,2′-methylene-bis (4,6-di-methylphenyl) phosphate, sodium-2,2′- Methylene-bis (4,6-di-ethylphenyl) phosphate, potassium-2,2′-ethylidene-bis (4,6-di-t-butylphenyl) phosphate, calcium-bis [2,2′- Ethylidene-bis (4,6-di-t-butylphenyl) phosphate], magnesium-bis [2,2′-ethylidene-bis (4,6-di-t-butyl) Ruphenyl) phosphate], barium-bis [2,2′-ethylidene-bis (4,6-di-t-butylphenyl) phosphate], aluminum-tris [2,2′-methylene-bis (4,6 -Di-t-butylfell) phosphate], aluminum-tris [2,2'-ethylidene-bis (4,6-di-t-butylphenyl) phosphate], aluminum hydroxy-bis [2,2'- Methylene-bis (4,6-di-t-butylphenyl) phosphate], aluminum dihydrooxy-2,2′-methylene-bis (4,6-di-t-butylphenyl) phosphate, etc. .

  Examples of the organic monocarboxylic acid metal salt include metal salts such as benzoic acid and allyl-substituted acetic acid. Specifically, benzoic acid, p-isopropylbenzoic acid, o-tertiary butylbenzoic acid, Examples include pt-butylbenzoic acid, monophenylacetic acid, diphenylacetic acid, phenyldimethylacetic acid, adipic acid and their Li, Na, Mg, Ca, Ba, Al salts, and the like. Examples of the organic dicarboxylic acid metal salt include succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, phthalic acid, cyclohexanecarboxylic acid, norbornane dicarboxylic acid and their Li, Na, Mg, Ca, Ba, Al A salt etc. can be mentioned. Examples of the polymer nucleating agent include polyvinylcyclohexane and poly-3-methyl-butene-1.

  Examples of the dibenzylidene sorbitol or derivatives thereof include 1,3,2,4-dibenzylidene sorbitol, 1,3-benzylidene-2,4-p-methylbenzylidene sorbitol, 1,3-benzylidene-2,4- p-ethylbenzylidene sorbitol, 1,3-p-methylbenzylidene-2,4-benzylidene sorbitol, 1,3-p-ethylbenzylidene-2,4-benzylidene sorbitol, 1,3-p-methylbenzylidene-2,4 -P-ethylbenzylidene sorbitol, 1,3-p-ethylbenzylidene-2,4-p-methylbenzylidene sorbitol, 1,3,2,4-di (p-methylbenzylidene) sorbitol, 1,3,2,4 -Di (p-ethylbenzylidene) sorbitol, 1,3,2,4-di (p- -Propylbenzylidene) sorbitol, 1,3,2,4-di (pi-propylbenzylidene) sorbitol, 1,3,2,4-di (pn-butylbenzylidene) sorbitol, 1,3,2, 4-di (ps-butylbenzylidene) sorbitol, 1,3,2,4-di (pt-butylbenzylidene) sorbitol, 1,3,2,4-di (p-methoxybenzylidene) sorbitol, , 3,2,4-di (p-ethoxybenzylidene) sorbitol, 1,3-benzylidene-2,4-p-chlorobenzylidenesorbitol, 1,3-p-chlorobenzylidene-2,4-benzylidenesorbitol, 3-p-chlorobenzylidene-2,4-p-methylbenzylidenesorbitol, 1,3-p-chlorobenzylidene-2,4-p-eth Benzylidene sorbitol, 1,3-p-methylbenzylidene-2,4-p-chlorobenzylidene sorbitol, 1,3-p-ethylbenzylidene-2,4-p-chlorobenzylidene sorbitol, 1,3,2,4-di Examples include (p-chlorobenzylidene) sorbitol, 1,2,3-trideoxy-4,6: 5,7-bis-O-[(4-propylphenyl) methylene] -nonitol. Particularly preferably, 1,3,2,4-dibenzylidene sorbitol, 1,3,2,4-di (p-methylbenzylidene) sorbitol, 1,3-p-chlorobenzylidene-2,4-p-methylbenzylidene Examples include sorbitol, 1,2,3-trideoxy-4,6: 5,7-bis-O-[(4-propylphenyl) methylene] -nonitol.

  The metal salt of the diterpenic acid is a reaction product of the diterpenic acid and a predetermined metal compound such as a magnesium compound or an aluminum compound. Diterpenic acid is a rosin generally known as a natural resin obtained from Pinaceae plants, specifically, natural rosins such as gum rosin, tall oil rosin, wood rosin; disproportionated rosin, hydrogenated rosin, dehydrogenated Various rosins such as rosin, polymerized rosin, α, β-ethylenically unsaturated carboxylic acid-modified rosin; and purified products of the natural rosin and modified rosin are used as raw materials. Examples of diterpenic acids include pimaric acid, sandaracopimalic acid, parastrinic acid, isopimaric acid, abietic acid, dehydroabietic acid, neoabietic acid, dihydropimaric acid, dihydroabietic acid, tetrahydroabietic acid, and the like.

Of these, preferred nucleating agents are organic phosphate metal salts and organic dicarboxylic acid metal salts, and more preferably sodium-2,2′-methylene-bis (4,6-di-t-butylphenyl). Phosphate, sodium-2,2′-ethylidene-bis (4,6-di-t-butylphenyl) phosphate, aluminum-tris [2,2′-methylene-bis (4,6-di-t-butylfellate) ) Phosphate], aluminum hydroxy-bis [2,2′-methylene-bis (4,6-di-t-butylphenyl) phosphate], aluminum dihydroxy-2,2′-methylene-bis (4 6-di-t-butylphenyl) phosphate metal salt having a substituted substituted aromatic group such as phosphate, or 2-cyclohexanedicarboxylic acid Thorium, 1,2 norbornane carboxylate, alicyclic hydrocarbon dicarboxylic acid metal salts such as 1,2-norbornane magnesium carboxylic acid. Examples of the metal salt include lithium, sodium, potassium, calcium, magnesium, aluminum salts and the like, and more preferred are Group 1 metals such as lithium, sodium and potassium.
Content of a nucleating agent is 0.01-0.7 weight part with respect to 100 weight part of polypropylene resin compositions for injection molding, Preferably it is 0.1-0.5 weight part. When the content of the nucleating agent is 0.01 parts by weight or more, the effect of improving the transparency is sufficient. Is advantageous.
In addition, you may use these nucleating agents in combination of 2 or more types.

[Other additives]
The polypropylene resin composition of the present invention is in a category that does not impair the performance, and various additives such as heat stabilizers, antioxidants, weathering stabilizers, ultraviolet absorbers, copper damage inhibitors, antistatic agents. , Flame retardant, hydrophilizing agent, slip agent, anti-blocking agent, anti-fogging agent, coloring agent, filler, polyethylene, elastomer, petroleum resin, antibacterial agent and the like.
Moreover, when MFR adjustment is required, an organic peroxide can also be mix | blended.

8). Method for Producing Polypropylene Resin Composition of the Present Invention The polypropylene resin composition of the present invention comprises the above-mentioned propylene-ethylene block copolymer component (a), ethylene polymer (C), polypropylene resin (Y), Mixing predetermined amounts of various compounding ingredients such as nucleating agents and other additives using ordinary mixing equipment such as Henschel mixer (trade name), super mixer, ribbon blender, tumbler mixer, Banbury mixer, etc. Can be obtained by: The obtained mixture is pelletized at a melt-kneading temperature of 150 to 300 ° C., preferably 180 to 250 ° C., using a single or twin screw extruder or a roll to obtain a pellet-shaped composition. You can also.

  The polypropylene resin composition of the present invention preferably has a HAZE with a molded body thickness of 1 mmt in accordance with JIS K7136 (ISO14782) of 30% or less. Within this range, sufficient visibility of the contents can be obtained.

Furthermore, the polypropylene resin composition of the present invention preferably has a Charpy impact strength at 0 ° C. of 2.5 kJ / m ² or more in accordance with JIS K7111. Within this range, it becomes difficult to break during transportation in a refrigerated environment.

  Furthermore, the polypropylene resin composition of the present invention preferably has a flexural modulus of 950 MPa or more in accordance with JIS K7171. Within this range, the molded product is pressed and hardly deformed during transportation of the molded product, and a mold release failure during injection molding is less likely to occur.

[Injection molded products]
By subjecting the polypropylene resin composition of the present invention to a normal injection molding method, injection compression molding method, injection foam molding method, injection stretch blow molding method and the like, an injection molded product (injection molded product) can be obtained.
Specific examples of the injection-molded product include food containers (pudding containers, jelly containers, yogurt containers, other dessert containers, side dish containers, tea-boiled containers, instant noodles such as instant noodles, and other instant food containers. , Cooked rice containers, retort containers, lunch containers, etc.), beverage containers (beverage bottles, chilled coffee containers, one-hand cup containers, other beverage containers, etc.), caps (plastic bottle caps, 1 piece caps, 2 piece caps, instant coffee Caps, seasoning caps, cosmetic container caps, etc.) and other various containers (ink containers, cosmetic containers, shampoo containers, detergent containers, etc.), daily necessities (costume cases, buckets, washbasins, writing utensils, containers, toys, cooking utensils, Other cases).

It is preferable that the thickness of such an injection-molded product is 1.0 mmt or less because high transparency is easily obtained and the product weight is reduced, thereby reducing the product cost. on the other hand,
A thickness of 0.3 mmt or more is preferable because sufficient product rigidity is easily obtained.
In addition, in the injection molded body having a thickness of 0.3 to 1.0 mmt, a material that can shorten the molding cycle is very suitable, and by using the polypropylene resin composition for injection molding used in the present invention, An injection-molded body with high productivity can be obtained.

  In order to efficiently produce injection-molded bodies, a multi-cavity mold that molds multiple products at the same time is used, but if the materials used do not satisfy sufficient rigidity, crystallinity and fluidity, high productivity will be achieved. I can't get it. By using the polypropylene resin composition used in the present invention, an injection molded product with high productivity can be obtained.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited at all by these examples. The physical property measurement methods and materials used are as follows.

1. Physical property evaluation method (1) MFR
The melt flow rate (MFR) of the polypropylene resin composition, the propylene homopolymer (A), and the propylene-ethylene block copolymer component (a) of the present invention is JIS K-7210-1999 (230 ° C., 2. 16 kg load). The melt flow rate (MFR) of the ethylene polymer (C) is measured in accordance with JIS K-6922-2 (190 ° C., 2.16 kg load).
(2) Flexural modulus After molding, a test piece is molded, and after molding, left in a temperature-controlled room adjusted to room temperature 23 ° C. and relative humidity 50% for 5 days or more, and obtained in accordance with JIS K7171 (ISO178). It was.
(3) Charpy impact strength Test specimens were molded by injection molding, and after molding, left in a temperature-controlled room adjusted to room temperature 23 ° C and relative humidity 50% for 5 days or longer, and then at 0 ° C for 30 minutes or longer. The state was adjusted and obtained according to JIS K7111 (ISO179).
(4) Transparency (Haze, haze)
A flat plate having a thickness of 0.5 mmt, 1.0 mmt, and 2.0 mmt was formed by an injection molding method. After molding, the plate was left for 24 hours in a temperature-controlled room adjusted to a room temperature of 23 ° C. and a relative humidity of 50%, and then JIS K7136 (ISO14782). ).
(5) Molding cycle Using a Sumitomo Heavy Industries injection molding machine SG125M-H, a dessert cup mold having a side wall thickness of 0.7 mm and an internal volume of 180 ml is set to a cylinder temperature of 200 ° C, a manifold temperature of 200 ° C, and a mold temperature of 20 ° C. The shortest cooling time that the product did not remain in the fixed mold for 20 shots was evaluated. With respect to this cooling time, 15 seconds or more were evaluated as x if the range was 11 to 15 seconds, Δ if the range was 5 to 10 seconds, and ◎ if it was less than 5 seconds.

[Materials used]
(1) Propylene-ethylene block copolymer component (A)
As propylene-ethylene block copolymers (PP-1 to 6) obtained in the following Production Examples 1 to 5 and (PP-7), Novatec PP BC03GS (trade name, manufactured by Nippon Polypro Co., Ltd.) is used. It was.

<Production Example 1 (PP-1)>
(I) Production of solid catalyst component (A) (1) Preparation of solid component A 10 L autoclave equipped with a stirrer was sufficiently substituted with nitrogen, and 2 L of purified toluene was introduced. 200 g of Mg (OEt) ₂ and 1 L of TiCl ₄ were added thereto at room temperature. The temperature was raised to 90 ° C. and 50 ml of di-n-butyl phthalate was added. Thereafter, the temperature was raised to 110 ° C., and 3Hr reaction was performed. The reaction product was thoroughly washed with purified toluene, and then purified toluene was added to make the total liquid volume 2L. 1 L of TiCl ₄ was added at room temperature, the temperature was raised to 110 ° C., and a 2Hr reaction was performed. After thoroughly washing the reaction product with purified toluene, toluene was replaced with n-heptane using purified n-heptane to obtain a slurry of solid component A1. When a part of this slurry was sampled, dried and analyzed, the Ti content of the solid component A1 was 2.7 wt%.
Next, a 20 L autoclave equipped with a stirrer was sufficiently replaced with nitrogen, and 100 g of the solid component A1 slurry was prepared as the solid component A1. Purified n-heptane was introduced into this to adjust the concentration of the solid component A1 to 25 g / L, 50 ml of SiCl ₄ was added, and a 1 Hr reaction was performed at 90 ° C.
The reaction product was thoroughly washed with purified n-heptane, and purified n-heptane was added to adjust the liquid volume to 4 L. To this, 30 ml of dimethyldivinylsilane, 30 ml of (i-Pr) ₂ Si (OMe) ₂ and 80 g of Et ₃ Al in an n-heptane diluted solution were added as Et ₃ Al, and a 2 Hr reaction was performed at 40 ° C. The reaction product was thoroughly washed with purified n-heptane, and a part of the obtained slurry was sampled, dried and analyzed. As a result, the Ti content of the solid component A1 was 1.2 wt%, (i-Pr) ₂ 8.8 wt% of Si (OMe) ₂ was contained.
(2) Prepolymerization Using the solid component A1 obtained above, prepolymerization was performed according to the following procedure. Purified n-heptane was introduced into the slurry, and the solid component concentration was adjusted to 20 g / L. Then, after cooling the slurry to 10 ° C., and 10g added n- heptane dilution of _Et 3 Al as _Et 3 Al, a propylene 280g were fed 4Hr seat. After the supply of propylene, the reaction was further performed for 30 min, and then the gas phase portion was sufficiently substituted with nitrogen, and the reaction product was sufficiently washed with purified n-heptane. The obtained slurry was extracted from the autoclave, and the solid catalyst component A was obtained by vacuum drying. This solid catalyst component A contained 2.5 g of polypropylene per 1 g of the solid component. Further, the portion of the solid catalyst component A excluding polypropylene contained 1.0 wt% Ti and 8.2 wt% (i-Pr) ₂ Si (OMe) ₂ .

(Ii) Production of propylene-ethylene block copolymer (PP-1) powder A continuous gas phase polymerization reactor comprising two horizontal polymerization tanks equipped with a stirrer was used. In the first reactor (inner volume 40 m ³ ), 130 g / Hr of the solid catalyst component A obtained above as a solid component, and 15 wt% hexane solution of triethylaluminum with respect to 1 mol of Ti atom in the solid catalyst component A, It was continuously fed so that the molar ratio was 350. In addition, hydrogen was added so that the ratio of hydrogen concentration in the polymerization vessel to propylene concentration was 0.051, and propylene monomer was added in the polymerization vessel so that the pressure in the polymerization vessel was 2.25 MPa and the temperature was kept at 65 ° C. The first polymerization reaction was carried out.
The heat of reaction was removed by the heat of vaporization of the raw material liquefied propylene.
The propylene homopolymer produced in the polymerization vessel was continuously withdrawn so that the retained level of the polymer was 50% by volume of the reaction volume, and supplied to the polymerization vessel in the second polymerization step.
In the second reactor (internal volume 40 m ³ ), the hydrogen from the first polymerization step and the ratio of the hydrogen concentration in the polymerization vessel to the propylene concentration is 0.020, and the propylene concentration in the ethylene concentration. The second polymerization reaction was carried out by supplying ethylene to the polymerizer so that the ratio to the ratio was 0.153, and propylene monomer to keep the pressure in the polymerizer at 2.2 MPa and the temperature at 60 ° C.
The polymerization amount of the propylene-ethylene copolymer was adjusted by supplying a polymerization activity inhibitor. The reaction heat was removed by the heat of vaporization of the raw material liquefied propylene.
The propylene-ethylene block copolymer produced in the second polymerization step was continuously extracted from the polymerization vessel so that the retained level of the polymer was 50% by volume of the reaction volume.
When the obtained propylene-ethylene block copolymer (PP-1) was analyzed, MFR was 29 g / 10min and ethylene content was 6.0 wt%.

(Iii) Production of Propylene-Ethylene Block Copolymer (PP-1) Pellets As a propylene-ethylene block copolymer, nucleating agent with respect to 100 parts by weight of (PP-1) powder obtained in Production Example 1. (A) 0.2 parts by weight, 0.05 part by weight of calcium stearate as a neutralizing agent, pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) as a phenolic antioxidant ) Propionate] (BASF; abbreviated as RA1010) 0.05 parts by weight, phosphorous antioxidant tris (2,4-di-t-butylphenyl) phosphate (BASF; abbreviated as RA168) .) 0.05 part by weight, 0.08 part by weight of oleic acid amide as a slip agent was added, and after nitrogen sealing with a super mixer, the mixture was mixed for 3 minutes.
Thereafter, the powder was granulated at a cylinder temperature of 200 ° C., a screw rotation speed of 150 rpm, and an extrusion rate of 15 kg / h using a twin-screw extruder TEM35 manufactured by Toshiba Machine Co., Ltd., and a propylene-ethylene block copolymer. A pellet of (PP-1) was obtained.
Table 1 shows the compositions of the propylene-based homopolymer (A) and the propylene-ethylene copolymer (B) in the propylene-ethylene block copolymer (PP-1) obtained in Production Example 1.

[Nucleating agent (a)]
Nucleating agent (a): Trade name, ADEKA STAB NA-21 manufactured by ADEKA Corporation, organophosphate metal salt nucleating agent

<Production Example 2 (PP-2)>
Propylene homopolymer (HPP-1): Novatec PP SA06GA (trade name, manufactured by Nippon Polypro Co., Ltd.) and catalyst with respect to 85 wt% of the propylene-ethylene block copolymer (PP-1) pellets obtained in Production Example 1. : Ziegler catalyst, MFR: 60 g / 10 min was added at 15 wt%, and blending and granulation were carried out in the same manner as in Production Example 1 to obtain propylene-ethylene block copolymer (PP-2) pellets. Each composition is shown in Table 2.

<Production Example 3 (PP-3)>
Propylene homopolymer (HPP-1) is added in an amount of 25 wt% to 75 wt% of the propylene-ethylene block copolymer (PP-1), blending and granulating are performed in the same manner as in Production Example 1, and propylene- Ethylene block copolymer (PP-3) pellets were obtained. Each composition is shown in Table 2.

<Production Example 4 (PP-4)>
Propylene homopolymer (HPP-1) is added in an amount of 40 wt% to 60 wt% of the propylene-ethylene block copolymer (PP-1), blending and granulating are performed in the same manner as in Production Example 1, and propylene- Ethylene block copolymer (PP-4) pellets were obtained. Each composition is shown in Table 2.

<Production Example 5 (PP-5)>
60 wt% of propylene homopolymer (HPP-1) is added to 40 wt% of propylene-ethylene block copolymer (PP-1), blending and granulation are performed in the same manner as in Production Example 2, and propylene- Ethylene block copolymer (PP-5) pellets were obtained. Each composition is shown in Table 2.

<Production Example 6 (PP-6)>
Propylene-ethylene-based elastomer (PE-1): Vistamaxx 6102 (trade name, manufactured by Exxonobibil), catalyst: metallocene catalyst, MFR (230 ° C.): 3 g / 10 min, ethylene content with respect to 80 wt% of propylene homopolymer (HPP) Amount: 20 wt% of 16 wt% was added, and blending and granulation were performed in the same manner as in Production Example 2 to obtain propylene-ethylene block copolymer (PP-6) pellets. Each composition is shown in Table 2.

<PP-7>
PP-7: Novatec PP BC03GS (trade name, manufactured by Nippon Polypro Co., Ltd.), catalyst: Ziegler catalyst, propylene-ethylene copolymer content: 17 wt%, ethylene content in propylene-ethylene copolymer: 38 wt%, propylene- Intrinsic viscosity [η] of the ethylene copolymer (B): 3.8 dl / g, MFR: 30 g / 10 min.
Each composition is shown in Table 2.

Ethylene polymer (C)
(C-1) LDPE: Novatec LD LJ802 (trade name, manufactured by Nippon Polyethylene Co., Ltd.), MFR (190 ° C.): 22 g / 10 min, density: 0.918 g / cm ³ , melting point: 106 ° C.
(C-2) LDPE: Novatec LD LJ902 (trade name, manufactured by Nippon Polyethylene Co., Ltd.), MFR (190 ° C.): 45 g / 10 min, density: 0.915 g / cm ³ , melting point: 102 ° C.
(C-3) LLDPE: Novatec LL UJ580 (trade name, manufactured by Nippon Polyethylene Co., Ltd.), MFR (190 ° C.): 20 g / 10 min, density: 0.925 g / cm ³ , melting point: 123 ° C.
(C-4) LLDPE: Novatec LL UJ370 (trade name, manufactured by Nippon Polyethylene Co., Ltd.), MFR (190 ° C.): 16 g / 10 min, density: 0.921 g / cm ³ , melting point: 121 ° C.
(C-5) Ethylene-based plastomer: Kernel KS571 (trade name, manufactured by Nippon Polyethylene Co., Ltd.), MFR (190 ° C.): 24 g / 10 min, density: 0.907 g / cm ³ , melting point: 100 ° C.
(C-6) Ethylene-based plastomer: Kernel KS560T (trade name, manufactured by Nippon Polyethylene Co., Ltd.), MFR (190 ° C.): 16.5 g / 10 min, density: 0.898 g / cm ³ , melting point: 90 ° C.

Polypropylene resin (Y)
As a polypropylene resin (Y), the polypropylene resin (Y-1) manufactured by the following manufacture example 7 was used.

[Production Example 7 (Production of Y-1)]
<Synthesis example 1 of catalyst component (B)>
Synthesis of dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-i-propylphenyl) indenyl}] hafnium (component [B-1] (complex 1) Synthesis):
(I) Synthesis of 4- (4-i-propylphenyl) indene To a 500 ml glass reaction vessel, 15 g (91 mmol) of 4-i-propylphenylboronic acid and 200 ml of dimethoxyethane (DME) were added, and 90 g of cesium carbonate ( 0.28 mol) and 100 ml of water were added, 13 g (67 mmol) of 4-bromoindene and 5 g (4 mmol) of tetrakistriphenylphosphinopalladium were added in this order, and the mixture was heated at 80 ° C. for 6 hours.
After allowing to cool, the reaction solution was poured into 500 ml of distilled water, transferred to a separatory funnel, and extracted with diisopropyl ether. The ether layer was washed with saturated brine and dried over sodium sulfate. Sodium sulfate was filtered, the solvent was distilled off under reduced pressure, and the residue was purified by a silica gel column to obtain 15.4 g (yield 99%) of 4- (4-i-propylphenyl) indene as a colorless liquid.

(Ii) Synthesis of 2-bromo-4- (4-i-propylphenyl) indene In a 500 ml glass reaction vessel, 15.4 g (67 mmol) of 4- (4-i-propylphenyl) indene and distilled water were added. 7.2 ml and 200 ml of DMSO were added, and 17 g (93 mmol) of N-bromosuccinimide was gradually added thereto. The mixture was stirred at room temperature for 2 hours, poured into 500 ml of ice water, and extracted three times with 100 ml of toluene. The toluene layer was washed with saturated brine, 2 g (11 mmol) of p-toluenesulfonic acid was added, and the mixture was heated to reflux for 3 hours while removing moisture. The reaction mixture was allowed to cool, washed with saturated brine, and dried over sodium sulfate. Sodium sulfate was filtered, the solvent was distilled off under reduced pressure, and the residue was purified with a silica gel column to obtain 19.8 g (yield 96%) of 2-bromo-4- (4-i-propylphenyl) indene as a yellow liquid. .

(Iii) Synthesis of 2- (2-methyl-5-furyl) -4- (4-i-propylphenyl) indene In a 500 ml glass reaction vessel, 6.7 g (82 ml mol) of 2-methylfuran and DME were added. 100 ml was added and cooled to -70 ° C. in a dry ice-methanol bath. To this, 51 ml (81 mmol) of a 1.59 mol / L n-butyllithium-n-hexane solution was added dropwise and stirred as it was for 3 hours. The solution was cooled to −70 ° C., and a solution of 20 ml (87 mmol) of triisopropyl borate and 50 ml of DME was added dropwise thereto. After dropping, the mixture was stirred overnight while gradually returning to room temperature.
After the reaction solution was hydrolyzed by adding 50 ml of distilled water, a solution of 223 g of potassium carbonate and 100 ml of water, and 19.8 gg (63 mmol) of 2-bromo-4- (4-i-propylphenyl) indene were added in order. The mixture was heated at 0 ° C. and reacted for 3 hours while removing low-boiling components.
After allowing to cool, the reaction solution was poured into 300 ml of distilled water, transferred to a separatory funnel and extracted three times with diisopropyl ether. The ether layer was washed with saturated brine and dried over sodium sulfate. Sodium sulfate was filtered off, the solvent was distilled off under reduced pressure, and the residue was purified with a silica gel column to give 19.6 g of 2- (2-methyl-5-furyl) -4- (4-i-propylphenyl) indene colorless liquid Yield 99%).

(Iv) Synthesis of dimethylbis (2- (2-methyl-5-furyl) -4- (4-i-propylphenyl) indenyl) silane In a 500 ml glass reaction vessel, 2- (2-methyl-5- Furyl) -4- (4-i-propylphenyl) indene (9.1 g, 29 mmol) and THF (200 ml) were added, and the mixture was cooled to -70 ° C in a dry ice-methanol bath. To this, 17 ml (28 mmol) of a 1.66 mol / L n-butyllithium-hexane solution was dropped, and the mixture was stirred as it was for 3 hours. The mixture was cooled to −70 ° C., 0.1 ml (2 mmol) of 1-methylimidazole and 1.8 g (14 mmol) of dimethyldichlorosilane were sequentially added, and the mixture was stirred overnight while gradually returning to room temperature.
Distilled water was added to the reaction solution, transferred to a separatory funnel and washed with brine until neutral, and sodium sulfate was added to dry the reaction solution. Sodium sulfate was filtered, the solvent was distilled off under reduced pressure, and the residue was purified with a silica gel column, and dimethylbis (2- (2-methyl-5-furyl) -4- (4-i-propylphenyl) indenyl) silane pale 8.6 g (88% yield) of a yellow solid was obtained.

(V) Synthesis of dimethylsilylenebis (2- (2-methyl-5-furyl) -4- (4-i-propylphenyl) indenyl) hafnium dichloride Into a 500 ml glass reaction vessel, dimethylbis (2- (2 -Methyl-5-furyl) -4- (4-i-propylphenyl) indenyl) silane (8.6 g, 13 mmol) and diethyl ether (300 ml) were added, and the mixture was cooled to -70 ° C in a dry ice-methanol bath.
Thereto was added dropwise 15 ml (25 mmol) of a 1.66 mol / L n-butyllithium-n-hexane solution, and the mixture was stirred for 3 hours. The solvent of the reaction solution was distilled off under reduced pressure, 400 ml of toluene and 40 ml of diethyl ether were added, and the solution was cooled to −70 ° C. in a dry ice-methanol bath. Thereto was added 4.0 g (13 mmol) of hafnium tetrachloride. Thereafter, the mixture was stirred overnight while gradually returning to room temperature.
The solvent was distilled off under reduced pressure and recrystallized from dichloromethane-hexane to obtain a racemic dimethylsilylenebis (2- (2-methyl-5-furyl) -4- (4-i-propylphenyl) indenyl) hafnium dichloride. As a yellow crystal, 7.6 g (yield 65%) was obtained.

The identified value by ^{1 H-NMR} of the obtained racemates are described below.
¹ H-NMR (C ₆ D ₆ ) identification result Racemate: δ 0.95 (s, 6H), δ 1.10 (d, 12H), δ 2.08 (s, 6H), δ 2.67 (m, 2H) , Δ 5.80 (d, 2H), δ 6.37 (d, 2H), δ 6.74 (dd, 2H), δ 7.07 (d, 2H), δ 7.13 (d, 4H), δ 7.28 ( s, 2H), δ 7.30 (d, 2H), δ 7.83 (d, 4H).

<Synthesis example 2 of catalyst component (B)>
Synthesis of rac-dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4-hydroazurenyl}] hafnium (synthesis of component [B-1] (complex 2)):
The synthesis of rac-dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4-hydroazurenyl}] hafnium is carried out according to the method described in Example 1 of JP-A-11-240909. It carried out like.

<Catalyst synthesis example 1>
(I) Chemical treatment of ion-exchanged layered silicate In a separable flask, 96% sulfuric acid (668 g) was added to 2,264 g of distilled water, and then montmorillonite (trade name, manufactured by Mizusawa Chemical Co., Ltd., Benclay) was used as the layered silicate. SL: average particle size 19 μm) 400 g was added. The slurry was heated at 90 ° C. for 210 minutes. When 4,000 g of distilled water was added to the reaction slurry and filtered, 810 g of a cake-like solid was obtained.
Next, 432 g of lithium sulfate and 1,924 g of distilled water were added to the separable flask to make a lithium sulfate aqueous solution, and the entire amount of the cake-like solid was charged. The slurry was reacted at room temperature for 120 minutes. 4 L of distilled water was added to this slurry, followed by filtration, and further washing with distilled water to pH 5-6, followed by filtration to obtain 760 g of a cake-like solid.
The obtained solid was preliminarily dried overnight at 100 ° C. under a nitrogen stream, and then coarse particles having a diameter of 53 μm or more were removed, followed by drying under reduced pressure at 200 ° C. for 2 hours to obtain 220 g of chemically treated smectite.
The composition of this chemically treated smectite is Al: 6.45 wt%, Si: 38.30 wt%, Mg: 0.98 wt%, Fe: 1.88 wt%, Li: 0.16 wt%, Al / Si = 0.175 [mol / mol].

(Ii) Catalyst preparation and prepolymerization In a three-necked flask (volume: 1 L), 20 g of the chemically treated smectite obtained above was placed, and heptane (132 mL) was added to form a slurry, which was triisobutylaluminum (25 mmol: concentration) 143 mg / mL heptane solution (68.0 mL) was added, and the mixture was stirred for 1 hour, washed with heptane until the residual liquid ratio became 1/100, and heptane was added so that the total volume became 100 mL.
In another flask (volume: 200 mL), rac-dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl)-] prepared in Synthesis Example 1 of the catalyst component (B) was used. 4- (4-i-propylphenyl) indenyl}] hafnium (210 μmol) is dissolved in toluene (42 mL) (solution 1), and the catalyst component (B) is synthesized in another flask (volume 200 mL). Rac-dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4-hydroazurenyl}] hafnium (90 μmol) prepared in Example 2 was dissolved in toluene (18 mL) (solution 2 ).
Triisobutylaluminum (0.84 mmol: 1.2 mL of a heptane solution with a concentration of 143 mg / mL) was added to a 1 L flask containing the chemically treated smectite, and then the above solution 1 was added and stirred at room temperature for 20 minutes. Thereafter, triisobutylaluminum (0.36 mmol: 0.50 mL of a heptane solution having a concentration of 143 mg / mL) was added, and then the above solution 2 was added and stirred at room temperature for 1 hour.
Thereafter, 338 mL of heptane was added, and this slurry was introduced into a 1 L autoclave.
After the internal temperature of the autoclave was set to 40 ° C., propylene was fed at a rate of 10 g / hour, and prepolymerization was performed while maintaining the temperature at 40 ° C. for 4 hours. Thereafter, propylene feed was stopped and residual polymerization was carried out for 1 hour. After removing the supernatant of the resulting catalyst slurry by decantation, triisobutylaluminum (6 mmol: 17.0 mL of a heptane solution having a concentration of 143 mg / mL) was added to the remaining portion and stirred for 5 minutes.
This solid was dried under reduced pressure for 1 hour to obtain 52.8 g of a dry prepolymerized catalyst. The prepolymerization ratio (value obtained by dividing the amount of prepolymerized polymer by the amount of solid catalyst) was 1.64.
Hereinafter, this is referred to as “preliminary polymerization catalyst 1”.

<Polymerization>
After sufficiently replacing the inside of the stirring autoclave having an internal volume of 200 liters with propylene, 40 kg of sufficiently dehydrated liquefied propylene was introduced. To this was added 4.4 liters of hydrogen (as a standard volume) and 470 ml (0.12 mol) of a triisobutylaluminum / n-heptane solution, and the internal temperature was raised to 70 ° C. Next, 2.4 g of the prepolymerized catalyst 1 (by weight excluding the prepolymerized polymer) was injected with argon to initiate polymerization, and the internal temperature was maintained at 70 ° C. After 2 hours, 100 ml of ethanol was injected, purged of unreacted propylene, and the inside of the autoclave was purged with nitrogen to terminate the polymerization.
The obtained polymer was dried at 90 ° C. under a nitrogen stream for 1 hour to obtain 16.5 kg of a polymer (Y-1). The catalytic activity was 6880 (g-PP / g-cat).

[Production of Pellet (Y-1) of Polypropylene Resin (Y-1)]
Tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-], which is a phenolic antioxidant, with respect to 100 parts by weight of the polypropylene resin (Y-1) produced in Production Example 7. Hydroxyphenyl) propionate] methane (trade name “IRGANOX1010”, manufactured by BASF Japan Ltd.) 0.125 parts by weight, tris (2,4-di-t-butylphenyl) phosphite which is a phosphite antioxidant (Product name “IRGAFOS 168”, manufactured by BASF Japan Ltd.) 0.125 parts by weight was mixed and mixed at room temperature for 3 minutes using a high-speed agitating mixer (Henschel mixer, product name), and then twin screw extrusion The mixture was melt-kneaded with a machine to obtain polypropylene resin (Y-1) pellets (Y-1).
For the twin screw extruder, KZW-25 manufactured by Technobel was used, the screw rotation speed was 400 RPM, and the kneading temperature was 80, 160, 210, 230 from the bottom of the hopper (hereinafter, the same temperature up to the die outlet). did.
This pellet (Y-1) was evaluated for MFR, CXS, mm, Mw / Mn, Mz / Mw, branching index g ′, MT, and λmax. In addition, the measuring method and calculating method of these physical properties are as described above.
The evaluation results are shown in Table 3.

[Example 1]
(1) Production of polypropylene resin composition As propylene-ethylene block copolymer component (a), (PP-1) is 85 wt%, ethylene polymer (C) is (C-1) 15 wt% As a polypropylene resin (Y), 2 parts by weight of (Y-1) was nitrogen-sealed with a super mixer and mixed for 3 minutes.
Thereafter, granulation was performed at a cylinder temperature of 200 ° C., a screw rotation speed of 150 rpm, and an extrusion rate of 15 kg / h while using a twin-screw extruder TEM35 manufactured by Toshiba Machine Co., Ltd., to obtain a polypropylene resin composition.

(2) Manufacture of injection molded product (injection molded body) Using the polypropylene resin composition pellets obtained above, the pellets are supplied to Toshiba injection molding machine EC100, injection primary pressure 50 MPa, molding temperature 200 ° C, gold A test piece and a test flat plate were molded at a mold cooling water temperature of 40 ° C. and a molding cycle of 15 seconds.
About the obtained test piece and the flat plate for a test, the physical-property evaluation of said item (a bending elastic modulus, Charpy impact strength, Haze, a molding cycle) was performed. The results are shown in Table 4.

[Example 2]
A polypropylene resin composition and an injection molded product were obtained in the same manner as in Example 1 except that 5 parts by weight of the polypropylene resin (Y-1) was used. The results are shown in Table 4.

[Example 3]
A polypropylene resin composition and an injection-molded product were obtained in the same manner as in Example 1 except that 10 parts by weight of the polypropylene resin (Y-1) was used. The results are shown in Table 4.

[Comparative Example 1]
A polypropylene resin composition and an injection-molded product were obtained in the same manner as in Example 1 except that the polypropylene resin (Y-1) was not used. The results are shown in Table 4.

[Comparative Example 2]
A polypropylene resin composition and an injection molded product were obtained in the same manner as in Example 1 except that 15 parts by weight of the polypropylene resin (Y-1) was used. The results are shown in Table 4.

[Comparative Example 3]
A polypropylene resin composition and an injection-molded product were obtained in the same manner as in Example 1 except that 20 parts by weight of polypropylene resin (Y-1) was used. The results are shown in Table 4.

As is clear from Table 4, Examples 1 to 3, which are the polypropylene resin compositions of the present invention, have good transparency, rigidity, impact resistance and moldability.
On the other hand, Comparative Example 1 that does not satisfy the constituent requirements of the polypropylene resin of the present invention is not good in transparency, and Comparative Examples 2 and 3 are not good in impact resistance.

[Example 4]
A polypropylene resin composition and an injection-molded product were obtained in the same manner as in Example 2 except that (C-2) was used as the ethylene polymer (C). The results are shown in Table 5.

[Example 5]
A polypropylene resin composition and an injection-molded product were obtained in the same manner as in Example 2 except that (C-5) was used as the ethylene polymer (C). The results are shown in Table 5.

[Comparative Example 4]
A polypropylene resin composition and an injection-molded product were obtained in the same manner as in Example 2 except that (C-3) was used as the ethylene polymer (C). The results are shown in Table 5.

[Comparative Example 5]
A polypropylene resin composition and an injection-molded product were obtained in the same manner as in Example 2 except that (C-4) was used as the ethylene polymer (C). The results are shown in Table 5.

[Comparative Example 6]
A polypropylene resin composition and an injection-molded product were obtained in the same manner as in Example 2 except that (C-6) was used as the ethylene polymer (C). The results are shown in Table 5.

Clearly from Table 5, Examples 4-5 which are the polypropylene-type resin compositions of this invention show that transparency, rigidity, impact resistance, and a moldability are favorable.
On the other hand, Comparative Example 5 that does not satisfy the constituent requirements of the polypropylene resin of the present invention does not have good transparency, and Comparative Example 6 does not have good moldability.

[Example 6]
A polypropylene resin composition and an injection-molded product were obtained in the same manner as in Example 2 except that 17 wt% of (C-1) was used as the ethylene polymer (C). The results are shown in Table 6.

[Example 7]
A polypropylene resin composition and an injection molded product were obtained in the same manner as in Example 2 except that 12 wt% of (C-1) was used as the ethylene polymer (C). The results are shown in Table 6.

[Comparative Example 7]
A polypropylene resin composition and an injection molded product were obtained in the same manner as in Example 2 except that 20 wt% of (C-1) was used as the ethylene polymer (C). The results are shown in Table 6.

[Comparative Example 8]
A polypropylene resin composition and an injection molded product were obtained in the same manner as in Example 2 except that 10 wt% of (C-1) was used as the ethylene polymer (C). The results are shown in Table 6.

[Comparative Example 9]
A polypropylene resin composition and an injection molded product were obtained in the same manner as in Example 2 except that 8 wt% of (C-1) was used as the ethylene polymer (C). The results are shown in Table 6.

From Table 6, it can be seen that Examples 6 to 7 which are the polypropylene resin compositions of the present invention have good transparency, rigidity, impact resistance and moldability.
On the other hand, Comparative Example 7 that does not satisfy the constituent requirements of the polypropylene resin of the present invention does not have good moldability, and Comparative Examples 8 and 9 do not have good transparency.

[Example 8]
A polypropylene resin composition and an injection molded product were obtained in the same manner as in Example 2 except that PP-2 was used as the propylene-ethylene block copolymer component (a). The results are shown in Table 7.

[Example 9]
A polypropylene resin composition and an injection molded product were obtained in the same manner as in Example 2 except that PP-3 was used as the propylene-ethylene block copolymer component (a). The results are shown in Table 7.

[Comparative Example 10]
A polypropylene resin composition and an injection molded product were obtained in the same manner as in Example 2 except that PP-4 was used as the propylene-ethylene block copolymer component (a). The results are shown in Table 7.

[Comparative Example 11]
A polypropylene resin composition and an injection-molded product were obtained in the same manner as in Example 2 except that PP-5 was used as the propylene-ethylene block copolymer component (a). The results are shown in Table 7.

[Comparative Example 12]
A polypropylene resin composition and an injection-molded product were obtained in the same manner as in Example 2, except that PP-6 was used as the propylene-ethylene block copolymer component (a). The results are shown in Table 7.

[Comparative Example 13]
A polypropylene resin composition and an injection-molded product were obtained in the same manner as in Example 2 except that PP-7 was used as the propylene-ethylene block copolymer component (a). The results are shown in Table 7.

From Table 7, it can be seen that Examples 8 to 9, which are polypropylene resin compositions of the present invention, have good transparency, rigidity, impact resistance and moldability.
On the other hand, Comparative Examples 10, 11, and 12 that do not satisfy the constituent requirements of the polypropylene resin of the present invention do not have good impact resistance, and Comparative Examples 12 and 13 do not have good transparency. Furthermore, the moldability of Comparative Example 12 is not good.

  The polypropylene resin composition of the present invention has good rigidity, impact resistance, transparency and moldability, and can be suitably used for food containers, beverage containers, caps, daily necessities, etc. The nature is extremely high.

Claims (7)

A polypropylene resin composition comprising 100 parts by weight of a polypropylene resin composition (X) and 1 to 10 parts by weight of a polypropylene resin (Y),
The polypropylene resin composition (X) is
75-85 wt% of a propylene-based homopolymer (A) having a melt flow rate (MFR) of 3.5 to 300 g / 10 min based on JIS K7210 (230 ° C., 2.16 kg load), and the following (B1) To 15 to 25 wt% of propylene-ethylene copolymer (B) satisfying (B2) (provided that the total of propylene-based homopolymer (A) and propylene-ethylene copolymer (B) is 100 wt%) Propylene-ethylene block copolymer component (A) 83-88 wt%; and ethylene-based polymer (C) satisfying the following (C1)-(C3) 12-17 wt% (provided that the propylene-ethylene block copolymer Component (a) and the ethylene polymer (C) is 100 wt% in total);
(B1) The ethylene content is 20 to 35 wt% (based on 100 wt% of the total weight of the propylene-ethylene copolymer B).
(B2) The intrinsic viscosity [η] B measured in 135 ° C. o-dichlorobenzene is 2.0 to 3.0 dl / g.
(C1) The density is 0.905 to 0.920 g / cm ³ .
(C2) The melting point is 100 ° C. or higher.
(C3) MFR based on JIS K6922-2 (190 degreeC, 2.16kg load) is 10-50 g / 10min.
The polypropylene resin composition (X) has an MFR in accordance with JIS K7210 (230 ° C., 2.16 kg load) of 5 to 100 g / 10 minutes; and the polypropylene resin (Y) has the following (Y1) to It is a polypropylene resin having the characteristics of (Y4) and having a long-chain branched structure. (Y1): MFR is 0.1 to 30 g / 10 min.
(Y2): GPC molecular weight distribution (Mw / Mn) is 3.0 to 10, and Mz / Mw is 2.5 to 10.
(Y3): Melt tension (MT) (unit: g) is
log (MT) ≧ −0.9 × log (MFR) +0.7 or MT ≧ 15
Satisfy one of the following.
(Y4): 25 degreeC paraxylene soluble component amount (CXS) is less than 5.0 weight% with respect to polypropylene resin (X) whole quantity.
The polypropylene resin composition characterized by the above-mentioned. The polypropylene resin composition according to claim 1, wherein the polypropylene resin (Y) further has the following property (Y5).
(Y5): The branching index g ′ when the absolute molecular weight (Mabs) is 1,000,000 is 0.30 or more and less than 1.00. The polypropylene resin composition according to claim 1 or 2, wherein the polypropylene resin (Y) further has the following property (Y6).
(Y6): The mm fraction of three propylene units by ¹³ C-NMR is 95% or more.   The polypropylene resin composition according to any one of claims 1 to 3, wherein HAZE having a molded body thickness of 1 mmt based on JIS K7136 (ISO14782) is 30% or less. The polypropylene resin composition according to any one of claims 1 to 4, wherein a Charpy impact strength at 0 ° C based on JIS K7111 (ISO179) is 2.5 kJ / m ² or more. The polypropylene resin composition according to any one of claims 1 to 5, wherein a flexural modulus according to JIS K7171 (ISO178) is 950 MPa or more.   An injection-molded article comprising the polypropylene resin composition according to any one of claims 1 to 6.