JP6822249B2 - Polypropylene resin composition - Google Patents

Description

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

Polypropylene is lightweight and has excellent mechanical strength and the like. In particular, propylene-ethylene block copolymer is inferior in transparency but has an excellent balance of impact resistance and rigidity. , Food packaging containers, etc. are widely used in various fields.

Further, the propylene-ethylene random copolymer is inferior in impact resistance, but is excellent in transparency and heat sealability, and is used for dessert cups, films and the like.
In recent years, polypropylene having rigidity, impact resistance, and transparency has been demanded, and Japanese Patent Application Laid-Open No. 2006-161033 (Patent Document 1) states that polypropylene and ethylene-α-olefin copolymer weight are used for retort food packaging. Compositions combined with coalescence are described.

Japanese Unexamined Patent Publication No. 2006-161033

An object (problem) of the present invention is to provide a polypropylene-based resin composition having excellent impact resistance, rigidity, transparency and moldability.

As a result of diligent studies to solve the above problems, the present inventor has made a polypropylene resin composition component composed of a specific propylene-ethylene block copolymer and an ethylene polymer, and a polypropylene containing a specific polypropylene resin component. The present invention has been completed by finding that a polypropylene-based resin composition having an excellent balance between rigidity, impact resistance, transparency and moldability can be obtained by using the based resin composition.
The present invention provides the following polypropylene-based resin compositions.

That is, according to the first aspect of the present invention, the polypropylene-based resin composition comprises 100 parts by weight of the polypropylene-based resin composition (X) and 1 to 10 parts by weight of the polypropylene resin (Y).
The polypropylene-based resin composition (X) is
75-85 wt% of the propylene-based homopolymer (A) having a melt flow rate (MFR) of 3.5 to 300 g / 10 minutes in accordance with JIS K7210 (230 ° C., 2.16 kg load), and the following (B1) Contains 15 to 25 wt% of the propylene-ethylene copolymer (B) satisfying (B2) (however, the total of the propylene-based homopolymer (A) and the propylene-ethylene copolymer (B) is 100 wt%). Protin-ethylene block copolymer component (a) 83 to 88 wt%; and 12 to 17 wt% of the ethylene-based polymer (C) satisfying the following (C1) to (C3) (however, propylene-ethylene block copolymer) The total of the component (a) and the ethylene-based polymer (C) is 100 wt%).
(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 ultimate viscosity [η] B measured in o-dichlorobenzene at 135 ° C. is 2.0 to 3.0 dl / g.
(C1) The density is more than 0.920 g / cm ³ and 0.930 g / cm ³ or less.
(C2) The melting point is 120 ° C. or higher.
(C3) The MFR according to JIS K6922-2 (190 ° C., 2.16 kg load) is 10 to 50 g / 10 minutes.
The polypropylene-based resin composition (X) has an MFR of 5 to 100 g / 10 minutes in accordance with JIS K7210 (230 ° C., 2.16 kg load); 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 minutes.
(Y2): The molecular weight distribution (Mw / Mn) by GPC is 3.0 to 10, and Mz / Mw is 2.5 to 10.
(Y3): The melt tension (MT) (unit: g) is
log (MT) ≧ -0.9 × log (MFR) +0.7 or MT ≧ 15
Satisfy either.
(Y4): The amount of the paraxylene-soluble component (CXS) at 25 ° C. is less than 5.0% by weight based on the total amount of the polypropylene resin (X).
Provided is the polypropylene-based resin composition.

Further, according to the second invention of the present invention, the polypropylene resin (Y) further provides the polypropylene-based resin composition according to the first invention, which is characterized by having the following characteristics (Y5). ..
(Y5): The branching index g'at an absolute molecular weight (Mabs) of 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 (Y) further comprises the polypropylene-based resin composition according to the first or second invention, which is characterized by having the following characteristics (Y6). provide.
(Y6): The mm fraction of 3 chains of propylene units by ¹³ C-NMR is 95% or more.

Further, according to the fourth invention of the present invention, the polypropylene-based resin composition according to any one of the third to third inventions, wherein the HAZE of a molded body thickness of 1 mmt according to JIS K7136 (ISO14782) is 35% or less. Provide things.

Further, according to the 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. according to JIS K7111 (ISO179) is 2.0 kJ / m ² or more. A based resin composition is provided.

Further, according to the sixth invention of the present invention, there is provided the polypropylene-based resin composition according to any one of the first to fifth inventions, which has a flexural modulus of 1030 MPa or more according to JIS K7171 (ISO178).

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

The polypropylene-based resin composition of the present invention has an excellent balance between rigidity, impact resistance, transparency and moldability.

Form for carrying out the invention

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

The polypropylene-based resin composition of the present invention is a polypropylene-based resin composition composed of 100 parts by weight of the polypropylene-based resin composition (X) and 1 to 10 parts by weight of the polypropylene resin (Y), and is characterized by the following. is there.
The polypropylene-based resin composition (X) is
75-85 wt% of the propylene-based homopolymer (A) having a melt flow rate (MFR) of 3.5 to 300 g / 10 minutes in accordance with JIS K7210 (230 ° C., 2.16 kg load), and the following (B1) Contains 15 to 25 wt% of the propylene-ethylene copolymer (B) satisfying (B2) (however, the total of the propylene-based homopolymer (A) and the propylene-ethylene copolymer (B) is 100 wt%). Protin-ethylene block copolymer component (a) 83 to 88 wt%; and 12 to 17 wt% of the ethylene-based polymer (C) satisfying the following (C1) to (C3) (however, propylene-ethylene block copolymer) The total of the component (a) and the ethylene-based polymer (C) is 100 wt%).
(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 ultimate viscosity [η] B measured in o-dichlorobenzene at 135 ° C. is 2.0 to 3.0 dl / g.
(C1) The density is more than 0.920 g / cm ³ and 0.930 g / cm ³ or less.
(C2) The melting point is 120 ° C. or higher.
(C3) The MFR according to JIS K6922-2 (190 ° C., 2.16 kg load) is 10 to 50 g / 10 minutes.
The polypropylene-based resin composition (X) has an MFR of 5 to 100 g / 10 minutes in accordance with JIS K7210 (230 ° C., 2.16 kg load); 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 minutes.
(Y2): The molecular weight distribution (Mw / Mn) by GPC is 3.0 to 10, and Mz / Mw is 2.5 to 10.
(Y3): The melt tension (MT) (unit: g) is
log (MT) ≧ -0.9 × log (MFR) +0.7 or MT ≧ 15
Satisfy either.
(Y4): The amount of the paraxylene-soluble component (CXS) at 25 ° C. is less than 5.0% by weight based on the total amount of the polypropylene resin (X).

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

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

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

1. 1. [Propylene homopolymer (A)]
The propylene-based 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). It is necessary, preferably 10 to 200 g / 10 minutes, more preferably 30 to 100 g / 10 minutes. When the MRF is 3.5 g / 10 minutes or more, sufficient fluidity during injection molding can be ensured, and a desired injection molded product can be obtained. On the other hand, if the MRF is 300 g / 10 minutes or less, sufficient impact resistance can be obtained. The propylene-based homopolymer (A) is in the range of 75 to 85 wt% in 100 wt% of the propylene-ethylene block copolymer component (A), preferably 77 to 84 wt%, and more preferably 78 to 83 wt%. Is.

2. 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 25 wt%. It is 23 wt%, more preferably 17 to 22 wt%. When the content of the propylene-ethylene copolymer (B) is 15 wt% or more, sufficient impact resistance can be obtained. On the other hand, when the content of the propylene-ethylene copolymer (B) is 25 wt% or less, sufficient rigidity and transparency can be obtained.

Further, the propylene-ethylene copolymer (B) satisfies the following properties (B1) to (B2) as described above.
(B1): The ethylene content in the propylene-ethylene copolymer (B) must be in the range of 20 to 35 wt% based on 100 wt% of the total weight of the propylene-ethylene copolymer (B). It is preferably 22 to 33 wt%, more preferably 25 to 30 wt%. When 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 ultimate viscosity [η] B measured in orthodichlorobenzene (o-dichlorobenzene) at 135 ° C. is 2.0 to 3.0 dl / g. It is necessary to be in the range of, preferably 2.0 to 2.8 dl / g, and more preferably 2.2 to 2.8 dl / g. When the ultimate 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 can be obtained.
For the ultimate viscosity [η] B, the propylene-ethylene block copolymer component (a) was dissolved in p-xylene at 130 ° C. to prepare a solution, and then left at 25 ° C. for 12 hours to filter out the precipitated polymer. Then, p-xylene is evaporated from the filtrate to obtain the propylene-ethylene copolymer (B), which can be measured using an orthodichlorobenzene as a solvent and a Uberode type viscometer at a temperature of 135 ° C.

3. 3. [Ethylene polymer (C)]
The ethylene-based polymer (C) used in the present invention needs to be contained in the polypropylene-based resin composition (X) in the range of 12 to 17 wt% in 100 wt%, preferably 13 to 17 wt%, and more preferably 14 It is ~ 17 wt%. When 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.

Further, the ethylene polymer (C) satisfies the following characteristics (C1) to (C3).
(C1): The density of the ethylene polymer (C) needs to be more than 0.920 g / cm ³ and 0.930 g / cm ³ or less, preferably 0.921 to 0.928 g / cm ³ . is there. 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 tube method) according to JIS K7112.
(C2): The melting point of the ethylene polymer (C) needs to be in the range of 120 ° C. or higher, preferably 121 ° C. or higher. When the melting point of the ethylene polymer (C) is 120 ° C. or higher, releasability during injection molding is ensured and continuous moldability is excellent. The upper limit of the melting point of the ethylene polymer (C) is not particularly limited, but is usually preferably 130 ° C. or lower.
Here, for specific measurement of the melting point, a differential scanning calorimeter (DSC) is used, a sample amount of 5 mg is taken, held at 200 ° C. for 5 minutes, and then crystallized at a temperature lowering rate of 10 ° C./min to 40 ° C. Further, the peak position of the curve drawn when melting at a heating rate of 10 ° C./min is defined as the melting peak temperature (melting point) Tm (° C.).
(C3): Further, for the ethylene polymer (C), the MFR according to JIS K6922-2 (190 ° C., 2.16 kg load) needs to be in the range of 10 to 50 g / 10 minutes, preferably 15 ~ 45 g / 10 minutes, more preferably 17-40 g / 10 minutes. When the MFR of the ethylene polymer (C) is 10 g / 10 minutes or more, sufficient fluidity during injection moldability can be ensured. On the other hand, if it is 50 g / 10 minutes or less, bleed-out on the surface of the molded product can be suppressed and the transparency is improved.

The ethylene-based polymer (C) used in the polypropylene-based resin composition of the present invention includes ethylene homopolymers and ethylene-α-olefin random copolymers, and ethylene-based elastomers are preferable. These ethylene-based elastomers can be used alone 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, etc. 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 products such as Novatec LL series and Harmorex series manufactured by Japan Polyethylene Corporation, Kernel series, and Toughmer P series and Toughmer A series manufactured by Mitsui Chemicals Co., Ltd. , Evolu series manufactured by Prime Polymer Co., Ltd., Sumikasen E, EP series, and Excellen GMH series manufactured by Sumitomo Chemicals Co., Ltd. can be exemplified.

4. [Polypropylene resin composition (X)]
The polypropylene-based 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 minutes in accordance with JIS K7210 (230 ° C., 2.16 kg load). Yes, preferably 10 to 90 g / 10 minutes, more preferably 20 to 80 g / 10 minutes. When the MFR is 5 g / 10 minutes or more, sufficient fluidity during injection molding can be ensured, and a desired injection molded product can be obtained. On the other hand, if it is 100 g / 10 minutes 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 device to be used (a) Cross sorting device CFC T-100 manufactured by Dia Instruments Co., Ltd. (abbreviated as CFC)
(B) Fourier transform 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 CFC to FT-IR shall be 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 in series.

(Ii) CFC measurement conditions (a) Solvent: Orthodichlorobenzene (ODCB)
(B) Sample concentration: 4 mg / ml
(C) Injection amount: 0.4 ml
(D) Crystallization: The temperature is lowered from 140 ° C. to 40 ° C. over about 40 minutes.
(E) Sorting method:
The fractionation temperature at the time of temperature-raising elution separation is 40 ° C., 100 ° C., and 140 ° C., and the fractions are separated into three fractions in total.
The elution ratio (unit: weight%) of the component eluted at 40 ° C. or lower (fraction 1), the component eluted at 40 to 100 ° C. (fraction 2), and the component eluted at 100 to 140 ° C. (fraction 3), respectively. It is defined as W40, W100, W140. W40 + W100 + W140 = 100. Further, each of the separated fractions is automatically transported to the FT-IR analyzer as it is.
(F) Solvent flow rate at elution: 1 ml / min

(Iii) FT-IR measurement conditions After the elution of the sample solution starts from the GPC in the subsequent stage of CFC, FT-IR measurement is performed under the following conditions, and GPC-IR data is collected for each of the above fractions 1 to 3. ..
(A) Detector: MCT
(B) Resolution: 8 cm ^-1
(C) Measurement interval: 0.2 minutes (12 seconds)
(D) Cumulative number of times 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 by using the absorbance of 2945 cm- ¹ obtained by FT-IR as a chromatogram. The elution amount is standardized so that the total elution amount of each elution component is 100%. The conversion from the holding capacity to the molecular weight is performed using a calibration curve prepared in advance using standard polystyrene.
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 0.4 ml of a solution dissolved in ODCB (containing 0.5 mg / ml BHT) so that each is 0.5 mg / ml. For the calibration curve, a cubic equation obtained by approximating with the least squares method is used.
For conversion to molecular weight, a general-purpose calibration curve is used with reference to "Size Exclusion Chromatography" (Kyoritsu Shuppan) by Sadao Mori. The following numerical values are used for the viscosity formula ([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 of the eluted parts separated by elution is defined as Mw (40), Mw (100), and Mw (140). The overall molecular weight distribution was calculated by summing up the data obtained by 3 classifications. From this, the content (% by weight) of the components having a weight average molecular weight of 3,000 or less, which will be described later, can be obtained by integrating.
For the ethylene content distribution of each eluted component (distribution of ethylene content along the molecular weight axis), the ratio of the absorbance of 2956 cm ^-1 obtained by FT-IR to the absorbance of 2927 cm ^-1 was used, and polyethylene, polypropylene, and ¹³ were used. Using ethylene propylene rubber (EPR) whose ethylene content is known by C-NMR measurement and a mixture thereof, it is converted to ethylene content (% by weight) by a calibration line prepared in advance. Ask.

The ratio (Wc) of the propylene-ethylene copolymer (B) portion in the propylene-ethylene block copolymer component (a) in the present invention is theoretically determined by the following formula (I) using the results measured by the above method. The above is defined and is obtained by the following procedure.
Wc (% by 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. Unit:% by weight), and B40 and B100 are ethylene contents (unit:% by weight) of (B) contained in each fraction. How to obtain A40, A100, B40, B100 will be described later.
The meaning of the formula (I) is as follows. That is, the first term on the right side of the formula (I) is a term for calculating the amount of (A) contained in fraction 1 (a portion soluble at 40 ° C.). When the 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 the fraction 1 includes (B). Since a small amount of the component derived from (A) (a component having an extremely low molecular weight) is contained in addition to the derived component, it is necessary to correct that portion. Therefore, by multiplying W40 by A40 / B40, the amount derived from the component (B) in 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 = 3/4 of fraction 1. (That is, 75% by weight) is derived from (B), and 1/4 is derived from (A). The operation of multiplying A40 / B40 in the first term on the right side as described above means that the contribution of (B) is calculated from the weight% (W40) of fraction 1.

Here, the calculation is further 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 (units are weight%). How to determine 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 weight%).
Regarding fraction 2, it is considered that the rubber portion is completely eluted at 40 ° C., and it cannot be defined by the same definition. Therefore, in this specification, B100 = 100 is substantially defined.
B40 and B100 are the ethylene contents of (B) contained in each fraction, but it is practically impossible to determine this value analytically. The reason is that there is no means to completely separate and separate (A) and (B) mixed in the fraction. As a result of studies using various model samples, B40 can well explain the effect of improving the material properties 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 crystallinity derived from an ethylene chain, and the amount of (A) contained in these fractions is relatively small compared to the amount of (A) contained in fraction 1. For this reason, approximation to 100 is closer to the actual situation and causes almost no error in calculation. Therefore, the analysis is performed with B100 = 100.

(C) For the above reason, the above ratio (Wc) is obtained according to the following formula (II).
Wc (% by weight) = W40 x A40 / B40 + W100 x A100 / 100 ... (II)
That is, W40 × A40 / B40, which is the first term on the right side of the formula (II), indicates a non-crystalline (B) content (% by weight), and W100 × A100 / 100, which is the second term, is crystalline. The (A) content (% by weight) having a 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.
Let B40 be the ethylene content corresponding to the peak position of the differential molecular weight distribution curve. Further, the sum of the product of the weight ratio of each data point and the ethylene content of each data point, which is taken in as data points at the time of measurement, is defined as the average ethylene content A40 of fraction 1. The average ethylene content A100 of fraction 2 is also determined in the same manner.

The significance of setting the above three types of sorting temperatures is as follows.
In the CFC analysis of the present invention, 40 ° C. is necessary and sufficient to separate only non-crystalline polymers (for example, most of (B) or components having an extremely low molecular weight among (A)). It has the significance of being a temperature condition. 100 ° C. refers to a component that is insoluble at 40 ° C. but soluble at 100 ° C. (for example, in (B), a component having crystallinity due to a chain of ethylene and / or propylene, and a component having low crystallinity. The temperature is sufficient to elute only (A)). 140 ° C means a component that is insoluble at 100 ° C but soluble at 140 ° C (for example, a component having particularly high crystallinity among (A) and ethylene having an extremely high molecular weight and extremely high content in (B)). The temperature is sufficient to elute only the crystalline component) and recover the entire amount of the propylene-ethylene block copolymer component (a) used for the analysis.
In addition, since W140 does not contain the component (B) at all, or even if it exists, it is extremely small and can be substantially ignored, so 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). , 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 characteristics of (Y1) to (Y4) as described above.
(1) Characteristics (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 0.3 to 20 g / 10 minutes. 0.5 to 10 g / 10 minutes.
When the MFR is 0.1 g / 10 minutes or more, sufficient fluidity can be ensured, and there is no problem of extrusion failure during injection molding. On the other hand, if it is 30 g / 10 minutes or less, high rigidity, high impact resistance and high transparency are exhibited.
The method of 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 hydrogenation in the method of adding a chain transfer agent such as hydrogen at the time of polymerization. Adjustments can be made easily.

In the present invention, the MFR of the propylene resin is the method A and the condition M (230) of JIS K7210: 1999 "Test method for melt mass flow rate (MFR) and melt volume flow rate (MVR) of plastic-thermoplastic plastic". Measured according to ° C., 2.16 kg load), the unit is g / 10 minutes.

(2) Characteristics (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 (Mw / Mn) obtained by gel permeation chromatography (GPC). Here, it is necessary that Mw has a weight average molecular weight and Mn has a number average molecular weight) of 3.0 or more and 10 or less. 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 remarkably expresses the breadth of the molecular weight distribution, is 2.5 or more and 10 or less. The preferred range of Mz / Mw is 2.8 to 8.0, more preferably 3.0 to 6.0.
The wider the molecular weight distribution, the better the molding processability, but those having Mw / Mn and Mz / Mw in this range are particularly excellent in molding processability.

The definitions of Mn, Mw, and Mz are described in "Basics of Polymer Chemistry" (edited by the Society of Polymer Chemistry, Tokyo Chemistry, 1978) and can be calculated from the molecular weight distribution curve by GPC.
The specific measurement method of GPC is as follows.
Equipment: Waters GPC (ALC / GPC 150C)
Detector: MIRAN 1A IR detector manufactured by FOXBORO (measurement wavelength: 3.42 μm)
Column: Showa Denko AD806M / S (3)
Mobile phase solvent: orthodichlorobenzene (ODCB)
Measurement temperature: 140 ° C
Flow velocity: 1.0 ml / min
Injection volume: 0.2 ml
Sample Preparation: Samples are prepared with ODCB (containing 0.5 mg / mL BHT) to prepare a 1 mg / mL solution and dissolved at 140 ° C. for about 1 hour.

The conversion from the retention capacity obtained by GPC measurement to the molecular weight is performed using a calibration curve prepared in advance using 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. For the calibration curve, a cubic equation obtained by approximating with the least squares method is used.
The following numerical values are used for the viscosity formula [η] = K × M ^α used for conversion to the molecular weight.
PS: K = 1.38 × 10 ^-4 , α = 0.7
PP: K = 1.03 × 10 ^-4 , α = 0.78

To adjust Mw / Mn to the range of 3.0 to 10 and Mz / Mw to the range of 2.5 to 10, change the temperature and pressure conditions of propylene polymerization, or the most common method is hydrogen or the like. The chain transfer agent can be easily adjusted by the method of adding the chain transfer agent at the time of propylene polymerization.
Further, when two or more kinds of metallocene catalysts and two or more kinds of catalysts, which will be described later, are used, the amount ratio can be changed for control.

(3) Characteristics (Y3): Melt tension (MT)
Further, the polypropylene resin (Y) used in the present invention has the following relational expression of melt tension (MT) and MFR:
log (MT) ≧ -0.9 × log (MFR) +0.7 or MT ≧ 15
It is necessary to meet one of the following.

Here, MT uses Capillograph 1B manufactured by Toyo Seiki Seisakusho Co., Ltd., Capillary: Diameter 2.0 mm, Length 40 mm, Cylinder diameter: 9.55 mm, Cylinder extrusion speed: 20 mm / min, Pick-up speed: 4. It represents the melt tension when measured under the conditions of 0 m / min and temperature: 230 ° C., and the unit is grams. However, when the MT of the polypropylene resin (Y) is extremely high, the resin may break at a pick-up speed of 4.0 m / min. In such a case, the pick-up speed can be reduced and the polypropylene resin (Y) can be picked up. Let MT be the tension at the highest speed. The measurement conditions and units of MFR are as described above.

This regulation regarding the melt tension is an index for the polypropylene resin (Y) having a branched structure to have a sufficient melt tension to exhibit high rigidity and high impact resistance, and in general, MT correlates with MFR. Since it has, it is specified by the relational expression with MFR.
The method of defining the melt tension MT by the relational expression with the MFR as described above is a usual method for those skilled in the art. The following relational expressions have been proposed.
log (MS)> -0.61 x log (MFR) +0.82
(Here, MS is synonymous with MT.)
Further, Japanese Patent Application Laid-Open No. 2003-64193 proposes the following relational expression as a definition of polypropylene having a high melt tension.
11.32 × MFR-0.7854 ≦ MT
Further, Japanese Patent Application 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 has a relational expression:
log (MT) ≧ -0.9 × log (MFR) +0.7 or MT ≧ 15
If any of the above conditions is satisfied, it can be said that the resin has a sufficiently high melt tension, and is useful for exhibiting high rigidity and high impact resistance.
Further, 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, and it is further preferable to satisfy the following relational expression.
log (MT) ≧ -0.9 × log (MFR) +1.1 or MT ≧ 15

It is not necessary to set the upper limit value of MT in particular, but when MT exceeds 40 g, the taking-up speed becomes remarkably slow by the above measurement method, and measurement becomes difficult. In such a case, since it is considered that the ductility 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 above-mentioned relational expression between MT and MFR, the amount of long-chain branching of the polypropylene resin (Y) may be increased to increase the melt tension, and the selection and combination of preferable metallocene catalysts described later, and the combination thereof, and This is possible by controlling the amount ratio and the prepolymerization conditions and introducing a large number of long-chain branches.

(4) Characteristics (Y4): 25 ° C. Paraxylene-soluble component amount (CXS)
The polypropylene resin (Y) used in the present invention preferably has high stereoregularity and few low crystallinity components that cause stickiness and bleed-out of the molded product. This low crystallinity component is evaluated by the amount of the 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). It is preferably 3.0% by weight or less, more preferably 1.0% by weight or less, and further preferably 0.5% by 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.

The details of the method for measuring the amount of xylene-soluble component (CXS) at 25 ° C. are as follows.
2 g of the sample (polypropylene resin (Y)) is dissolved in 300 ml of p-xylene (containing 0.5 mg / ml of BHT) at 130 ° C. to make a solution, and then left at 25 ° C. for 12 hours. Then, the precipitated polymer is filtered off, p-xylene is evaporated from the filtrate, dried under reduced pressure at 100 ° C. for 12 hours, and the xylene-soluble component is recovered at room temperature. The ratio (% by weight) of the weight of the recovered component to the weight of the charged sample is defined as CXS.

CXS can be reduced to less than 5% by weight by manufacturing using a metallocene catalyst as described later, but in addition to maintaining the purity of the catalyst above a certain level, the method for manufacturing the catalyst and the time of polymerization It is necessary that the reaction conditions of the above are not extremely high and that the amount ratio of the organoaluminum compound to the metallocene complex is not increased too much.

Further, the polypropylene resin (Y) used in the present invention preferably satisfies the following characteristics (Y5) to (Y7) in addition to the above characteristics (Y1) to (Y4).

(5) Characteristic (Y5): Branch index g'
As a direct index that the polypropylene resin (Y) used in the present invention has a long-chain branch, the branch 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 to the intrinsic viscosity [η] br of the polymer having a long-chain branched structure, that is, by [η] br / [η] lin. Given a long-chain branched structure, it takes a value less than 1.
The definition is described, for example, in "Developments in Polymer Charation-4" (JV Dawkins ed. Applied Science Publics, 1983) and is an index known to those skilled in the art.
The branching index g'can be obtained as a function of the absolute molecular weight Mabs, for example, by using a GPC equipped with a light scatterometer and a viscometer as described below in the detector.

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, and more preferably 0. 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 considered to have a comb-shaped chain preferably formed as a molecular structure, and when the branching index g'is less than 0.30, the main chain is small and the side chain is formed. The ratio is extremely large, and in such a case, the melt tension may not be improved or gel may be formed, which is not preferable. On the other hand, when it is 1.00 or more, this means that there is no long chain branch, and high rigidity, high impact resistance and high transparency are not exhibited.

The lower limit of the branch index g'is preferably the above value for the following reasons.
According to the document "Encyclopedia of Polymer Science and Engineering vol.2" (John Wiley & Sons 1985 p.485), the g'value of the comb-shaped polymer is expressed by the following formula.

Here, g is a branching index defined by the radius of gyration ratio of the polymer, and ε is a constant determined by the shape of the branched chain and the solvent, and p. According to Table 3 of 487, a value of about 0.7 to 1.0 is reported for the comb-shaped chain in a good solvent. λ is the ratio of the main chain in the comb-shaped chain, and p is the average number of branches.
According to this equation, in the case of a comb-shaped chain, the number of branches becomes extremely large, that is, g'= g ^ε = λ ^ε at the limit of infinity, and it does not fall below the value of λ ^ε. , Generally there will be a lower limit.

On the other hand, the conventionally known equation of the randomly branched chain which is considered to occur in the case of electron beam irradiation or peroxide reduction is given by the equation (19) on page 485 in the same document, and according to this, it is random. In a branched chain, as the number of branch points increases, the g'and g values decrease monotonically without any particular lower limit. 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-shaped chain. As a result, the distinction from the random branched chain generated by conventional electron beam irradiation or peroxide reduction becomes clearer.

Further, in the branched polymer having a structure similar to a comb-shaped chain in which the branching index g'is in the above range, the degree of decrease in the melt tension after repeated kneading is small, and the polymer is industrially used again as a recycled material for molding. At that time, the deterioration of physical properties and moldability becomes small.

The specific calculation method of the branch index g'is as follows.
The Alliance GPCV2000 from Waters is used as a GPC apparatus equipped with a differential refractometer (RI) and a viscosity detector (Viscometer). Further, as the light scattering detector, 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 the column is used by connecting two GMHHR-H (S) HTs manufactured by Tosoh Corporation. The temperature of the column, the sample injection part and each detector is 140 ° C. The sample concentration is 1 mg / mL, and the injection amount (sample loop volume) is 0.2175 mL.

The data processing software ASTRA (version 4.73.04) attached to MALLS is used to obtain the absolute molecular weight (Mabs) obtained from MALLS, the root mean square radius (Rg), and the limit viscosity ([η]) obtained from Viscometer. Then, calculate with reference to the following documents.
1. 1. "Developments in Polymer Charation-4" (JV Dawkins ed. Applied Science Publics, 1983. Chapter 1.)
2. 2. Polymer, 45, 6495-6505 (2004)
3. 3. Macromolecules, 33, 2424-2436 (2000)
4. Macromolecules, 33, 6945-6952 (2000)

The branching index g'is the ratio ([η] lin) of the ultimate viscosity ([η] br) obtained by measuring the sample with the above Viscometer and the ultimate viscosity ([η] lin) separately obtained by measuring the linear polymer. It is calculated as 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. As the radius of inertia decreases, the ultimate viscosity decreases. Therefore, as the long-chain branched structure is introduced, the ultimate viscosity of the branched polymer ([η] br) with respect to the ultimate viscosity ([η] lin) of the linear polymer having the same molecular weight. ) ([Η] br / [η] lin) becomes smaller.
Therefore, when the branch index (g'= [η] br / [η] lin) is less than 1, it means that the branch is introduced. Here, as the linear polymer for obtaining [η] lin, commercially available homopolypropylene (“Novatec PP (registered trademark)” manufactured by Japan Polypropylene Corporation, grade name: FY6) is used. Since it is known as the Mark-Houwink-Sakurada formula that the logarithm of [η] lin of a linear polymer has a linear relationship with the logarithm of molecular weight, [η] lin is appropriately set on the low molecular weight side or the high molecular weight side. It can be extrapolated to obtain numerical values.

The branching index g'to be 0.30 or more and less than 1.00 is achieved by introducing a large number of long-chain branches, and the selection and combination of preferable metallocene catalysts described later, their amount ratios, and prepolymerization. This is possible by controlling the conditions and polymerizing.

(6) Characteristics (Y6): ¹³ mm fraction of 3 chains of propylene units by C-NMR The polypropylene resin (Y) used in the present invention is characterized by having 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.
For the mm fraction, the upper limit of the proportion of the propylene unit 3 chain having the same direction of methyl branching in each propylene unit in any propylene unit 3 chain consisting of a head-tail bond is 100%. This mm fraction is a value indicating that the three-dimensional structure of the methyl group in the polypropylene molecular chain is isotactically controlled, and the higher the value, the higher the control. If the mm fraction is smaller than this value, the mechanical properties tend to deteriorate.
Therefore, the mm fraction is preferably 95% or more, more preferably 96% or more, and further preferably 97% or more.

The details of the method for measuring the mm fraction of 3 chains of propylene units by ¹³ C-NMR are as follows.
After completely dissolving 375 mg of the sample in 2.5 ml of deuterated 1,1,2,2-tetrachloroethane in an NMR sample tube (10φ), the measurement is carried out at 125 ° C. by the 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. Chemical shifts of other carbon peaks are based on this.
Flip angle: 90 degrees Pulse interval: 10 seconds Resonance frequency: 100 MHz or more Accumulation frequency: 10,000 times or more Observation range: -20 ppm to 179 ppm
Number of data points: 32768

The mm fraction analysis is performed using the measured ¹³ C-NMR spectrum.
The spectrum is assigned with reference to Macromolecules, (1975), 8 squares, p. 687, Polymer, vol. 30, p. 1350 (1989).
A more specific method for determining the mm fraction is described in detail in paragraphs [0053] to [0065] of JP2009-275207A, and the present invention also follows this method. ..

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

(7) Characteristics (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 the extensional viscosity at a strain rate of 0.1 s- ¹ is 6.0. The above is mentioned.
The degree of strain hardening (λmax (0.1)) is an index showing the strength at the time of melting, and when this value is large, there is an effect that the melting tension is improved. As a result, there is an effect of finely dispersing the rubber during injection molding, and the impact resistance of the injection molded product is improved. The degree of strain hardening is preferably 6.0 or more, more preferably 8.0 or more.

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

The elongation viscosity becomes a simple increasing function in the region of low strain rate, gradually approaches a constant value, and matches the Truton viscosity after a sufficient time without strain hardening, but is common in the case of strain hardening. From about 1 strain amount (= strain rate x time), the elongation viscosity begins 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 amount, and there is an inflection point on the curve when the elongation viscosity is plotted against time. .. Therefore, in the range of the strain amount of about 0.1 to 2.5, find the point where the slope of each time obtained above takes the minimum value, draw a tangent line at that point, and draw a straight line with the strain amount of 4.0. Extrapolate until The maximum value (ηmax) of the extensional viscosity ηE until the strain amount reaches 4.0 is obtained, and the viscosity on the approximate straight line up to that time is defined as ηlin. ηmax / ηlin is defined as λmax (0.1).

6. Method for Producing Polypropylene Resin (Y) Having a Branched Structure As long as the polypropylene resin (Y) having a branched structure satisfies the above-mentioned characteristics, the manufacturing method is not particularly limited, but as described above, low crystallinity is low. The preferred production method for satisfying all the conditions of component amount, high stereoregularity, relatively wide molecular weight distribution, branch index g'range, and high melt tension is a macromer copolymerization method using a combination of metallocene catalysts. This is the method to use. Examples of such a method include the methods disclosed in JP-A-2009-57542.
In this method, polypropylene having a long-chain branched structure is produced by using a catalyst that combines a catalyst component having a specific structure having a macromer-forming ability and a catalyst component having a specific structure having a macromer copolymerization ability at a high molecular weight. According to this method, an industrially effective method such as a bulk polymerization method or a gas phase polymerization method can be used for single-stage polymerization under particularly practical pressure-temperature conditions, and hydrogen, which is a molecular weight modifier, can be used. By using it, it is possible to produce a polypropylene resin having a long-chain branched structure having the desired physical properties.

Further, conventionally, it has been necessary to increase the branch generation efficiency by reducing the crystallinity by using a polypropylene component having low stereoregularity, but in the above method, a polypropylene component having sufficiently high stereoregularity must be used. , Which can be introduced into the side chain by a simple method, and is preferable as the polypropylene resin (Y) used in the present invention, and has a high stereoregularity and a low crystallinity component amount in mm. It is suitable for satisfying the characteristics regarding the rate and the amount of paraxylene-soluble component (CXS).
Further, by using the above method, the molecular weight distribution can be widened by using two kinds of catalysts having significantly different polymerization characteristics, and the characteristics related to the melt tension, the molecular weight distribution Mw / Mn and the branching index g'can be satisfied at the same time. Is preferable.

Therefore, a preferred method for producing the polypropylene resin (Y) having a branched structure used in the present invention will be described in detail below.
A preferred method for producing the polypropylene resin (Y) having a branched structure is a method for producing a propylene-based polymer using the following catalyst components (A), (B) and (C) as the propylene polymerization catalyst.
(A): At least one kind from the component [A-1] which is a compound represented by the following general formula (a1) and at least one from the component [A-2] which is a compound represented by the general formula (a2) described later. One or more types of transition metal compounds of Group 4 of the Periodic Table.
(B): Ion-exchangeable layered silicate (C): Organoaluminium 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 the 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. Further, R ¹³ and R ¹⁴ may each independently contain halogen, silicon, oxygen, sulfur, nitrogen, boron, phosphorus or a plurality of heteroelements selected from these, and have 6 to 16 carbon atoms. Represents an aryl group, a heterocyclic group containing nitrogen, oxygen or sulfur having 6 to 16 carbon atoms. Further, X ¹¹ and Y ¹¹ independently have 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, and a halogenation having 1 to 20 carbon atoms. hydrocarbon group, an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, an amino group or a nitrogen-containing hydrocarbon group having a carbon number of 1 to 20, Q ¹¹ is a divalent hydrocarbon group having 1 to 20 carbon atoms, Represents a silylene group or a gelmilene 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, or a substituted 2-thienyl group. It is a substituted 2-furfuryl group, more preferably a substituted 2-furyl group.
Further, as the substituent of the substituted 2-furyl group, the substituted 2-thienyl group and the 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 can be used. Examples thereof include a halogen atom such as a fluorine atom and a chlorine atom, an alkoxy group having 1 to 6 carbon atoms such as a methoxy group and an ethoxy group, and a trialkylsilyl group. Of these, a methyl group and a trimethylsilyl group are preferable, and a methyl group is particularly preferable.
In addition, R ¹¹ and R ¹² are particularly preferably 2- (5-methyl) -frill groups. Further, it is preferable that R ¹¹ and R ¹² are the same as each other.

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

In the general formula (a1), X ¹¹ and Y ¹¹ are co-ligands and react with the catalyst component (B) to produce an active metallocene having an olefin polymerization ability. Therefore, as long as this object is achieved, the types of ligands of X ¹¹ and Y ¹¹ are not limited, and each of them independently has a hydrogen atom, a halogen atom, and a hydrocarbon group having 1 to 20 carbon atoms. , Silicon-containing hydrocarbon groups with 1 to 20 carbon atoms, halogenated hydrocarbon groups with 1 to 20 carbon atoms, oxygen-containing hydrocarbon groups with 1 to 20 carbon atoms, amino groups or nitrogen-containing hydrocarbon groups with 1 to 20 carbon atoms. Indicates a group.

In the general formula (a1), Q ¹¹ couples the two five-membered ring, a divalent hydrocarbon group having 1 to 20 carbon atoms, which may have a hydrocarbon group having 1 to 20 carbon atoms silylene Indicates either a group or a gelmilene group. When two hydrocarbon groups are present on the silylene group or the gelmilene group, they may be bonded to each other to form a ring structure.
Specific examples of the above Q ^11, methylene, methylmethylene, dimethylmethylene, alkylene group of 1,2-ethylene and the like; silylene group; arylalkylene groups such as diphenylmethylene methylsilylene, dimethylsilylene, diethyl silylene, di ( Alkyl silylene groups such as n-propyl) silylene, di (i-propyl) silylene, di (cyclohexyl) silylene, (alkyl) (aryl) silylene groups such as methyl (phenyl) silylene; aryl silylene groups such as diphenyl silylene; tetra Alkyloligosilylene group such as methyldisyrylene; Germilene group; Alkyl gelmilene group in which silicon of the silylene group having a divalent hydrocarbon group having 1 to 20 carbon atoms is replaced with germanium; (alkyl) (aryl) gelmilene Group: An arylgelmilene group and the like can be mentioned. Among these, a silylene group having a hydrocarbon group having 1 to 20 carbon atoms or a gelmilene group having a hydrocarbon group having 1 to 20 carbon atoms is preferable, and an alkylsilylene group and an alkyl gelmilene group are particularly preferable.

Among 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'-dimethylgermilenebis {2- (5-methyl-2-furyl) -4-phenyl-indenyl} ] Hafnium, dichloro [1,1'-dimethylgelmilenebis {2- (5-methyl-2-thienyl) -4-phenyl-indenyl}] Hafnium, dichloro [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- (4,4) 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- (4-methylphenyl) -indenyl}] hafnium, dichloro [1,1'-dimethylsilylenebis {2- (5- (5-) Methyl-2-furyl) -4- (4-ipropylphenyl) -indenyl}] hafnium, dichloro [1,1'-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4- (4-) Methylsilylphenyl) -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}] hafnium, dichloro [1,1'-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-trifluoromethylphenyl) -indenyl}] hafnium, dichloro [1, 1'-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-t-butylphenyl) -indenyl}] hafnium, dichloro [1,1'-dimethylsilylenebis {2- (2) -Frill) -4- (1-naphthyl) -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-phenanthrill) ) -Indenyl}] Hafnium, dichloro [1,1'-dimethylsilylenebis {2- (5-t-butyl-2-furyl) -4- (1-naphthyl) -indenyl}] hafnium, dichloro [1,1 '-Dimethylsilylenebis {2- (5-t-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) -Fenanceril) -Indenyl}] Hafnium and the like can be mentioned.

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}] 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- (4-t-Butylphenyl) -indenyl}] Hafnium.

Particularly preferred are dichloro [1,1'-dimethylsilylenebis {2- (5-methyl-2-furyl) -4-phenyl-indenyl}] naphthium, 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} ] It is phenylnium.

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

[In the general formula (a2), R ²¹ and R ²² are independently hydrocarbon groups having 1 to 6 carbon atoms, and R ²³ and R ²⁴ are independently halogen, silicon, oxygen, and so on. It is an aryl group having 6 to 16 carbon atoms, which may contain sulfur, nitrogen, boron, phosphorus or a plurality of hetero elements selected from these. X ²¹ and Y ²¹ independently have 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, and a halogenated hydrocarbon having 1 to 20 carbon atoms. group, an oxygen-containing hydrocarbon group, an amino group or nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms having 1 to 20 carbon atoms, Q ²¹ is a divalent hydrocarbon group having 1 to 20 carbon atoms, carbon atoms Represents a silylene group or a gelmilene group which may have 1 to 20 hydrocarbon groups. M ²¹ is zirconium or hafnium. ]

The R ²¹ and R ²² are independently hydrocarbon groups 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 the like, with preference given to methyl. , Ethyl, n-propyl.

Further, each of the above R ²³ and R ²⁴ independently contains a halogen, silicon, or a plurality of heteroelements selected from these, which have 6 to 16 carbon atoms, preferably 6 to 12 carbon atoms. Is also a good aryl group. Preferred examples are 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 thereof include 5-dimethyl-4-t-butylphenyl, 3,5-dimethyl-4-trimethylsilylphenyl and 3,5-dichloro-4-trimethylsilylphenyl.

Further, X ²¹ and Y ²¹ are co-ligands and react with the catalyst component (B) to generate active metallocene having an olefin polymerization ability. Therefore, as long as this purpose is achieved, X ²¹ and Y ²¹ are not limited in the type of ligand, and are independently hydrogen atoms, halogen atoms, and hydrocarbon groups having 1 to 20 carbon atoms. Silicon-containing hydrocarbon groups with 1 to 20 carbon atoms, halogenated hydrocarbon groups with 1 to 20 carbon atoms, oxygen-containing hydrocarbon groups with 1 to 20 carbon atoms, amino groups or nitrogen-containing hydrocarbon groups with 1 to 20 carbon atoms Is shown.

Further, Q ²¹ is a bonding 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. It is a gelmilene group having a silylene group or a hydrocarbon group having 1 to 20 carbon atoms, and is preferably a substituted silylene group or a substituted gelmilene group. The substituent bonded to silicon or germanium is preferably a hydrocarbon group having 1 to 12 carbon atoms, and the two substituents may be linked.
Specific examples of Q ^21, methylene, dimethylmethylene, ethylene-1,2-diyl, dimethylsilylene, diethyl silylene, diphenyl silylene, methyl silylene, 9-silafluorene-9,9-diyl, dimethylsilylene, Examples thereof include diethyl silylene, diphenyl silylene, methylphenyl silylene, 9-silafluorene-9,9-diyl, dimethyl gel millene, diethyl gel millene, diphenyl gel millene, methyl phenyl gel millene and the like.

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

As a non-limiting example of the metallocene compound represented by the above general formula (a2), the following can be preferably mentioned.
However, the following describes only representative exemplary compounds, avoiding a large number of complicated examples, and the present invention is not construed as being limited to these compounds, and various ligands, cross-linking groups or auxiliary compounds. It is self-evident that the ligand can be used arbitrarily. Further, in the following, the compound in which the central metal is hafnium is described, but the compound in place of 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-hydroazulenyl}] 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-Hydroazurenyl}] hafnium, dichloro [1,1'-dimethylsilylenebis {2-methyl-4- (3-methyl-4-t-butylphenyl) -4-hydroazulenyl}] 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-hydroazulenyl}] hafnium, dichloro [1,1' -Dimethylsilylenebis {2-methyl-4- (2-naphthyl) -4-hydroazurenyl}] Hafnium, dichloro [1,1'-dimethylsilylenebis {2-methyl-4- (4-chloro-2-naphthyl) -4-hydroazurenyl}] hafnium, dichloro [1,1'-dimethylsilylenebis {2-methyl-4- (2-fluoro-4-biphenylyl) -4-hydroazulenyl}] hafnium, dichloro [1,1'-dimethyl Silyrenbis {2-methyl-4- (2-chloro-4-biphenylyl) -4-hydroazurenyl}] hafnium, dichloro [1,1'-dimethylsilylenebis {2-methyl-4- (9-phenanthril) -4 -Hydroazulenyl}] 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 Nium, dichloro [1,1'-dimethylsilylenebis {2-ethyl-4- (3-chloro-4-t-butylphenyl) -4-hydroazurenyl}] hafnium, dichloro [1,1'-dimethylsilylenebis { 2-Ethyl-4- (3-Methyl-4-trimethylsilylphenyl) -4-hydroazurenyl}] hafnium, dichloro [1,1'-dimethylgermilenebis {2-methyl-4- (2-fluoro-4-biphenylyl) ) -4-Hydroazurenyl}] hafnium, dichloro [1,1'-dimethylgelmilenebis {2-methyl-4- (4-t-butylphenyl) -4-hydroazulenyl}] hafnium, dichloro [1,1'- (9-Silafluorene-9,9-diyl) Bis {2-ethyl-4- (4-chlorophenyl) -4-hydroazurenyl}] Hafnium, dichloro [1,1'-dimethylsilylenebis {2-ethyl-4- (4-Chloro-2-naphthyl) -4-hydroazulenyl}] 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, etc. Be done.

Of these, preferably 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 -Hydroazulenyl}] hafnium, dichloro [1,1'-dimethylsilylenebis {2-ethyl-4- (4-chloro-2-naphthyl) -4-hydroazulenyl}] 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.

Further, 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, dichloromethane [1,1'-dimethylsilylenebis {2-ethyl-4- (3-methyl-4-trimethylsilylphenyl) -4- Hydroazulenyl}] Hafnium, Dichloro [1,1'-(9-silafluorene-9,9-diyl) bis {2-ethyl-4- (3,5-dichloro-4-trimethylsilylphenyl) -4-hydroazulenyl}] Hafnium.

(2) Catalyst component (B)
The catalyst component (B) preferably used for producing the polypropylene resin (Y) is an ion-exchangeable layered silicate.
(I) Types of ion-exchangeable layered silicates With ion-exchangeable layered silicates (hereinafter, may be simply abbreviated as silicates), surfaces formed by ion bonds and the like are parallel to each other due to their binding force. A silicate compound having a stacked crystal structure and exchangeable ions contained therein. Since most silicates are naturally produced mainly as the main component of clay minerals, they often contain impurities (quartz, cristobalite, etc.) other than ion-exchange layered silicates, but even if they are included. Good. Depending on the type, amount, particle size, crystallinity, and dispersed state of these impurities, it may be preferable to pure silicate or higher, and such a complex is also included in the catalyst component (B).
The silicate used is not limited to naturally occurring ones, and may be artificial synthetic compounds or may contain them.

Specific examples of silicates include the following layered silicates described in "Clay Mineralogy" by Haruo Shiramizu, Asakura Shoten (1995).
That is, montmorillonite, sauconite, byderite, nontronite, saponite, hectorite, stevensite and other smectites, vermiculite and other vermiculite, mica, illite, sericite, glauconite and other mica, attapargit, sepiolite, parigolskite. , Bentonite, pyrophyllite, talc, chlorite group, etc.
The silicate is preferably a silicate having a 2: 1 type structure as a main component silicate, more preferably a smectite group, and particularly preferably montmorillonite. The type of the interlayer cation is not particularly limited, but a silicate having an alkali metal or an alkaline earth metal as a main component of the interlayer cation is preferable from the viewpoint that it can be obtained relatively easily and inexpensively 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 special treatment, but it is preferable to carry out chemical treatment. Here, as the chemical treatment of the ion-exchangeable layered silicate, either a surface treatment for removing impurities adhering to the surface or a treatment for affecting the structure of clay can be used, and specifically, an acid. Treatments, alkali treatments, salts treatments, organic matter treatments and the like can be mentioned.

<Acid treatment>:
The acid treatment can remove impurities on the surface and elute some or all of the cations such as Al, Fe, and Mg 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.
The number of salts (described in the next section) and acids used in the treatment may be two or more. The treatment conditions with salts and acids are not particularly limited, but 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 preferably carried out under the condition that at least a part of the substance constituting at least one compound selected from the group consisting of ion-exchangeable layered silicates is eluted. In addition, salts and acids are generally used in aqueous solutions.

A combination of the following acids and salts may be used as the treatment agent. Further, it may be a combination of these acids and salts.
<Salt treatment>:
Preferably 40% or more, more preferably 60% or more of the cations of the exchangeable Group 1 metal contained in the ion-exchangeable layered silicate before being treated with salts, are dissociated from the salts shown below. And ion exchange is preferable.
The salts used in the salt treatment for the purpose of such ion exchange are a group consisting of a cation containing at least one atom selected from the group consisting of groups 1 to 14 atoms, a halogen atom, an inorganic acid and an organic acid. A compound consisting of at least one anion selected from the above, more preferably a cation containing at least one atom selected from the group consisting of group 2 to 14 atoms, and 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 ) , 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 etc. are compounds composed of at least one anion selected from the group.

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 , sulfonyl ₄ , Mg Examples thereof include (PO ₄ ) ₂ , Mg (ClO ₄ ) ₂ , MgC ₂ O ₄ , Mg (NO ₃ ) ₂ , Mg (OOCCH ₃ ) ₂ , and MgC ₄ H ₄ O ₄ .
In addition, 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.

In addition, 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.

<Alkaline treatment>:
In addition to the acid and salt treatments, the following alkali treatments and organic matter treatments may be performed as necessary. Examples of the treatment agent used in the alkaline treatment include LiOH, NaOH, KOH, Mg (OH) ₂ , Ca (OH) ₂ , Sr (OH) ₂ , and Ba (OH) ₂ .

<Organic matter treatment>:
Further, examples of the organic treatment agent used for the treatment of organic substances include trimethylammonium, triethylammonium, N, N-dimethylanilinium, triphenylphosphonium and the like.
In addition to the anions exemplified as the anions constituting the salt treatment agent, examples of the anions constituting the organic matter treatment agent include hexafluoroborate, tetrafluoroborate, and tetraphenylborate. , Not limited to these.

Further, these treatment agents may be used alone or in combination of two or more. 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 in the middle of the treatment. Further, the chemical treatment can be performed a plurality of times using the same or different treatment agents.

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

As described above, a particularly preferable catalyst component (B) is an ion-exchangeable layered silicate having a water content of 3% by weight or less, which is obtained by salt treatment and / or acid treatment.
The ion-exchangeable layered silicate can be treated with the catalyst component (C) of the organoaluminum compound described later before forming a catalyst or using it as a catalyst, which is preferable. The amount of the catalyst component (C) used with respect to 1 g of the ion-exchangeable layered silicate is not limited, but is usually 20 mmol or less, preferably 0.5 mmol or more and 10 mmol or less. There is no limitation on the treatment temperature and time, and the treatment temperature is usually 0 ° C. or higher and 70 ° C. or lower, and the treatment time is 10 minutes or longer and 3 hours or shorter. It is also possible and preferable to wash after the treatment. As the solvent, a hydrocarbon solvent similar to the solvent used in the prepolymerization or slurry polymerization method described later is used.

Further, as the catalyst component (B), it is preferable to use spherical particles having an average particle size of 5 μm or more. As long as the shape of the particles is spherical, a natural product or a commercially available product may be used as it is, or a particle whose shape and particle size are controlled by granulation, fragmentation, separation 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.
In addition, an organic substance, an inorganic solvent, an inorganic salt, and various binders may be used for granulation.
The spherical particles obtained as described above preferably have a compressive fracture strength of 0.2 MPa or more, particularly preferably 0.5 MPa or more, in order to suppress crushing and formation of fine powder in the polymerization step. In the case of such particle strength, the effect of improving the particle properties is effectively exhibited, especially when prepolymerization is performed.

(3) Catalyst component (C)
The catalyst component (C) is an organoaluminum compound. As the organoaluminum compound used as the catalyst component (C), a compound represented by the general formula: (AlR ³¹ _q Z _3-q ) _p is suitable.
Needless to say, in the present invention, the compounds represented by the above formulas can be used alone, in combination of a plurality of types, or in combination.
In the above formula, R ³¹ represents a hydrocarbon group having 1 to 20 carbon atoms, and Z represents a halogen, hydrogen, alkoxy group or amino group. q represents an integer of 1 to 3 and p represents an integer of 1 to 2.
As R ³¹ , an alkyl group is preferable, and Z is chlorine when it is a halogen, an alkoxy group having 1 to 8 carbon atoms when it is an alkoxy group, and 1 carbon atom when it is an amino group. Amino groups of ~ 8 are preferred.

Specific examples of the organic aluminum 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, diisobutylaluminum chloride and the like.

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

(4) Formation / Prepolymerization of Catalyst The catalyst brings the above catalyst components (A) to (C) into contact with each other in the (preliminary) polymerization tank simultaneously or continuously, or at one time or multiple times. Can be formed by.
Contact of each component is usually carried out in an aliphatic hydrocarbon or aromatic hydrocarbon solvent. The contact temperature is not particularly limited, but is preferably between −20 ° C. and + 150 ° C. As the contact order, any combination for the purpose is possible, and a particularly preferable one is as follows for each component.

When the catalyst component (C) is used, before the catalyst component (A) and the catalyst component (B) are brought into contact with each other, the catalyst component (A), the catalyst component (B), or the catalyst component (A) and the catalyst are used. The catalyst component (C) is brought into contact with both of the components (B), or the catalyst component (A) and the catalyst component (B) are brought into contact with each other at the same time, or the catalyst component (C) is brought into contact with the catalyst component (C). It is possible to bring the catalyst component (C) into contact after contacting the catalyst component (B) with the catalyst component (A), but preferably, the catalyst is brought into contact with the catalyst component (A) before the catalyst component (B) is brought into contact with each other. This is a method of contacting with the component (C).
Further, after contacting each component, it is possible to wash with an aliphatic hydrocarbon or an aromatic hydrocarbon solvent.

The amounts of the catalyst components (A), (B) and (C) used are arbitrary. For example, the amount of the catalyst component (A) used with respect 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 with respect to 1 g of the catalyst component (B). The amount of the catalyst component (C) with respect to the catalyst component (A) is preferably in the range of 0.01 to 5 × 10 ⁶ and particularly preferably 0.1 to 1 × 10 ⁴ in terms of the molar ratio of the transition metal. ..

The ratio of the component [A-1] (compound represented by the general formula (a1)) to the component [A-2] (compound represented by the general formula (a1)) is that of the polypropylene resin (Y). The molar ratio of the transition metal of [A-1] to the total amount of each component [A-1] and [A-2] is preferably 0.30 or more, 0. It is 99 or less.

By changing this ratio, it is possible to adjust the balance between melt properties and catalytic activity. That is, a low molecular weight terminal vinyl macromer is produced from the component [A-1], and a high molecular weight compound partially copolymerized with the macromer is produced from the component [A-2]. Therefore, by changing the ratio of the component [A-1], the average molecular weight, the molecular weight distribution, the bias of the molecular weight distribution toward the high molecular weight side, the very high molecular weight component, the branch (amount, length, Distribution) can be controlled, thereby controlling melt properties such as branching index g', strain hardening degree λmax, melt tension, and ductility.

In order to produce the polypropylene resin (Y), the molar ratio is preferably 0.30 or more, more preferably 0.40 or more, still more preferably 0.5 or more. The upper limit is preferably 0.99 or less, preferably 0.95 or less, and more preferably 0.90 or less in order to efficiently obtain the polypropylene resin (Y) with high catalytic activity. Is.
Further, by using the component [A-1] in 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 comprising contacting it with an olefin and polymerizing in a small amount. By performing the prepolymerization treatment, it is possible to prevent the formation of a gel when the main polymerization is performed. It is considered that the reason is that the long-chain branches can be uniformly distributed among the polymer particles when the main polymerization is carried out, and thereby the melt property can be improved.

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

The prepolymerization temperature and time are not particularly limited, but are preferably in the range of −20 ° C. to + 100 ° C., 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 weight ratio of the amount of prepolymerized polymer with respect to the catalyst component (B). Further, the catalyst component (C) can be added or added at the time of prepolymerization. It is also possible to wash after the completion of prepolymerization.
Further, it is also possible to allow a polymer such as polyethylene or polypropylene or a solid of an inorganic oxide such as silica or titania to coexist at the time of or after the contact of each of the above components.

(5) Use of catalyst / Propylene polymerization The polymerization mode can be any mode as long as the olefin polymerization catalyst containing the catalyst component (A), the catalyst component (B) and the catalyst component (C) and the monomer are in efficient contact with each other. Can be adopted.
Specifically, the slurry method using an inert solvent, the so-called bulk method in which propylene is used as a solvent without substantially using the inert solvent, the solution polymerization method, or each monomer is made into a gas state substantially without using a liquid solvent. The vapor phase method for keeping can be adopted. Further, a method of performing continuous polymerization or batch polymerization is also applied. In addition to single-stage polymerization, multi-stage polymerization of two or more stages is also possible.
In the case of the slurry polymerization method, a single or a mixture of saturated aliphatic or aromatic hydrocarbons such as hexane, heptane, pentane, cyclohexane, benzene and toluene is used as the polymerization solvent.

The polymerization temperature is usually 0 ° C. or higher and 150 ° C. or lower. In particular, when the bulk polymerization method is used, the temperature is preferably 40 ° C. or higher, more preferably 50 ° C. or higher. The upper limit is preferably 80 ° C. or lower, more preferably 75 ° C. or lower.
Further, when the vapor phase polymerization method is used, the temperature 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 the bulk polymerization method is used, it is preferably 1.5 MPa or more, and more preferably 2.0 MPa or more. The upper limit is preferably 4.0 MPa or less, more preferably 3.5 MPa or less.
Further, when the vapor phase polymerization method is used, it is preferably 1.5 MPa or more, more preferably 1.7 MPa or more. The upper limit is preferably 2.5 MPa or less, more preferably 2.3 MPa or less.

Further, as a molecular weight modifier, and for activity enhancement effect, an auxiliary molar ratio of hydrogen with respect to propylene, preferably 1.0 × ^{10 -6} or more, the range of 1.0 × ^{10 -2} or less Can be used.
In addition to the average molecular weight of the polymer produced by changing the amount of hydrogen used, the molecular weight distribution, the bias of the molecular weight distribution toward the high molecular weight side, the extremely high molecular weight component, and the branching (amount, length, Distribution) can be controlled, thereby controlling the melt properties that characterize polypropylene having a long-chain branched structure, such as MFR, branching index, strain hardening degree, melt tension MT, and ductility.
Therefore, hydrogen is preferably used at a molar ratio of 1.0 × ^10-6 or more, preferably 1.0 × ^10-5 or more, and more preferably 1.0 × 10 ^-4 or more in terms of molar ratio to propylene. Is good. The upper limit is preferably 1.0 × ^10-2 or less, preferably 0.9 × ^10-2 or less, and more preferably 0.8 × ^10-2 or less.

In addition to the propylene monomer, copolymerization may be carried out using an α-olefin comonomer having 2 to 20 carbon atoms excluding propylene, for example, ethylene and / or 1-butene as the comonomer, depending on the intended use.

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, and the amount of copolymerization is as follows. , It is preferably used in an amount of 15 mol% or less, more preferably 10 mol% or less, still more preferably 7 mol% or less, based on propylene.

When propylene is polymerized using the catalyst and polymerization method exemplified here, propenyl is mainly produced at one end of the polymer by a special chain transfer reaction generally called β-methyl elimination from the active species derived from the catalyst component [A-1]. It shows the structure and is generated by so-called macromers. It is considered that this macromer is incorporated into an active species derived from the catalyst component [A-2], which can generate a higher molecular weight and has better copolymerizability, and the macromer copolymerization proceeds. Therefore, it is considered that the comb-shaped chain is the main branched structure of the polypropylene resin having the long-chain branched structure to be produced.

7. Method for producing propylene-based homopolymer (A) and propylene-ethylene copolymer (B) Used to obtain the propylene-based homopolymer (A) and propylene-ethylene copolymer (B) used in the present invention. The polymer is not particularly limited, and a known polymer can be used.
For example, a so-called Ziegler-Natta catalyst or a metallocene catalyst (for example, described in JP-A-5-295022), which is a combination of a titanium compound and organic aluminum, can be used.
In the present invention, since a propylene-based 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.

Regarding the production process of the propylene-based homopolymer (A) and the propylene-ethylene copolymer (B), any method may be used as long as the above-mentioned characteristics are satisfied, but the vapor phase method is used from the viewpoint of economy. The process is preferable, and among them, it is more preferable to produce by a process having a horizontal reactor having a stirrer rotating around the horizontal axis in a form of removing the heat of polymerization by utilizing the latent heat of evaporation of liquefied propylene.
Further, the mixing of the propylene-based homopolymer (A) and the propylene-ethylene copolymer (B) may be produced by any method as long as the above-mentioned characteristics are satisfied, but a two-stage continuous polymerization method may be used. By adopting the above, the dispersion of the propylene-ethylene copolymer (B) with respect to the propylene-based homopolymer (A) becomes good, and the transparency is further improved.
The propylene-based homopolymer (A) and the propylene-ethylene copolymer (B) may be used alone or in combination of two or more.

[Nucleating agent]
By containing a nucleating agent in the polypropylene-based resin composition of the present invention, a molded product having better transparency can be obtained.
As the nucleating agent, an organic phosphoric acid ester 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 diterponic acids and the like are used.

Examples of the organic phosphate metal salt include sodium-2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate and 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, Sodium-2,2'-Butylidene-Bis (4) , 6-Di-Methylphenyl) Phosphate, Sodium-2,2'-Butylidene-bis (4,6-di-t-Butylphenyl) Phosphate, Sodium-2,2'-t-octylmethylene-bis (4,6-di-t-butylphenyl) 4,6-di-methylphenyl) phosphate, sodium-2,2'-t-octylmethylene-bis (4,6-di-t-butylphenyl) phosphate, calcium-bis [(2,2'-) Methylene-bis (4,6-di-t-butylphenyl) phosphate], magnesium-bis [2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate], barium-bis [2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate], sodium-2,2'-methylene-bis (4-methyl-6-t-butylphenyl) phosphate, Sodium-2,2'-methylene-bis (4-ethyl-6-t-butylphenyl) phosphate, sodium-2,2'-ethylidene-bis (4-s-butyl-6-t-butylphenyl) phos Fate, sodium-2,2'-methylene-bis (4,6-di-methylphenyl) phosphate, sodium-2,2'-methylene-bis (4,6-di-ethylphenyl) phosphate, potassium- 2,2'-Etilidene-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-butylfel) phosphate], aluminum-tris [2,2'-ethylidene-bis (4,6-di-t-butylphenyl) phosphate], aluminum hydrooxy-bis [2,2'- Methylene-bis (4,6-di-t-butylphenyl) phosphate], aluminum dihydrooxy-2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate and the like are exemplified. ..

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

Examples of the above-mentioned dibenzylidene sorbitol or a derivative thereof include 1,3,2,4-dibenzidene sorbitol, 1,3-benziliden-2,4-p-methylbenzidene sorbitol, and 1,3-benziliden-2,4-. p-ethylbendylidene sorbitol, 1,3-p-methylbendylidene-2,4-bendylidene sorbitol, 1,3-p-ethylbendylidene-2,4-bendylidene sorbitol, 1,3-p-methylbendylidene-2,4 -P-ethylbenzylene sorbitol, 1,3-p-ethylbenzylidene-2,4-p-methylbenzylene sorbitol, 1,3,2,4-di (p-methylbenzylidene) sorbitol, 1,3,2,4 -Di (p-ethylbenzylidene) sorbitol, 1,3,2,4-di (pn-propylbenziliden) sorbitol, 1,3,2,4-di (pi-propylbenziliden) sorbitol, 1, 3,2,4-di (pn-butylbenzylidene) sorbitol, 1,3,2,4-di (ps-butylbenziliden) sorbitol, 1,3,2,4-di (pt-) Butylbenzylidene) sorbitol, 1,3,2,4-di (p-methoxybenziliden) sorbitol, 1,3,2,4-di (p-ethoxybenzylidene) sorbitol, 1,3-benzylene-2,4-p -Chlorbenzylidene sorbitol, 1,3-p-Chlorbendylidene-2,4-benzylidene sorbitol, 1,3-p-Chlorbendylidene-2,4-p-methylbenzidene sorbitol, 1,3-p-Chlorbendylidene-2 , 4-p-Ethylbenzylidene sorbitol, 1,3-p-methylbenzylene sorbitol, 1,3-p-methylbenzylidene sorbitol, 1,3-p-ethylbenzylidene-2,4-p-chlorobenzylidene sorbitol, 1,3 , 2,4-Di (p-chlorobenzylidene) sorbitol, 1,2,3-trideoxy-4,6: 5,7-bis-O-[(4-propylphenyl) methylene] -nonitol and the like. Can be done. Particularly preferred are 1,3,2,4-dibenzylidene sorbitol, 1,3,2,4-di (p-methylbenzylidene) sorbitol, 1,3-p-chlorobenzylidene-2,4-p-methylbenzylidene. Examples thereof include sorbitol, 1,2,3-trideoxy-4,6: 5,7-bis-O-[(4-propylphenyl) methylene] -nonitol and the like.

The metal salt of diterpene acids is a reaction product of diterpenic acids and a predetermined metal compound such as a magnesium compound and an aluminum compound. Diterpenic acid is a rosin commonly known as a natural resin obtained from pine plants, specifically natural rosins such as gum rosin, tall oil rosin, wood rosin; disproportionated rosin, hydride rosin, dehydrogenated. Various modified rosins such as rosin, polymerized rosin, α, β-ethylenic unsaturated carboxylic acid modified rosin; and purified products of the natural rosin and modified rosin can be obtained as raw materials. Examples of diterpene acids include pimaric acid, sandalacopimaric acid, palastolic acid, isopimal acid, abietic acid, dehydroabietic acid, neoavietic acid, dihydropimaric acid, dihydroabietic acid, tetrahydroabietic acid and the like.

Of these, preferred nucleating agents are organic phosphoric acid ester 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-butylphenyl) ) Phosphate], Aluminum Hydrooxy-Bis [2,2'-Methylene-Bis (4,6-di-t-Butylphenyl) Phosphate], Aluminum Dihydrooxy-2,2'-Methylene-Bis (4, A phosphoric acid ester metal salt having a crosslinked substituted aromatic group such as 6-di-t-butylphenyl) phosphate, or sodium 2-cyclohexanedicarboxylate, sodium 1,2-norbornane dicarboxylate, 1,2-norbornane. Examples thereof include alicyclic hydrocarbon dicarboxylic acid metal salts such as magnesium dicarboxylate. Examples of the metal salt include lithium, sodium, potassium, calcium, magnesium, aluminum salt and the like, and more preferably a group 1 metal such as lithium, sodium and potassium.
The content of the nucleating agent is 0.01 to 0.7 parts by weight, preferably 0.1 to 0.5 parts by weight, based on 100 parts by weight of the polypropylene resin composition for injection molding. When the content of the nucleating agent is 0.01 parts by weight or more, the effect of improving transparency is sufficient, while when it is 0.7 parts by weight or less, the cost-effectiveness (cost performance) is achieved. It is advantageous from.
In addition, these nucleating agents may be used in combination of 2 or more types.

[Other additives]
The polypropylene-based resin composition of the present invention includes various additives such as heat-resistant stabilizers, antioxidants, weather-resistant stabilizers, ultraviolet absorbers, copper damage inhibitors, and antistatic agents, as long as the performance is not impaired. , Flame retardant, hydrophilic agent, slip agent, antiblocking agent, antifogging agent, colorant, filler, polyethylene, elastomer, petroleum resin, antibacterial agent and the like.
Further, when MFR adjustment is required, an organic peroxide can be 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), and the like. Mixing predetermined amounts of various compounding components such as nucleating agents and other additives using a normal mixing device such as a polypropylene mixer (trade name), a super mixer, a ribbon blender, a tumbler mixer, a Banbury mixer, or the like. 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-screw or twin-screw extruder, a roll, or the like to obtain a pellet-like composition. You can also.

The polypropylene-based resin composition of the present invention preferably has a HAZE of 35% or less in a molded product thickness of 1 mmt in accordance with JIS K7136 (ISO14782). Within this range, sufficient visibility of the contents can be obtained.

Further, the polypropylene-based resin composition of the present invention preferably has a Charpy impact strength of 2.0 kJ / m ² or more at 0 ° C. in accordance with JIS K7111. Within this range, it is less likely to be damaged during transportation in a refrigerated environment.

Further, the polypropylene-based resin composition of the present invention preferably has a flexural modulus of 1030 MPa or more in accordance with JIS K7171. Within this range, the molded product is pressed and less likely to be deformed during transportation of the molded product, and mold release defects during injection molding are less likely to occur.

[Injection molded product]
By subjecting the polypropylene-based resin composition of the present invention to an ordinary injection molding method, injection compression molding method, injection foam molding method, injection stretch blow molding method, or the like, an injection molded product (injection molded product) can be obtained.
Specific examples of this injection-molded product include food containers (pudding containers, jelly containers, yogurt containers, other dessert containers, side dish containers, tea bowl steaming containers, containers for instant foods such as instant ramen, etc. , Rice container, retort container, lunch container, etc.), Beverage container (beverage bottle, chilled coffee container, one-hand cup container, other beverage container, etc.), cap (pet bottle cap, 1 piece cap, 2 piece cap, instant coffee Caps, seasoning caps, cosmetic container caps, etc.), various other containers (ink containers, cosmetic containers, shampoo containers, detergent containers, etc.), daily necessities (clothing cases, buckets, washbasins, writing utensils, containers, toys, cooking utensils, etc.) Other various cases, etc.) can be mentioned.

When the thickness of such an injection-molded product is 1.0 mmt or less, high transparency is easily obtained, and the product weight is reduced, which is preferable because the product cost is reduced. On the other hand, when the thickness is 0.3 mmt or more, sufficient product rigidity can be easily obtained, which is preferable.
Further, in an injection-molded article having a thickness of 0.3 to 1.0 mmt, a material capable of shortening the molding cycle is very suitable, and by using the polypropylene-based resin composition for injection molding used in the present invention, An injection molded product with high productivity can be obtained.

In order to efficiently produce an injection molded product, a large number of molds for molding multiple products at the same time are used, but if the material used does not satisfy sufficient rigidity, crystallinity and fluidity, high productivity will be achieved. I can't get it. By using the polypropylene-based resin composition used in the present invention, a highly productive injection-molded product can be obtained.

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these examples. The physical property measurement method and the materials used are as follows.

1. 1. Evaluation method of physical properties (1) MFR
The melt flow rate (MFR) of the polypropylene-based resin composition, the propylene-based homopolymer (A), and the propylene-ethylene block copolymer component (A) of the present invention is JIS K-7210-1999 (230 ° C., 2. It is measured according to 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) Bending elastic modulus A test piece is molded by an injection molding method, and after molding, it is left in a thermostatic chamber adjusted to a room temperature of 23 ° C. and a relative humidity of 50% for 5 days or more, and then determined in accordance with JIS K7171 (ISO178). It was.
(3) Charpy impact strength A test piece is molded by an injection molding method, and after molding, it is left in a constant temperature room adjusted to a room temperature of 23 ° C and a relative humidity of 50% for 5 days or more, and then left in an environment of 0 ° C for 30 minutes or more. Was adjusted and obtained in accordance with JIS K7111 (ISO179).
(4) Transparency (Haze)
Flat plates having thicknesses of 0.5 mmt, 1.0 mmt, and 2.0 mmt are molded by an injection molding method, and after molding, they are left in a thermostatic chamber adjusted to room temperature of 23 ° C. and relative humidity of 50% for 24 hours, and then JIS K7136 (ISO14782). ) Was obtained.
(5) Molding Cycle Using an injection molding machine SG125M-H manufactured by Sumitomo Heavy Industries, a dessert cup mold with a side wall thickness of 0.7 mmt and an internal capacity of 180 ml was molded with a cylinder temperature of 200 ° C, a manifold temperature of 200 ° C, and a mold temperature of 20 ° C. The shortest cooling time was evaluated so that the product did not remain in the fixed mold for 20 consecutive shots. With respect to this cooling time, 11 seconds or more was evaluated as ×, 5 to 10 seconds as Δ, and less than 5 seconds as ◯.

[Material used]
(1) Propylene-ethylene block copolymer component (a)
Novatec PP BC03GS (trade name manufactured by Japan Polypropylene Corporation) is used as each of the propylene-ethylene block copolymers (PP-1 to 6) obtained in Production Examples 1 to 5 below and (PP-7). There was.

<Manufacturing Example 1 (PP-1)>
(I) Production of solid catalyst component (A) (1) Preparation of solid component An autoclave having a capacity of 10 L equipped with a stirrer was sufficiently replaced with nitrogen, and 2 L of purified toluene was introduced. To this, 200 g of Mg (OEt) ₂ and 1 L of TiCl ₄ were added at room temperature. The temperature was raised to 90 ° C. and 50 ml of di-n-butyl phthalate was added. Then, the temperature was raised to 110 ° C. and a 3 Hr reaction was carried out. The reaction product was thoroughly washed with purified toluene, and then purified toluene was added to bring the total liquid volume to 2 L. 1 L of TiCl ₄ was added at room temperature, the temperature was raised to 110 ° C., and a 2 Hr reaction was carried out. The reaction product was thoroughly washed with purified toluene, and then the 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, an autoclave having a capacity of 20 L equipped with a stirrer was sufficiently replaced with nitrogen, and 100 g of the slurry of the solid component A1 was prepared as the solid component A1. By introducing heptane purified n- thereto to adjust so that the concentration of the solid components A1 becomes 25 g / L, the SiCl ₄ was added 50 ml, was 1Hr reaction at 90 ° C..
The reaction product was thoroughly washed with purified n-heptane, and then purified n-heptane was added to adjust the liquid volume to 4 L. Here, dimethyl divinyl silane 30 _ml, was added 80g as (i-Pr) 2 Si ( OMe) 2 to 30 ml, _Et 3 Al of n- heptane dilution _Et 3 Al, were 2Hr reaction 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 Si (OMe) ₂ was contained in an amount of 8.8 wt%.
(2) Prepolymerization Using the solid component A1 obtained above, prepolymerization was carried out according to the following procedure. Purified n-heptane was introduced into the above slurry to adjust the concentration of the solid component 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 carried out for 30 minutes, the gas phase portion was sufficiently replaced with nitrogen, and the reaction product was thoroughly washed with purified n-heptane. The obtained slurry was extracted from the autoclave and vacuum dried to obtain a solid catalyst component A. The 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% of Ti and 8.2 wt% of (i-Pr) ₂ Si (OMe) ₂ .

(Ii) Production of Propylene-Ethylene Block Copolymer (PP-1) Powder A continuous vapor phase polymerization reactor consisting of two horizontal polymerization tanks equipped with a stirrer was used. In the first reactor (internal volume 40 m ³ ), 130 g / Hr of the solid catalyst component A obtained above as a solid component and a 15 wt% hexane solution of triethylaluminum were added to 1 mol of Ti atoms in the solid catalyst component A. It was continuously supplied so that the molar ratio was 350. Further, hydrogen is placed in the polymer so that the ratio of the hydrogen concentration in the polymer to the propylene concentration is 0.051, and a propylene monomer is placed in the polymer so that the pressure in the polymer is 2.25 MPa and the temperature is 65 ° C. It was supplied and the first polymerization reaction was carried out.
The heat of reaction was removed by the heat of vaporization of the raw material liquefaction propylene.
The propylene-based homopolymer produced in the polymer was continuously extracted so that the holding level of the polymer was 50% by volume of the reaction volume, and supplied to the polymer in the second polymerization step.
In the second reactor (internal volume 40 m ³ ), hydrogen was added to the polymer from the first polymerization step, and hydrogen was added to the propylene concentration in the ethylene concentration so that the ratio of the hydrogen concentration in the polymerizer to the propylene concentration was 0.020. Ethylene was supplied into the polymer so that the ratio to 0.151 was 0.151, and propylene monomer was supplied into the polymer so that the pressure in the polymer was 2.2 MPa and the temperature was 60 ° C., respectively, and the second polymerization reaction was carried out.
The polymerization amount of the propylene-ethylene copolymer was prepared by supplying a polymerization activity inhibitor. The heat of reaction 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 withdrawn from the polymer so that the holding level of the polymer was 50% by volume of the reaction volume.
When the obtained propylene-ethylene block copolymer (PP-1) was analyzed, the MFR was 29 g / 10 min and the ethylene content was 5.8 wt%.

(Iii) Production of propylene-ethylene block copolymer (PP-1) pellets As a propylene-ethylene block copolymer, a nucleating agent with respect to 100 parts by weight of the (PP-1) powder obtained in Production Example 1. (A) 0.2 parts by weight, 0.05 parts by weight of calcium stearate as a neutralizing agent, pentaerythrityl-tetrakis as a phenolic antioxidant [3- (3,5-di-t-butyl-4-hydroxyphenyl) ) Propionate] (BASF; hereinafter abbreviated as RA1010) 0.05 parts by weight, phosphorus-based antioxidant tris (2,4-di-t-butylphenyl) phosphite (BASF; hereinafter abbreviated as RA168) .) 0.05 parts by weight and 0.08 part by weight of oleic acid amide as a slip agent were added, and the mixture was mixed with a super mixer for 3 minutes after nitrogen sealing.
After that, 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 while sealing the hopper with nitrogen using a twin-screw extruder TEM35 manufactured by Toshiba Machine Co., Ltd., and propylene-ethylene block copolymer. Pellets of (PP-1) were 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 above.

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

<Manufacturing Example 2 (PP-2)>
Propylene homopolymer (HPP-1): Novatec PP SA06GA (trade name manufactured by Nippon Polypro Co., Ltd.), catalyst, based on 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 in an amount of 15 wt%, and blending and granulation were carried out in the same manner as in Production Example 1 to obtain pellets of propylene-ethylene block copolymer (PP-2). Table 2 shows each composition and the like.

<Manufacturing Example 3 (PP-3)>
25 wt% of propylene homopolymer (HPP-1) was added to 75 wt% of propylene-ethylene block copolymer (PP-1), and blending and granulation were carried out in the same manner as in Production Example 1, and propylene-. Pellets of ethylene block copolymer (PP-3) were obtained. Table 2 shows each composition and the like.

<Manufacturing Example 4 (PP-4)>
40 wt% of propylene homopolymer (HPP-1) was added to 60 wt% of propylene-ethylene block copolymer (PP-1), blended and granulated in the same manner as in Production Example 1, and propylene-. Pellets of ethylene block copolymer (PP-4) were obtained. Table 2 shows each composition and the like.

<Manufacturing Example 5 (PP-5)>
60 wt% of propylene homopolymer (HPP-1) was added to 40 wt% of propylene-ethylene block copolymer (PP-1), and blending and granulation were performed in the same manner as in Production Example 2, and propylene-. Pellets of ethylene block copolymer (PP-5) were obtained. Table 2 shows each composition and the like.

<Manufacturing Example 6 (PP-6)>
Propylene homopolymer to (HPP -1) 80 wt%, a propylene - ethylene-based elastomer (PE-1): Vistamaxx6102 ( Exxonmobil trade name), catalyst: metallocene catalyst, MFR (230 ℃): 3g / 10 min, Ethylene content: 16 wt% was added in an amount of 20 wt%, and blending and granulation were carried out in the same manner as in Production Example 2 to obtain pellets of a propylene-ethylene block copolymer (PP-6). Table 2 shows each composition and the like.

<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- Extreme viscosity of ethylene copolymer (B) [η]: 3.8 dl / g, MFR: 30 g / 10 minutes.
Table 2 shows each composition and the like.

Ethylene polymer (C)
(C-1) LDPE: Novatec LD LJ802 (trade name manufactured by Japan Polyethylene Corporation), MFR (190 ° C.): 22 g / 10 minutes, density: 0.918 g / cm ³ , melting point: 106 ° C.
(C-2) LDPE: Novatec LD LJ902 (trade name manufactured by Japan Polyethylene Corporation), MFR (190 ° C.): 45 g / 10 minutes, density: 0.915 g / cm ³ , melting point: 102 ° C.
(C-3) LLDPE: Novatec LL UJ580 (trade name manufactured by Japan Polyethylene Corporation), MFR (190 ° C.): 20 g / 10 minutes, density: 0.925 g / cm ³ , melting point: 123 ° C.
(C-4) LLDPE: Novatec LL UJ370 (trade name manufactured by Japan Polyethylene Corporation), MFR (190 ° C.): 16 g / 10 minutes, density: 0.921 g / cm ³ , melting point: 121 ° C.
(C-5) LLDPE: Novatec LL UJ790 (trade name manufactured by Japan Polyethylene Corporation), MFR (190 ° C.): 50 g / 10 minutes, density: 0.928 g / cm ³ , melting point: 124 ° C.
(C-6) LLDPE: Novatec LL UJ960 (trade name manufactured by Japan Polyethylene Corporation), MFR (190 ° C.): 5 g / 10 minutes, density: 0.935 g / cm ³ , melting point: 126 ° C.
(C-7) Ethylene plastomer: Kernel KS571 (trade name manufactured by Japan Polyethylene Corporation), MFR (190 ° C.): 24 g / 10 minutes, density: 0.907 g / cm ³ , melting point: 100 ° C.
(C-8) Ethylene plastomer: Kernel KS560T (trade name manufactured by Japan Polyethylene Corporation), MFR (190 ° C.): 16.5 g / 10 minutes, density: 0.898 g / cm ³ , melting point: 90 ° C.

Polypropylene resin (Y)
As the polypropylene resin (Y), the polypropylene resin (Y-1) produced in Production Example 7 below was used.

[Manufacturing Example 7 (Manufacturing 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) inden 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 (DME) was added. 0.28 mol) and 100 ml of water were added, 13 g (67 mmol) of 4-bromoinden 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 separating funnel, and extracted with diisopropyl ether. The ether layer was washed with saturated brine and dried over sodium sulfate. The sodium sulfate was filtered, the solvent was distilled off under reduced pressure, and the residue was purified on a silica gel column to obtain 15.4 g (yield 99%) of a colorless liquid of 4- (4-i-propylphenyl) inden.

(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 as it was at room temperature for 2 hours, the reaction solution was poured into 500 ml of ice water, and the mixture was extracted 3 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 under reflux for 3 hours while removing water. The reaction mixture was allowed to cool, washed with saturated brine, and dried over sodium sulfate. Sodium sulfate was filtered, the solvent was evaporated under reduced pressure, and the residue was purified on a silica gel column to obtain 19.8 g (yield 96%) of a yellow liquid of 2-bromo-4- (4-i-propylphenyl) inden. ..

Synthesis of (iii) 2- (2-methyl-5-frill) -4- (4-i-propylphenyl) inden In a 500 ml glass reaction vessel, 6.7 g (82 m1 mol) of 2-methylfuran and DME were added. 100 ml was added and cooled to −70 ° C. in a dry ice-methanol bath. 51 ml (81 mmol) of a 1.59 mol / L n-butyllithium-n-hexane solution was added dropwise thereto, and the mixture was stirred as it was for 3 hours. The mixture was cooled to −70 ° C., and a solution of 20 ml (87 mmol) of triisopropylborate and 50 ml of DME was added dropwise thereto. After the dropping, the mixture was stirred overnight while gradually returning to room temperature.
After hydrolyzing by adding 50 ml of distilled water to the reaction solution, 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) inden were added in this order to 80. The mixture was heated at ° C. and reacted for 3 hours while removing low boiling water.
After allowing to cool, the reaction solution was poured into 300 ml of distilled water, transferred to a separating funnel and extracted three times with diisopropyl ether. The ether layer was washed with saturated brine and dried over sodium sulfate. The sodium sulfate was filtered, the solvent was evaporated under reduced pressure, and the residue was purified on a silica gel column. 19.6 g (19.6 g) of a colorless liquid of 2- (2-methyl-5-furyl) -4- (4-i-propylphenyl) indene. Yield 99%) was obtained.

(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-) 9.1 g (29 mmol) of frill) -4- (4-i-propylphenyl) indene and 200 ml of THF were added, and the mixture was cooled to −70 ° C. in a dry ice-methanol bath. 17 ml (28 mmol) of a 1.66 mol / L n-butyllithium-hexane solution was added dropwise thereto, 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 added in this order, and the mixture was stirred overnight while gradually returning to room temperature.
Distilled water was added to the reaction solution, the mixture was transferred to a separating funnel, washed with brine until neutral, sodium sulfate was added, and the reaction solution was dried. Sodium sulfate was filtered, the solvent was evaporated under reduced pressure, purified on a silica gel column, and the yield of dimethylbis (2- (2-methyl-5-furyl) -4- (4-i-propylphenyl) indenyl) silane was reduced. 8.6 g (yield 88%) of a yellow solid was obtained.

(V) Synthesis of dimethylsilylenebis (2- (2-methyl-5-furyl) -4- (4-i-propylphenyl) indenyl) hafnium dichloride In a 500 ml glass reaction vessel, dimethylbis (2- (2) 8.6 g (13 mmol) of −methyl-5-frill) -4- (4-i-propylphenyl) indenyl) silane and 300 ml of diethyl ether were added, and the mixture was cooled to −70 ° C. in a dry ice-methanol bath.
To this, 15 ml (25 mmol) of a 1.66 mol / L n-butyllithium-n-hexane solution was added dropwise, 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 mixture was cooled to −70 ° C. in a dry ice-methanol bath. To this, 4.0 g (13 mmol) of hafnium tetrachloride was added. Then, the mixture was stirred overnight while gradually returning to room temperature.
The solvent was evaporated under reduced pressure and recrystallized from dichloromethane-hexane to give a racemic mixture of dimethylsilylenebis (2- (2-methyl-5-furyl) -4- (4-i-propylphenyl) indenyl) hafnium dichloride. 7.6 g (65% yield) was obtained as yellow crystals.

The identification values of the obtained racemic mixture by ¹ H-NMR are described below.
^{1 1} H-NMR (C ₆ D ₆ ) identification result Racemic: δ0.95 (s, 6H), δ1.10 (d, 12H), δ2.08 (s, 6H), δ2.67 (m, 2H) , Δ5.80 (d, 2H), δ6.37 (d, 2H), δ6.74 (dd, 2H), δ7.07 (d, 2H), δ7.13 (d, 4H), δ7.28 ( s, 2H), δ7.30 (d, 2H), δ7.83 (d, 4H).

<Synthesis example 2 of catalyst component (B)>
rac-dichloro [1,1'-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4-hydroazurenyl}] Hafnium synthesis (synthesis of component [B-1] (complex 2)):
The synthesis of rac-dichloro [1,1'-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4-hydroazurenyl}] hafnium is described in Example 1 of JP-A-11-240909. It was carried out in the same manner as above.

<Catalyst synthesis example 1>
(I) Chemical treatment of ion-exchangeable layered silicates 96% sulfuric acid (668 g) was added to 2,264 g of distilled water in a separable flask, and then montmorillonite (trade name, manufactured by Mizusawa Industrial Chemicals, Inc., 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 this reaction slurry and then 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 a separable flask to prepare an aqueous solution of lithium sulfate, and the entire amount of the cake-like solid was put into the flask. The slurry was reacted at room temperature for 120 minutes. After adding 4 L of distilled water to this slurry, it was filtered, further washed with distilled water to pH 5 to 6, and filtered to obtain 760 g of a cake-like solid.
The obtained solid was pre-dried at 100 ° C. under a nitrogen stream for a whole day and night, coarse particles having a diameter of 53 μm or more were removed, and the obtained solid was further dried 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% by weight, Si: 38.30% by weight, Mg: 0.98% by weight, Fe: 1.88% by weight, Li: 0.16% by weight. Al / Si = 0.175 [mol / mol].

(Ii) Catalyst preparation and prepolymerization 20 g of the chemically treated smectite obtained above was placed in a three-necked flask (volume 1 L), and heptane (132 mL) was added to prepare a slurry, to which triisobutylaluminum (25 mmol: concentration) was prepared. A 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.
Further, in another flask (volume 200 mL), the rac-dichloro [1,1'-dimethylsilylenebis {2- (5-methyl-2-furyl)-) prepared in Synthesis Example 1 of the catalyst component (B). 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). ).
After adding triisobutylaluminum (0.84 mmol: 1.2 mL of a heptane solution having a concentration of 143 mg / mL) to the 1 L flask containing the chemically treated smectite, the above solution 1 was added and the mixture was stirred at room temperature for 20 minutes. Then, triisobutylaluminum (0.36 mmol: 0.50 mL of a heptane solution having a concentration of 143 mg / mL) was further added, the above solution 2 was added, and the mixture was stirred at room temperature for 1 hour.
Then, 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 40 ° C. for 4 hours. Then, the propylene feed was stopped and residual polymerization was carried out for 1 hour. After removing the supernatant of the obtained catalyst slurry by decantation, triisobutylaluminum (6 mmol: 17.0 mL of heptane solution having a concentration of 143 mg / mL) was added to the remaining portion, and the mixture was stirred for 5 minutes.
The solid was dried under reduced pressure for 1 hour to obtain 52.8 g of a dry prepolymerization 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 "prepolymerization catalyst 1".

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

[Manufacturing of polypropylene resin (Y-1) pellets (Y-1)]
With respect to 100 parts by weight of the polypropylene resin (Y-1) produced in Production Example 7, tetrakis [methylene-3- (3', 5'-di-t-butyl-4'-), which is a phenolic antioxidant. Hydroxyphenyl) propionate] methane (trade name "IRGANOX1010", manufactured by BASF Japan Co., Ltd.) 0.125 parts by weight, tris (2,4-di-t-butylphenyl) phosphite, which is a phosphite-based antioxidant. (Product name "IRGAFOS 168", manufactured by BASF Japan Co., Ltd.) 0.125 parts by weight is blended, mixed using a high-speed stirring mixer (Henchel mixer, product name) at room temperature for 3 minutes, and then twin-screw extrusion. It was melt-kneaded with a machine to obtain pellets (Y-1) of polypropylene resin (Y-1).
For the twin-screw extruder, KZW-25 manufactured by Technobel Co., Ltd. is used, the screw rotation speed is 400 RPM, and the kneading temperature is set to 80, 160, 210, 230 (hereinafter, the same temperature up to the die outlet) ° C. from the bottom of the hopper. did.
The pellets (Y-1) were evaluated for MFR, CXS, mm, Mw / Mn, Mz / Mw, branch index g', MT, and λmax. The methods for measuring and calculating these physical properties are as described above.
The evaluation results are shown in Table 3.

[Example 1]
(1) Production of polypropylene-based resin composition As the propylene-ethylene block copolymer component (a), (PP-1) is 85 wt%, and the ethylene-based polymer (C) is (C-3) 15 wt%. Then, as a polypropylene resin (Y), 2 parts by weight of (Y-1) was sealed with a super mixer and mixed for 3 minutes.
Then, while the hopper was nitrogen-sealed using a twin-screw extruder TEM35 manufactured by Toshiba Machine Co., Ltd., 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 to obtain a polypropylene resin composition.

(2) Manufacture of injection molded product (injection molded product) Using the pellet of the polypropylene-based resin composition obtained above, it was supplied to the Toshiba injection molding machine EC100, and the primary injection pressure was 50 MPa, the molding temperature was 200 ° C., and 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.
The physical properties of the above-mentioned items (flexural modulus, Charpy impact strength, Haze, molding cycle) were evaluated for the obtained test piece and test flat plate. 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 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 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 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, it can be seen that Examples 1 to 3 of the polypropylene-based resin composition of the present invention have good transparency, rigidity, impact resistance and moldability.
On the other hand, Comparative Example 1 which does not satisfy the constituent requirements of the polypropylene resin of the present invention is not good in transparency and moldability, and Comparative Examples 2 and 3 are not good in impact resistance.

[Example 4]
A polypropylene-based 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-based polymer (C). The results are shown in Table 5.

[Example 5]
A polypropylene-based 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-based polymer (C). The results are shown in Table 5.

[Comparative Example 4]
A polypropylene-based resin composition and an injection-molded product were obtained in the same manner as in Example 2 except that (C-1) was used as the ethylene-based polymer (C). The results are shown in Table 5.

[Comparative Example 5]
A polypropylene-based 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-based polymer (C). The results are shown in Table 5.

[Comparative Example 6]
A polypropylene-based 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-based polymer (C). The results are shown in Table 5.

[Comparative Example 7]
A polypropylene-based resin composition and an injection-molded product were obtained in the same manner as in Example 2 except that (C-7) was used as the ethylene-based polymer (C). The results are shown in Table 5.

[Comparative Example 8]
A polypropylene-based resin composition and an injection-molded product were obtained in the same manner as in Example 2 except that (C-8) was used as the ethylene-based polymer (C). The results are shown in Table 5.

As is clear from Table 5, it can be seen that Examples 4 to 5, which are polypropylene-based resin compositions of the present invention, have good transparency, rigidity, impact resistance, and moldability.
On the other hand, Comparative Examples 4 to 5 and 7 to 8 which do not satisfy the constituent requirements of the polypropylene resin of the present invention do not have good moldability, and Comparative Example 6 does not have good transparency. Further, in Comparative Examples 4, 5 and 8, the value of the flexural modulus is also not preferable.

[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-3) 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-3) 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 20 wt% of (C-3) was used as the ethylene polymer (C). The results are shown in Table 6.

[Comparative Example 10]
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-3) was used as the ethylene polymer (C). The results are shown in Table 6.

[Comparative Example 11]
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-3) was used as the ethylene polymer (C). The results are shown in Table 6.

As is clear from Table 6, it can be seen that Examples 6 to 7, which are polypropylene-based resin compositions of the present invention, have good transparency, rigidity, impact resistance, and moldability.
On the other hand, Comparative Example 9 which does not satisfy the constituent requirements of the polypropylene resin of the present invention does not have good moldability, and Comparative Examples 10 and 11 do not have good transparency. Further, in Comparative Example 9, the value of the flexural modulus is also not preferable.

[Example 8]
A polypropylene-based 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-based 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 12]
A polypropylene-based 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 13]
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 14]
A polypropylene-based 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 15]
A polypropylene-based 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.

As is clear from Table 7, it can be seen that Examples 8 to 9, which are polypropylene-based resin compositions of the present invention, have good transparency, rigidity, impact resistance, and moldability.
On the other hand, Comparative Examples 12 to 14 which do not satisfy the constituent requirements of the polypropylene-based resin of the present invention do not have good impact resistance, and Comparative Examples 14 and 15 do not have good transparency. Further, Comparative Example 14 is not good in flexural modulus and moldability.

The polypropylene-based resin composition of the present invention has good rigidity, impact resistance, transparency, and moldability, and can be suitably used for applications such as food containers, beverage containers, caps, and daily necessities, and is used industrially. The sex is extremely high.

Claims (7)

A polypropylene resin composition comprising 100 parts by weight of the polypropylene resin composition (X) and 1 to 10 parts by weight of the polypropylene resin (Y).
The polypropylene-based resin composition (X) is
JIS K7210 (230 ℃, 2.16kg load) melt flow rate conforming to (MFR) is Ri Ah at 3.5~300g / 10 min, and the propylene homopolymer except polypropylene resin (Y) (A) 75 to 85 wt% and 15 to 25 wt% of the propylene-ethylene copolymer (B) satisfying the following (B1) to (B2) (provided that the propylene-based homopolymer (A) and the propylene-ethylene copolymer are contained. The total of (B) is 100 wt%) Propylene-ethylene block copolymer component (a) 83 to 88 wt%; and 12 to 17 wt% of the ethylene-based polymer (C) satisfying the following (C1) to (C3). % (However, the total of the propylene-ethylene block copolymer component (a) and the ethylene-based polymer (C) is 100 wt%);
(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 ultimate viscosity [η] B measured in o-dichlorobenzene at 135 ° C. is 2.0 to 3.0 dl / g.
(C1) The density is more than 0.920 g / cm ³ and 0.930 g / cm ³ or less.
(C2) The melting point is 120 ° C. or higher.
(C3) The MFR according to JIS K6922-2 (190 ° C., 2.16 kg load) is 10 to 50 g / 10 minutes.
The polypropylene-based resin composition (X) has an MFR of 5 to 100 g / 10 minutes in accordance with JIS K7210 (230 ° C., 2.16 kg load); 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 minutes.
(Y2): The molecular weight distribution (Mw / Mn) by GPC is 3.0 to 10, and Mz / Mw is 2.5 to 10.
(Y3): The melt tension (MT) (unit: g) is
log (MT) ≧ -0.9 × log (MFR) +0.7 or MT ≧ 15
Satisfy either.
(Y4): The amount of the paraxylene-soluble component (CXS) at 25 ° C. is less than 5.0% by weight based on the total amount of the polypropylene resin (X).
The polypropylene-based resin composition. The polypropylene resin composition according to claim 1, wherein the polypropylene resin (Y) further has the following characteristics (Y5).
(Y5): The branching index g'at an absolute molecular weight (Mabs) of 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 characteristics (Y6).
(Y6): The mm fraction of 3 chains of propylene units by ¹³ C-NMR is 95% or more. The polypropylene-based resin composition according to any one of claims 1 to 3, wherein the HAZE of a molded product having a thickness of 1 mmt according to JIS K7136 (ISO14782) is 35% or less. The polypropylene resin composition according to any one of claims 1 to 4, wherein the Charpy impact strength at 0 ° C. according to JIS K7111 (ISO179) is 2.0 kJ / m ² or more. The polypropylene-based resin composition according to any one of claims 1 to 5, wherein the flexural modulus according to JIS K7171 (ISO178) is 1030 MPa or more. An injection-molded article comprising the polypropylene-based resin composition according to any one of claims 1 to 6.