JP2015199860A - Blow molded product composed of propylene-ethylene copolymer resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a blow molded product composed of a resin composition having transparency and flexibility and excellent blow moldability while maintaining excellent characteristics such as non-stickiness.SOLUTION: There is provided a blow molded product composed of a resin composition which comprises: 65 to 97 pts.wt. of a propylene-ethylene copolymer (A) which is obtained using a metallocene-based catalyst, has an MFR of 0.5 to 5 g/10 min and in which in a temperature-loss tangent (tanδ) curve, the peak of the tanδ curve shows a single peak at 0°C or less; and 3 to 35 pts.wt. of a propylene-ethylene copolymer (B) which has an ethylene content of 0.4 to 13 wt.% and an MFR of 0.5 to 20 g/10 min, wherein the copolymer (A) is composed of 30 to 80 wt.% of a propylene-based polymer component (A1) having an ethylene content of 0 to 6.0 wt.% and a molecular weight distribution of 2 to 4 and 20 to 70 wt.% of a propylene-ethylene copolymer component (A2) having an ethylene content of 8 to 15 wt.% and the copolymer (B) is composed of 65 to 95 wt.% of a propylene-based polymer component (B1) having an ethylene content of 0 to 6.0 wt.% and 5 to 35 wt.% of a propylene-ethylene copolymer component (B2) having an ethylene content of 8 to 25 wt.% and an MFR of 0.0001 to 0.5 g/10 min.

Description

  The present invention relates to a blow molded article comprising a propylene-ethylene copolymer resin composition, and in particular, while maintaining the properties of the soft propylene-ethylene copolymer obtained with a metallocene catalyst, excellent in transparency and flexibility. The present invention also relates to a blow molded article comprising a propylene-ethylene copolymer resin composition having excellent blow moldability even when blow molded at a low temperature.

Olefin-based thermoplastic elastomers have moderate flexibility and strength, excellent recyclability, low environmental impact that does not produce dioxins and environmental hormones during incineration, and are lightweight and easy to mold. Therefore, it is used in a wide range of fields such as films and sheets, various containers and blow molded products.
In recent years, with the expansion of usage of such olefinic thermoplastic elastomers, there has been an increasing demand for materials that have flexibility and heat resistance while maintaining the transparency unique to polypropylene. Improvement proposals have been made.

For example, in order to improve flexibility and solve the deterioration of transparency, polypropylene or propylene-ethylene copolymer having a low ethylene content in the first step and ethylene content in the second step is higher than that in the first step. However, a technique of continuously polymerizing relatively little propylene-ethylene copolymer elastomer using a Ziegler-Natta catalyst is disclosed (for example, see Patent Documents 1 and 2).
However, since Ziegler-Natta catalysts have multiple types of active sites, the produced propylene-ethylene copolymer has a wide crystallinity and molecular weight distribution, and produces a large amount of low-crystal and low-molecular weight components. Stickiness and bleed-out (exudation of low molecular weight components and additives) are strongly observed, and there is a drawback that problems such as poor appearance of the product are likely to occur.

In order to improve the appearance defects due to stickiness and bleedout caused by low crystalline and low molecular weight components, which are problems of olefinic thermoplastic elastomers produced using such Ziegler-Natta catalysts, metallocene catalysts are used. In the first step, the crystalline propylene-ethylene copolymer component having a peak between 65 ° C. and 88 ° C. in the temperature rising elution fractionation by TREF is changed to a low temperature side peak T ( A propylene-ethylene copolymer obtained by polymerizing a low-crystalline or amorphous propylene-ethylene random copolymer component that exhibits B) or does not exhibit a peak is disclosed (for example, see Patent Document 3). Since the molecular weight distribution and crystallinity distribution are narrow, it is characterized in that stickiness and bleed out are suppressed.
The polymer obtained by such a technique is widely used because it has good quality such as transparency, flexibility, moderate heat resistance, no stickiness, and no deterioration in appearance over time. However, since the olefinic thermoplastic elastomer has significantly reduced crystallinity, there is a problem that the solidification time is slow at the time of blow molding, sheet molding, and injection molding, and the molding temperature is lowered. As a result, measures have been taken to shorten the solidification time.

However, the olefinic thermoplastic elastomers obtained with these metallocene catalysts have the disadvantage that the extrusion characteristics are generally poor because of not only the composition distribution but also the narrow molecular weight distribution. In particular, an industrial problem as extrusion characteristics is a phenomenon that, in blow molding, surface roughness called shark skin or melt fracture occurs on the parison surface discharged from the die, resulting in an unusable appearance.
These surface roughness improvements can be made by increasing the die temperature and widening the die exit as molding conditions. However, the increase in die temperature is likely to cause thickness fluctuations due to worsening of drawdown. Or a problem of deterioration of the molding cycle due to an increase in the solidification time occurs. Moreover, when the width | variety of die exit is expanded, the problem that the product of the wall thickness requested | required cannot be shape | molded arises (for example, refer nonpatent literature 1).

Thus, many attempts have been made to improve the extrusion characteristics of propylene-ethylene copolymers using these metallocene catalysts.
First, as a proposal to broaden the molecular weight distribution with catalysts and polymerization methods,
(1) Proposals for broadening the molecular weight distribution by using a specific metallocene catalyst (see Patent Documents 4 and 5),
(2) Proposal for performing multistage polymerization in order to obtain two-component propylene-ethylene copolymers having different molecular weights (see Patent Documents 6 to 8),
(3) Proposal for introducing long chain branching by copolymerization of graft modification or macromonomer or diene (see Patent Documents 9 to 13),
Has been made.

However, regarding the proposal (1), for example, according to Patent Document 4, a propylene copolymer having a Mw / Mn of 4.0 to 7.7 produced by a metallocene catalyst is disclosed. Propylene copolymers and metallocenes produced using Ziegler-Natta catalysts with no disclosed Mz / Mn suggesting the presence of ultra-high molecular weight components that contribute to the improvement of When comparing the Mz / Mn of the propylene copolymer produced using the catalyst, the propylene copolymer produced using the Ziegler-Natta catalyst has a clearly high Mz / Mn and good extrusion characteristics. Since it is well known, it is clear that the improvement effect of the extrusion characteristics proposed above is insufficient.
In the proposal (2), in order to improve surface roughness while ensuring melt fluidity, it is necessary to provide a molecular weight difference between a low molecular weight component and a high molecular weight component. However, when a metallocene catalyst is used, it is difficult to produce a high molecular weight component, so it is necessary to increase the molecular weight of the high molecular weight component. As a result, the molecular weight disparity increases, but a poor appearance called gel or fish eye tends to occur. Therefore, it is not preferable.
In the proposal (3), it is difficult to control the cross-linking reaction that occurs as a side reaction, and since gel formation is induced, there is a problem that a poor appearance tends to occur.

In addition, as a proposal to blend materials with excellent extrusion characteristics,
(4) Proposal of blending other resins such as polyethylene (see Patent Document 14),
(5) Proposal of blending a propylene-ethylene copolymer having a wide molecular weight distribution (see Patent Documents 15 and 16),
Has been made.

However, in the proposal (4), since polypropylene and polyethylene are incompatible with each other, blending until the extrusion characteristics are improved results in extremely poor transparency. is there.
In the proposal (5), for example, according to Patent Document 15, the propylene-based random copolymer (A) obtained by a metallocene catalyst is 1 to 70% by weight, and a conventional Ziegler-Natta catalyst. A copolymer resin composition comprising 30 to 99% by weight of the resulting propylene random copolymer (B) is disclosed. However, since the propylene-based random copolymer (B) used in the present invention has a high MFR of 9.2 g / 10 min and does not have a high molecular weight component necessary for improving the surface roughness, There is a problem that surface roughness is not improved.
Patent Document 16 discloses a method for improving extrusion characteristics by blending polypropylene produced by a metallocene catalyst with polypropylene having a high melt tension produced by two-stage polymerization using a metallocene catalyst. Yes. However, since the polypropylene having a high melt tension used in the present invention does not contain a comonomer, when extrusion is performed at a relatively low temperature of about 180 ° C., a molecular chain having a long relaxation time in the flow in the die. Causes orientational crystallization and presents an aspect of solid-liquid phase separation at the die outlet, and therefore, when the blow ratio is increased, there is a problem that thickness unevenness occurs in the molded body and the shape is not suitable for practical use.

Further, (6) a proposal for improving surface roughness by using a specific additive (see Patent Document 17) has been made.
This proposal discloses that the generation of melt fracture can be suppressed by adding a fluoroelastomer as a processing aid. Generally, by adding fluorine elastomer, when the resin flows in the die, the surface of the die is coated with fluorine elastomer, the resin pressure near the die wall surface is reduced, and as a result, the occurrence of melt fracture is suppressed. It has been known. However, when such a method is used, if continuous molding is performed for a long time, the fluoroelastomer coated on the die wall surface deteriorates due to heat and burns, and appears as a black spot in the blow molded product. It may become a practical problem.

JP-A 63-159212 JP 63-168414 A JP 2005-132679 A Japanese Patent Laid-Open No. 04-110308 JP 2001-288220 A JP 10-338705 A International Publication No. WO94 / 16009 JP 2001-64314 A JP 10-338704 A JP 11-292944 A JP 2001-226497 A JP 2001-253913 A JP 2001-253922 A JP 2000-136274 A Japanese Patent Laid-Open No. 05-112683 International Publication WO02 / 8304 JP 2009-155357 A

Extrusion molding 7th edition revision, Kenkichi Murakami, Plastics Age, 1989

  The object of the present invention is to maintain the excellent characteristics such as the transparency and flexibility of the soft propylene-ethylene copolymer obtained by the metallocene catalyst, and no stickiness, in view of the above-mentioned problems of the prior art. However, an object of the present invention is to provide a blow molded article comprising a propylene-ethylene copolymer resin composition having excellent blow moldability even when blow molded at a low temperature.

  As a result of intensive research to solve the above problems, the present inventor used a specific propylene-ethylene copolymer obtained by a metallocene catalyst, and blended a specific amount of a specific propylene-ethylene copolymer. It has been found that a blow molded article made of the resin composition can solve the above problems, and based on these findings, the present invention has been completed.

That is, according to the first invention of the present invention, the propylene-ethylene copolymer having the following characteristics (Ai) to (A-iii) based on the total of 100 parts by weight of the following (A) and (B): (A) Propylene-ethylene copolymer resin composition containing 65-97 parts by weight and 3-35 parts by weight of propylene-ethylene copolymer (B) having the following characteristics (Bi)-(B-ii) A blow molded article made of a material,
The propylene-ethylene copolymer (A) is a propylene-based polymer component (A1) 30 having the following characteristics (A1-i) and (A1-ii) based on a total of 100% by weight of (A1) and (A2). And 80% by weight, and 20 to 70% by weight of a propylene-ethylene copolymer component (A2) having the following characteristics (A2-i), and the propylene-ethylene copolymer (B) comprises (B1) and (B2) based on a total of 100% by weight, propylene polymer component (B1) having the following characteristics (B1-i) 65 to 95% by weight, and having the following characteristics (B2-i) and (B2-ii) A blow molded article comprising a propylene-ethylene copolymer resin composition comprising 5 to 35% by weight of a propylene-ethylene copolymer component (B2) is provided.
Propylene-ethylene copolymer (A);
Characteristic (Ai): obtained by polymerization using a metallocene catalyst.
Characteristic (A-ii): Melt flow rate [MFR (A)] (230 ° C., 2.16 kg load) is in the range of 0.5 to 5 g / 10 min.
Characteristic (A-iii): In the temperature-loss tangent (tan δ) curve obtained by solid viscoelasticity, the peak of the temperature-loss tangent (tan δ) curve representing the glass transition observed in the range of −60 to 20 ° C. is 0. A single peak is shown below ℃.
Characteristic (A1-i): Propylene homopolymer or propylene-ethylene copolymer, whose ethylene content [E (A1)] is in the range of 0 to 6.0% by weight.
Characteristic (A1-ii): The molecular weight distribution [Mw / Mn (A1)] represented by the ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn) determined by GPC of the polymer component (A1) is 2 It is in the range of ~ 4.
Characteristic (A2-i): The ethylene content [E (A2)] of the copolymer component (A2) is in the range of 8 to 15% by weight.
Propylene-ethylene copolymer (B);
Characteristic (Bi): The ethylene content [E (B)] in the copolymer (B) is in the range of 0.4 to 13% by weight.
Characteristic (B-ii): The melt flow rate [MFR (B)] (230 ° C., 2.16 kg load) of the copolymer (B) is in the range of 0.5 to 20 g / 10 minutes.
Characteristic (B1-i): The ethylene content [E (B1)] in the polymer component (B1) is in the range of 0 to 6.0% by weight.
Characteristic (B2-i): The ethylene content [E (B2)] in the copolymer component (B2) is in the range of 8 to 25% by weight.
Characteristic (B2-ii): The melt flow rate [MFR (B2)] (230 ° C., 2.16 kg load) of the copolymer component (B2) is in the range of 0.0001 to 0.5 g / 10 minutes.

According to the second invention of the present invention, in the first invention, the propylene-ethylene copolymer (A) comprises a step of producing a propylene-based polymer component (A1) and a propylene-ethylene copolymer component. There is provided a blow molded article made of a propylene-ethylene copolymer resin composition, which is produced by multi-stage polymerization having a step of producing (A2).
Furthermore, according to the third invention of the present invention, in the first or second invention, the propylene-ethylene copolymer (B) comprises a step of producing a propylene-ethylene polymer component (B1) and a propylene-ethylene copolymer. There is provided a blow molded article made of a propylene-ethylene copolymer resin composition, which is produced by multistage polymerization having a step of producing a polymer component (B2).

The propylene-ethylene copolymer resin composition according to the present invention has improved extrusion characteristics of the propylene-ethylene copolymer obtained by the metallocene catalyst, and increases the extrusion amount during blow molding and the die exit width. Even under molding conditions that are superior in productivity and performance such as narrowing of the extrusion and lowering of the extrusion temperature, it is possible to obtain a blow molded article with excellent appearance that suppresses the occurrence of surface roughness called melt fracture or shark skin. .
Therefore, the blow molded article comprising the propylene-ethylene copolymer resin composition of the present invention maintains excellent properties such as excellent transparency and flexibility and no stickiness at a high level. It is suitable for use as a medical container or cosmetic container.

It is a perspective view which shows an example of the surface roughness in a blow molding. In an Example, it is a graph which shows the temperature-loss tangent (tan-delta) curve obtained by the solid-viscoelasticity measurement (DMA) of the press sheet of the polymer (A-1) obtained by manufacture example (A-1). It is an example showing a single peak. In an Example, it is a graph which shows the temperature-loss tangent (tan-delta) curve obtained by the solid-viscoelasticity measurement (DMA) of the press sheet of the polymer (A-9) obtained by manufacture example (A-9). It is an example showing a non-single peak.

A blow molded article made of the propylene-ethylene copolymer resin composition of the present invention (hereinafter sometimes simply referred to as a resin composition) is produced by the following propylene-ethylene copolymer (A ) Is a blow molded article made of a resin composition containing a specific amount of a specific propylene-ethylene copolymer (B) described later.
Hereinafter, the blow molded product made of the propylene-ethylene copolymer resin composition of the present invention will be described in detail for each item.

I. Resin composition I-1. Propylene-ethylene copolymer (A)
1. Properties of Propylene-Ethylene Copolymer (A) The propylene-ethylene copolymer (A) used in the resin composition according to the present invention (hereinafter sometimes referred to as copolymer (A)) is ( 30 to 80% by weight of a propylene polymer component (A1) having the following characteristics (A1-i) and (A1-ii) based on a total of 100% by weight of A1) and (A2), and the following characteristics (A2-i The propylene-ethylene copolymer component (A2) having 20 to 70% by weight.
Characteristic (Ai): obtained by polymerization using a metallocene catalyst.
Characteristic (A-ii): Melt flow rate [MFR (A)] (230 ° C., 2.16 kg load) is in the range of 0.5 to 5 g / 10 min.
Characteristic (A-iii): In the temperature-loss tangent (tan δ) curve obtained by solid viscoelasticity, the peak of the temperature-loss tangent (tan δ) curve representing the glass transition observed in the range of −60 to 20 ° C. is 0. A single peak is shown below ℃.
Characteristic (A1-i): Propylene homopolymer or propylene-ethylene copolymer, whose ethylene content [E (A1)] is in the range of 0 to 6.0% by weight.
Characteristic (A1-ii): The molecular weight distribution [Mw / Mn (A1)] represented by the ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn) determined by GPC of the polymer component (A1) is 2 It is in the range of ~ 4.
Characteristic (A2-i): The ethylene content [E (A2)] of the copolymer component (A2) is in the range of 8 to 15% by weight.

Here, W (A1) and W (A2) are the propylene-based polymer component (A1) (hereinafter referred to as component (A1)) and propylene-ethylene copolymer in the propylene-ethylene copolymer (A). The weight ratio of the union (A2) (hereinafter referred to as the component (A2)) is defined as W (A1) + W (A2) = 100.
Further, when E (A) is defined as the ethylene content of the propylene-ethylene copolymer (A), E (A2) is expressed as follows using W (A1) and W (A2) defined above. It is determined by the formula.
E (A2) = {E (A) −E (A1) × [W (A1) ÷ 100]} ÷ [W (A2) ÷ 100]

Hereinafter, characteristics to be satisfied by the copolymer (A) will be described in order.
(1) Characteristic (Ai): Metallocene catalyst The copolymer (A) used in the present invention is obtained by polymerization using a metallocene catalyst.
By using a metallocene-based catalyst, it is possible to obtain a propylene-ethylene copolymer having a narrow molecular weight distribution, a narrow crystallinity distribution, and a low amount of low crystalline components. When using a Ziegler-Natta catalyst, the molecular weight distribution is wide, the crystallinity distribution is wide, and the amount of low-crystalline components is increased, so at least one of transparency, flexibility, and non-stickiness is deteriorated. It is not preferable.

(2) Characteristic (A-ii): MFR of copolymer (A)
The melt flow rate [MFR (A)] of the copolymer (A) is 0.5 to 5 g / 10 minutes, preferably 1 to 3 g / 10 minutes. If the MFR (A) is less than 0.5 g / 10 min, the molding processability and the melt fluidity are inferior. On the other hand, if the MFR is greater than 5 g / 10 min, the parison drawdown increases, It becomes impossible.
The melt flow rate [MFR (A)] is measured at 230 ° C. and a load of 2.16 kg according to JIS K7210.

Since the copolymer (A) consists of the component (A1) and the component (A2), the MFR (A) of the copolymer (A) is the MFR (A1) of the component (A1) and the MFR of the component (A2). It has a certain relationship with (A2). Actually, since the MFR of the component (A2) cannot be directly measured, the MFR (A2) in the present invention is the same as the component (A1) in the MFR (A), MFR (A1), and copolymer (A). Using the weight ratio of the component (A2), the value is defined by the following equation, which is well known as a logarithmic addition rule of viscosity.
MFR (A2) = exp {(log _e [MFR (A)] − (W (A1) ÷ 100) × log _e [MFR (A1)]) ÷ (W (A2) ÷ 100)}
(Wherein, MFR (A1) is a MFR of the propylene-based polymer component (A1), W (A1) , W (A2) are those defined above. In addition, log _e is the e Log base.)

  In the production of the copolymer (A), how to adjust the MFR (A) will be described later. As is apparent from the above formula, the MFR (A) includes MFR (A1), MFR (A2). ), W (A1), and W (A2). In this invention, if MFR (A) exists in the range of 0.5-5 g / 10min, MFR (A1) can be arbitrarily adjusted in the range which does not impair the effect of this invention. MFR (A2) can also be arbitrarily adjusted in the same manner. However, when it is in the range of 1 to 3 g / 10 minutes, the effect of suppressing appearance defects such as bleed out is increased, which is more preferable.

(3) Characteristic (A-iii): Peak of temperature-loss tangent (tan δ) curve This characteristic indicates the compatibility between the component (A1) and the component (A2) contained in the copolymer (A). In order to exhibit transparency, the peak of the temperature-loss tangent (tan δ) curve defined as the glass transition point observed in the range of −60 to 20 ° C. shows a single peak at 0 ° C. or lower. There is a need.
When the copolymer (A) exhibits a phase separation structure, the glass transition temperature of the amorphous part contained in the component (A1) and the glass transition temperature of the amorphous part contained in the component (A2) are observed. Therefore, the peak is not single. In this case, there arises a problem that transparency as a molded product is deteriorated.

Here, the solid viscoelasticity measurement (DMA) is specifically performed by applying a sine distortion of a specific frequency to a strip-shaped sample piece and detecting the generated stress. The frequency is 1 Hz, and the measurement temperature is raised stepwise from −60 ° C. until the sample is melted and cannot be measured. Further, it is recommended that the magnitude of the strain is about 0.1 to 0.5%.
From the obtained stress, the storage elastic modulus G ′ and the loss elastic modulus G ″ are obtained by a known method, and the loss tangent (= loss elastic modulus / storage elastic modulus) defined by this ratio is plotted against the temperature. The peak of the tan δ curve at 20 ° C. or lower generally observes the glass transition of the amorphous part, and in the present invention, this peak temperature is the glass transition temperature. It is defined as Tg (° C.) A specific method of solid viscoelasticity measurement (DMA) is described in Examples.

(4) Characteristic (A1-i): Ethylene content of component (A1) Component (A1) is a component that suppresses stickiness to the copolymer (A) and needs to have crystallinity. Therefore, the ethylene content [E (A1)] of the component (A1) is 6.0% by weight (% by weight) or less, more preferably 1.0 to 5.0% by weight. When the ethylene content [E (A1)] exceeds 6.0% by weight, the crystallinity decreases, and stickiness occurs.

(5) Characteristic (A1-ii): Mw / Mn ratio of component (A1) Mw / Mn (A1) is the weight average molecular weight (Mw) and number average molecular weight obtained by GPC measurement of component (A1). It is defined by the ratio of (Mn) and needs to be 2-4.
When Mw / Mn (A1) is larger than 4, the low molecular weight component is increased, which is not preferable because it adversely affects the gloss of the blow molded product or causes stickiness.
The specific method of GPC measurement will be described in detail in the examples.

(6) Characteristic (A2-i): ethylene content of component (A2) Component (A2) is a component necessary for improving the flexibility and transparency of the copolymer (A). In general, in the propylene-ethylene copolymer, the crystallinity is lowered and the flexibility improving effect is increased as the ethylene content is increased. Therefore, the ethylene content [E (A2)] in the component (A2) is 8% by weight or more, preferably 9% by weight or more.
When E (A2) is less than 8% by weight, sufficient flexibility cannot be exhibited.
On the other hand, if E (A2) is excessively increased in order to lower the crystallinity of component (A2), the compatibility of component (A1) and component (A2) decreases, and component (A2) becomes component (A1). Domains are formed without compatibilization. In such a phase separation structure, if the refractive indexes of the matrix and the domain are different, the transparency is drastically lowered. Therefore, E (A2) of the component (A2) in the copolymer (A) used in the present invention needs to be 15% by weight or less, preferably 14% by weight or less.
In addition, about the measuring method of ethylene content used in this invention, the detail is described in an Example.

(7) Quantity ratio of component (A1) and component (A2) Next, the quantity ratio of the component (A1) and the component (A2) of the copolymer (A) will be described.
The component (A1) is a component that imparts appropriate crystallinity to the copolymer (A) and suppresses stickiness, and the ratio of the component (A1) to the copolymer (A) [W (A1)] Is 30 to 80% by weight, preferably 40 to 70% by weight.
When W (A1) is less than 30% by weight, the component (A2) exhibits a sea structure, and thus the stickiness is remarkably deteriorated. On the other hand, if W (A1) exceeds 80% by weight, the flexibility of the copolymer (A) is impaired.
As defined above, since the sum of W (A1) and W (A2) is 100, if the range of W (A1) is determined, W (A2) is determined at the same time, so W (A2) Needs to be 20 to 70% by weight, preferably 30 to 60% by weight.

2. Method for Preparing Propylene-Ethylene Copolymer (A) As the copolymer (A) according to the present invention, a copolymer obtained by polymerization using a metallocene catalyst is used.
The one using the metallocene catalyst has better transparency and flexibility because the molecular weight distribution is narrower, the crystallinity distribution is narrower, and the amount of low crystalline components is less than that using the Ziegler-Natta catalyst. In addition, a propylene-ethylene random copolymer having no stickiness can be produced.
An appropriate form for producing the copolymer (A) will be described in detail below sequentially.

(1) Metallocene catalyst A feature of the resin composition according to the present invention is that a propylene-ethylene copolymer (A) obtained by polymerization using a metallocene catalyst and a specific propylene-ethylene copolymer (B) are used. Thus, the type of the metallocene catalyst used in the former production is not particularly limited.

As a typical example of the metallocene catalyst that can be used in the present invention, a metallocene catalyst comprising the following components (a) and (b) and an optional component (c) can be mentioned.
Component (a): At least one metallocene transition metal compound selected from transition metal compounds represented by the following general formula (1) Component (b): At least selected from the following (b-1) to (b-4) One solid component (b-1) A particulate carrier on which an organoaluminum compound is supported (b-2) An ionic compound capable of reacting with component (a) to convert component (a) into a cation Or a particulate carrier on which a Lewis acid is supported (b-3) a solid acid particulate (b-4) an ion-exchange layered silicate Component (c): an organoaluminum compound

(1-1) Component (a)
Component (a) is at least one metallocene transition metal compound selected from transition metal compounds represented by the following general formula (1).

（式中、ＡおよびＡ’は、置換基を有していてもよい共役五員環配位子、Ｑは、二つの共役五員環配位子間を任意の位置で架橋する結合性基、Ｘ及びＹは、成分（ｂ）と反応してオレフィン重合能を発現させるσ共有結合性補助配位子、Ｍは、周期表第４族の遷移金属である。）

(In the formula, A and A ′ are conjugated five-membered ring ligands that may have a substituent, and Q is a binding group that bridges two conjugated five-membered ring ligands at an arbitrary position. , X and Y are σ covalent auxiliary ligands that react with the component (b) to develop olefin polymerization ability, and M is a transition metal of Group 4 of the periodic table.

In the general formula (1), the conjugated five-membered ring ligand is a cyclopentadienyl group derivative that may have a substituent.
When it has a substituent, examples of the substituent include a hydrocarbon group having 1 to 30 carbon atoms (which may contain a heteroatom such as halogen, silicon, oxygen, sulfur, etc.), and this hydrocarbon. The group may be bonded to the cyclopentadienyl group as a monovalent group, or when there are a plurality of groups, two of them are bonded to the other end (ω-end) to form cyclopentadienyl. A ring may be formed together with a part of the enyl.
Examples of such a conjugated five-membered ring ligand include an indenyl group, a fluorenyl group, or a hydroazurenyl group, and these groups may further have a substituent, and in particular, an indenyl group or a hydroazurenyl group. Groups are preferred.

Q is preferably a methylene group, an ethylene group, a silylene group, a germylene group, a group in which these are substituted with a hydrocarbon group, a silafluorene group, or the like.
The auxiliary ligands X and Y react with the component (b) to generate an active metallocene having an olefin polymerization ability, and are each a hydrogen atom, a halogen atom, a hydrocarbon group, or oxygen, nitrogen. And a hydrocarbon group optionally having a heteroatom such as silicon. Of these, a hydrocarbon group having 1 to 10 carbon atoms or a halogen atom is preferred.
M is titanium, zirconium, or hafnium. In particular, zirconium and hafnium are preferable.

Further, among the above transition metal compounds, those in which stereoregular polymerization of propylene proceeds and the obtained propylene polymer has a high molecular weight are preferable.
Specifically, JP-A-1-301704, JP-A-4-221694, JP-A-6-1005909, JP-T 2002-535339, JP-A-6-239914, JP-A-10-226712. Preferably, transition metal compounds described in JP-A No. 3-193396 and JP-A No. 2001-504824 are listed.

Non-limiting examples of the transition metal compound include the following.
(1) Dichloro [1,1′-dimethylsilylenebis (2-methylcyclopentadienyl)] zirconium (2) Dichloro [1,1′-dimethylsilylenebis (2-methyl-4-phenylcyclopentadienyl) Zirconium (3) Dichloro [1,1′-dimethylsilylenebis (2,4,5-trimethylcyclopentadienyl)] zirconium (4) Dichloro [1,1′-dimethylsilylenebis (2-methyl-4-) Phenyl-indenyl)] zirconium (5) dichloro [1,1′-dimethylsilylenebis (2-ethyl-4-phenyl-indenyl)] zirconium (6) dichloro [1,1′-dimethylsilylene (2-methyl-4) -Phenyl-indenyl) (2-isopropyl-4-phenyl-indenyl)] zirconium (7) dichloro [1,1'- Dimethylsilylene (2-methyl-4-t-butylphenyl-indenyl) (2-isopropyl-4-t-butylphenyl-indenyl)] zirconium (8) dichloro [1,1′-dimethylsilylenebis {2- (5 -Methyl-2-furyl) -4-phenyl-indenyl}] zirconium (9) dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-thienyl) -4-phenyl-indenyl}] zirconium (10) Dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (2-naphthyl) -indenyl}] zirconium (11) dichloro [1,1′-dimethylsilylene Bis {2- (5-methyl-2-furyl) -4- (4-t-butylphenyl) -indenyl}] zirconium (12) dichloro {1,1 '-Dimethylsilylenebis (2-methyl-4-phenyl-4H-azurenyl)} zirconium (13) dichloro [1,1'-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4H-azurenyl} ] Zirconium (14) dichloro [1,1'-dimethylsilylenebis {2-methyl-4- (4-t-butylphenyl) -4H-azulenyl}] zirconium (15) dichloro [1,1'-dimethylsilylenebis] {2-Ethyl-4- (2-fluoro-4-biphenyl) -4H-azurenyl}] zirconium (16) dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4H -5,6,7,8-tetrahydroazurenyl}] zirconium (17) dichloro {1,1'-dimethylsilylene (2,3-dimethyl) Cyclopentadienyl) (2-methyl-4-phenyl-4H-azulenyl)} zirconium (18) dichloro {1,1′-dimethylsilylene (2-methyl-4-phenylcyclopentadienyl) (2-methyl- 4-phenyl-4H-azurenyl)} zirconium (19) dichloro {1,1′-dimethylsilylene (2,3,4-trimethylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} zirconium (20) dichlorodimethylmethylene (3-t-butyl-5-methylcyclopentadienyl) fluorenyl) zirconium (21) dichlorodimethylmethylene (3-t-butyl-5-methylcyclopentadienyl) (2,7- Di-t-butylfluorenyl) zirconium (22) dichlorodimethylmethylene (3-t-butyl) 5-methylcyclopentadienyl) (1,1,4,4,7,7,10,10-octamethyl-1,2,3,4,7,8,9,10-octahydrodibenzofluorene Nyl) zirconium

  For the preferred compounds represented above, only representative exemplary compounds are described avoiding many complicated examples. Although a compound in which the central metal is zirconium has been described, it goes without saying that similar hafnium compounds can also be used, and various ligands, cross-linking groups, or auxiliary ligands can be arbitrarily used. It is self-explanatory.

(1-2) Component (b)
As the component (b), at least one solid component selected from the components (b-1) to (b-4) described above is used.
Each of these components is a well-known thing, and can be used selecting it suitably from well-known techniques. Specific examples and manufacturing methods thereof are described in detail in JP-A No. 2002-284808, JP-A No. 2002-53609, JP-A No. 2002-69116, and the like.

  Examples of the particulate carrier used for the component (b-1) and the component (b-2) include inorganic oxides such as silica, alumina, magnesia, silica alumina, and silica magnesia, magnesium chloride, magnesium oxychloride, aluminum chloride, and chloride. Examples thereof include inorganic halides such as lanthanum, and porous organic carriers such as polypropylene, polyethylene, polystyrene, styrene divinyl benzene copolymer, and acrylic acid copolymer.

Moreover, as a non-limiting specific example of a component (b),
As a component (b-1), a particulate carrier on which methylalumoxane, isobutylalumoxane, methylisobutylalumoxane, aluminum butylboronate tetraisobutyl, etc. are supported,
As component (b-2), triphenylborane, tris (3,5-difluorophenyl) borane, tris (pentafluorophenyl) borane, triphenylcarbonium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium A particulate carrier carrying tetrakis (pentafluorophenyl) borate or the like,
As component (b-3), after treating with alumina, silica alumina, magnesium chloride, fluorine compound, calcined silica alumina, pentafluorophenol and organometallic compound such as diethyl zinc are reacted, and after further reaction with water, the same Silica etc. carrying the product,
As component (b-4), montmorillonite, zakonite, beidellite, nontronite, saponite, hectorite, stevensite, bentonite, teniolite and the like smectite group, vermiculite group, mica group, etc.
Can be mentioned. These may form a mixed layer.

  Among the components (b), particularly preferable is the ion-exchange layered silicate of the component (b-4), and more preferable are chemical treatments such as acid treatment, alkali treatment, salt treatment, and organic matter treatment. Is an ion-exchange layered silicate.

(1-3) Component (c)
Examples of organoaluminum compounds used as component (c) as necessary include trialkylaluminum or diethylaluminum such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, trioctylaluminum represented by the following general formula Halogen or alkoxy-containing alkylaluminum such as monochloride and diethylaluminum monomethoxide.
General formula: AlR _a X _3-a
(In the formula, R is a hydrocarbon group having 1 to 20 carbon atoms, X is a hydrogen atom, a halogen atom or an alkoxy group, and a is a number of 0 <a ≦ 3.)
In addition, aluminoxanes such as methylaluminoxane can also be used.
Of these, trialkylaluminum is particularly preferable as component (c).

(1-4) Formation of catalyst Component (a), component (b) and, if necessary, component (c) are brought into contact to form a catalyst.
Although the contact method is not specifically limited, Contact can be made in the following order. Further, this contact may be performed not only at the time of catalyst preparation but also at the time of prepolymerization with olefin.
(I) The component (a) is contacted with the component (b).
(Ii) After contacting the component (a) and the component (b), the component (c) is added.
(Iii) After contacting the component (a) and the component (c), the component (b) is added.
(Iv) Component (b) and component (c) are contacted, and then component (a) is added.
(V) contacting the three components simultaneously.

  The amount of components (a), (b) and (c) used in the present invention is arbitrary. For example, the amount of component (a) used relative to component (b) is preferably in the range of 0.1 μmol to 500 μmol, particularly preferably 0.5 μmol to 100 μmol, relative to 1 g of component (b). The amount of component (c) used relative to component (b) is preferably such that the amount of transition metal is 0.001 mmol to 100 mmol, particularly preferably 0.005 mmol to 50 mmol, relative to 1 g of component (b). Therefore, the amount of component (c) to component (a) is in the range of 0.002 to 106, preferably 0.02 to 105, particularly preferably 0.2 to 104, in terms of the molar ratio of transition metal.

The metallocene catalyst is preferably subjected to a prepolymerization treatment in which a small amount of polymer is brought into contact with an olefin in advance.
The olefin to be used is not particularly limited, but ethylene, propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, 3-methyl-1-butene, vinylcycloalkane, styrene and the like can be used. It is possible to use, and it is particularly preferable to use propylene.

The olefin can be supplied by any method such as a supply method for maintaining the olefin at a constant speed or in a constant pressure state, a combination thereof, or a stepwise change.
The prepolymerization temperature and time are not particularly limited, but are preferably in the range of −20 ° C. to 100 ° C. and 5 minutes to 24 hours, respectively. The amount of prepolymerization is preferably 0.01 to 100, more preferably 0.1 to 50 with respect to the component (b). After completion of the prepolymerization, the catalyst can be used as it is, depending on the usage form of the catalyst. However, if necessary, drying can be performed.
Furthermore, a polymer such as polyethylene, polypropylene, or polystyrene, or an inorganic oxide solid such as silica or titania can be allowed to coexist during or after the contact of the above components.

(2) Production Method The copolymer (A) according to the present invention is a mixture of two components, a propylene polymer component (A1) and a propylene-ethylene copolymer component (A2).
In producing the copolymer (A), it is possible to use a production method in which the component (A1) and the component (A2) are separately produced and blended, but the mixing of the component (A1) and the component (A2) is possible. From the viewpoint of making the state as uniform as possible, it is desirable to produce by multistage polymerization.
That is, it is desirable to produce the copolymer (A) by multistage polymerization having a step of producing the component (A1) and a step of producing the component (A2).
At this time, the step of manufacturing the component (A1) may be performed first, followed by the step of manufacturing the component (A2). Conversely, the step of manufacturing the component (A2) may be performed first. Thereafter, the component (A2) may be performed. Since component (A2) has a higher ethylene content and lower crystallinity than component (A1), if anything, the step of producing component (A1) is carried out first, and then component (A2) is added. It is desirable to perform the manufacturing process because the particle properties can be improved.
Hereinafter, the details of the production method will be described by taking the case of using multistage polymerization as an example.

(2-1) Polymerization process Any polymerization process can be used.
First, the operation method over time will be described. From this point of view, it is possible to use either a batch method or a continuous method, but it is generally desirable to use a continuous method from the viewpoint of productivity. In the case of the batch method, it is possible to individually polymerize the component (A1) and the component (A2) using a single polymerization reactor by changing the polymerization conditions with time. As long as the effects of the present invention are not impaired, a plurality of polymerization reactors may be connected in parallel.
In the case of a continuous process, since it is necessary to polymerize component (A1) and component (A2) separately, it is necessary to use a production facility in which two or more polymerization reactors are connected in series. The polymerization reactor corresponding to the first step for producing the component (A1) and the polymerization reactor corresponding to the second step for producing the component (A2) must be in series, but the first step, For each of the second steps, a plurality of polymerization reactors may be connected in series and / or in parallel.

Next, regarding the reaction phase, it is preferable to use a bulk method or a gas phase method. Although supercritical conditions can be used as intermediate conditions between the bulk method and the gas phase method, they are substantially the same as the gas phase method, and are therefore included in the gas phase method without particular distinction. In the case of a multi-tank continuous polymerization process, a bulk-phase polymerization reactor may be followed by a gas-phase polymerization reactor. In the case of the batch method, the first step may be performed by a bulk method, and the second step may be performed by a vapor phase method. This case is also referred to as a bulk method.
Various processes have been proposed in each of the bulk method and the gas phase method. Although there is a difference in the stirring (mixing) method and the heat removal method, in this aspect, in the present invention, the special process species is not limited.
Since component (A2) is easily soluble in organic solvents such as hydrocarbons and liquefied propylene, the step of producing component (A2) preferably uses a gas phase method.
The process for producing the component (A1) may be a bulk method or a gas phase method, but in order to produce a more flexible product, the component (A1) having relatively low crystallinity. In order to avoid problems such as adhesion, it is desirable to use a gas phase method.
Therefore, using the continuous method, first, the first step for producing the component (A1) is carried out by the vapor phase method, and then the second step for producing the component (A2) is carried out by the vapor phase method. Most desirable.

(2-2) General polymerization conditions The polymerization temperature can be used without any particular problem as long as it is within a commonly used temperature range. Specifically, a range of 0 ° C to 200 ° C, preferably 40 ° C to 100 ° C can be used.
Although the polymerization pressure varies depending on the process to be selected, it can be used without any problem as long as it is in a pressure range usually used. Specifically, a range of greater than 0 to 200 MPa, preferably 0.1 to 50 MPa can be used. At this time, there is no problem even if an inert gas such as nitrogen coexists.

(2-3) Organoaluminum compound Unlike a Ziegler catalyst, it is not essential for a metallocene catalyst to use an organoaluminum compound as a promoter.
Therefore, it is not always necessary to add an organoaluminum compound to the polymerization reactor in terms of forming an activated catalyst. However, the polymerization reaction of olefins is unique in that it has a very large number of catalyst cycles in a very short time compared to other catalytic reactions, so there is a technical problem that it is susceptible to impurities. To do.
In order to solve this problem, it is a well-known fact that a much higher purity raw material is used compared to a normal chemical product, or the raw material is further refined and used in various ways. . From this point of view, a method is often used in which a highly reactive organoaluminum compound is added to the polymerization reactor and reacted with the organoaluminum compound before the impurities react with the metallocene catalyst to render them harmless.
Also in this invention, it is desirable to use an organoaluminum compound (C) from this viewpoint. Although any compound can be used as the organoaluminum compound (C), examples of suitable compounds are the same as those of the component (c) which is an optional component of the metallocene catalyst, and in particular, triisobutylaluminum and trioctylaluminum. Is preferred.

  The amount of the organoaluminum compound (C) used can be arbitrarily set according to the level of impurities. Generally, it adds so that it may become in the range of 0.001-1000 mmol-Al / kg as the number-of-moles of aluminum atom with respect to the weight of the propylene-ethylene copolymer (A) to manufacture. Preferably, it is added in a range of 0.01 to 100 mmol-Al / kg, more preferably 0.1 to 20 mmol / kg.

3. Next, a method for controlling the index of the propylene-ethylene copolymer (A) will be described in detail.
The propylene-ethylene copolymer (A) according to the present invention is a mixture of two components, a propylene-based polymer component (A1) and a propylene-ethylene copolymer component (A2).
An index control method will be described for each component.

(1) Propylene polymer component (A1)
First, regarding the ethylene content, as described above, the ethylene content [E (A1)] of the propylene polymer component (A1) is 0 to 6.0% by weight, more preferably 1.0 to 5%. 0.0% by weight.
As a means for controlling the ethylene content, it is convenient to use a method for controlling the amount of ethylene supplied to the polymerization tank.
Specifically, if the ratio of ethylene to propylene supplied to the polymerization tank is increased (ethylene supply amount ÷ propylene supply amount), the ethylene content of the resulting propylene polymer component (A1) increases. The reverse is also true.
The relationship between the amount ratio of propylene and ethylene supplied to the polymerization tank and the ethylene content of the resulting propylene polymer component (A1) varies depending on the type of metallocene catalyst used, but the supply amount ratio should be adjusted appropriately. It is very easy for those skilled in the art to obtain the propylene-based polymer component (A1) having the desired ethylene content.

Next, MFR will be described.
As described above, the MFR (A1) of the propylene-based polymer component (A1) is not particularly limited as long as the MFR (A) of the propylene-ethylene copolymer (A) is within the specified range. Can be a value. A method for controlling the MFR (A) of the propylene-ethylene copolymer (A) will be described later. As one means, there is a method for controlling the MFR (A1) of the propylene-based polymer component (A1).
The MFR (A1) of the propylene-based polymer component (A1) can be adjusted by using hydrogen as a chain transfer agent. Specifically, when the concentration of hydrogen as a chain transfer agent is increased, the MFR of the propylene polymer component (A1) is increased. The reverse is also true. In order to increase the concentration of hydrogen in the polymerization tank, it is sufficient to increase the amount of hydrogen supplied to the polymerization tank, and adjustment is very easy for those skilled in the art.

Finally, Mw / Mn, which is the ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn) in GPC measurement, will be described. As described above, the Mw / Mn (A1) of the propylene polymer component (A1) is 2 to 4.
By using a metallocene catalyst, the Mw / Mn can be made smaller than when using a Ziegler-Natta catalyst, but when controlling the Mw / Mn, select an appropriate metallocene catalyst for the target value. At the same time, it is also effective to devise polymerization conditions.
For example, if a two-tank continuous polymerization process is employed to produce propylene-ethylene copolymers having different molecular weights in the first and second polymerization tanks, the Mw is higher than the value originally given by the metallocene catalyst used. / Mn can be increased. At this time, the relationship between the polymerization conditions to be used, particularly the hydrogen concentration and the molecular weight of the resulting propylene-ethylene copolymer is known in advance, and the Mw / Mn is set to a desired value by appropriately adjusting the hydrogen concentration in each tank. It is easy for those skilled in the art to adjust the value.

(2) Propylene-ethylene copolymer component (A2)
First, regarding the ethylene content, as described above, the ethylene content [E (A2)] of the propylene-ethylene copolymer component (A2) is 8 to 15% by weight, more preferably 9 to 14% by weight. It is. The ethylene content [E (A2)] can be controlled by the same method as the method for controlling the ethylene content [E (A1)].

  Next, MFR will be described. As described above, the MFR (A2) of the propylene-based polymer component (A2) is not particularly limited as long as the MFR (A) of the propylene-ethylene copolymer (A) is within the specified range. However, when MFR (A2) is in the range of 1 to 15 g / 10 min, the effect of suppressing poor appearance such as bleed out is enhanced, which is more preferable. Moreover, although the control method of MFR (A) of a propylene-ethylene copolymer (A) is mentioned later, the method of controlling MFR (A2) of a propylene-type polymer component (A2) is mentioned as the one means. is there. MFR (A2) can be controlled by a method similar to the method for controlling MFR (A1).

(3) Propylene-ethylene copolymer (A)
The copolymer (A) according to the present invention is a mixture of two components, a propylene-based polymer component (A1) and a propylene-ethylene copolymer component (A2). Therefore, the index of the copolymer (A) can be controlled by controlling the index of the component (A1) and the component (A2). Hereinafter, it demonstrates in order.

First, a method for controlling the weight ratio [W (A1) and W (A2)] of the component (A1) and the component (A2) will be described.
The weight ratio [W (A1) and W (A2)] of the component (A1) and the component (A2) is the production amount in the first step for producing the component (A1) and the second step for producing the component (A2). Control by production volume. For example, in order to increase the amount of the component (A1) and reduce the amount of the component (A2), the production amount of the second step may be reduced while maintaining the production amount of the first step. The residence time may be shortened or the polymerization temperature may be lowered. There is also a method of adding an electron donor such as alcohol, ester or ether, or a gas such as oxygen as a polymerization inhibitor. In that case, the amount of the component (A2) can be increased by increasing the addition amount of the polymerization inhibitor. The amount can be reduced. The reverse is also true.

Usually, the weight ratio of the component (A1) and the component (A2) is defined by the ratio of the production amount in the first step for producing the component (A1) and the production amount in the second step for producing the component (A2).
In addition, when the crystallinity of the component (A1) and the component (A2) is sufficiently different, an analysis method such as TREF (temperature rising elution fractionation method) can be used to separate and identify the two and obtain the quantitative ratio. Good. A technique for evaluating the crystallinity distribution of a propylene-ethylene copolymer by TREF measurement is well known to those skilled in the art. Glokner, J. et al. Appl. Polym. Sci: Appl. Poly. Symp. 45, 1-24 (1990), L .; Wild, Adv. Polym. Sci. 98, 1-47 (1990), J .; B. P. Soares, A .; E. Detailed measurement methods are shown in documents such as Hamielec, Polymer; 36, 8, 1639-1654 (1995).

Next, the MFR (A) of the copolymer (A) will be described. As described above, MFR (A) is 0.5 to 5 g / 10 minutes, preferably 1 to 3 g / 10 minutes.
As a method of controlling the MFR (A) of the copolymer (A), a method of controlling the MFR (A1) of the component (A1), a method of controlling the MFR (A2) of the component (A2), a component (A1) and A method for controlling the weight ratio [W (A1) and W (A2)] of the component (A2) can be exemplified. For example, if MFR (A1) is controlled and increased by the above-described method, MFR (A) can be increased even if other factors MFR (A2), W (A1), and W (A2) are constant. Can be high. This is because the following relational expression holds as already described.
MFR (A2) = exp {(log _e [MFR (A)] − (W (A1) ÷ 100) × log _e [MFR (A1)]) ÷ (W (A2) ÷ 100)}

  It is also apparent from this equation that MFR (A) can be controlled by controlling MFR (A2), W (A1) and W (A2).

Next, a method for controlling the copolymer (A) to have a single peak observed in the range of −60 to 20 ° C. in the temperature-loss tangent (tan δ) curve will be described.
First, a method for controlling the glass transition point of the copolymer (A) will be described.
In the present invention, when solid viscoelasticity is measured, the peak of the temperature-loss tangent (tan δ) curve defined as the glass transition point needs to show a single peak at −60 to 20 ° C.
Here, a method of controlling so as to obtain a single peak will be described.
Whether or not a single peak is obtained depends on whether the copolymer (A) exhibits a phase separation structure. When the copolymer (A) exhibits a phase separation structure, the glass transition temperature of the amorphous part contained in the component (A1) and the glass transition temperature of the amorphous part contained in the component (A2) are observed. Therefore, the peak is not single. Conversely, when the copolymer (A) does not show a phase separation structure, the peak is single.
Whether the copolymer (A) exhibits a phase separation structure depends on the compatibility of the component (A1) and the component (A2). In the present invention, the ethylene content [E (A1)] of the component (A1) and The difference [Egap (A)] in the ethylene content [E (A2)] of the component (A2) is determined depending on whether it is large or small. When Egap (A) is large, for example, when the value of E (A1) is low and the value of E (A2) is high, the compatibility between component (A1) and component (A2) becomes small, and the phase separation structure Indicates. On the contrary, when Egap (A) is small, for example, when E (A1) is high and E (A2) is low, the compatibility of component (A1) and component (A2) is improved, The compatible structure is shown.
Therefore, in order to obtain a single peak, a copolymer (A) having a certain value of E (A1) and E (A2) is produced, and the solid viscoelasticity is measured. If it is not a single peak, for example, if E (A1) is further increased and the difference [Egap (A)] between E (A1) and E (A2) is reduced, a single peak can be obtained. Can be adjusted as follows. The value of Egap (A) to be adjusted can be easily determined by adjusting the viscoelasticity while appropriately measuring solid viscoelasticity, but usually Egap (A) is 2 to 15. It is preferably in the range of wt%, more preferably in the range of 5 to 13 wt%.

Next, a method for controlling the position of the glass transition point will be described.
When E (A1) and E (A2) are in the above-described preferable range, the glass transition point decreases as E (A1) and E (A2) increase. That is, when it is desired to lower the glass transition point, E (A1) and E (A2) may be increased. At this time, it is necessary to simultaneously adjust Egap (A) so that a single peak is obtained. That is, in order to control the peak of the temperature-loss tangent (tan δ) curve to show a single peak at −60 to 20 ° C. when the solid viscoelasticity of the copolymer (A) is measured, E It can be said that (A1) and E (A2) may be controlled. The control method of E (A1) and E (A2) is as already described.
In addition, although a component (A1) and a component (A2) are essential components of the copolymer (A) based on this invention, unless the effect of this invention is inhibited, arbitrary polymers are made into a copolymer (A ) May be included. This arbitrary polymer is preferably polymerized using the same metallocene catalyst. For example, the first step for producing the component (A1) and the polymerization step other than the second step for producing the component (A2) are subjected to multistage polymerization. It can be realized by including it. As an example of such a polymer, a polyolefin obtained by polymerizing an arbitrary α-olefin selected from the group consisting of ethylene and an α-olefin having 3 to 8 carbon atoms (however, corresponds to the component (A1) and the component (A2)). Excluding those).

I-2. Propylene-ethylene copolymer (B)
1. Characteristics of Propylene-Ethylene Copolymer (B) The propylene-ethylene copolymer (B) used in the resin composition according to the present invention (hereinafter sometimes referred to as copolymer (B)) has characteristics. It is necessary to have (Bi) to (B-ii).
Characteristic (Bi): The ethylene content [E (B)] in the copolymer (B) is in the range of 0.4 to 13% by weight.
Characteristic (B-ii): The melt flow rate [MFR (B)] (230 ° C., 2.16 kg load) of the copolymer (B) is in the range of 0.5 to 20 g / 10 minutes.

Further, the propylene-ethylene copolymer (B) includes a propylene-based polymer component (B1) (hereinafter referred to as component (B1)) and a propylene-ethylene copolymer component (B2) (hereinafter referred to as component (B2). The component (B1) having the following characteristics (B1-i): 65 to 95% by weight, and the following characteristics (B2-i) to (B2-ii): Component (B2): A propylene-ethylene copolymer comprising 5 to 35% by weight is required.
Characteristic (B1-i): The ethylene content [E (B1)] in the polymer component (B1) is in the range of 0 to 6.0% by weight.
Characteristic (B2-i): The ethylene content [E (B2)] in the copolymer component (B2) is in the range of 8 to 25% by weight.
Characteristic (B2-ii): The melt flow rate [MFR (B2)] (230 ° C., 2.16 kg load) of the copolymer component (B2) is in the range of 0.0001 to 0.5 g / 10 minutes.

The ethylene content [E (B2)] in the copolymer component (B2) uses E (B), E (B1), and the weight ratio of the component (B1) to the component (B2) in the polymer (B). And the value defined by the following formula.
E (B2) = {E (B) −E (B1) × [W (B1) ÷ 100]} ÷ [W (B2) ÷ 100]
(W (B1) and W (B2) are weight ratios of the component (B1) and the component (B2) in the copolymer (B), and the relationship of W (B1) + W (B2) = 100 is established. Fulfill.)
In addition, about the measuring method of ethylene content used in this invention, the detail is described in an Example.

Similarly to the above, the melt flow rate [MFR (B2)] of the copolymer component (B2) is MFR (B), MFR (B1), the component (B1) and the component (B2) in the copolymer (B). Is a value defined by the following formula, which is well known as a logarithmic additive law of viscosity.
MFR (B2) = exp {(log _e [MFR (B)] − (W (B1) ÷ 100) × log _e [MFR (B1)]) ÷ (W (B2) ÷ 100)}
(Here, MFR (B1) is the MFR of the propylene polymer component (B1), and W (B1) and W (B2) are defined above.)
The melt flow rate [MFR (B)] is measured at 230 ° C. and a load of 2.16 kg according to JIS K7210.

(1) Characteristic (Bi): Ethylene content in copolymer (B) The ethylene content [E (B)] in the copolymer (B) is in the range of 0.4 to 13% by weight. Yes, preferably in the range of 0.5 to 12% by weight.
When the ethylene content [E (B)] in the copolymer (B) is in this range, a sufficient surface roughness improving effect can be obtained. Further, when the ethylene content [E (B)] is less than 0.4% by weight, deterioration of heat seal characteristics and induction of oriented crystals may occur, while the ethylene content [E (B)] If it exceeds 13% by weight, the effect of improving the surface roughness may not be obtained.

(2) Characteristic (B-ii): MFR of copolymer (B)
The melt flow rate [MFR (B)] of the copolymer (B) is 0.5 to 20 g / 10 minutes, preferably 1.0 to 15 g / 10 minutes. When MFR (B) is smaller than 0.5 g / 10 min, the dispersibility in the propylene-ethylene copolymer (A) is inferior, and the blow molded product has a non-uniform pattern, resulting in an unusable appearance. On the other hand, when MFR (B) is larger than 20 g / 10 min, the difference in melt flow characteristics between the propylene polymer component (B1) and the propylene-ethylene copolymer component (B2) becomes remarkable, and the propylene-ethylene copolymer It is not preferable because fish eyes and gel are generated due to poor dispersion of the polymer component (B2), resulting in a blow molded product that cannot be put into practical use.

(3) Characteristic (B1-i): Ethylene content in component (B1) Component (B1) is a component having crystallinity, and ethylene content [E (B1)] is 0 to 6.0% by weight. Preferably, it is 0.5 to 5.0% by weight. When the ethylene content [E (B1)] in the component (B1) exceeds 6.0% by weight, the properties of the polymer are extremely deteriorated, not only causing blockage in the polymerization equipment, but also the surface of the molded product The low crystallinity component, which is a factor causing the stickiness, increases.

(4) Characteristic (B2-i): Ethylene content in component (B2) When component (B2) is extruded at a relatively low temperature of about 180 ° C., the relaxation time in the flow in the die However, the crystallinity is controlled by the ethylene content, so that the ethylene content [E (B2)] is 8% by weight. It is necessary to be above, preferably 10% by weight or more. On the other hand, if the ethylene content [E (B2)] is too high, the compatibility between the propylene molecular chain of the component (A) and the component (B1) and the molecular chain of the component (B2) is significantly reduced, and the shear flow field In this case, the ethylene content [E (B2)] is required to be 25% by weight or less, and preferably 20% by weight or less. That is, the ethylene content [E (B2)] in the component (B2) is in the range of 8 to 25% by weight, preferably 10 to 20% by weight.

(5) Characteristic (B2-ii): MFR of component (B2)
The component (B2) is a component that suppresses the slip phenomenon on the die wall surface that occurs in the flow field in the die, and needs to have an extremely high molecular weight component. Therefore, the component (B2) needs to have an MFR (B2) in the range of 0.0001 to 0.5 g / 10 minutes, and preferably the upper limit is 0.2 g / 10 minutes or less. On the other hand, if the molecular weight is too high, the dispersibility deteriorates and the fish eye and gel are generated. Therefore, the MFR (B2) is 0.0001 g / 10 min or more, preferably 0.001 g / 10 min or more. is there.

(6) Quantity ratio of component (B1) and component (B2) The proportion of component (B2) in the propylene-ethylene copolymer (B) is that component (B2) has a remarkably high molecular weight. When the ratio is too large, it is necessary to increase the difference between the component (B1) and the MFR, and it is a cause of the generation of fish eye and gel. % Or less. On the other hand, if the amount of the component (B2) is too small, the component (B) needs to be contained excessively in the resin composition, which may lead to deterioration in dispersibility and a decrease in transparency of the blow molded article. The ratio of (B2) is required to be 5% by weight or more, preferably 10% by weight or more. That is, the proportion of the component (B2) in the copolymer (B) is 5 to 35% by weight, preferably 10 to 30% by weight. In other words, the proportion of the component (B1) in the copolymer (B) is 65 to 95% by weight, preferably 70 to 90% by weight.

2. Method for Preparing Propylene-Ethylene Copolymer (B) The propylene-ethylene copolymer (B) according to the present invention has the characteristics (Bi) to (B-ii) described above, and Propylene-based polymer component (B1) having a characteristic (B1-i) 65 to 95% by weight and propylene-ethylene copolymer component (B2) 5 to 35 having characteristics (B2-i) to (B2-ii) The production method is not particularly limited as long as it is a propylene-ethylene copolymer characterized by comprising% by weight and has this requirement.
Hereinafter, an appropriate form for producing the propylene-ethylene copolymer (B) according to the present invention will be described with specific examples.

(1) Catalyst A propylene-ethylene copolymer (B) can be produced using any catalyst, but propylene-ethylene copolymer having characteristics (B2-i) to (B2-ii). From the viewpoint of producing the combined component (B2) as a constituent component, it is preferable to use a Ziegler-Natta catalyst.
When the Ziegler-Natta catalyst is used, a specific method for producing the catalyst is not particularly limited, but as an example, a catalyst disclosed in JP 2007-254671 A can be exemplified.
Specifically, as a typical example of a Ziegler-Natta catalyst suitable for the production of the propylene-ethylene copolymer (B) according to the present invention, the following components, (a1) titanium, magnesium and halogen are essential components: And a catalyst comprising (a2) an organoaluminum compound and (a3) an electron donor.

(1-1) Solid component (a1)
The solid component (a1), which is a constituent component of the Ziegler-Natta catalyst suitable for the production of the propylene-ethylene copolymer (B) according to the present invention, must contain titanium (a1a), magnesium (a1b), and halogen (a1c). It is contained as a component, and an electron donor (a1d) can be used as an optional component.
Here, “containing as an essential component” indicates that any component may be included in any form within the range not impairing the effects of the present invention, in addition to the listed three components. .
This will be described in detail below.

(I) Titanium (a1a)
Any titanium compound can be used as the titanium source. Typical examples include compounds disclosed in JP-A-3-234707. With respect to the valence of titanium, a titanium compound having any valence of tetravalent, trivalent, divalent, and zero can be used, preferably tetravalent and trivalent titanium compounds, more preferably tetravalent. It is desirable to use the titanium compound.
Specific examples of tetravalent titanium compounds include titanium halide compounds typified by titanium tetrachloride, alkoxy titanium compounds typified by tetrabutoxy titanium, tetrabutoxy titanium dimer (BuO) ₃ Ti—O—Ti ( Examples thereof include condensation compounds of alkoxy titanium having a Ti—O—Ti bond typified by OBu) ₃ and organometallic titanium compounds typified by dicyclopentadienyl titanium dichloride. Of these, titanium tetrachloride and tetrabutoxy titanium are particularly preferred.
The above titanium compounds can be used not only alone but also in combination with a plurality of compounds. Further, a mixture of the above titanium compounds or a compound whose average composition formula is a mixed formula thereof (for example, a compound such as Ti (OBu) _m Cl _4-m ; 0 <m <4), or a phthalate ester Complexes with other compounds such as Ph (COOBu) ₂ .TiCl ₄ and the like can be used.

(Ii) Magnesium (a1b)
Any magnesium compound can be used as the magnesium source. Representative examples include compounds disclosed in JP-A-234707.
In general, magnesium halide compounds represented by magnesium chloride, alkoxymagnesium compounds represented by diethoxymagnesium, metal magnesium, oxymagnesium compounds represented by magnesium oxide, and magnesium hydroxide Hydroxymagnesium compounds, Grignard compounds typified by butylmagnesium chloride, organometallic magnesium compounds typified by butylethylmagnesium, magnesium salts of inorganic and organic acids typified by magnesium carbonate and magnesium stearate, In addition, a compound in which a mixture thereof or an average composition formula thereof is a mixed formula thereof (for example, a compound such as Mg (OEt) _m Cl _2-m ; 0 <m <2) can be used. Of these, magnesium chloride, diethoxymagnesium, metallic magnesium and butylmagnesium chloride are particularly preferred.

(Iii) Halogen (a1c)
As the halogen, fluorine, chlorine, bromine, iodine, and a mixture thereof can be used. Of these, chlorine is particularly preferred.
The halogen is generally supplied from the above titanium compounds and / or magnesium compounds, but can also be supplied from other compounds. Typical examples include silicon halide compounds typified by silicon tetrachloride, aluminum halide compounds typified by aluminum chloride, halogenated organic compounds typified by 1,2-dichloroethane and benzyl chloride, Halogenated borane compounds represented by trichloroborane, phosphorus halide compounds represented by phosphorus pentachloride, tungsten halide compounds represented by tungsten hexachloride, molybdenum halide compounds represented by molybdenum pentachloride , Etc. These compounds can be used not only alone but also in combination. Of these, silicon tetrachloride is particularly preferred.

(Iv) electron donor (a1d)
The solid component (a1) may contain an electron donor as an optional component.
Representative examples of the electron donor (a1d) include compounds disclosed in JP-A No. 2004-124090. In general, organic acids and inorganic acids and derivatives thereof (esters, acid anhydrides, acid halides, amides) compounds, ether compounds, ketone compounds, aldehyde compounds, alcohol compounds, amine compounds, etc. It is desirable to use

  Examples of the organic acid compound that can be used as an electron donor include aromatic polycarboxylic acid compounds represented by phthalic acid, aromatic carboxylic acid compounds represented by benzoic acid, and 2-n-butyl-malonic acid. One or two substituents such as malonic acid or 2-n-butyl-succinic acid having one or two substituents at the 2-position as shown above or one or more at the 2-position and 3-position respectively Aliphatic carboxylic acid compounds typified by succinic acid having the above-mentioned substituents, aliphatic carboxylic acid compounds typified by propionic acid, aromatic and aliphatic typified by benzenesulfonic acid and methanesulfonic acid Examples thereof include sulfonic acid compounds. These carboxylic acid compounds and sulfonic acid compounds may have an arbitrary number of unsaturated bonds at arbitrary positions in the molecule like maleic acid, regardless of whether they are aromatic or aliphatic.

Examples of the organic acid derivative compound that can be used as an electron donor include the above-mentioned organic acid esters, acid anhydrides, acid halides, amides, and the like.
Aliphatic and aromatic alcohols can be used as the alcohol that is a constituent of the ester. Among these alcohols, alcohols composed of aliphatic free radicals having 1 to 20 carbon atoms such as ethyl group, butyl group, isobutyl group, heptyl group, octyl group and dodecyl group are preferable. More preferably, an alcohol composed of an aliphatic radical having 2 to 12 carbon atoms is desirable. In addition, an alcohol having an alicyclic free group such as a cyclopentyl group, a cyclohexyl group, or a cycloheptyl group can also be used.
Further, fluorine, chlorine, bromine, iodine, or the like can be used as the halogen that is a component of the acid halide. Of these, chlorine is most preferred. In the case of polyhalides of polyvalent organic acids, the plurality of halogens may be the same or different.

Examples of inorganic acid compounds that can be used as electron donors include carbonic acid, phosphoric acid, silicic acid, sulfuric acid, and nitric acid. As derivatives of these inorganic acids, it is desirable to use esters. Specific examples include tetraethoxysilane (ethyl silicate), tetrabutoxysilane (butyl silicate), and the like.
Examples of ether compounds that can be used as an electron donor include aliphatic ether compounds typified by dibutyl ether, aromatic ether compounds typified by diphenyl ether, 2-isopropyl-2-isobutyl-1,3- Aliphatic polyhydric ether compounds represented by 1,3-dimethoxypropane having one or two substituents at the 2-position, such as dimethoxypropane and 2-isopropyl-2-isopentyl-1,3-dimethoxypropane; Examples thereof include polyvalent ether compounds having an aromatic free radical represented by 9,9-bis (methoxymethyl) fluorene in the molecule.
Further, examples of alcohol compounds that can be used as electron donors include aliphatic alcohol compounds typified by butanol and 2-ethylhexanol, phenol derivative compounds typified by phenol and cresol, glycerin and 1,1′- Examples thereof include aliphatic or aromatic polyhydric alcohol compounds represented by bi-2-naphthol.

  These electron donors can be used not only alone but also in combination with a plurality of compounds. Among these, preferred are dibutyl phthalate, dibutyl phthalate, diisobutyl phthalate, phthalic acid ester compounds typified by diheptyl phthalate, phthalic acid halide compounds typified by phthaloyl dichloride, 2-n- Malonic acid ester compounds having one or two substituents at the 2-position such as butyl-diethyl malonate, one or two substituents at the 2-position such as 2-n-butyl-diethyl succinate, or 2 Succinic acid ester compounds having one or more substituents at each of the 3-position and 2-isopropyl-2-isobutyl-1,3-dimethoxypropane or 2-isopropyl-2-isopentyl-1,3-dimethoxypropane Aliphatic polyhydric ether compounds represented by 1,3-dimethoxypropane having one or two substituents at the 2-position , Polyvalent ether compounds having 9,9-bis radical of aromatic typified by (methoxymethyl) fluorene in the molecule, and the like.

(V) Amount ratio of each component constituting the solid component (a1) The amount ratio of the amount of each component constituting the solid component (a1) may be arbitrary as long as the performance of the catalyst is not impaired. In general, the following range is preferable.
The amount of the titanium compound used is a molar ratio (number of moles of titanium compound / number of moles of magnesium compound) with respect to the amount of magnesium compound used, and is preferably in the range of 0.0001 to 1,000. In particular, the range of 0.01 to 10 is desirable. In the case of using a halogen source compound in addition to the magnesium compound and the titanium compound, the amount used is the magnesium compound to be used regardless of whether each of the magnesium compound and the titanium compound contains a halogen or not. Is preferably in the range of 0.01 to 1,000, particularly preferably in the range of 0.1 to 100. Within range is desirable.
When the solid component (a1) is prepared, the amount used when an electron donor is used as an optional component is the molar ratio (number of moles of electron donor / mol of magnesium compound) with respect to the amount of magnesium compound used. Number), preferably in the range of 0.001 to 10, particularly preferably in the range of 0.01 to 5.

The solid component (a1) is obtained by contacting each component constituting the above in the above quantitative ratio. Although it is necessary for the contact condition of each component not to make oxygen exist, arbitrary conditions can be used in the range which does not impair the effect of this invention. In general, the following conditions are preferred.
The contact temperature is about −50 to 200 ° C., preferably 0 to 100 ° C.
Examples of the contact method include a mechanical method using a rotating ball mill and a vibration mill, and a method of contacting by stirring in the presence of an inert diluent.

(1-2) Organoaluminum compound (a2)
Examples of the organoaluminum compound (a2) that is a constituent of the Ziegler-Natta catalyst suitable for the production of the propylene-ethylene copolymer (B) according to the present invention include compounds disclosed in JP-A No. 2004-124090. Can be used. In general, it is desirable to use a compound represented by the following general formula.
R ⁹ _c AlX _d (OR ¹⁰ ) _e
(In the formula, R ⁹ represents a hydrocarbon group. X represents a halogen atom or a hydrogen atom. R ¹⁰ represents a hydrocarbon group or a bridging group by Al. C ≧ 1, 0 ≦ d ≦ 2, (0 ≦ e ≦ 2, c + d + e = 3)

In the above general formula, R ⁹ is a hydrocarbon group, preferably having 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, particularly preferably 1 to 6 carbon atoms.
Specific examples of R ⁹ include a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group, a hexyl group, and an octyl group. Of these, a methyl group, an ethyl group, and an isobutyl group are most preferable.
In the above formula, X is a halogen atom or a hydrogen atom. Examples of the halogen atom that can be used as X include fluorine, chlorine, bromine, iodine, and the like. Of these, chlorine is particularly preferred.
In the above formula, R ¹⁰ is a hydrocarbon group or a cross-linking group by Al. When R ¹⁰ is a hydrocarbon group, R ¹⁰ can be selected from the same group as exemplified for the hydrocarbon group of R ⁹ . It is also possible to use alumoxanes compounds represented by methylalumoxane as the organoaluminum compound (a2), in which case, R ¹⁰ represents a linking group by Al.

Examples of compounds that can be used as the organoaluminum compound (a2) include trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylaluminum, diethylaluminum chloride, ethylaluminum chloride, diethylaluminum ethoxide, methylalumoxane, and the like. Can be mentioned. Of these, triethylaluminum and triisobutylaluminum are preferable.
As the organoaluminum compound (a2), not only a single compound but also a plurality of compounds can be used in combination.

(1-3) Electron donor (a3)
The electron donor (a3) which is a constituent of the Ziegler-Natta catalyst suitable for the production of the propylene-ethylene copolymer (B) according to the present invention includes an organosilicon compound having an alkoxy group, or at least two ether bonds The compound which has can be illustrated.

(I) Organosilicon compound having an alkoxy group An organosilicon compound having an alkoxy group that is a constituent of a Ziegler-Natta catalyst suitable for the production of the propylene-ethylene copolymer (B) according to the present invention is disclosed in The compound etc. which were indicated by -1224090 gazette can be used.
In general, it is desirable to use a compound represented by the following general formula.
R ³ R ⁴ _a Si (OR ⁵ ) _b
(In the formula, R ³ represents a hydrocarbon group or a hetero atom-containing hydrocarbon group. R ⁴ represents an arbitrary radical selected from a hydrogen atom, a halogen atom, a hydrocarbon group, or a hetero atom-containing hydrocarbon group. R ⁵ represents a hydrocarbon group, 0 ≦ a ≦ 2, 1 ≦ b ≦ 3, a + b = 3.)

In the above formula, R ³ represents a hydrocarbon group or a heteroatom-containing hydrocarbon group.
The hydrocarbon group that can be used as R ³ is generally one having 1 to 20 carbon atoms, preferably 3 to 10 carbon atoms. Specific examples of the hydrocarbon group that can be used as R ³ include a linear aliphatic hydrocarbon group typified by an n-propyl group, a branched chain typified by an i-propyl group and a t-butyl group. Examples thereof include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group typified by a cyclopentyl group and a cyclohexyl group, and an aromatic hydrocarbon group typified by a phenyl group. More preferably, as R ³ , it is desirable to use a branched aliphatic hydrocarbon group or an alicyclic hydrocarbon group. , A cyclohexyl group, and the like are preferable.
When R ³ is a heteroatom-containing hydrocarbon group, the heteroatom is preferably selected from nitrogen, oxygen, sulfur, phosphorus, and silicon, and particularly preferably nitrogen or oxygen. The skeleton structure of the hetero atom-containing hydrocarbon group R ^3, it is desirable to select from the example of the case where R ³ is a hydrocarbon group. In particular, N, N-diethylamino group, quinolino group, isoquinolino group and the like are preferable.

In the above formula, R ⁴ represents a hydrogen atom, a halogen atom, a hydrocarbon group or a heteroatom-containing hydrocarbon group.
Examples of the halogen atom that can be used as R ⁴ include fluorine, chlorine, bromine, iodine, and the like.
When R ⁴ is a hydrocarbon group, it generally has 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms. Specific examples of the hydrocarbon group that can be used as R ⁴ include a linear aliphatic hydrocarbon group represented by a methyl group and an ethyl group, a branch represented by an i-propyl group and a t-butyl group. And an aliphatic hydrocarbon group typified by a cycloaliphatic hydrocarbon group, a cyclopentyl group and a cyclohexyl group, and an aromatic hydrocarbon group typified by a phenyl group. Among these, it is desirable to use methyl group, ethyl group, propyl group, i-propyl group, i-butyl group, s-butyl group, t-butyl group, cyclopentyl group, cyclohexyl group, and the like.
In addition, when R ⁴ is a heteroatom-containing hydrocarbon group, it is desirable to select from the examples when R ³ is a heteroatom-containing hydrocarbon group. In particular, N, N-diethylamino group, quinolino group, isoquinolino group and the like are preferable.
When the value of a is 2, two R ⁴ may be the same or different. Regardless of the value of a, R ⁴ and R ³ may be the same or different.

In the above formula, R ⁵ represents a hydrocarbon group. The hydrocarbon group that can be used as R ⁵ is generally one having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 5 carbon atoms. Specific examples of the hydrocarbon group that can be used as R ⁵ include a linear aliphatic hydrocarbon group represented by a methyl group or an ethyl group, a branch represented by an i-propyl group or a t-butyl group. And an aliphatic hydrocarbon group. Of these, a methyl group and an ethyl group are most preferable. When the value of b is 2 or more, a plurality of R ⁵ may be the same or different.

Preferred examples of the organosilicon compound having an alkoxy group include t-Bu (Me) Si (OMe) ₂ , t-Bu (Me) Si (OEt) ₂ , t-Bu (Et) Si (OMe) ₂ , t _{-Bu (n-Pr) Si (} OMe) 2, c-Hex (Me) Si (OMe) 2, c-Hex (Et) Si (OMe) 2, c-Pen 2 Si (OMe) 2, i-Pr ₂ Si (OMe) ₂ , i-Bu ₂ Si (OMe) ₂ , i-Pr (i-Bu) Si (OMe) ₂ , n-Pr (Me) Si (OMe) ₂ , t-BuSi (OEt) _{3 , (Et 2 N) 2 Si} (OMe) 2, Et 2 N-Si (OEt) 3,

などを挙げることができる。
これらの有機ケイ素化合物類は、単独で用いるだけでなく、複数の化合物を併用することもできる。

And so on.
These organosilicon compounds can be used not only alone but also in combination with a plurality of compounds.

(Ii) Compound having at least two ether bonds The compound having at least two ether bonds, which is a constituent of the Ziegler-Natta catalyst suitable for the production of the propylene-ethylene copolymer (B) according to the present invention, The compounds disclosed in Kaihei 3-294302 and JP-A-8-333413 can be used.
In general, it is desirable to use a compound represented by the following general formula.
_{^{R 8 O-C (R 7}} ) 2 -C (R 6) 2 -C (R 7) 2 -OR 8
(Wherein R ⁶ and R ⁷ represent any free radical selected from the group consisting of a hydrogen atom, a hydrocarbon group and a heteroatom-containing hydrocarbon group. R ⁸ represents a hydrocarbon group or a heteroatom-containing hydrocarbon. Represents a group.)

In the above formula, R ⁶ represents any free radical selected from the group consisting of a hydrogen atom, a hydrocarbon group, and a heteroatom-containing hydrocarbon group.
The hydrocarbon group that can be used as R ⁶ is generally one having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms. Specific examples of the hydrocarbon group that can be used as R ⁶ include a linear aliphatic hydrocarbon group typified by an n-propyl group, a branched chain typified by an i-propyl group and a t-butyl group. Examples thereof include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group typified by a cyclopentyl group and a cyclohexyl group, and an aromatic hydrocarbon group typified by a phenyl group. More preferably, it is desirable to use a branched aliphatic hydrocarbon group or an alicyclic hydrocarbon group as R ⁶ , and in particular, i-propyl group, i-butyl group, i-pentyl group, cyclopentyl group, cyclohexyl group, Etc. are desirable.
Two R ⁶ may combine to form one or more rings. In this case, a cyclopolyene structure containing 2 or 3 unsaturated bonds in the ring structure can be taken. Further, it may be condensed with other cyclic structures. Regardless of whether monocyclic, polycyclic, or condensed, one or more hydrocarbon groups may be present as substituents on the ring. Substituents on the ring are generally those having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms.
Specific examples include linear aliphatic hydrocarbon groups typified by n-propyl groups, branched aliphatic hydrocarbon groups typified by i-propyl groups and t-butyl groups, cyclopentyl groups, and cyclohexyl groups. And alicyclic hydrocarbon groups, and aromatic hydrocarbon groups typified by phenyl groups.

In the above formula, R ⁷ represents any free radical selected from the group consisting of a hydrogen atom, a hydrocarbon group, and a heteroatom-containing hydrocarbon group. Specifically, R ⁷ can be selected from the examples of R ⁶ . Preferably it is a hydrogen atom.
In the formula, R ⁸ represents a hydrocarbon group or a heteroatom-containing hydrocarbon group. Specifically, R ⁸ can be selected from the examples when R ⁶ is a hydrocarbon group. Preferably, it is a C1-C6 hydrocarbon group, and more preferably an alkyl group. Most preferred is a methyl group.
When R ^{6 to} R ⁸ are hetero atom-containing hydrocarbon groups, the hetero atom is preferably selected from nitrogen, oxygen, sulfur, phosphorus, and silicon.
Regardless of whether R ^{6 to} R ⁸ are hydrocarbon groups or heteroatom-containing hydrocarbon groups, they may optionally contain halogen. When R ^{6 to} R ⁸ contain a hetero atom and / or halogen, the skeleton structure is preferably selected from the examples in the case of a hydrocarbon group. Moreover, the eight substituents of R ^{6 to} R ⁸ may be the same as or different from each other.

Preferred examples of the compound having at least two ether bonds include 2,2-diisopropyl-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, and 2,2-diisobutyl-1,3- Diethoxypropane, 2-isobutyl-2-isopropyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2,2-dicyclopentyl-1,3-dimethoxypropane, 2, 2-dicyclohexyl-1,3-dimethoxypropane, 2-isopropyl-1,3-dimethoxypropane, 2-tert-butyl-1,3-dimethoxypropane, 2,2-dipropyl-1,3-dimethoxypropane, 2- Methyl-2-phenyl-1,3-dimethoxypropane, 9,9-bis (meth Cymethyl) fluorene, 9,9-bis (methoxymethyl) -1,8-dichlorofluorene, 9,9-bis (methoxymethyl) -2,7-dicyclopentylfluorene, 9,9-bis (methoxymethyl) -1 , 2,3,4-tetrahydrofluorene, 1,1-bis (1′-butoxyethyl) cyclopentadiene, 1,1-bis (α-methoxybenzyl) indene, 1,1-bis (phenoxymethyl) -3, Examples thereof include 6-dicyclohexylindene, 1,1-bis (methoxymethyl) benzonaphthene, 7,7-bis (methoxymethyl) -2,5-nobornadinene, and the like.
Among them, 2,2-diisopropyl-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, 2-isobutyl-2-isopropyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl Particularly preferred are -1,3-dimethoxypropane, 2,2-dicyclopentyl-1,3-dimethoxypropane, and 9,9-bis (methoxymethyl) fluorene.
These compounds having at least two ether bonds can be used alone or in combination with a plurality of compounds. Moreover, it may be the same as or different from the polyvalent ether compound used as the optional component (A1d) in the solid component (A1).

(1-4) Amount of Catalyst Component Used The amount of each component used in the catalyst exemplified above is not particularly limited, but is generally preferably within the following range.
The amount of the organoaluminum compound (a2) used is a molar ratio (the number of moles of the organoaluminum compound (a2) / the number of moles of titanium atoms) to the titanium component constituting the solid component (a1), preferably 1 to 1,000. And particularly preferably within the range of 10 to 500.
When the organosilicon compound (a3a) is used as the electron donor (a3), the amount used is the molar ratio to the titanium component constituting the solid component (a1) (mole number of organosilicon compound (a3a) / mol of titanium atom). Number), preferably in the range of 0.01 to 10,000, particularly preferably in the range of 0.5 to 500.
When the compound (a3b) having at least two ether bonds is used as the electron donor (a3), the amount used is the molar ratio with respect to the titanium component constituting the solid component (a1) (mole of the compound having at least two ether bonds). Number / number of moles of titanium atoms), preferably in the range of 0.01 to 10,000, particularly preferably in the range of 0.5 to 500.

(1-5) Prepolymerization The catalyst exemplified above may be prepolymerized before being used in the main polymerization. Prior to the polymerization process, a small amount of polymer is generated around the catalyst in advance, so that the catalyst becomes more uniform and the generation amount of fine powder can be suppressed.
As the monomer in the prepolymerization, compounds disclosed in JP-A No. 2004-124090 can be used. Specific examples of the compound include olefins represented by ethylene, propylene, 1-butene, 3-methylbutene-1, 4-methylpentene-1, and the like, styrene, α-methylstyrene, allylbenzene, and chlorostyrene. Styrene-like compounds typified by, etc., and 1,3-butadiene, isoprene, 1,3-pentadiene, 1,5-hexadiene, 2,6-octadiene, dicyclopentadiene, 1,3-cyclohexadiene, 1 , 9-decadiene, divinylbenzenes, and the like, and the like. Of these, ethylene, propylene, 3-methylbutene-1, 4-methylpentene-1, styrene, divinylbenzenes, and the like are particularly preferable.

The reaction conditions for the catalyst exemplified above and the above monomer are not particularly limited, but generally are preferably within the following ranges.
The amount of prepolymerization is in the range of 0.001 to 100 g, preferably 0.1 to 50 g, more preferably 0.5 to 10 g, based on the solid component (a1) per gram.
The reaction temperature at the time of prepolymerization is −150 to 150 ° C., preferably 0 to 100 ° C. And it is desirable to make the reaction temperature at the time of preliminary polymerization lower than the polymerization temperature at the time of main polymerization. In general, the reaction is preferably carried out with stirring, and an inert solvent such as hexane or heptane can also be present.
The prepolymerization may be performed a plurality of times, and the monomers used at this time may be the same or different. Moreover, it can wash | clean with inert solvents, such as hexane and heptane, after preliminary polymerization.

(2) Manufacturing method Next, the manufacturing method of the propylene-ethylene copolymer (B) based on this invention is explained in full detail.
The propylene-ethylene copolymer (B) in the present invention has a propylene polymer component (B1) having a characteristic (B1-i) of 65 to 95% by weight and characteristics (B2-i) to (B2-ii). The propylene-ethylene copolymer component (B2) has a content of 5 to 35% by weight, and the propylene-ethylene copolymer (B) is produced by a propylene-based heavy polymer. It is necessary to produce two polymer components, a combined component (B1) and a propylene-ethylene copolymer component (B2).
Both polymer components can be produced separately and then blended, but the propylene-ethylene copolymer component (B2) having a relatively high molecular weight and low viscosity and MFR can be used as a propylene-based polymer. From the viewpoint of neatly dispersing in the coalescing component (B1) and expressing the original performance of the propylene-ethylene copolymer (B), the two components are subjected to multistage polymerization (hereinafter sometimes referred to as “sequential polymerization”). It is preferable to manufacture.

(2-1) Sequential polymerization Specifically, it is desirable to polymerize the propylene-ethylene copolymer component (B2) in the second step after polymerizing the propylene-based polymer component (B1) in the first step. . Although it is possible to reverse the production order, the propylene-ethylene copolymer component (B2) has an ethylene content [E (B2)] of 8 to 8 from the definition of (B2-i). Since the polymer is in the range of 25% by weight and has low crystallinity, if it is produced in the first step, there is a high possibility of causing production trouble such as adhering inside the polymerization tank or clogging the transfer pipe. , Not very preferable.
When performing sequential polymerization, either a batch method or a continuous method can be used, but it is generally desirable to use a continuous method from the viewpoint of productivity.
In the case of the batch method, the propylene polymer component (B1) and the propylene-ethylene copolymer component (B2) are individually polymerized using a single polymerization reactor by changing the polymerization conditions with time. Is possible. As long as the effects of the present invention are not impaired, a plurality of polymerization reactors may be connected in parallel.
In the case of a continuous process, since it is necessary to individually polymerize the propylene polymer component (B1) and the propylene-ethylene copolymer component (B2), a production facility in which two or more polymerization reactors are connected in series. Must be used. The polymerization reactor corresponding to the first step for producing the propylene-based polymer component (B1) and the polymerization reactor corresponding to the second step for producing the propylene-ethylene copolymer component (B2) are in a series relationship. Although it is necessary, a plurality of polymerization reactors may be connected in series and / or in parallel for each of the first step and the second step.

(2-2) Polymerization process Any polymerization process can be used.
The reaction phase may be a method using a liquid medium or a method using a gas medium.
Specific examples include a slurry method, a bulk method, and a gas phase method. Although supercritical conditions can be used as intermediate conditions between the bulk method and the gas phase method, they are substantially the same as the gas phase method, and are therefore included in the gas phase method without particular distinction.
In the case of a multi-tank continuous polymerization process, a gas phase polymerization reactor may be attached after a bulk polymerization reactor.
In the case of the batch method, the first step may be performed by the bulk method and the second step may be performed by the vapor phase method. This case is also referred to as the bulk method.
As described above, the reaction phase is not particularly limited, but the slurry method has a problem that production costs are generally increased because of the use of an organic solvent such as hexane and heptane because there are many attached facilities. Therefore, it is more desirable to use a bulk method or a gas phase method.
Various processes have been proposed for the bulk method and the gas phase method. Although there is a difference in the stirring (mixing) method and the heat removal method, the present invention does not limit the particular process type in this respect.

(2-3) General polymerization conditions The polymerization temperature can be used without any particular problem as long as it is within a commonly used temperature range. Specifically, a range of 0 ° C to 200 ° C, preferably 40 ° C to 100 ° C can be used.
In addition, the polymerization pressure varies depending on the process to be selected, but can be used without any particular problem as long as it is in a pressure range usually used. Specifically, a range of greater than 0 to 200 MPa, preferably 0.1 to 50 MPa can be used. At this time, there is no problem even if an inert gas such as nitrogen coexists.
In the second step of producing the propylene-ethylene copolymer component (B2), a polymerization inhibitor such as ethanol or oxygen can be added. When such a polymerization inhibitor is used, not only the polymerization amount in the second step can be easily controlled, but also the properties of the polymer particles can be improved.

3. Next, a method for controlling the index of the propylene-ethylene copolymer (B) will be described in detail.

(1) Index control method of propylene-based polymer component (B1) First, the ethylene content, as described above, the ethylene content of the propylene-based polymer component (B1) is 0 to 6.0 wt%, More preferably, it is 0.5 to 5.0% by weight.
As a means for controlling the ethylene content, it is convenient to use a method for controlling the amount of ethylene supplied to the polymerization tank. Specifically, if the ratio of ethylene to propylene supplied to the polymerization tank is increased (ethylene supply amount ÷ propylene supply amount), the ethylene content of the resulting propylene polymer component (B1) increases. The reverse is also true.
The relationship between the amount ratio of propylene and ethylene supplied to the polymerization tank and the ethylene content of the resulting propylene polymer component (B1) varies depending on the type of Ziegler-Natta catalyst used, but the supply amount ratio is adjusted appropriately. Thus, it is very easy for those skilled in the art to obtain the propylene polymer component (B1) having the desired ethylene content.

Next, MFR will be described.
The MFR (B1) of the propylene-based polymer component (B1) is not particularly limited, but as a means for controlling the MFR (B) of the propylene-ethylene copolymer (B) as described later, a propylene-based polymer component (B1) The MFR (B1) of the polymer component (B1) may be controlled. The MFR (B1) of the propylene-based polymer component (B1) can be adjusted by using hydrogen as a chain transfer agent.
Specifically, when the concentration of hydrogen as a chain transfer agent is increased, the MFR (B1) of the propylene polymer component (B1) is increased. The reverse is also true. In order to increase the concentration of hydrogen in the polymerization tank, it is sufficient to increase the amount of hydrogen supplied to the polymerization tank, and adjustment is very easy for those skilled in the art.

(2) Index control method of propylene-ethylene copolymer component (B2) The propylene-ethylene copolymer component (B2), which is a constituent component of the propylene-ethylene copolymer (B), contains ethylene in the copolymer. The amount [E (B2)] is in the range of 8 to 25% by weight, and the MFR (B2) of the copolymer is in the range of 0.0001 to 0.5 g / 10 min. Although it is necessary to control ethylene content and MFR, both can be controlled similarly to the propylene polymer (B1).

(3) Index control method of propylene-ethylene copolymer (B) The propylene-ethylene copolymer (B) has an ethylene content [E (B)] in the copolymer of 0.4 to 13% by weight. The MFR (B) of the copolymer is in the range of 0.5 to 20 g / 10 minutes, and 65 to 95% by weight of the propylene-based polymer component (B1) and the propylene-ethylene copolymer component ( B2) 5 to 35% by weight.
Accordingly, items to be considered in controlling the index of the propylene-ethylene copolymer (B) are ethylene content [E (B)], MFR (B), propylene-based polymer component (B1) and propylene- The weight ratio of the ethylene copolymer component (B2) is three.

First, the control method of the weight ratio of the propylene-based polymer component (B1) and the propylene-ethylene copolymer component (B2) will be described.
The weight ratio of the propylene-based polymer component (B1) and the propylene-ethylene copolymer component (B2) is the same as the production amount in the first step for producing the propylene-based polymer component (B1) and the propylene-ethylene copolymer (B2). ) Is controlled by the manufacturing amount in the second step of manufacturing. For example, in order to increase the amount of the propylene polymer component (B1) and reduce the amount of the propylene-ethylene copolymer (B2), the production amount of the second step is maintained while maintaining the production amount of the first step. What is necessary is just to reduce the residence time of a 2nd process, or just to reduce polymerization temperature. It can also be controlled by adding a polymerization inhibitor such as ethanol or oxygen, or by increasing the amount of addition when it is originally added. The reverse is also true.

Usually, the weight ratio of the propylene-based polymer component (B1) and the propylene-ethylene copolymer component (B2) is determined according to the production amount in the first step for producing the propylene-based polymer component (B1) and the propylene-ethylene copolymer. (B2) is defined by the production amount in the second step of producing.
The formula is shown below.
Weight of component (B1): Weight of component (B2) = W (B1): W (B2)
W (B1) = Production amount of the first step / (Production amount of the first step + Production amount of the second step) × 100
W (B2) = Production amount of the second step / (Production amount of the first step + Production amount of the second step) × 100
W (B1) + W (B2) = 100
(W (B1) and W (B2) are weight ratios of the propylene-based polymer component (B1) and the propylene-ethylene copolymer component (B2) in the propylene-ethylene copolymer (B), respectively. .)

In an industrial production facility, the production amount is usually obtained from the heat balance and material balance of each polymerization tank. Further, when the crystallinity of the propylene polymer component (B1) and the propylene-ethylene copolymer component (B2) are sufficiently different, both are analyzed using an analytical method such as TREF (temperature rising elution fractionation method). Separation and identification may be performed to determine the quantity ratio.
A technique for evaluating the crystallinity distribution of polypropylene by TREF measurement is well known to those skilled in the art. Glokner, J. et al. Appl. Polym. Sci: Appl. Poly. Symp. 45, 1-24 (1990), L .; Wild, Adv. Polym. Sci. 98, 1-47 (1990), J .; B. P. Soares, A .; E. Detailed measurement methods are shown in documents such as Hamielec, Polymer; 36, 8, 1639-1654 (1995).

Next, a method for controlling the ethylene content [E (B)] will be described.
Since the propylene-ethylene copolymer (B) is a mixture of the propylene-based polymer component (B1) and the propylene-ethylene copolymer component (B2), the following relational expression is present between the respective ethylene contents. To establish.
E (B) = E (B1) × W (B1) + E (B2) × W (B2)
This formula shows the material balance regarding ethylene content. In the paragraph [0072], since the ethylene content [E (B2)] of the propylene-ethylene copolymer component (B2) is defined by the following formula, the above formula is the formula used for the definition. It was only deformed.
E (B2) = {E (B) −E (B1) × [W (B1) ÷ 100]} ÷ [W (B2) ÷ 100]

Therefore, if the weight ratio of the propylene-based polymer component (B1) and the propylene-ethylene copolymer component (B2) is determined, that is, if W (B1) and W (B2) are determined, E (B) becomes E It is uniquely determined by (B1) and E (B2). That is, E (B) is controlled by controlling the weight ratio of the propylene-based polymer component (B1) and the propylene-ethylene copolymer component (B2), and the three factors E (B1) and E (B2). can do. For example, in order to increase E (B), E (B1) may be increased or E (B2) may be increased. If it is noted that E (B2) is higher than E (B1), it can be easily understood that W (B1) can be reduced and W (B2) can be increased. The reverse control method is the same.
In addition, it is E (B) and E (B1) that the measurement values can be obtained directly, and E (B2) is calculated using the measurement values of both.
Therefore, if an operation to increase E (B2), that is, an operation to increase the amount of ethylene supplied to the second step is selected as a means when performing an operation to increase E (B), the measured value is directly It can be confirmed that E (B) is not E (B2), but it is obvious that the reason why E (B) increases is that E (B2) increases.

Finally, a method for controlling MFR (B) will be described.
Similar to the ethylene content E (B), the following relational expression holds for MFR (B).
log _e [MFR (B)] = (W (B1) ÷ 100) × log _e [MFR (B1)] + (W (B2) ÷ 100) × log _e [MFR (B2)]
(Where log _e is the logarithm with e as the base)
This formula is an empirical formula called the logarithm addition rule of viscosity, and is used routinely in the industry.
In the paragraph [0073], the MFR (B2) of the propylene-ethylene copolymer component (B2) is defined by the following formula, so the above formula is only a modification of the formula used for the definition. Absent.
MFR (B2) = exp {(log _e [MFR (B)] − (W (B1) ÷ 100) × log _e [MFR (B1)]) ÷ (W (B2) ÷ 100)}

In any case, the weight ratio of the propylene polymer component (B1) to the propylene-ethylene copolymer component (B2), MFR (B), MFR (B1), and MFR (B2) are not independent. Therefore, in order to control MFR (B), the weight ratio of propylene-ethylene copolymer component (B2), MFR (B1), and MFR (B2) may be controlled.
For example, in order to increase MFR (B), MFR (B1) may be increased or MFR (B2) may be increased. Moreover, since MFR (B2) is below MFR (B), it can be seen that MFR (B2) is below MFR (B1), but when MFR (B2) is lower than MFR (B1), It can be easily understood that MFR (B) can be increased even if W (B1) is increased and W (B2) is decreased. The reverse control method is the same.
It is to be noted that MFR (B) and MFR (B1) can actually obtain the measured values directly, and MFR (B2) is calculated using the measured values of both.
Therefore, if an operation to increase MFR (B2), that is, an operation to increase the amount of hydrogen supplied to the second step is selected as a means when performing an operation to increase MFR (B), it is directly confirmed as a measured value. What can be done is MFR (B) and not MFR (B2), but it is obvious that the reason why MFR (B) increases is that MFR (B2) increases.

I-3. Propylene-ethylene copolymer resin composition The propylene-ethylene copolymer resin composition according to the present invention comprises a copolymer (A) based on a total of 100% by weight of the copolymer (A) and the copolymer (B). ) 65 to 97% by weight and copolymer (B) 3 to 35% by weight. When the amount is outside this range, that is, when the amount of the copolymer (A) exceeds 97% by weight, the amount of the component (B2) contained in the propylene-ethylene copolymer resin composition is insufficient. As a result, it becomes impossible to obtain a molded article having an excellent appearance. On the other hand, when the amount of the copolymer (A) is less than 65 parts by weight, the component (B2) contained in the propylene-ethylene copolymer resin composition is excessively contained, and dispersibility with other components is increased. Due to the inferiority, the resulting streak-like pattern is scattered, and as a result, the molded article has an inferior appearance.
From the above viewpoint, it is necessary that the copolymer (A) is 65 to 97% by weight and the copolymer (B) is 3 to 35% by weight, and the copolymer (A) is 70 to 95% by weight. The blend (B) is more preferably 5 to 30% by weight.

  The propylene-ethylene copolymer resin composition according to the present invention is a composition containing the copolymer (A) and the copolymer (B) as essential components, but does not impair the purpose of the present invention. Various components can be added and used.

(1) Other additives To the propylene-ethylene copolymer resin composition according to the present invention, additives such as an antioxidant that can be added to the propylene-based resin are appropriately added as long as the effects of the present invention are not hindered. be able to.
Specifically, 2,6-di-t-butyl-p-cresol (BHT), tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane (“IRGANOX 1010 ") and a phenolic stabilizer represented by n-octadecyl-3- (4'-hydroxy-3,5'-di-t-butylphenyl) propionate (" IRGANOX 1076 "), bis (2,4- Di-t-butylphenyl) pentaerythritol diphosphite, tris (2,4-di-t-butylphenyl) phosphite and other phosphite stabilizers, represented by higher fatty acid amides and higher fatty acid esters Lubricants, glycerin esters, sorbitan acid esters, polyethylene glycol esters of fatty acids having 8 to 22 carbon atoms, etc. An antistatic agent, an antiblocking agent represented by silica, calcium carbonate, talc and the like may be added.

(2) Other polymers The propylene-ethylene copolymer resin composition of the present invention is provided with modifiers such as elastomers and alicyclic hydrocarbon resins that can be added to the propylene-based resin as long as the effects of the present invention are not hindered. Can be added as appropriate.
Specifically, ethylene-α-olefin copolymer, for example, polyethylene resin represented by low density polyethylene, high density polyethylene, etc., binary random copolymer of propylene and α-olefin having 4 to 12 carbon atoms. Examples thereof include a coalescent resin, a ternary random copolymer resin of propylene, ethylene, and an α-olefin having 4 to 12 carbon atoms. Here, as the α-olefin, butene is preferable.
In addition, alicyclic hydrocarbon resins represented by petroleum resins, terpene resins, rosin resins, coumarone indene resins, and hydrogenated derivatives thereof may be added.
Further, a styrene-based elastomer can be added, and the styrene-based elastomer can be appropriately selected from commercially available ones. For example, as a hydrogenated product of a styrene-butadiene block copolymer, Kraton “Clayton G” from Polymer Japan Co., Ltd., and “Tuftec” from Asahi Kasei Kogyo Co., Ltd. As a hydrogenated product of styrene-vinylated polyisoprene block copolymer, Kuraray Co., Ltd. under the trade name “Hibler”, and as a hydrogenated product of styrene-butadiene random copolymer, JSR Co., Ltd. Is sold under the trade name of “ Good.

(3) Production method of resin composition The propylene-ethylene copolymer resin composition according to the present invention comprises the above-mentioned copolymer (A), copolymer (B), and other additives as required. The elastomer can be obtained by mixing with an Henschel mixer, v blender, ribbon blender, tumbler blender or the like and then kneading with a kneader such as a single screw extruder, multi-screw extruder, kneader, Banbury mixer or the like.

II. Blow-molded product A blow-molded product comprising the propylene-ethylene copolymer resin composition of the present invention has improved blow characteristics of a propylene-ethylene copolymer obtained by a metallocene-based catalyst, and is extruded during blow molding. Excellent appearance with reduced surface roughness called melt fracture or shark skin even under molding conditions that are superior in productivity and performance, such as increased quantity, narrow die exit width, and lower extrusion temperature A molded body can be obtained.
The blow molded product thus obtained maintains the excellent properties of the propylene-ethylene copolymer based on the metallocene catalyst, such as excellent transparency and no stickiness, so that it can be used for food containers and medical containers. It is suitable for use as.

The blow molding machine used for producing the blow molded product is not particularly limited, and examples thereof include a known direct blow molding machine, a rotary blow molding machine, and an accumulator blow molding machine.
As preferable blow molding conditions, a resin temperature of 160 to 260 ° C., a blowing pressure of ^{2 to} 10 kg / cm ² , and a mold temperature of 10 to 50 ° C. can be applied.

The resulting blow molded article may be a single layer or a multilayer molded article in which a layer made of the propylene-ethylene copolymer resin composition is a surface layer.
Moreover, the use which uses this molded object is although it does not specifically limit, For example, it can utilize as food containers, such as a drink and a seasoning, and medical containers, such as a chemical | medical agent and a chemical | medical solution.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.
In addition, the physical-property evaluation methods and resin used in the examples and comparative examples are as follows.

1. Propylene-ethylene copolymer (A)
(1) Methods for measuring physical properties of copolymer (A) (1-1) Ethylene content [E (A1), E (A)]
The ethylene content [E (A1)] in the component (A1) extracted from the polymerization tank after the first step of the sequential polymerization, and the ethylene content [E in the copolymer (A) obtained after the second step [E (A)] was measured by ¹³ C-NMR according to the following conditions.
Model: GSX-400 manufactured by JEOL Ltd. or equivalent device (carbon nuclear resonance frequency of 100 MHz or more)
Solvent: o-dichlorobenzene + heavy benzene (4: 1 (volume ratio))
Concentration: 100 mg / mL
Temperature: 130 ° C
Pulse angle: 90 °
Pulse interval: 15 seconds Integration count: 5,000 times or more

The spectrum may be assigned with reference to Macromolecules 17, 1950 (1984), for example. The attribution of spectra measured under the above conditions is as shown in Table 1. Table 1 Symbols such as S _{alpha alpha} in accordance with conventions of Carman et al. (Macromolecules 10,536 (1977)), P represents methyl carbon, S is methylene carbon, T is a methine carbon, respectively.

Hereinafter, when “P” is a propylene unit in a copolymer chain and “E” is an ethylene unit, six types of triads of PPP, PPE, EPE, PEP, PEE, and EEE may exist in the chain. . As described in Macromolecules 15, 1150 (1982), the concentration of these triads and the peak intensity of the spectrum are linked by the following relational expressions (1) to (6).
[PPP] = k × I (T _ββ ) (1)
[PPE] = k × I (T _βδ ) (2)
[EPE] = k × I (T _δδ ) (3)
[PEP] = k × I (S _ββ ) (4)
[PEE] = k × I (S _βδ ) (5)
[EEE] = k × {I (S _δδ ) / 2 + I (S _γδ ) / 4} (6)
Here, [] indicates the fraction of triads, for example, [PPP] is the fraction of PPP triads in all triads. Therefore,
[PPP] + [PPE] + [EPE] + [PEP] + [PEE] + [EEE] = 1 (7)
It is. Further, k is a constant, I indicates the spectral intensity, and for example, I (T _ββ ) means the intensity of the peak at 28.7 ppm attributed to T _ββ .
By using the relational expressions (1) to (7) above, the fraction of each triad is obtained, and the ethylene content is obtained from the following expression.
Ethylene content (mol%) = ([PEP] + [PEE] + [EEE]) × 100
In addition, the propylene-ethylene copolymer according to the present invention contains a small amount of a propylene hetero bond (2,1-bond and / or 1,3-bond), thereby generating the minute peak in Table 2. .

In order to obtain an accurate ethylene content, it is necessary to consider the peaks derived from these heterogeneous bonds, and to include them in the calculation. Therefore, the ethylene content [E (A1)] of the component (A1) and the ethylene content [E (A)] of the copolymer (A) are substantially free of heterogeneous bonds. As in the case of analysis of a copolymer produced with a Natta-based catalyst, it is determined using the relational expressions (1) to (7).
The conversion of the ethylene content from mol% to wt% is performed using the following formula.
Ethylene content (% by weight) = (28 × X / 100) / {28 × X / 100 + 42 × (1−X / 100)} × 100
Here, X is the ethylene content in mol%.

(1-2) MFR (A1), MFR (A)
The MFR (A1) of the component (A1) obtained after the first step and the MFR (A) of the copolymer (A) obtained after the second step are as follows according to JIS K7210 A method condition M: Measured with
Test temperature: 230 ° C
Nominal load: 2.16kg
Die shape: 2.095mm diameter, 8.00mm length

(1-3) Mw / Mn (A1)
The Mw / Mn (A1) of the component (A1) obtained after the first step is the number average molecular weight Mn and the weight average molecular weight Mw determined from the gel permeation chromatography (GPC) measurement performed according to the following conditions. It is determined by the ratio.
Conversion from the retention capacity to the molecular weight in the GPC measurement is performed using a standard curve prepared in advance by standard polystyrene.
The standard polystyrene used is F380, F288, F128, F80, F40, F20, F10, F4, F1, A5000, A2500, and A1000, all of which are manufactured by Tosoh Corporation. A calibration curve is created by injecting 0.2 mL of a solution dissolved in ODCB (containing 0.5 mg / mL BHT) to 5 mg / mL. The calibration curve uses a cubic equation obtained by approximation by the least square method. The following numerical value is used for the viscosity formula [η] = K × M ^α used for conversion to molecular weight.
PS: K = 1.38 × 10 ⁻⁴ , α = 0.7
PP: K = 1.03 × 10 ⁻⁴ , α = 0.78

The measurement conditions for GPC are as follows.
Apparatus: Waters GPC (ALC / GPC 150C)
Detector: MIRAN 1A IR detector manufactured by FOXBORO Measurement wavelength: 3.42 μm
Column: AD806M / S (3 pieces) manufactured by Showa Denko KK
Mobile phase solvent: o-dichlorobenzene Measurement temperature: 140 ° C
Flow rate: 1.0 ml / min Injection volume: 0.2 ml
Sample preparation: Prepare a 1 mg / mL solution using ODCB (containing 0.5 mg / mL BHT) and dissolve at 140 ° C. for about 1 hour.

(1-4) Solid viscoelasticity measurement (DMA)
The sample used was a sheet of 2 mm thickness obtained by press molding under the following conditions, cut into a strip shape of 10 mm width × 18 mm length. As the apparatus, ARES manufactured by Rheometric Scientific was used.
The frequency is 1 Hz. The measurement temperature was raised stepwise from −60 ° C., and measurement was performed until the sample melted and became impossible to measure, and the glass transition point (Tg) was obtained. The strain was performed in the range of 0.1 to 0.5%.
·Press molding:
Preheat at 230 ° C for 5 minutes, then pressurize at the same temperature for 3 minutes at a pressure of 50 kgf / cm ² , and immediately solidify by cooling at 30 ° C with a pressure of 100 kgf / cm ² And a 2 mm thick press sheet was obtained.

(1-5) Identification of Weight Ratio [W (A1) and W (A2)] of Each Component As described above, the weight ratio of the component (A1) and the component (A2) is defined by the following formula.
W (B1) = Production amount of the first step / (Production amount of the first step + Production amount of the second step) × 100
W (B2) = Production amount of the second step / (Production amount of the first step + Production amount of the second step) × 100
As will be described later in [Production Example A-1], when the copolymer (A) is produced, the polymer obtained after the first step of producing the component (A1) is finished once. The whole volume flask was extracted and the yield of the first step was measured.
After separating 10 g of the obtained component (A1) as a sample, the rest was filled in the polymerization tank, and the second step of producing the component (A2) was performed. After the second step was completed, the yield of the obtained copolymer (A) was measured.
From this result, the production amount of the first step and the production amount of the second step were calculated by the following formulas, and W (A1) and W (A2) were calculated by the above formulas using the results.
Production amount of the first step = Yield of the first step−10 g (sampling amount)
Production amount of the second step = Yield of the copolymer (A) −Production amount of the first step

(1-6) Ethylene content in component (A2) [E (A2)]
The ethylene content [E (A2)] in the component (A2) is obtained by using the ethylene content [E (A1), E (A)] and the respective component amounts W (A1) and W (A2). It was calculated from the following formula.
E (A2) = {E (A) −E (A1) × [W (A1) ÷ 100]} ÷ [W (A2) ÷ 100]

(1-7) Melt flow rate of component (A2) [MFR (A2)]
The MFR (A2) of the component (A2) was calculated from the following formula using the MFR (A1) and MFR (A) described above and W (A1) and W (A2).
MFR (A2) = exp {(log _e [MFR (A)] − (W (A1) ÷ 100) × log _e [MFR (A1)]) ÷ (W (A2) ÷ 100)}
(Where log _e is the logarithm with e as the base)

(2) Production of propylene-ethylene copolymer (A) [Production Example A-1]
(2-1) Preliminary Polymerization Catalyst (i) Measurement of Carrier Particle Size In this production example, catalyst synthesis was performed using ion-exchange layered silicate (Montmorillonite: Benclay SL manufactured by Mizusawa Chemical Co., Ltd.) as a carrier. Prior to catalyst synthesis, the average particle size of the carrier was measured using a laser diffraction / scattering particle size distribution analyzer (“LA-920” manufactured by Horiba, Ltd.). In the measurement, ethanol was used as a dispersion medium, and the average particle diameter was determined with a shape factor of 1.0. The value obtained was 50 μm.

(Ii) Preparation of prepolymerization catalyst (chemical treatment of silicate)
To a 10-liter glass separable flask with a stirring blade, 3.75 liters of distilled water was added slowly followed by 2.5 kg of concentrated sulfuric acid (96%). At 50 ° C., 1 kg of the above-mentioned montmorillonite (Menzawa Chemical Co., Ltd. Benclay SL; average particle size = 50 μm) was dispersed, heated to 90 ° C., and maintained at that temperature for 6.5 hours. After cooling to 50 ° C., the slurry was filtered under reduced pressure to recover the cake. 7 liters of distilled water was added to this cake to reslurry it, and then filtered. This washing operation was performed until the pH of the washing solution (filtrate) exceeded 3.5. The collected cake was dried at 110 ° C. overnight under a nitrogen atmosphere. The weight after drying was 707 g.

(Drying silicate)
The silicate previously chemically treated was dried with a kiln dryer. Specifications and drying conditions are as follows.
Rotating cylinder: Cylindrical inner diameter 50mm Heating zone 550mm (electric furnace)
Rotating speed with lifting blade: 2rpm
Tilt angle: 20/520
Silicate supply rate: 2.5 g / min Gas flow rate: Nitrogen 96 liters / hour Countercurrent drying temperature: 200 ° C. (powder temperature)

(Preparation of catalyst)
20 g of dry silicate was introduced into a glass reactor equipped with a stirring blade with an internal volume of 1 liter, 116 ml of mixed heptane and 84 ml of a heptane solution of triethylaluminum (0.60 M) were added, and the mixture was stirred at room temperature. After 1 hour, the mixture was washed with mixed heptane to prepare a silicate slurry to 200 ml. Next, 0.96 ml of a heptane solution of triisobutylaluminum (0.71 M / L) was added to the silicate slurry prepared above and reacted at 25 ° C. for 1 hour. In parallel, 218 mg (0.3 mM) of [(r) -dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4H-azurenyl}] zirconium] in 87 ml of mixed heptane Then, 3.31 ml of a heptane solution of triisobutylaluminum (0.71 M) was added, and the mixture reacted at room temperature for 1 hour was added to the silicate slurry. After stirring for 1 hour, mixed heptane was added to prepare 500 ml. did.

(Prepolymerization / washing)
Subsequently, the previously prepared silicate / metallocene complex slurry was introduced into a stirring autoclave having an internal volume of 1.0 liter sufficiently substituted with nitrogen. When the temperature was stabilized at 40 ° C., propylene was supplied at a rate of 10 g / hour to maintain the temperature. After 4 hours, the supply of propylene was stopped and maintained for another 2 hours.
After completion of the prepolymerization, the residual monomer was purged, stirring was stopped and the mixture was allowed to stand for about 10 minutes, and then the supernatant was decanted. Subsequently, 0.95 ml of a heptane solution of triisobutylaluminum (0.71 M / L) and 560 ml of mixed heptane were further added, stirred at 40 ° C. for 30 minutes, allowed to stand for 10 minutes, and then 560 ml of the supernatant was removed. This operation was further repeated 3 times. When the component analysis of the final supernatant was conducted, the concentration of the organoaluminum component was 1.23 mmol / liter, the Zr concentration was 8.6 × 10 ⁻⁶ g / L, and the abundance in the supernatant with respect to the amount charged. Was 0.016%. Subsequently, 17.0 ml of a heptane solution of triisobutylaluminum (0.71 M / L) was added, followed by drying at 45 ° C. under reduced pressure.
A prepolymerized catalyst A containing 2.0 g of polypropylene per 1.0 g of catalyst was obtained.

(2-2) Production of Propylene-Ethylene Copolymer (A) Propylene-ethylene copolymer (A) was produced according to the following procedure using the above prepolymerized catalyst A.

(I) First Step: Production of Propylene Polymer Component (A1) An autoclave having an internal volume of 3 L having a stirring and temperature control device was sufficiently substituted with propylene, and then 2.76 ml of triisobutylaluminum / n-heptane solution (2 0.0 mmol), 16 g of ethylene, 30 ml of hydrogen, and then 750 g of liquid propylene were introduced, and the temperature was raised to 70 ° C. to maintain the temperature.
The above prepolymerized catalyst A was slurried with n-heptane, and 25 mg of the catalyst (excluding the weight of the prepolymerized polymer) was injected to initiate polymerization. Polymerization was continued for 60 minutes while maintaining the temperature in the tank at 70 ° C. Thereafter, the residual monomer was purged to normal pressure and further completely replaced with purified nitrogen.
Prepare a 2 L glass flask fully substituted with nitrogen in advance, and pass the propylene polymer component (A1) polymer obtained in the first step through a Teflon (registered trademark) tube under a nitrogen stream. The entire amount was extracted into the flask.
As a result of weighing, the propylene polymer component (A1) obtained in the first step was 184 g. Of these, 10 g was separated and used for analysis.

(Ii) Second step: Production of propylene-ethylene copolymer component (A2) After the first step was completed, the autoclave used for the polymerization was opened, and it was confirmed that no polymer remained inside. After cleaning, it was reassembled, and it was thoroughly dried by flowing nitrogen while heating.
After drying, the mixture was cooled to room temperature. Thereafter, of the 184 g of the propylene polymer component (A1) obtained in the first step, the remaining 174 g obtained by separating 10 g for analysis was filled in the autoclave through a Teflon (registered trademark) tube under a nitrogen stream. .
Separately, a mixed gas used in the second step was prepared using an autoclave having an internal volume of 20 L having a stirring and temperature control device. The preparation temperature was 85 ° C., and the mixed gas composition was ethylene 25 vol%, propylene 75 vol%, and hydrogen 200 ppm. This mixed gas was supplied to a 3 L autoclave and the pressure was increased to 2.5 MPaG to start polymerization in the second step.
The polymerization continued at 80 ° C. for 66 minutes. Thereafter, 10 ml of ethanol was introduced to terminate the polymerization. The recovered polymer was sufficiently dried in an oven.
As a result of weighing, the obtained propylene-ethylene copolymer (A) was 310 g. Of these, 174 g was a propylene-based polymer component (A1), so the obtained propylene-ethylene copolymer component (A2) was 136 g. As a result of calculating the weight ratio of the propylene-based polymer component (A1) and the propylene-ethylene copolymer component (A2) based on these yield values, W (A1) was 56% by weight and W (A2) was 44 It became weight%.
The propylene-based polymer component (A1) prepared for analysis after the end of the first step and the propylene-ethylene copolymer (A) obtained after the end of the second step are analyzed, and the ethylene content [E (A1) , E (A)], MFR (A1), and MFR (A).
The results are shown in Table 3. Further, E (A2) and MFR (A2) were calculated using the values of W (A1), W (A2), E (A1), E (A), MFR (A1), and MFR (A). These values are also shown in Table 3.
The same polymerization was carried out 8 times and used as the raw material of Example 1.

[Production Examples A-2 to A-16]
Except for using the polymerization conditions described in Table 3, sequential polymerization was carried out in the same manner as in Production Example A-1 to produce propylene-ethylene copolymer (A).
The results are shown in Table 3.

2. Propylene-ethylene copolymer (B)
(1) Measuring method of physical properties of component (B) (1-1) Ethylene content [E (B1), E (B)]
The ethylene content [E (B1)] in the polymer component (B1) extracted from the polymerization tank after the first step of sequential polymerization, and the propylene-ethylene copolymer (B) obtained after the second step The ethylene content [E (B)] was measured by ¹³ C-NMR as described above.

(1-2) MFR (B1), MFR (B)
The MFR (B1) of the propylene-ethylene copolymer (B1) obtained after the first step and the MFR (B) of the propylene-ethylene copolymer (B) obtained after the second step are propylene-ethylene. It measured by the same method as MFR of a copolymer (A).

(1-3) Specification of Weight Ratio W (B1) and W (B2) of Each Component As described above, the weight ratio of the propylene-based polymer component (B1) and the propylene-ethylene copolymer component (B2) is It is defined by the following formula.
W (B1) = Production amount of the first step / (Production amount of the first step + Production amount of the second step) × 100
W (B2) = Production amount of the second step / (Production amount of the first step + Production amount of the second step) × 100
As will be described later in [Production Example B-1], when the copolymer (B) is produced, the polymer obtained after the first step of producing the component (B1) is finished. The whole volume flask was extracted and the yield of the first step was measured. After separating 10 g of the obtained component (B1) as a sample, the remainder was filled in the polymerization tank, and the second step of producing the component (B2) was performed. After the 2nd process was completed, the yield of the obtained copolymer (B) was measured.
From this result, the manufacturing amount of the first step and the manufacturing amount of the second step were calculated by the following formulas, and W (B1) and W (B2) were calculated by the above formulas using the results.
Production amount of the first step = Yield of the first step−10 g (sampling amount)
Production amount of the second step = Yield of the copolymer (B) −Production amount of the first step

(1-4) Ethylene content in component (B2) [E (B2)]
The ethylene content [E (B2)] in the component (B2) is obtained by using the ethylene content [E (B1), E (B)] and the respective component amounts W (B1) and W (B2). It was calculated from the following formula.
E (B2) = {E (B) −E (B1) × [W (B1) ÷ 100]} ÷ [W (B2) ÷ 100]

(1-5) Melt flow rate of component (B2) [MFR (B2)]
The MFR (B2) of the component (B2) was calculated from the following formula using the MFR (B1) and MFR (B) described above and W (B1) and W (B2).
MFR (B2) = exp {(log _e [MFR (B)] − (W (B1) ÷ 100) log _e [MFR (B1)]) ÷ (W (B2) ÷ 100)}
(Where log _e is the logarithm with e as the base)

(2) Propylene-ethylene copolymer (B) production [Production Example B-1]
(2-1) Analysis of catalyst composition (i) Ti content:
The sample was accurately weighed, hydrolyzed, and measured using a colorimetric method. About the sample after prepolymerization, content was calculated using the weight remove | excluding prepolymerized polymer.
(Ii) Silicon compound content:
The sample was accurately weighed and decomposed with methanol. The silicon compound concentration in the obtained methanol solution was determined by comparison with a standard sample using gas chromatography. The content of the silicon compound contained in the sample was calculated from the concentration of the silicon compound in methanol and the weight of the sample. About the sample after prepolymerization, content was calculated using the weight remove | excluding prepolymerized polymer.

(2-2) Preparation of prepolymerization catalyst (i) Preparation of solid component A 10 L autoclave equipped with a stirrer was sufficiently substituted with nitrogen, and 2 L of purified toluene was introduced. Here, 200 g of Mg (OEt) ₂ was added at room temperature, and 1 L of TiCl ₄ was slowly added thereto. The temperature was raised to 90 ° C. and 50 ml of di-n-butyl phthalate was introduced. Thereafter, the temperature was raised to 110 ° C. to carry out a reaction for 3 hours. The reaction product was thoroughly washed with purified toluene.
Subsequently, the refined toluene was introduce | transduced and the whole liquid quantity was adjusted to 2L. 1 L of TiCl ₄ was added at room temperature, the temperature was raised to 110 ° C., and the reaction was performed for 2 hours. The reaction product was thoroughly washed with purified toluene. Subsequently, the refined toluene was introduce | transduced and the whole liquid quantity was adjusted to 2L. 1 L of TiCl ₄ was added at room temperature, the temperature was raised to 110 ° C., and the reaction was performed for 2 hours. The reaction product was thoroughly washed with purified toluene. Furthermore, using purified n-heptane, toluene was replaced with n-heptane to obtain a solid component slurry.
A portion of this slurry was sampled and dried. As a result of analysis, the Ti content of the solid component was 2.7% by weight.

Next, a 20 L autoclave equipped with a stirrer was sufficiently replaced with nitrogen, and 100 g of the solid component slurry was introduced as a solid component. Purified n-heptane was introduced to adjust the solid component concentration to 25 g / L. 50 ml of SiCl ₄ was added and a reaction was performed at 90 ° C. for 1 hr. The reaction product was thoroughly washed with purified n-heptane.
Thereafter, purified n-heptane was introduced to adjust the liquid level to 4 L. Here, dimethyl divinyl silane 30 ml, 80 g was added _{t-BuMeSi (OMe) 2 30ml} , the n- heptane dilution of _Et 3 Al as _Et 3 Al, were 2hr reaction at 40 ° C.. The reaction product was thoroughly washed with purified n-heptane to obtain a solid catalyst. A portion of the resulting solid catalyst slurry was sampled and dried for analysis. The solid catalyst contained 1.2 wt% Ti and 8.9 wt% t-BuMeSi (OMe) ₂ .

(Ii) Prepolymerization Prepolymerization was performed by the following procedure using the solid catalyst obtained above. Purified n-heptane was introduced into the slurry, and the solid catalyst concentration was adjusted to 20 g / L. After cooling the slurry to 10 ° C., 10 g was added n- heptane dilution of _Et 3 Al as _Et 3 Al, were fed over 4hr of propylene 280 g. After the supply of propylene was completed, the reaction was further continued for 30 minutes.
Next, the gas phase 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 prepolymerized catalyst B.
This prepolymerized catalyst B contained 2.5 g of polypropylene per 1 g of the solid catalyst. As a result of analysis, the portion of the prepolymerized catalyst B excluding polypropylene contained 1.0% by weight of Ti and 8.3% by weight of t-BuMeSi (OMe) ₂ .
Using this prepolymerized catalyst B, a propylene-ethylene copolymer (B) was produced according to the following procedure.

(2-3) Production of propylene-ethylene copolymer (B) (i) First step: Production of propylene-based polymer component (B1) The autoclave with an internal volume of 3 L having a stirring and temperature control device is sufficiently substituted with propylene. after, and 550mg added n- heptane dilution of _Et 3 Al as _Et 3 Al, hydrogen 15 NL, ethylene 10.5 g, followed by introducing the liquid propylene 750 g, were maintained raised temperature to 60 ° C. .
The prepolymerized catalyst B was slurried with n-heptane, and 9 mg (excluding the weight of the prepolymerized polymer) was injected as a solid catalyst to initiate polymerization. Polymerization was continued for 30 minutes while maintaining the temperature in the tank at 60 ° C. Thereafter, the residual monomer was purged to normal pressure and further completely replaced with purified nitrogen.
Prepare a 2 L glass flask thoroughly substituted with nitrogen in advance, and pass the propylene polymer component (B1) polymer obtained in the first step through a Teflon (registered trademark) tube under a nitrogen stream. The entire amount was extracted into the flask.
As a result of weighing, the propylene-based polymer component (B1) obtained in the first step was 252 g. Of these, 10 g was separated and used for analysis.

(Ii) Second step: Production of propylene-ethylene copolymer component (B2) After completion of the first step, the autoclave used for the polymerization was opened, and it was confirmed that no polymer remained in the interior. After cleaning, it was reassembled, and it was thoroughly dried by flowing nitrogen while heating. After drying, the mixture was cooled to room temperature. Thereafter, of the 252 g of the propylene polymer component (B1) obtained in the first step, the remaining 242 g obtained by separating 10 g for analysis was filled in the autoclave through a Teflon (registered trademark) tube under a nitrogen stream. .
Separately, a mixed gas used in the second step was prepared using an autoclave having an internal volume of 20 L having a stirring and temperature control device. The preparation temperature was 75 ° C., and the composition of the mixed gas was 19 vol% ethylene, 81 vol% propylene, and 320 ppm hydrogen. This mixed gas was supplied to a 3 L autoclave and the pressure was increased to 2.0 MPaG to start polymerization in the second step. The polymerization was continued at 70 ° C. for 14 minutes. Thereafter, 10 ml of ethanol was introduced to terminate the polymerization.
The recovered polymer was sufficiently dried in an oven. As a result of weighing, the obtained propylene-ethylene copolymer (B) was 302 g. Of these, 242 g was a propylene-based polymer component (B1), so the obtained propylene-ethylene copolymer component (B2) was 60 g. As a result of calculating the weight ratio of the propylene-based polymer component (B1) and the propylene-ethylene copolymer component (B2) based on these yield values, W (B1) was 80% by weight and W (B2) was 20 It became weight%.
The propylene-based polymer component (B1) prepared for analysis after the end of the first step and the propylene-ethylene copolymer (B) obtained after the end of the second step are analyzed, and the ethylene content [E (B1) , E (B)], MFR (B1), and MFR (B).
The results are shown in Table 4. Further, E (B2) and MFR (B2) were calculated using the values of W (B1), W (B2), E (B1), E (B), MFR (B1), and MFR (B). These values are also shown in Table 4.

[Production Examples B-2 to B-6]
A propylene-ethylene copolymer (B) was produced in the same manner as in Production Example B-1, except that the polymerization conditions described in Table 4 were used. The results are shown in Table 4.

[Production Examples B-7 to B-12]
A propylene-ethylene copolymer (B) was produced in the same manner as in Production Example B-1, except that the polymerization conditions described in Table 5 were used. The results are shown in Table 5.

[Production Examples B-13 to B-19]
A propylene-ethylene copolymer (B) was produced in the same manner as in Production Example B-1, except that the polymerization conditions shown in Table 6 were used. The results are shown in Table 6.

[Production Examples B-20 to B-23]
A propylene-ethylene copolymer (B) was produced in the same manner as in Production Example B-1, except that the polymerization conditions described in Table 7 were used. At this time, in Production Example B-20, only the first step was performed, and the second step was not performed.
The results are shown in Table 7.

[Production Examples B-24 to B-30]
A propylene-ethylene copolymer (B) was produced in the same manner as in Production Example B-1, except that the polymerization conditions described in Table 8 were used. The results are shown in Table 8.

[Example 1]
1. Compound A-1 obtained in Production Example A-1 as a copolymer (A), and B-1 obtained in Production Example B-1 as a copolymer (B) were 95% by weight and 5% by weight, respectively. The following antioxidant and neutralizing agent are added in the following amounts to 100 parts by weight of the mixture of component (A) and component (B), and charged into a Henschel mixer. Mixed.
·Antioxidant:
Tetrakis {methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate} methane (BASF, trade name “Irganox 1010”) 500 ppm
Tris (2,4-di-t-butylphenyl) phosphite (manufactured by BASF Corporation, trade name “Irgaphos 168”) 500 ppm
・ Neutralizer: Calcium stearate 500ppm

2. Granulation In a “KZW” twin screw extruder manufactured by Technobel with a screw diameter of 15 mm, melt-mixed under the conditions of extruder temperature = 200 ° C., screw rotation speed = 300 rpm, discharge rate = 3.0 kg / h, and from strand die The extruded molten resin was taken out while being cooled and solidified in a cooling water tank, and the strand was cut into a diameter of 3 mm and a length of 2 mm using a strand cutter to obtain a propylene-ethylene copolymer resin composition raw material pellet.

3. Blow Molding The resulting propylene-ethylene copolymer resin composition raw material pellets are made by Nippon Steel Works Co., Ltd., having a diameter of 50 mmφ with a dalmage kneading part at the tip, and a L / D22 screw and die having a crosshead structure. Using a direct blow molding machine JB105, a polypropylene blow molded body (cylindrical bottle) with a bottle weight of 30 g and an internal capacity of 550 cc is molded under conditions of a molding temperature of 180 ° C., a blow mold cooling temperature of 15 ° C., and a cooling time of 24 seconds. did.

4). Appearance Evaluation of Blow Molded Body (1) Surface Roughness Surface roughness is an appearance defect that occurs on the blow molded body surface as shown in FIG. In FIG. 1, the arrow indicates the MD direction.
Ten persons visually observed the obtained blow molded body, and evaluated and determined according to the following criteria. ◯ and △ judgments are at a level that causes no problem in practical use.
◯: A blow molded article determined by 8 or more people that no wave pattern has occurred.
(Triangle | delta): The blow molded object which 5 or more and 7 or less determined that the wave pattern did not arise, and determined that there was no problem in practical use.
X: A blow molded article in which six or more people determine that there is a wave pattern, the wave pattern is clear, and the sense of transparency is poor.

(2) Oriented Crystal Oriented crystal is a phenomenon in which a lump of crystal structure (white spots) that can be visually observed at the die exit is scattered, and the entire blow molded product becomes cloudy. When orientational crystallization is extremely promoted, a solid-liquid phase separation is present at the die outlet, resulting in white turbidity.
Ten persons visually observed the obtained blow molded body, and evaluated and determined according to the following criteria. ◯ and △ judgments are at a level that causes no problem in practical use.
◯: A blow molded article in which 8 or more people determined that no white spots or cloudiness occurred.
(Triangle | delta): The blow molded object which 5 or more and 7 or less determined that there was no white spot and cloudiness, and determined that there was no problem in practical use.
X: A blow molded article in which 6 or more people determined that white spots or cloudiness occurred overall.

(3) Fish Eye (FE)
The appearance of the resulting blow molded article was visually observed and evaluated according to the following criteria to confirm the presence or absence of fish eyes.
○: Fish eyes are hardly seen and the appearance is excellent.
X: Many fish eyes are generated and the appearance is remarkably inferior.

(4) Dispersed state When the dispersed state of the resin is inferior, several stripes are generated in the flow direction of the blow molded article.
Ten people visually observed the appearance of the resulting blow molded article, and evaluated and judged according to the following criteria. ◯ and △ judgments are at a level that causes no problem in practical use.
○: A blow molded article in which 8 or more people determined that no streaking occurred.
(Triangle | delta): The blow molded object which 5 or more and 7 or less determined that the streak did not arise, and determined that there was no problem practically.
X: A blow molded article in which 6 or more people judged that streaks were scattered over several lines as a whole.

(5) Stickiness evaluation It confirmed with the adhesion state to the metal mold | die of the molded object at the time of blow molding.
○: Can be molded without problems.
X: The molded body adheres to the mold, and the molded body cannot be automatically dropped from the mold.

(6) HAZE (transparency) measurement Based on JIS K7136-2000, it measured with the haze meter in the blow molded body trunk cut piece. The smaller the value obtained, the better the transparency.

(7) Flexibility evaluation Based on JIS K7127-1989, the tensile elasticity modulus about the bottle cut piece was measured.
Sample shape: strip Sample length: 150 mm
Sample width: 15mm
Distance between chucks: 100mm
Crosshead speed: 1mm / min

[Examples 2 to 5]
Compounding, granulation, molding, appearance evaluation, and physical property evaluation were carried out in the same manner as in Example 1 except that the ratio of the copolymer (A) and the copolymer (B) was changed as shown in Table 9. The results are shown in Table 9.
In Example 5, although some dispersion | distribution defect was seen, it was a level which is satisfactory practically. Otherwise, all the evaluation results were satisfactory.

[Comparative Examples 1-3]
Compounding, granulation, molding, appearance evaluation, and physical property evaluation were carried out in the same manner as in Example 1 except that the ratio of the copolymer (A) and the copolymer (B) was changed as shown in Table 9. The results are shown in Table 9.
In Comparative Examples 1 and 2, since the blending amount of the copolymer (B) was insufficient, a remarkable surface roughness was generated, and a molded product that could withstand evaluation could not be obtained. In Comparative Example 3, the blending amount of the copolymer (B) was excessive, streaks due to the deterioration of the dispersion state were scattered, and a molded product that could withstand evaluation could not be obtained.

[Examples 6 to 9]
The copolymer (A) of Example 1 was changed to A-2 to A-5 obtained in Production Examples A-2 to 5, and the ratio of the copolymer (A) and the copolymer (B) was changed. Except that it was set to 90:10, compounding, granulation, molding, appearance evaluation, and physical property evaluation were performed in the same manner as in Example 1. The results are shown in Table 10.
All the evaluation results were satisfactory results.

[Examples 10 and 11]
The copolymer (A) of Example 1 was changed to A-7 and A-8 obtained in Production Examples A-7 and A-8, and the copolymer (A) and copolymer (B) Except for changing the ratio to 90:10, blending, granulation, molding, appearance evaluation, and physical property evaluation were performed in the same manner as in Example 1. The results are shown in Table 11.
All the evaluation results were satisfactory results.

[Comparative Examples 4 and 5]
The copolymer (A) of Example 1 was changed to A-6 and A-9 obtained in Production Examples A-6 and A-9, and the copolymer (A) and copolymer (B) Except for changing the ratio to 90:10, blending, granulation, molding, appearance evaluation, and physical property evaluation were performed in the same manner as in Example 1. The results are shown in Table 11.
In Comparative Example 4, since E (A2) of the copolymer (A) was as low as 6% by weight, the container had a high tensile elastic modulus and was inferior in flexibility. In Comparative Example 5, since E (A2) of copolymer (A) is as high as 16% by weight and Tg is two peaks, component (A) has a phase separation structure, and thus becomes cloudy. The blow molded product had a HAZE of 40, indicating poor transparency.

[Examples 12 and 13]
The copolymer (A) of Example 1 was changed to A-11 and A-12 obtained in Production Examples A-11 and A-12, and the copolymer (A) and copolymer (B) Except for changing the ratio to 90:10, blending, granulation, molding, appearance evaluation, and physical property evaluation were performed in the same manner as in Example 1. The results are shown in Table 12.
In Example 12, since the copolymer (A) contained a small amount of W (A2), a slight deterioration in flexibility was observed, but it was at a level of no practical problem. Further, in Example 13, since W (A2) of the copolymer (A) was increased, the stickiness was slightly deteriorated, but it was at a level with no problem in use.

[Comparative Examples 6 and 7]
The copolymer (A) of Example 1 was changed to A-10 and A-13 obtained in Production Examples A-10 and A-13, and the copolymer (A) and copolymer (B) Except for changing the ratio to 90:10, blending, granulation, molding, appearance evaluation, and physical property evaluation were performed in the same manner as in Example 1. The results are shown in Table 12.
In Comparative Example 6, since W (A2) of the copolymer (A) was below the range of the invention, the tensile modulus of the container cut piece was high and the result was inferior in flexibility. Further, in Comparative Example 7, since W (A2) of the copolymer (A) exceeds the range of the invention, the stickiness of the molded body deteriorates rapidly, and the molded body does not automatically drop from the mold. It was.

[Example 14]
The copolymer (A) of Example 1 was changed to A-14 obtained in Production Example A-14, and the ratio of the copolymer (A) and the copolymer (B) was changed to 90:10. In the same manner as in Example 1, blending, granulation, molding, appearance evaluation, and physical property evaluation were performed. The results are shown in Table 13.
The evaluation result was a satisfactory result.

[Comparative Examples 8 and 9]
The copolymer (A) of Example 1 was changed to A-15 and A-16 obtained in Production Examples A-15 and A-16, and the ratio of copolymer (A) and copolymer (B) The composition, granulation, molding, appearance evaluation, and physical property evaluation were carried out in the same manner as in Example 1 except that the ratio was 90:10.
Since the comparative example 8 had high MFR, the drawdown of a parison was large and it was unmoldable. Moreover, since W (A2) of the copolymer (A) was less than the scope of the invention, Comparative Example 9 had a high tensile elastic modulus of the container cut piece and a poor flexibility. The results are shown in Table 13.

[Examples 15 to 19]
The copolymer (B) of Example 1 was changed to B-2 to B-6 obtained in Production Examples B-2 to 6, and the ratio of the copolymer (A) and the copolymer (B) was changed. Except that it was set to 90:10, compounding, granulation, molding, appearance evaluation, and physical property evaluation were performed in the same manner as in Example 1. The results are shown in Table 14.
All the evaluation results were satisfactory results.

[Examples 20 to 23]
The copolymer (B) of Example 1 was changed to B-8 to B-11 obtained in Production Examples B-8 to 11, and the ratio of the copolymer (A) and the copolymer (B) was changed. Except that it was set to 90:10, compounding, granulation, molding, appearance evaluation, and physical property evaluation were performed in the same manner as in Example 1. The results are shown in Table 15.
In Example 20, white spots due to the oriented crystals were slightly observed, but the level was satisfactory for use. Further, in Example 23, although the surface roughness was slightly generated, it was at a level with no problem in use. Otherwise, all the evaluation results were satisfactory.

[Comparative Examples 10 and 11]
The copolymer (B) of Example 1 was changed to B-7 and B-12 obtained in Production Examples B-7 and B-12, and the copolymer (A) and copolymer (B) Except for changing the ratio to 90:10, blending, granulation, molding, appearance evaluation, and physical property evaluation were performed in the same manner as in Example 1.
Since Comparative Example 10 exhibited extremely oriented crystals and rupture occurred during blow molding, a blow molded article could not be obtained. Further, in Comparative Example 11, since the surface roughness was remarkably generated, a blow molded article that could withstand the evaluation could not be obtained. The results are shown in Table 15.

[Examples 24-29]
The copolymer (B) of Example 1 was changed to B-13 to B-18 obtained in Production Examples B-13 to 18, and the ratio of the copolymer (A) and the copolymer (B) was changed. Except that it was set to 90:10, compounding, granulation, molding, appearance evaluation, and physical property evaluation were performed in the same manner as in Example 1. The results are shown in Table 16.
In Example 24, white spots due to the oriented crystals were slightly observed, but the level was satisfactory for use. Further, in Example 29, although the surface roughness was slightly generated, it was at a level with no problem in use. Otherwise, all the evaluation results were satisfactory.

[Comparative Example 12]
The copolymer (B) of Example 1 was changed to B-19 obtained in Production Example B-19, and the ratio of copolymer (A) and copolymer (B) was changed to 90:10. In the same manner as in Example 1, compounding, granulation, molding, appearance evaluation, and physical property evaluation were performed.
Since the surface roughness was conspicuous, a blow molded product that could withstand the evaluation could not be obtained.
The results are shown in Table 16.

[Examples 30 and 31]
The copolymer (B) of Example 1 was changed to B-21 and B-22 obtained in Production Examples B-21 and B-22, and the copolymer (A) and copolymer (B) Except for changing the ratio to 90:10, blending, granulation, molding, appearance evaluation, and physical property evaluation were performed in the same manner as in Example 1. The results are shown in Table 17.
All the evaluation results were satisfactory results.

[Comparative Examples 13 and 14]
The copolymer (B) of Example 1 was changed to B-20 and B-23 obtained in Production Examples B-20 and B-23, and the copolymer (A) and copolymer (B) Except for changing the ratio to 90:10, blending, granulation, molding, appearance evaluation, and physical property evaluation were performed in the same manner as in Example 1. The results are shown in Table 17.
In Comparative Example 13, since the surface roughness was remarkable, a blow molded article that could withstand the evaluation could not be obtained. In Comparative Example 14, the component (B2) contained in the copolymer (B) was excessive, streaks due to the deterioration of the dispersion state were scattered, and a blow molded product that could withstand the evaluation was not obtained.

[Examples 32-36]
The copolymer (B) of Example 1 was changed to B-25 to B-29 obtained in Production Examples B-25 to 29, and the ratio of the copolymer (A) and the copolymer (B) was changed. Except that it was set to 90:10, compounding, granulation, molding, appearance evaluation, and physical property evaluation were performed in the same manner as in Example 1. The results are shown in Table 18.
In Example 36, a slight amount of fine fish eyes due to poor dispersion of the high molecular weight component was observed, but the level was satisfactory for use. Otherwise, all the evaluation results were satisfactory.

[Comparative Examples 15 and 16]
The copolymer (B) of Example 1 was changed to B-25 and B-30 obtained in Production Examples B-24 and B-30, and the ratio of copolymer (A) and copolymer (B) The composition, granulation, molding, appearance evaluation, and physical property evaluation were carried out in the same manner as in Example 1 except that the ratio was 90:10. The results are shown in Table 18.
In Comparative Example 15, since the MFR (B) of the copolymer (B) is low, the dispersibility with the copolymer (A) is inferior, and thus streaks due to the deterioration of the dispersion state are occasionally observed and can withstand the evaluation. A molded product could not be obtained. Further, Comparative Example 16 is a molded article that can withstand evaluation because fish eyes caused by high molecular weight gel are remarkably generated due to a large difference between MFR (B1) and MFR (B2) in the copolymer (B). Could not get.

  If each of the above examples and each comparative example are compared, using a propylene-ethylene copolymer resin composition satisfying the respective regulations in the present invention, even if blow molding is performed at a low temperature of about 180 ° C., surface roughness and orientation It can be seen that a blow molded article exhibiting excellent characteristics such as excellent transparency, flexibility, and excellent stickiness performance without causing appearance defects such as white spots due to crystals can be obtained.

  The propylene-ethylene copolymer resin composition according to the present invention is useful as a material for blow molding, and the blow molded product comprising the resin composition of the present invention is used as various food containers, medical containers, cosmetic containers, and the like. Can be widely used.

Claims (3)

Based on a total of 100 parts by weight of the following (A) and (B), 65 to 97 parts by weight of a propylene-ethylene copolymer (A) having the following characteristics (Ai) to (A-iii) and the following characteristics ( A blow molded article comprising a propylene-ethylene copolymer resin composition containing 3 to 35 parts by weight of a propylene-ethylene copolymer (B) having (Bi) to (B-ii),
The propylene-ethylene copolymer (A) is a propylene-based polymer component (A1) 30 having the following characteristics (A1-i) and (A1-ii) based on a total of 100% by weight of (A1) and (A2). And 80% by weight, and 20 to 70% by weight of a propylene-ethylene copolymer component (A2) having the following characteristics (A2-i), and the propylene-ethylene copolymer (B) comprises (B1) and (B2) based on a total of 100% by weight, propylene polymer component (B1) having the following characteristics (B1-i) 65 to 95% by weight, and having the following characteristics (B2-i) and (B2-ii) A blow molded article comprising a propylene-ethylene copolymer resin composition comprising 5 to 35% by weight of a propylene-ethylene copolymer component (B2).
Propylene-ethylene copolymer (A);
Characteristic (Ai): obtained by polymerization using a metallocene catalyst.
Characteristic (A-ii): Melt flow rate [MFR (A)] (230 ° C., 2.16 kg load) is in the range of 0.5 to 5 g / 10 min.
Characteristic (A-iii): In the temperature-loss tangent (tan δ) curve obtained by solid viscoelasticity, the peak of the temperature-loss tangent (tan δ) curve representing the glass transition observed in the range of −60 to 20 ° C. is 0. A single peak is shown below ℃.
Characteristic (A1-i): Propylene homopolymer or propylene-ethylene copolymer, whose ethylene content [E (A1)] is in the range of 0 to 6.0% by weight.
Characteristic (A1-ii): The molecular weight distribution [Mw / Mn (A1)] represented by the ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn) determined by GPC of the polymer component (A1) is 2 It is in the range of ~ 4.
Characteristic (A2-i): The ethylene content [E (A2)] of the copolymer component (A2) is in the range of 8 to 15% by weight.
Propylene-ethylene copolymer (B);
Characteristic (Bi): The ethylene content [E (B)] in the copolymer (B) is in the range of 0.4 to 13% by weight.
Characteristic (B-ii): The melt flow rate [MFR (B)] (230 ° C., 2.16 kg load) of the copolymer (B) is in the range of 0.5 to 20 g / 10 minutes.
Characteristic (B1-i): The ethylene content [E (B1)] in the polymer component (B1) is in the range of 0 to 6.0% by weight.
Characteristic (B2-i): The ethylene content [E (B2)] in the copolymer component (B2) is in the range of 8 to 25% by weight.
Characteristic (B2-ii): The melt flow rate [MFR (B2)] (230 ° C., 2.16 kg load) of the copolymer component (B2) is in the range of 0.0001 to 0.5 g / 10 minutes.   The propylene-ethylene copolymer (A) is produced by multistage polymerization having a step of producing a propylene-based polymer component (A1) and a step of producing a propylene-ethylene copolymer component (A2). A blow molded article comprising the propylene-ethylene copolymer resin composition according to claim 1.   The propylene-ethylene copolymer (B) is produced by multistage polymerization having a step of producing a propylene-ethylene polymer component (B1) and a step of producing a propylene-ethylene copolymer component (B2). A blow molded article comprising the propylene-ethylene copolymer resin composition according to claim 1 or 2.

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