JP7014819B2 - Propylene resin compositions, moldings and containers - Google Patents

Description

The present invention relates to a propylene-based resin composition, a molded product formed from the composition, and a container formed from the composition.

As a packaging container for foods such as jelly, pudding, and coffee (hereinafter, also referred to as a chilled container), a container having excellent visibility of the contents, that is, transparency has been conventionally required. As a container having excellent transparency, polypropylene resin having excellent heat resistance, rigidity and transparency is often used as a raw material thereof.

However, since the polypropylene resin itself does not always have sufficient transparency and mechanical strength characteristics, various nucleating agents are usually added to the polypropylene resin to improve the transparency and mechanical strength characteristics, and a rubber component is added. The method of improving the impact resistance is taken.

As a propylene-based resin composition having excellent impact resistance, a composition containing a propylene-ethylene block copolymer, a nucleating agent, and a low-density polyethylene resin or a linear low-density polyethylene resin is known (for example, a patent). See Document 1). The low-density polyethylene resin or the linear low-density polyethylene resin is blended in a ratio of 20 to 100 parts by weight with respect to 100 parts by weight of the propylene-ethylene block copolymer.

Further, as a polypropylene-based resin composition having improved rigidity, transparency and impact resistance at the same time, a specific polypropylene (propylene homopolymer) and two types of ethylene / α-olefin copolymers (ethylene / 1) are used. -It has been proposed to combine an octene copolymer) with a nucleating agent (Patent Document 2). The upper limit of the polypropylene compounding ratio is specified as 90% by weight, but since the total of the lower limit of the compounding ratio of the two types of ethylene / α-olefin copolymer is 13% by weight, the maximum compounding ratio of polypropylene is 87% by weight. %. In the examples, only an example containing 80% by weight of polypropylene is shown.

Further, a propylene-based resin composition having excellent rigidity, impact resistance, and transparency even when exposed to a low temperature as a chilled container has been proposed as well as thinning and weight reduction of the container itself (Patent Document 3). In Patent Document 3, 60 to 80 parts by weight of a propylene-based polymer and 20 to 40 parts by weight of an ethylene / α-olefin copolymer are blended.

Japanese Unexamined Patent Publication No. 2001-26686 Japanese Unexamined Patent Publication No. 2002-105257 International Publication WO2010 / 074001 Pamphlet

Since the propylene-based resin composition conventionally proposed contains a relatively large amount of ethylene / α-olefin copolymer, there is a problem of poor mold release from an injection molding mold, for example, when molding a chilled container or the like. , Deterioration of impact resistance due to injection orientation of ethylene / α-olefin copolymer has become a problem, and there has been a problem in production such as inability to perform high-speed molding. In addition, the conventional propylene-based resin composition has a high content of a skeleton derived from ethylene in the decane-soluble portion of the propylene-based polymer (propylene / α-olefin copolymer), so that the density is linear and low. When the amount of the ethylene-α-olefin copolymer component represented by polyethylene is reduced, there is a problem that the balance between impact resistance and transparency as a container in chilled applications is deteriorated.

Further, the chilled container may be broken to generate debris in the case of a container that cracks in a trampling test or the like when an excessive stress due to a trouble such as a food filling line is applied. However, there are great risks such as the suspension of the food filling line due to the contamination of debris into food, and the recovery of all products manufactured on that line if the product is sold without noticing the contamination of debris. .. Therefore, there is a demand for a container that does not break even when trampled and does not generate debris.

An object of the present invention is to provide a propylene-based resin composition capable of forming a container having both impact resistance and transparency in chilled applications without impairing high-speed moldability even in a thin-walled and lightweight product. Another object of the present invention is to provide a propylene-based resin composition that can provide a molded product that does not generate debris in the manufacturing process, and a molded product and a container that use the resin composition.

One aspect of the present invention is an ethylene / α-olefin copolymer satisfying 82 to 92 parts by mass of a propylene-based polymer (A) satisfying the following requirements (A1) to (A5) and the following requirements (B1) to (B2). (B) 8 to 18 parts by mass (however, the total of the propylene-based polymer (A) and the ethylene / α-olefin copolymer (B) is 100 parts by mass), and the nucleating agent (D) 0.1. The present invention relates to a propylene-based resin composition containing up to 0.6 parts by mass.
(A1): The melt flow rate (MFR) of the propylene-based polymer (A) measured at a measurement temperature of 230 ° C. and a load of 2.16 kg according to ASTM D-1238 is 1 to 100 g / 10 minutes.
(A2): The room temperature n-decane-insoluble portion (D _insol ) of the propylene-based polymer (A) is 88 to 96% by mass, and the room temperature n-decane-soluble portion (D _sol ) is 4 to 12% by mass. % (However, the total of D _insol and D _sol is 100% by mass).
(A3): The content of the skeleton derived from ethylene in the D _insol is 0.2 to 6% by mass.
(A4): The content of the skeleton derived from ethylene in the D _sol is 20 to 30% by mass.
(A5): The ultimate viscosity [η] of the D _sol in 135 ° C. decalin is 1.0 to 2.5 dl / g.
(B1): The melt flow rate (MFR) of the ethylene / α-olefin copolymer (B) measured at a measurement temperature of 190 ° C. and a load of 2.16 kg according to ASTM D-1238 is 0.5 to 50 g. / 10 minutes.
(B2): The density of the ethylene / α-olefin copolymer (B) is 886 to 920 kg / m ³ .

One aspect of the present invention includes 86 to 92 parts by mass of the propylene-based polymer (A) satisfying the above requirements (A1) to (A5), and both ethylene and α-olefin satisfying the following requirements (B1') to (B2'). 8 to 14 parts by mass of the polymer (B') (however, the total of the propylene-based polymer (A) and the ethylene / α-olefin copolymer (B') is 100 parts by mass), and the above (A) and Ethylene / α-olefin copolymer (E) satisfying 0.1 to 0.6 parts by mass of the nucleating agent (D) and the following requirements (E1) to (E2) with respect to a total of 100 parts by mass of (B'). ) Regarding a propylene-based resin composition containing 2 to 15 parts by mass:
(B1'): The melt flow rate (MFR) of the ethylene / α-olefin copolymer (B') measured at a measurement temperature of 190 ° C. and a load of 2.16 kg according to ASTM D-1238 is 0.5. ~ 50 g / 10 minutes.
(B2'): The density DB of the ethylene / α-olefin copolymer ( _B ') is 886 to 915 kg / m ³ .
(E1): The melt flow rate (MFR) of the ethylene / α-olefin copolymer (E) measured at a measurement temperature of 190 ° C. and a load of 2.16 kg according to ASTM D-1238 is 0.5 to 50 g. / 10 minutes.
(E2): The density DE of the ethylene / α _- olefin copolymer ( _E ) is 900 to 920 kg / m ³ , and the density _DE is 5 kg / m ³ or more higher than the density DB.
Further, one aspect of the present invention relates to a molded product containing the propylene-based resin composition, particularly a container.

According to one aspect of the present invention, it is possible to provide a propylene-based resin composition capable of forming a container having both impact resistance and transparency in chilled applications without impairing high-speed moldability even in a thin-walled and lightweight product. It will be possible. In addition, it is possible to provide a propylene-based resin composition that can provide a molded product that does not generate debris in the manufacturing process, and a molded product and a container that use the resin composition.

Next, a specific embodiment of the present invention will be described.
(First Embodiment)
The propylene-based resin composition (X) according to the first embodiment of the present invention has 82 to 92 parts by mass of the propylene-based polymer (A) satisfying the following requirements (A1) to (A5), and the following requirements (B1) to. 8 to 18 parts by mass of the ethylene / α-olefin copolymer (B) satisfying (B2) (however, the total of the propylene-based polymer (A) and the ethylene / α-olefin copolymer (B) is 100 parts by mass. ), And contains 0.1-0.6 parts by mass of the nucleating agent (D):
(A1): The melt flow rate (MFR) of the propylene-based polymer (A) measured at a measurement temperature of 230 ° C. and a load of 2.16 kg according to ASTM D-1238 is 1 to 100 g / 10 minutes.
(A2): The room temperature n-decane-insoluble portion (D _insol ) of the propylene-based polymer (A) is 88 to 96% by mass, and the room temperature n-decane-soluble portion (D _sol ) is 4 to 12% by mass. % (However, the total of D _insol and D _sol is 100% by mass).
(A3): The content of the skeleton derived from ethylene in the D _insol is 0.2 to 6% by mass.
(A4): The content of the skeleton derived from ethylene in the D _sol is 20 to 30% by mass.
(A5): The ultimate viscosity [η] of the D _sol in 135 ° C. decalin is 1.0 to 2.5 dl / g.
(B1): The melt flow rate (MFR) of the ethylene / α-olefin copolymer (B) measured at a measurement temperature of 190 ° C. and a load of 2.16 kg according to ASTM D-1238 is 0.5 to 50 g. / 10 minutes.
(B2): The density of the ethylene / α-olefin copolymer (B) is 886 to 920 kg / m ³ .

Hereinafter, each component will be described.
[Propylene-based polymer (A)]
The propylene-based resin composition (X) of the first embodiment contains a propylene-based polymer (A) that satisfies the above requirements (A1) to (A5). The "propylene-based polymer (A) satisfying the requirements (A1) to (A5)" is also referred to as "propylene-based polymer (A)".

The propylene-based polymer (A) used in the first embodiment may satisfy the requirements (A1) to (A5) and is not particularly limited, but is usually obtained by copolymerizing propylene and ethylene. It is a copolymer mainly composed of a propylene-derived constituent unit (hereinafter, also referred to as a propylene homopolymer portion) and a component mainly composed of propylene and ethylene-derived constituent units (hereinafter, propylene / ethylene copolymer weight). It is preferably a propylene-based copolymer (so-called block copolymer) containing (also referred to as a coalesced portion).

(Requirement (A1))
The MFR of the propylene-based polymer (A) is 1 to 100 g / 10 minutes, preferably 10 to 100 g / 10 minutes, and more preferably 20 to 100 g / 10 minutes.
When the MFR of the propylene-based polymer (A) exceeds the above range, the impact resistance of the molded product such as a container obtained from the propylene-based resin composition is inferior, and the MFR of the propylene-based polymer (A) is in the above range. If it is less than the above, the fluidity of the resin when producing a molded product such as a container by using the propylene-based resin composition is inferior, and it becomes difficult to produce a thin-walled molded product.

The MFR of the propylene-based polymer (A) can be adjusted to an arbitrary amount by adjusting the production conditions described later.

(Requirement (A2))
The room temperature n-decane-insoluble portion (D _insol ) of the propylene-based polymer (A) is 88 to 96% by mass, and the room temperature n-decane-soluble portion (D _sol ) is 4 to 12% by mass. However, the total of D _insol and D _sol is 100% by mass. Preferably, D _insol is 88 to 94% by mass, and D _sole is 6 to 12% by mass.

In the propylene-based polymer (A), the component ( _Dinsol ) that is normally insoluble in n-decane is a component mainly composed of a propylene-derived structural unit, and is considered to have crystallinity and exhibit high rigidity. .. The component soluble in n-decane (D _sol ) is a component mainly composed of a constituent unit derived from propylene and ethylene. It is considered that the D _sol component does not show crystallinity or has low crystallinity, has a low glass transition temperature, and exhibits impact resistance and compatibility. This is sometimes referred to as the rubber component. The propylene-based polymer (A) of the first embodiment is a propylene-based copolymer (so-called block) having a component (D _insol ) that is normally insoluble in n-decane and a component (D _sol ) that is soluble in n-decane. Copolymer).

As will be described later, the propylene-based resin composition of the first embodiment forms a so-called sea-island structure, in which the _Dinsol component mainly forms a sea portion and the ethylene / α-olefin copolymer (B) described later mainly forms an island portion. However, it is considered that the D _sol component is mainly involved in the compatibility between the D in _sol component and the ethylene / α-olefin copolymer (B) and the improvement of impact resistance.

When the D _insol is below the above range and the D _sol is above the above range, the proportion of the highly rigid D _insol is reduced, so that the rigidity of the molded product such as a container obtained from the propylene resin composition is lowered. Further, the propylene-based resin composition (X) of the first embodiment has a so-called sea-island structure in which D _insol is a continuous phase, but when D _sol exceeds the above range, the transparency tends to decrease. It is considered that this is because the islands increase and the reflected light increases. On the other hand, when D _sol is below the above range and D in _sol is above the above range, the impact resistance of the molded product obtained from the propylene-based resin composition tends to decrease. It is considered that the absorption energy for impact decreases as the ratio of D _sol decreases.

The ratio of D _insol and D _sol of the propylene-based polymer (A) can be determined by the method described in Examples described later.
Further, the ratio of D _insol and D _sol in the propylene-based polymer can be adjusted to an arbitrary amount by adjusting the production conditions described later.

(Requirement (A3))
The content of the skeleton derived from ethylene in the D _insol is 0.2 to 6% by mass. The content is preferably 0.4 to 5% by mass, more preferably 0.6 to 4% by mass. The D _insol is a component mainly composed of a constituent unit derived from propylene, but may contain a skeleton derived from ethylene. If the content exceeds the above range, the rigidity of a molded product such as a container obtained from the propylene-based resin composition tends to decrease. It is considered that this is because the crystallinity of D _insol is lowered. When the content is lower than the above range, the transparency of a molded product such as a container obtained from the propylene-based resin composition tends to decrease. The propylene-based resin composition (X) of the first embodiment has a so-called sea-island structure in which D _insol is a continuous phase, that is, a sea portion, D _sol and an ethylene / α-olefin copolymer (B) mainly constitute an island portion. Take. Therefore, when the crystallinity of the D _insol constituting the sea part becomes too high, the compatibilization effect of the D _sol constituting the island part and the ethylene / α-olefin copolymer (B) is lowered, and the dispersed particles of the island part are reduced. It is considered that the transparency is lowered because the diameter becomes large.

(Requirement (A4))
The content of the skeleton derived from ethylene in the D _sol is 20 to 30% by mass. The content is preferably 20 to 26% by mass, more preferably 20 to 24% by mass.
When the content is less than the above range, the impact resistance (particularly low temperature impact resistance) of the molded product such as a container obtained from the propylene resin composition tends to be inferior. It is considered that the glass transition temperature is lowered, the crystallinity is increased, and the absorbed energy for impact is lowered due to the decrease in the proportion of ethylene in D _sol .

On the other hand, if the content exceeds the above range, the transparency of the molded product such as a container obtained from the propylene-based resin composition tends to decrease. It is considered that this is because D _sol becomes difficult to be compatible with D in _sol and the dispersed particle size of the island portion becomes large as described above.
The content of the ethylene-derived skeleton in the D _insol and the D _sol can be determined by ¹³ CNMR measurement of the separated D _insol and D _sol under the conditions described in Examples described later, respectively. Details will be shown in Examples.

(Requirement (A5))
The ultimate viscosity [η _sol ] of the D _sol in 135 ° C. decalin is 1.0 to 2.5 dl / g, preferably 1.5 to 2.5 dl / g, and more preferably 1.6 to 1. It is 2.2 dl / g.
When the ultimate viscosity [η _sol ] is lower than the above range, the impact resistance of a molded product such as a container obtained from the propylene-based resin composition tends to decrease. It is considered that this is because the molecular weight of D _sol decreases and the impact absorption energy decreases. Further, when the ultimate viscosity [η _sol ] exceeds the above range, the transparency of a molded product such as a container obtained from the propylene-based resin composition tends to decrease. It is considered that this is because the molecular weight of D _sol is high and the dispersion is poor.

The ultimate viscosity [η _sol ] of the D _sol of the propylene-based polymer (A) measured at 135 ° C. in decalin can be determined by the method described in Examples described later.
The extreme viscosity [η _sol ] of D _sol measured at 135 ° C. in decalin can be adjusted to an arbitrary amount by adjusting the production conditions described later.

The method for producing the propylene-based polymer (A) used in the first embodiment is not particularly limited, but usually, propylene and ethylene are copolymerized in the presence of a metallocene compound-containing catalyst or a Ziegler-Natta catalyst. Obtained by doing.

The propylene-based polymer (A) is preferably obtained by copolymerizing propylene and ethylene in the presence of a Ziegler-Natta catalyst. This is because it is easy to obtain a resin having a wide molecular weight distribution and good moldability.

(Catalyst containing metallocene compound)
As the metallocene compound-containing catalyst, at least one compound selected from a metallocene compound and a compound capable of reacting with an organic metal compound, an organic aluminumoxy compound and a metallocene compound to form an ion pair, and further required. Accordingly, a metallocene catalyst composed of a particulate carrier can be mentioned, and preferably a metallocene catalyst capable of performing stereoregular polymerization such as an isotactic or syndiotactic structure can be mentioned. Among the metallocene compounds, the crosslinkable metallocene compound exemplified in International Publication No. 01/27124 pamphlet is preferably used.

(Ziegler-Natta catalyst)
The propylene-based polymer (A) used in the first embodiment can be produced by using a highly stereoregular Ziegler-Natta catalyst. As the highly stereoregular Ziegler-Natta catalyst, various known catalysts can be used. For example, (a) a solid titanium catalytic component containing magnesium, titanium, halogen and an electron donor, (b) an organometallic compound catalytic component, and (c) a cyclopentyl group, a cyclopentenyl group, a cyclopentadienyl group and A catalyst composed of an organosilicon compound catalyst component having at least one group selected from the group consisting of these derivatives can be used. As such a highly stereoregular Ziegler-Natta catalyst, the catalyst for olefin polymerization described in EP0350170 can be preferably used. When the propylene-based polymer (A) is produced using the Ziegler-Natta catalyst, prepolymerization can be carried out as described in the publication.
The prepolymerization involves polymerizing the olefin in the presence of the solid titanium catalyst component (a), the organometallic compound catalyst component (b), and optionally the organosilicon compound catalyst component (c).

As the prepolymerized olefin, an α-olefin having 2 to 8 carbon atoms can be used. Specifically, linear olefins such as ethylene, propylene, 1-butene, 1-octene; 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4- Methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, etc. An olefin or the like having a branched structure of can be used. These may be copolymerized.

It is desirable that the prepolymerization is carried out so as to produce a polymer of about 0.1 to 1000 g, preferably about 0.3 to 500 g, per 1 g of the solid titanium catalyst component (a). If the amount of prepolymerization is too large, the efficiency of producing the (co) polymer in the main polymerization may decrease. In the prepolymerization, the catalyst can be used at a concentration considerably higher than the concentration of the catalyst in the system in the main polymerization. When propylene is continuously multi-stage polymerized using the above catalyst, propylene and ethylene may be copolymerized at any stage or at all stages as long as the object of the present invention is not impaired. good.

In the case of continuous multi-stage polymerization, propylene is homopolymerized in each stage, or propylene and ethylene are copolymerized to produce polypropylene. At the time of the main polymerization, the solid titanium catalyst component (a) (or the prepolymerization catalyst) is converted into titanium atoms per 1 L of the polymerization volume in an amount of about 0.0001 to 50 mmol, preferably about 0.001 to 10 mmol. It is desirable to use in quantity. The organic metal compound catalyst component (b) is preferably used in an amount of about 1 to 2000 mol, preferably about 2 to 500 mol, with respect to 1 mol of titanium atom in the polymerization system. The organosilicon compound catalyst component (c) is preferably used in an amount of about 0.001 to 50 mol, preferably about 0.01 to 20 mol, per 1 mol of the metal atom of the organometallic compound catalyst component (b).

(Production method of propylene-based polymer (A))
The propylene-based polymer (A) used in the first embodiment can be obtained by copolymerizing propylene and ethylene in the presence of the above-mentioned metallocene compound-containing catalyst or in the presence of a Ziegler-Natta catalyst.

The polymerization may be carried out by any of a liquid phase polymerization method such as a vapor phase polymerization method, a solution polymerization method and a suspension polymerization method, and each step may be carried out by a separate method. Further, either a continuous system or a semi-continuous system may be used, and each stage may be divided into a plurality of polymerizers, for example, 2 to 10 polymerizers. Industrially, it is most preferable to polymerize by a continuous method, and in this case, it is preferable to carry out the polymerization of the second and subsequent stages separately in two or more polymerizers, which is called a gel, which has impact resistance and transparency. It is possible to suppress the generation of a high molecular weight component, which is a compound-generated component that has an unfavorable negative effect on sex.

As the polymerization medium, inert hydrocarbons may be used, or liquid propylene may be used as the polymerization medium. The polymerization conditions of each stage are such that the polymerization temperature is in the range of about -50 to + 200 ° C., preferably about 20 to 100 ° C., and the polymerization pressure is normal pressure to 10 MPa (gauge pressure), preferably about 0.2 to 5 MPa. It is appropriately selected within the range of (gauge pressure).

When producing the propylene-based polymer (A), the following two steps ([step 1] and [step 2]) are continuously carried out in a reaction apparatus in which two or more polymerizers are connected in series. Obtained by that. In the present invention, [Step 1] can be performed in each polymerization apparatus using a polymerization apparatus in which two or more reactors are connected in series, and a polymerization apparatus in which two or more reactors are connected in series is used. [Step 2] can be performed in each polymerization apparatus.

In addition to the above methods, [Step 1] and [Step 2] are performed separately, and the obtained products are melt-kneaded using a single-screw extruder, a multi-screw extruder, a kneader, a Banbury mixer, etc., and propylene. The system polymer (A) can also be produced. Hereinafter, a method for producing the propylene-based polymer (A) by continuously carrying out [Step 1] and [Step 2] will be described.

In [Step 1], propylene and a required amount of ethylene are copolymerized at a polymerization temperature of 0 to 100 ° C. and a polymerization pressure of normal pressure to 5 MPa gauge pressure. In [Step 1], the feed amount of ethylene is small with respect to propylene so that the propylene-based copolymer produced in [Step 1] becomes the main component of D _insol that satisfies the requirement (A3). do. Further, if necessary, a chain transfer agent typified by hydrogen gas can be introduced to adjust the ultimate viscosity [η] of the polymer produced in [Step 1].

In [Step 2], propylene and ethylene are copolymerized at a polymerization temperature of 0 to 100 ° C. and a polymerization pressure of normal pressure to 5 MPa gauge pressure. In [Step 2], the feed amount of ethylene to propylene is made larger than that in [Step 1] so that the propylene-ethylene copolymer rubber produced in [Step 2] becomes the main component of D _sol . do. Further, if necessary, a chain transfer agent typified by hydrogen gas can be introduced to adjust the ultimate viscosity [η] of the polymer produced in [Step 2].

The propylene-based polymer (A) can be obtained by continuously carrying out the above steps [step 1] and [step 2], and the requirements (A1) to (A5) can be adjusted as follows. can.

The requirement (A1) is the feed amount of hydrogen gas as a chain transfer agent with respect to the feed amount of propylene when performing [Step 1] or [Step 2] or the feed amount of propylene and ethylene when feeding propylene and ethylene. It can be adjusted by adjusting the amount. The MFR can be increased by increasing the hydrogen feed amount relative to the propylene feed amount or the propylene and ethylene feed amount, and the propylene feed amount or the propylene and ethylene feed amount. The MFR can be lowered by reducing the hydrogen feed amount with respect to the propylene and ethylene feed amounts.

In addition to the above methods, the propylene-based polymer obtained by polymerization is melt-kneaded in the presence of an organic peroxide to melt flow rate (MFR) (ASTM D-1238, measurement temperature 230 ° C., load 2. 16 kg) can be adjusted. The MFR is increased by performing a melt-kneading treatment on the propylene-based polymer obtained by the polymerization in the presence of an organic peroxide, and the organic peroxide when the melt-kneading treatment is performed in the presence of an organic peroxide. The MFR becomes higher by increasing the amount of the substance added. When the propylene-based polymer obtained by polymerization is melt-kneaded in the presence of an organic peroxide, the amount of the organic peroxide is between 0.005 and 0.05 parts by mass with respect to 100 parts by mass of the propylene-based polymer. It is desirable to use. Further, the melt-kneading treatment in the presence of the organic peroxide may be performed after the following post-treatment step.

The organic peroxide that can be used in the melt-kneading treatment in the presence of the organic peroxide is not particularly limited, but is benzoyl peroxide, t-butyl perbenzoate, t-butyl peracetate, and t-butyl. Peroxyisopropyl carbonate, 2,5-di-methyl-2,5-di- (benzoylperoxy) hexane, 2,5-di-methyl-2,5-di- (benzoylperoxy) hexin-3, t -Butyl-di-peradipate, t-butylperoxy-3,5,5-trimethylhexanoate, methyl-ethylketone peroxide, cyclohexanone peroxide, di-t-butyl peroxide, dichyumyl peroxide, 2 , 5-Di-Methyl-2,5-di- (t-butylperoxy) hexane, 2,5, -di-methyl-2,5-di- (t-butylperoxy) hexin-3,1, 3-Bis- (t-butylperoxyisopropyl) benzene, t-butylchyumyl peroxide, 1,1-bis- (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis -(T-Butylperoxy) cyclohexane, 2,2-bis- (t-butylperoxy) butane, p-menthan hydroperoxide, di-isopropylbenzenehydroperoxide, kyumenhydroperoxide, t-butylhydro Organic compounds such as peroxide, p-cymen hydroperoxide, 1,1,3,3-tetra-methylbutylhydroperoxide or 2,5-di-methyl-2,5-di- (hydroperoxy) hexane. An oxide can be exemplified. Of these, 2,5-di-methyl-2,5-di- (benzoylperoxy) hexane and 1,3-bis- (t-butylperoxyisopropyl) benzene are more preferable.

The requirement (A2), that is, the ratio of D in _sol to D _sol can be prepared by adjusting the polymerization time of the above-mentioned [Step 1] and [Step 2]. That is, by lengthening the polymerization time of the above [step 1] as compared with the polymerization time of [step 2], the proportion of D in _{sol can be increased and the proportion of D sol can} be decreased. Further, by lengthening the polymerization time in [Step 2] as compared with the polymerization time in [Step 1], the proportion of D in _{sol can be reduced and the proportion of D sol can} be increased.

The requirement (A3) relating to D _insol can be adjusted by adjusting the propylene feed amount and the ethylene feed amount when performing [Step 1]. That is, by increasing the ethylene feed amount with respect to the propylene feed amount, the mass of the constituent unit derived from ethylene in the D _insol can be increased. Further, by reducing the ethylene feed amount with respect to the propylene feed amount, the mass of the constituent unit derived from ethylene in the D _insol can be reduced.

The requirement (A4) relating to D _sol can be adjusted by adjusting the propylene feed amount and the ethylene feed amount when performing [Step 2]. That is, by increasing the ethylene feed amount with respect to the propylene feed amount, the mass of the constituent unit derived from ethylene in the D _sol can be increased. Further, by reducing the ethylene feed amount with respect to the propylene feed amount, the mass of the constituent unit derived from ethylene in the D _sol can be reduced.

The requirement (A5) relating to D _sol can be adjusted by the feed amount of hydrogen gas used as a chain transfer agent when performing [Step 2]. In other words, the ultimate viscosity [η _sol ] can be reduced by increasing the feed amount of hydrogen gas with respect to the feed amount of propylene or the feed amount of propylene and ethylene when feeding propylene and ethylene. When the feed amount or propylene and ethylene are fed, the ultimate viscosity [η _sol ] can be increased by reducing the feed amount of hydrogen gas with respect to the feed amount of propylene and ethylene.

After completion of the polymerization, a known post-treatment step such as a catalyst deactivation treatment step, a catalyst residue removal step, and a drying step is performed as necessary to obtain the propylene-based polymer (A) as a powder.

[Ethylene / α-olefin copolymer (B)]
The propylene-based resin composition (X) of the first embodiment contains an ethylene / α-olefin copolymer (B) that satisfies the above requirements (B1) to (B2). The "ethylene / α-olefin copolymer (B) satisfying the requirements (B1) to (B2)" is also referred to as "ethylene / α-olefin copolymer (B)".

The ethylene / α-olefin copolymer (B) used in the first embodiment may satisfy the requirements (B1) to (B2), and is not particularly limited, but is ethylene and α having 3 to 20 carbon atoms. -A copolymer obtained by copolymerizing an olefin is preferable from the viewpoint of good impact resistance and transparency.

Examples of the α-olefin having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, and the like. Examples thereof include 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eikosen and the like. Of these, α-olefins having 4 to 10 carbon atoms are preferable from the viewpoints of transparency, impact resistance, rigidity, and economy.

The ethylene / α-olefin copolymer (B) used in the first embodiment is preferably an ethylene / α-olefin copolymer polymerized using a single-site catalyst as a catalyst.

Examples of the single-site catalyst include (a) a transition metal compound as described later, (b) an organoaluminum oxy compound, (c) a particulate carrier, and, if necessary, (d) an organoaluminum compound. Olefin polymerization catalyst can be used.

When the ethylene / α-olefin copolymer (B) used in the first embodiment is an ethylene / α-olefin copolymer polymerized using a single site catalyst, a highly transparent propylene resin composition can be obtained. Tend to get. Since the composition distribution of the component (B) of the first embodiment is more uniform than that of the conventional ethylene / α-olefin copolymer polymerized using a so-called Ziegler-Natta catalyst, the component (B) is compatible with the D _sol component. It is presumed that this is because the molecular weight distribution is narrowed and the number of low molecular weight components that cause deterioration of low temperature impact resistance is reduced.

From the above, it is possible to obtain a propylene-based resin composition having excellent transparency and low-temperature impact resistance by using an ethylene / α-olefin copolymer polymerized using a single-site catalyst. ..

Examples of the single-site catalyst include a catalyst containing a constrained geometric complex (so-called constrained geometry catalyst (CGC (constrained geometry catalyst) catalyst)), a metallocene compound-containing catalyst, and the like. Among these, it is preferable to use a metallocene compound-containing catalyst from the viewpoint of particularly good low-temperature impact resistance.

(Requirement (B1))
The melt flow rate (MFR) (ASTM D-1238, measurement temperature 190 ° C., load 2.16 kg) of the ethylene / α-olefin copolymer (B) used in the first embodiment is 0.5 to 50 g / 10 minutes. Is. The MFR is preferably 1 to 10 g / 10 minutes, more preferably 2.0 to 5.0 g / 10 minutes.

When the MFR of the ethylene / α-olefin copolymer (B) is lower than the above range, the transparency of the molded product such as a container obtained from the propylene resin composition tends to decrease. This is thought to be due to poor dispersion due to the high molecular weight. If it exceeds the above range, the molecular weight is low and the absorption energy against impact is low, so that the impact resistance of the molded product such as a container obtained from the propylene resin composition is inferior.

The MFR of the ethylene / α-olefin copolymer (B) can be adjusted to an arbitrary amount by adjusting the production conditions.

Specifically, it can be adjusted by adjusting the feed amount of hydrogen gas with respect to the feed amount of ethylene and / or α-olefin at the time of polymerization. It is possible to increase the MFR by increasing the feed amount of ethylene gas at the time of polymerization or the feed amount of hydrogen gas with respect to the feed amount of ethylene and α-olefin when feeding ethylene and α-olefin. When feeding the gas feed amount or ethylene and α-olefin, the MFR can be lowered by reducing the feed amount of hydrogen gas with respect to the feed amount of ethylene and α-olefin.

(Requirement (B2))
The density of the ethylene / α-olefin copolymer (B) used in the first embodiment is 886 to 920 kg / m ³ , preferably 890 to 920 kg / m ³ .

When the density of the ethylene / α-olefin copolymer (B) is lower than the above range, the rigidity and transparency of the molded product such as a container obtained from the propylene resin composition tend to be inferior. It is presumed that this is because the crystallinity of the component (B) is lowered and the difference in the refractive index from the propylene-based polymer (A) is also large. On the other hand, when the density of the ethylene / α-olefin copolymer (B) exceeds the above range, the transparency of the molded product such as a container obtained from the propylene resin composition tends to decrease. It is considered that this is also because the difference in refractive index between the ethylene / α-olefin copolymer (B) and the propylene-based polymer (A) becomes large. That is, when the density range of the ethylene / α-olefin copolymer (B) deviates from the above range, the transparency deteriorates.

The density of the ethylene / α-olefin copolymer (B) can be adjusted to an arbitrary amount by adjusting the production conditions.
Specifically, it can be adjusted by changing the ratio of the feed amount of ethylene and α-olefin when polymerizing the ethylene / α-olefin copolymer. More specifically, the density can be lowered by increasing the feed amount of α-olefin with respect to the feed amount of ethylene, and the feed amount of α-olefin is reduced with respect to the feed amount of ethylene. By doing so, it is possible to increase the density.

The density of the ethylene / α-olefin copolymer (B) is determined by heat-treating the strands obtained during the MFR measurement of the ethylene / α-olefin copolymer (B) at 120 ° C. for 1 hour at room temperature over 1 hour. Using the sample slowly cooled to the above, the density was measured by the density gradient tube method and determined as the density of the ethylene / α-olefin copolymer (B).

Hereinafter, the single-site olefin polymerization catalyst used for producing the ethylene / α-olefin copolymer (B) and each catalyst component will be described. The (a) transition metal compound used in the present invention (hereinafter sometimes referred to as “component (a)”) is a transition metal compound represented by the following formula (I).
MLx ... (I)
In the formula (I), M is a transition metal atom selected from Group IVB of the Periodic Table, specifically zirconium, titanium or hafnium, preferably zirconium.

x is the valence of the transition metal atom M and indicates the number of L coordinated to the transition metal atom. L is a ligand that coordinates with the transition metal atom M, and at least two of these ligands L are a cyclopentadienyl group, a methylcyclopentadienyl group, and an ethylcyclopentadienyl group. A substituted cyclopentadienyl group having at least one substituent, which is present or has at least one substituent selected from a hydrocarbon group having 3 to 10 carbon atoms, and the ligand L other than the (substituted) cyclopentadienyl group is carbon. The number 1 to 12 is a hydrocarbon group, an alcohol group, an aryloxy group, a halogen atom, a trialkylsilyl group or a hydrogen atom.

The substituted cyclopentadienyl group may have two or more substituents, and the two or more substituents may be the same or different. When the substituted cyclopentadienyl group has two or more substituents, at least one substituent may be a hydrocarbon group having 3 to 10 carbon atoms, and the other substituents are a methyl group and an ethyl group. Alternatively, it is a hydrocarbon group having 3 to 10 carbon atoms. Further, the substituted cyclopentadienyl group coordinated to M may be the same or different.

[Nucleating agent (D)]
The propylene-based resin composition (X) of the first embodiment contains a nucleating agent (D).
The nucleating agent contained in the propylene-based resin composition (X) of the first embodiment is not particularly limited, but is a sorbitol-based nucleating agent, a phosphorus-based nucleating agent, a carboxylic acid metal salt-based nucleating agent, and the like. Polymer nucleating agents, inorganic compounds and the like can be used. As the nucleating agent, it is preferable to use a sorbitol-based nucleating agent, a phosphorus-based nucleating agent, or a polymer nucleating agent.

As a sorbitol-based nucleating agent, for example, nonitol 1,2,3-trideoxy-4,6: 5,7-bis-O-[(4-propylphenyl) methylene] (commercially available product containing the compound under the trade name “ Mirrored NX8000 series, manufactured by Milliken ("NX8000" is the above chemical substance + fluorescent whitening agent + blooming agent, "NX8000K" is "NX8000" without fluorescent whitening agent, "NX8000J" is fluorescent whitening agent and blooming (Without both agents)), 1,3,2,4-dibenzylidene sorbitol, 1,3,2,4-di- (p-methylbenzylidene) sorbitol, 1,3-p-chlorbenzylidene-2, 4-p-Methylbenzylidene sorbitol can be used.

Examples of the phosphorus-based nucleating agent include sodium-bis- (4-t-butylphenyl) phosphate, potassium-bis- (4-t-butylphenyl) phosphate, and sodium-2,2'-ethylidene-bis ( 4,6-di-t-butylphenyl) phosphate, sodium-2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate, bis (2,4,8,10-tetra) -T-butyl-6-hydroxy-12H-dibenzo [d, g] [1,3,2] dioxaphosphocin-6-oxide) sodium salt (trade name "Adecastab NA-11", manufactured by ADEKA), bis (2,4,8,10-tetra-t-butyl-6-hydroxy-12H-dibenzo [d, g] [1,3,2] dioxaphosphocin-6-oxide) Main component is aluminum hydroxide salt Complex (trade name "Adecastab NA-21", manufactured by ADEKA), lithium-2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate and 12-hydroxystearic acid. A composite containing and containing lithium as an essential component (trade name "Adecastab NA-71", manufactured by ADEKA) or the like can be used.

As the carboxylic acid metal salt nucleating agent, for example, pt-butyl benzoic acid aluminum salt, aluminum adipate, and sodium benzoate can be used.
A branched α-olefin polymer is preferably used as the polymer nucleating agent. Examples of branched α-olefin polymers are 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene. , 4,4-Dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene homopolymers, or copolymers thereof, and further. Can be mentioned as a copolymer of them with other α-olefins. A polymer of 3-methyl-1-butene is particularly preferable from the viewpoints of good transparency, low-temperature impact resistance, rigidity, and economic efficiency.
As the inorganic compound, for example, talc, mica, and calcium carbonate can be used.
As described above, some of the nucleating agents used in the first embodiment can be easily obtained as commercial products.

Among these nucleating agents, nonitol, 1,2,3-trideoxy-4,6: 5,7-bis-O-[((), from the viewpoint of transparency, low temperature impact resistance, rigidity and low odor". 4-Propiphenyl) Methylene] and / or bis (2,4,8,10-tetra-t-butyl-6-hydroxy-12H-dibenzo [d, g] [1,3,2] dioxaphosphocin -6-Oxide) It is preferable to use an aluminum hydroxide salt.
Further, these nucleating agents may be used alone or in combination of two or more.

The propylene-based resin composition (X) of the first embodiment contains the nucleating agent (D), so that the rigidity and transparency of a molded body such as a container formed from the composition of the first embodiment Excellent for. It is presumed that this is due to the improvement in transparency by reducing the spherulite size of the crystals in the propylene resin composition (X) and reducing the diffused reflection of light, and the increase in rigidity by improving the crystallinity. ..
Further, if the content of the nucleating agent is less than the following range, the effect of improving the rigidity and transparency is insufficient, and if the content of the nucleating agent is more than the following range, the effect of further improving is small and economical. Not.

[Propene-based resin composition (X)]
The propylene-based resin composition (X) of the first embodiment contains 82 to 92 parts by mass of the above-mentioned propylene-based polymer (A), 8 to 18 parts by mass of the ethylene / α-olefin copolymer (B), and nucleation. Agent (D) contains 0.1 to 0.6 parts by mass (however, the total of the propylene-based polymer (A) and the ethylene / α-olefin copolymer (B) is 100 parts by mass), preferably propylene. The system polymer (A) is 84 to 90 parts by mass, the ethylene / α-olefin copolymer (B) is 10 to 16 parts by mass, and the nucleating agent is 0.15 to 0.4 parts by mass.

Further, the propylene-based resin composition (X) of the first embodiment is appropriately used as a neutralizing agent, an antioxidant, a heat stabilizer, a weather resistant agent, a lubricant, an ultraviolet absorber, and a charge as long as the object of the present invention is not impaired. Additives such as inhibitors, anti-blocking agents, anti-fog agents, anti-bubble agents, dispersants, flame retardants, antibacterial agents, fluorescent whitening agents, cross-linking agents, cross-linking aids; exemplified by colorants such as dyes and pigments. It may contain other components.

When the propylene-based resin composition (X) of the first embodiment contains other components, the total of the propylene-based polymer (A) and the ethylene / α-olefin copolymer (B) is usually 100% by mass. In terms of parts, other components can be contained in the range of 0.01 to 5 parts by mass.

The propylene-based resin composition (X) of the first embodiment preferably has a melt flow rate (MFR) (measurement temperature 230 ° C., load 2.16 kg) of 20 to 80 g / 10 minutes, preferably 30 to 30. More preferably, it is 60 g / 10 minutes. The above range is preferable because it has excellent fluidity when molding a molded product such as a container using a propylene-based resin composition.
The melt flow rate (MFR) (ASTM D-1238, measurement temperature 230 ° C., load 2.16 kg) of the propylene-based resin composition (X) is the melt of the propylene-based polymer (A) used in the propylene-based resin composition. Flow rate (MFR) (ASTM D-1238, measured temperature 230 ° C., load 2.16 kg) or melt flow rate (MFR) of ethylene / α-olefin copolymer (B) (ASTM D-1238, measured temperature 190). It can be adjusted by appropriately selecting (° C., load 2.16 kg).

In addition to the above methods, adjustment is possible by allowing organic peroxides to coexist when each component is melt-kneaded with a kneader. That is, by adding an organic peroxide during melt-kneading or by increasing the amount of the organic peroxide added during melt-kneading, the melt flow rate (MFR) (ASTM D) of the propylene-based resin composition is increased. -1238, measurement temperature 230 ° C., load 2.16 kg) can be increased.

As the organic peroxide that can be used in the present invention, the organic peroxide described in the above requirement (A1) can be used. When using an organic peroxide, use it in an amount of 0.005 to 0.05 parts by mass or less with respect to a total of 100 parts by mass of the propylene-based polymer (A) and the ethylene / α-olefin copolymer (B). Is desirable.

As described above, the propylene-based resin composition (X) of the first embodiment mainly contains D _insol as a continuous phase, that is, the sea part, and D _sol and the ethylene / α-olefin copolymer (B) are mainly islands. It has a so-called sea island structure. Therefore, the propylene-based resin composition (X) of the first embodiment can achieve both high rigidity and impact resistance.

The propylene-based resin composition (X) of the first embodiment contains the above-mentioned propylene-based polymer (A), ethylene / α-olefin copolymer (B) and nucleating agent (D) in specific amounts, and is described above. It tends to have a peculiar sea-island structure such as.

Since the propylene-based resin composition of the first embodiment contains each of the above-mentioned components in the above range, it is thinner and lighter than the conventional one when a molded product such as a container such as a food packaging container is manufactured. Even if it is used, it has excellent rigidity, low temperature impact resistance, and transparency.

The method for producing the propylene-based resin composition (X) of the first embodiment is not particularly limited, but as the production method, for example, each component is melt-kneaded with a kneader to obtain the propylene-based resin composition (X). The manufacturing method can be mentioned. Examples of the kneader include a single-screw kneading extruder, a multi-screw kneading extruder, a kneader, a Banbury mixer, a Henschel mixer and the like. The melt-kneading conditions are not particularly limited as long as the molten resin does not deteriorate due to shearing during kneading, heating temperature, heat generation due to shearing, or the like. From the viewpoint of preventing deterioration of the molten resin, it is effective to set the heating temperature appropriately and to add an antioxidant or a heat stabilizer.

By molding the above propylene-based resin composition (X) or (Y) (hereinafter referred to as the propylene-based resin composition of the present invention) according to a known molding technique, various molded products can be obtained. The molding technology includes, for example, injection molding, injection stretch blow molding, compression molding, injection compression molding, T-die film molding, stretch film molding, inflation film molding, sheet molding, calender molding, pneumatic molding, vacuum molding, pipe molding, and irregular molding. Extrusion molding, hollow molding, laminate molding and the like can be mentioned.

Examples of the molded product formed from the propylene-based resin composition of the present invention include containers, home appliance parts, daily necessities and the like. Of these, the container is preferable from the viewpoint of impact resistance and rigidity.

The container of the present invention is formed from the above-mentioned propylene-based resin composition. Containers include packaging containers for liquid daily necessities such as hair wash, hair conditioner, cosmetics, detergents, and bactericides; food packaging containers for liquids such as refreshing drinking water, water, and seasonings; solids such as jelly, pudding, and yogurt. Food packaging container (desert cup); packaging container for other chemicals; packaging container for industrial liquids, etc. Can be widely used.

Above all, it can be suitably used as a food packaging container (dessert cup) which is required to be thinner and lighter than the conventional one, and is required to have excellent visibility of the contents and less odor.

As the dessert cup, it is preferable that the wall thickness of the container body (thinnest part) is in the range of 0.3 to 2.0 mm. The propylene-based resin composition of the present invention has sufficient impact strength even when thinned in this way, and is not damaged during the manufacturing process to generate debris.

The container (for example, a food packaging container) formed from the propylene-based resin composition of the present invention is preferably obtained by injection molding or injection stretch blow molding.
As a method of injection molding, for example, molding can be performed by the following method using an injection molding machine. First, the propylene-based resin composition is introduced into the hopper of the injection mechanism, and the propylene-based resin composition is sent into a cylinder heated to about 200 ° C. to 250 ° C. and kneaded and plasticized to be in a molten state. This is heated from a nozzle at high pressure and high speed (maximum pressure 700 to 1500 kg / cm ³ ) with cooling water or hot water to 5 to 50 ° C, preferably 10 to 40 ° C, and is closed by a mold clamping mechanism. Inject into the mold. This can be done by cooling and solidifying the propylene-based resin composition injected by cooling from the mold, opening the mold with a mold clamping mechanism, and obtaining a molded product.

For injection stretch blow molding, for example, a propylene-based resin composition is introduced into the hopper of an injection molding machine, the resin is sent to a cylinder heated to about 200 ° C. to 250 ° C., and the resin is kneaded and plasticized into a molten state. do. This is heated from a nozzle at high pressure and high speed (maximum pressure 700 to 1500 kg / cm ³ ) with cooling water or hot water to 5 to 80 ° C, preferably 10 to 60 ° C, and is closed by a mold clamping mechanism. Injection molding is performed in the mold, where it is cooled for 1.0 to 3.0 seconds to form a preform, then the mold is immediately opened and stretch-oriented in the vertical direction using a draw rod, and further laterally by blow molding. It can be carried out by stretching and orienting and obtaining a molded product.

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.

[Manufacturing of Propylene Polymer (A-1)]
(1) Preparation of solid catalyst component 95.2 g of anhydrous magnesium chloride, 442 ml of decane and 390.6 g of 2-ethylhexyl alcohol were heated at 130 ° C. for 2 hours to form a uniform solution, and then phthalic anhydride 21 was added to this solution. .3 g was added, and the mixture was further stirred and mixed at 130 ° C. for 1 hour to dissolve phthalic anhydride.
After cooling the uniform solution thus obtained to room temperature, 75 ml of this uniform solution was added dropwise over 200 ml of titanium tetrachloride kept at −20 ° C. for 1 hour. After the charging is completed, the temperature of this mixed solution is raised to 110 ° C. over 4 hours, 5.22 g of diisobutyl phthalate (DIBP) is added when the temperature reaches 110 ° C., and the mixture is stirred at the same temperature for 2 hours. Retained.
After the reaction for 2 hours was completed, the solid part was collected by hot filtration, the solid part was resuspended in 275 ml of titanium tetrachloride, and then heated again at 110 ° C. for 2 hours. After completion of the reaction, the solid part was collected again by hot filtration and washed thoroughly with decane and hexane at 110 ° C. until no free titanium compound was detected in the solution.

Here, the detection of the free titanium compound was confirmed by the following method. 10 ml of the supernatant liquid of the above solid catalyst component was collected by a syringe and charged into 100 ml of Candelabra with nitrogen substituted in advance. Next, the solvent hexane was dried in a nitrogen stream and vacuum dried for another 30 minutes. 40 ml of ion-exchanged water and 10 ml of 50% by volume sulfuric acid were charged therein and stirred for 30 minutes. This aqueous solution was transferred through a filter paper to a 100 ml volumetric flask, followed by conc. As a masking agent for iron (II) ions. 1 ml of H ₃ PO ₄ and 5 ml of a 3% H ₂ O ₂ aqueous solution as a color-developing reagent for titanium were added, and the volume was further increased to 100 ml with ion-exchanged water. This measuring flask was shaken, and after 20 minutes, the absorbance at 420 nm was observed using UV to detect free titanium. Free titanium was washed and removed and free titanium was detected until this absorption was no longer observed.
The solid titanium catalyst component (A) prepared as described above was stored as a decan slurry, and a part of the solid titanium catalyst component (A) was dried for the purpose of examining the catalyst composition. The composition of the solid titanium catalyst component (A) thus obtained was 2.3% by mass of titanium, 61% by mass of chlorine, 19% by mass of magnesium, and 12.5% by mass of DIBP.

(2) Preparation of prepolymerization catalyst component After replacing a three-necked flask with a stirrer with an internal volume of 500 ml with nitrogen gas, 400 ml of dehydrated heptane, 19.2 mmol of triethylaluminum, 3.8 mmol of dicyclopentyldimethoxysilane, the above. 4 g of the solid titanium catalyst component (A) was added. The internal temperature was maintained at 20 ° C., and propylene was introduced while stirring. After 1 hour, stirring was stopped, and as a result, a prepolymerization catalyst component (B) in which 2 g of propylene was polymerized per 1 g of the solid titanium catalyst component (A) was obtained.

(3-1) Polymerization-1 (Polymerization [Step 1])
A stainless steel autoclave with an internal volume of 10 liters was sufficiently dried, and after nitrogen substitution, 6 liters of dehydrated heptane, 12.5 mmol of triethylaluminum, and 0.6 mmol of dicyclopentyldimethoxysilane were added. After replacing the nitrogen in the system with propylene, hydrogen was charged at 0.25 MPa-G, and then propylene and ethylene were introduced with stirring. The introduction amount was adjusted so that the ethylene concentration in the gas phase portion in the polymerization tank was 0.6 mol%.
After the inside of the system was stabilized at an internal temperature of 80 ° C. and a total pressure of 0.8 MPa-G, 20.8 ml of a heptane slurry containing 0.10 mmol of the prepolymerization catalyst component (B) in terms of Ti atoms was added, and propylene was continuously added. The polymerization was carried out at 80 ° C. for 3 hours while being supplied to the water.

(3-2) Polymerization-2 (Polymerization [Step 2])
After the polymerization of the propylene homopolymer was completed (after the above [step 1]), the internal temperature was lowered to 30 ° C. and depressurized. Then, hydrogen 0.90 MPa-G was charged, and then a mixed gas of propylene / ethylene: (4.0 l / min) / (1.4 l / min) was introduced. Propylene / ethylene copolymerization was carried out for 60 minutes at an internal temperature of 60 ° C. and a total pressure of 0.30 MPa-G (varies depending on the amount of introduced gas).
After a lapse of a predetermined time, 50 ml of methanol was added to stop the reaction, and the temperature was lowered and depressurized. The entire contents were transferred to a filtration tank equipped with a filter, heated to 60 ° C., and solid-liquid separated. Further, the solid part was washed twice with 6 liters of heptane at 60 ° C. The propylene / ethylene copolymer thus obtained was vacuum dried. The melt flow rate (MFR) (ASTM D-1238, measurement temperature 230 ° C., load 2.16 kg) of the obtained propylene-based polymer (A-1) was 46 g / 10 minutes, and _ethylene was 91.0% by mass. , D _sol is 9.0 mass%, [η _sol ] is 2.0 dl / g, the mass of the constituent unit derived from ethylene in D in _sol is 0.8 mass%, and the constituent unit derived from ethylene in D _sol . Was 22.0% by mass.

[Manufacturing of propylene-based polymer (A-2)]
In the production of the propylene-based polymer (A-1), the polymerization was carried out in the same manner as in the production of the propylene-based polymer (A-1) except that the propylene / ethylene copolymer of Polymerization-2 was carried out for 40 minutes. The melt flow rate (MFR) (ASTM D-1238, measurement temperature 230 ° C., load 2.16 kg) of the obtained propylene-based polymer (A-2) was 52 g / 10 minutes, and _ethylene was 96.0% by mass. , D _sol is 4.0% by mass, [η _sol ] is 2.0 dl / g, the mass of the constituent unit derived from ethylene in D _insol is 0.8% by mass, and the constituent unit derived from ethylene in D _sol . Was 22.0% by mass.

[Manufacturing of propylene-based polymer (A-3)]
In the production of the propylene-based polymer (A-1), the polymerization was carried out in the same manner as in the production of the propylene-based polymer (A-1) except that the propylene / ethylene copolymer of Polymerization-2 was carried out for 80 minutes. The melt flow rate (MFR) (ASTM D-1238, measurement temperature 230 ° C., load 2.16 kg) of the obtained propylene-based polymer (A-3) was 42 g / 10 minutes, and _ethylene was 88.0% by mass. , D _sol is 12.0% by mass, [η _sol ] is 2.0 dl / g, the mass of the constituent unit derived from ethylene in D _insol is 0.8% by mass, and the constituent unit derived from ethylene in D _sol . Was 22.0% by mass.

[Manufacturing of Propylene Polymer (A-4)]
In the production of the propylene-based polymer (A-1), the amount of propylene and ethylene introduced in the polymerization-1 is adjusted so that the ethylene concentration in the gas phase portion in the polymerization tank is 0.15 mol%, and the polymerization-2 Production of propylene-based polymer (A-1) except that the introduction of hydrogen was 0.60 MPa-G and the introduction of propylene / ethylene mixed gas was (4.0 l / min) / (1.2 l / min). Polymerization was carried out in the same manner as in the above. The melt flow rate (MFR) (ASTM D-1238, measurement temperature 230 ° C., load 2.16 kg) of the obtained propylene-based polymer (A-4) was 40 g / 10 minutes, and _ethylene was 91.0% by mass. , D _sol is 9.0 mass%, [η _sol ] is 2.5 dl / g, the mass of the constituent unit derived from ethylene in D in _sol is 0.2 mass%, and the constituent unit derived from ethylene in D _sol . Was 20.0% by mass.

[Manufacturing of Propylene Polymer (A-5)]
In the production of the propylene-based polymer (A-1), the amount of propylene and ethylene introduced in the polymerization-1 is adjusted so that the ethylene concentration in the gas phase portion in the polymerization tank is 1.9 mol%, and the polymerization-2 The introduction of hydrogen was 2.5 MPa-G, the introduction of propylene / ethylene mixed gas was (4.0 l / min) / (2.4 l / min), and propylene / ethylene copolymerization was carried out for 40 minutes. Polymerization was carried out in the same manner as in the production of the system polymer (A-1). The melt flow rate (MFR) (ASTM D-1238, measurement temperature 230 ° C., load 2.16 kg) of the obtained propylene-based polymer (A-5) was 54 g / 10 minutes, and _ethylene was 96.0% by mass. , D _sol is 4.0% by mass, [η _sol ] is 1.0 dl / g, the mass of the constituent unit derived from ethylene in D _insol is 4.0% by mass, and the constituent unit derived from ethylene in D _sol . Was 30.0% by mass.

[Manufacturing of propylene-based polymer (A-c1)]
In the production of the propylene-based polymer (A-1), the propylene-based polymer (A) is produced except that the introduction of the propylene / ethylene mixed gas of Polymerization-2 is (4.0 l / min) / (1.0 l / min). Polymerization was carried out in the same manner as in the production of -1). The melt flow rate (MFR) (ASTM D-1238, measurement temperature 230 ° C., load 2.16 kg) of the obtained propylene-based polymer (A-c1) was 46 g / 10 minutes, and _ethylene was 91.0% by mass. , D _sol is 9.0 mass%, [η _sol ] is 2.0 dl / g, the mass of the constituent unit derived from ethylene in D in _sol is 0.8 mass%, and the constituent unit derived from ethylene in D _sol . Was 18.0% by mass.

[Manufacturing of propylene-based polymer (A-c2)]
In the production of the propylene-based polymer (A-1), the amount of propylene and ethylene introduced in the polymerization-1 is adjusted so that the ethylene concentration in the gas phase portion in the polymerization tank is 1.9 mol%, and the polymerization-2 In the production of the propylene-based polymer (A-1) except that the introduction of the propylene / ethylene mixed gas was set to (4.0 l / min) / (2.6 l / min) and the propylene / ethylene copolymerization was carried out for 30 minutes. Polymerization was carried out in the same manner as in the above. The melt flow rate (MFR) (ASTM D-1238, measurement temperature 230 ° C., load 2.16 kg) of the obtained propylene-based polymer (A-c2) was 54 g / 10 minutes, and _ethylene was 96.0% by mass. , D _sol is 4.0% by mass, [η _sol ] is 2.0 dl / g, the mass of the constituent unit derived from ethylene in D _insol is 4.0% by mass, and the constituent unit derived from ethylene in D _sol . Was 32.0% by mass.

[Manufacturing of propylene-based polymer (A-c3)]
In the production of the propylene-based polymer (A-1), the polymerization was carried out in the same manner as in the production of the propylene-based polymer (A-1) except that the propylene / ethylene copolymer of Polymerization-2 was carried out for 25 minutes. The melt flow rate (MFR) (ASTM D-1238, measurement temperature 230 ° C., load 2.16 kg) of the obtained propylene-based polymer (A-c3) was 54 g / 10 minutes, and _ethylene was 97.0% by mass. , D _sol is 3.0% by mass, [η _sol ] is 2.0 dl / g, the mass of the constituent unit derived from ethylene in D _insol is 0.8% by mass, and the constituent unit derived from ethylene in D _sol . Was 22.0% by mass.

[Manufacturing of propylene-based polymer (A-c4)]
In the production of the propylene-based polymer (A-1), the polymerization was carried out in the same manner as in the production of the propylene-based polymer (A-1) except that the propylene / ethylene copolymer of Polymerization-2 was carried out for 95 minutes. The melt flow rate (MFR) (ASTM D-1238, measurement temperature 230 ° C., load 2.16 kg) of the obtained propylene-based polymer (A-c4) was 40 g / 10 minutes, and _ethylene was 86% by mass, D. 14.0% by mass of _sol , 2.0 dl / g of [η _sol ], 0.8% by mass of the constituent unit derived from ethylene in D _insol , and the mass of the constituent unit derived from ethylene in D _sol . Was 22.0% by mass.

[Manufacturing of Propylene Polymer (A-c5)]
In the production of the propylene-based polymer (A-1), the polymerization was carried out in the same manner as in the production of the propylene-based polymer (A-1) except that only propylene was introduced without introducing ethylene in the polymerization-1. The melt flow rate (MFR) (ASTM D-1238, measurement temperature 230 ° C., load 2.16 kg) of the obtained propylene-based polymer (A-c5) was 46 g / 10 minutes, and _ethylene was 91.0% by mass. , D _sol is 9.0 mass%, [η _sol ] is 2.0 dl / g, the mass of the constituent unit derived from ethylene in D in _sol is 0 mass%, and the mass of the constituent unit derived from ethylene in D _sol is 0 mass%. Was 22.0% by mass.

[Manufacturing of Propylene Polymer (A-c6)]
In the production of the propylene-based polymer (A-1), the polymerization was carried out in the same manner as in the production of the propylene-based polymer (A-1) except that the introduction of hydrogen in the polymerization-2 was 0.5 MPa-G. The melt flow rate (MFR) (ASTM D-1238, measurement temperature 230 ° C., load 2.16 kg) of the obtained propylene-based polymer (A-c6) was 38 g / 10 minutes, and _ethylene was 91.0% by mass. , D _sol is 9.0 mass%, [η _sol ] is 2.6 dl / g, the mass of the constituent unit derived from ethylene in D in _sol is 0.8 mass%, and the constituent unit derived from ethylene in D _sol . Was 22.0% by mass.

[Production of ethylene / α-olefin copolymer (B-1)]
(Catalyst preparation)
A 300 liter reactor fully substituted with nitrogen was charged with 10.0 kg of silica and 154 liters of toluene dried at 600 ° C. for 10 hours, suspended and cooled to 0 ° C. Then, 23.4 liters of a toluene solution of methylaminoxane (Al = 3.02 mol / liter) was added dropwise to this suspension over 1 hour. At this time, the temperature in the system was kept in the range of 0 to 5 ° C. The reaction was subsequently carried out at 0 ° C. for 30 minutes, then the temperature was raised to 95 ° C. over 1.5 hours, and the reaction was carried out at that temperature for 4 hours. Then, the temperature was lowered to 60 ° C., and the supernatant was removed by a decantation method. The solid component thus obtained was washed twice with toluene and then resuspended with 100 liters of toluene to bring the total volume to 160 liters.
To the suspension thus obtained, 20.0 liters of a toluene solution (Zr = 25.6 mmol / liter) of bis (1,3-n-butylmethylcyclopentadienyl) zirconium dichloride was added at 35 ° C. The mixture was added dropwise over 30 minutes and further reacted at 35 ° C. for 2 hours. Then, the supernatant was removed and washed twice with hexane to obtain a solid catalyst component (1) containing 3.2 mg of zirconium per 1 g of the solid catalyst component.

(Preparation of prepolymerization catalyst)
7.0 kg of the solid catalyst component (1) prepared above and hexane were charged into a 350 liter reactor sufficiently substituted with nitrogen to make the total volume 285 liters. After cooling the inside of the system to 10 ° C., ethylene was blown into hexane at a flow rate of 8 Nm ³ / hr for 5 minutes. During this period, the temperature in the system was maintained at 10 to 15 ° C. After that, the supply of ethylene was stopped, and 2.4 mol of diisobutylaluminum hydride (DIBALH) and 1.2 kg of 1-hexene were charged. After closing the system, the supply of ethylene was restarted at a flow rate of 8 Nm ³ / hr. After 15 minutes, the ethylene flow rate was reduced to 2 Nm ³ / hr and the pressure in the system was 0.08 MPaG. During this time, the temperature in the system rose to 35 ° C. Then, while adjusting the temperature in the system to 32 to 35 ° C., ethylene was supplied at a flow rate of 4 Nm ³ / hr for 3.5 hours. During this period, the pressure in the system was maintained at 0.07 to 0.08 MPaG. Then, the inside of the system was replaced with nitrogen, the supernatant was removed, and the mixture was washed twice with hexane. In this way, a prepolymerized catalyst (2) was obtained by prepolymerizing 3 g of the polymer per 1 g of the solid catalyst component.

(polymerization)
Copolymerization of ethylene and 1-hexene was carried out using a continuous flow bed gas phase polymerization apparatus at a total pressure of 2.0 MPaG, a polymerization temperature of 70 ° C., and a gas linear velocity of 0.7 m / sec.
Polymerization was started while continuously supplying the prepolymerization catalyst (2) prepared above at a ratio of 4.1 g / hr and TIBA at a ratio of 5 mmol / hr. Ethylene, 1-hexene, hydrogen and nitrogen were continuously supplied to maintain a constant gas composition during polymerization (gas composition: 1-hexene / ethylene = 0.033, hydrogen / ethylene = 4.4 × 10). ^-4 , ethylene concentration = 49.7%). The yield of the obtained ethylene / 1-hexene copolymer is 6.0 kg / hr, the density is 903 kg / m ³ , and the MFR (ASTM D-1238, measurement temperature 190 ° C., load 2.16 kg) is 3. It was 0.8 g / 10 minutes.
The obtained ethylene / 1-hexene copolymer is also referred to as an ethylene / α-olefin copolymer (B-1).

[Production of ethylene / α-olefin copolymer (B-2)]
In the production (polymerization) of the ethylene / α-olefin copolymer (B-1), the gas composition was 1-hexene / ethylene = 0.038, hydrogen / ethylene = 4.2 × 10 ^-4 , ethylene concentration =. An ethylene / 1-hexene copolymer was obtained in the same manner as in the production of the ethylene / α-olefin copolymer (B-1) except that the content was changed to 40.4%. The yield of the obtained ethylene / 1-hexene copolymer is 6.0 kg / hr, the density is 890 kg / m ³ , and the MFR (ASTM D-1238, measurement temperature 190 ° C., load 2.16 kg) is 3. It was 0.8 g / 10 minutes.
The obtained ethylene / 1-hexene copolymer is also referred to as an ethylene / α-olefin copolymer (B-2).

[Production of ethylene / α-olefin copolymer (B-3)]
In the production (polymerization) of the ethylene / α-olefin copolymer (B-1), the polymerization temperature was set to 80 ° C., and the gas composition was 1-hexene / ethylene = 0.026 and hydrogen / ethylene = 4.5 × 10. An ethylene / 1- ^hexene copolymer was obtained in the same manner as in the production of the ethylene / α-olefin copolymer (B-1) except that the ethylene concentration was changed to 61.0%. The yield of the obtained ethylene / 1-hexene copolymer was 5.8 kg / hr, the density was 920 kg / m ³ , and the MFR (ASTM D-1238, measurement temperature 190 ° C., load 2.16 kg) was 3. It was 0.8 g / 10 minutes.
The obtained ethylene / 1-hexene copolymer is also referred to as an ethylene / α-olefin copolymer (B-3).

[Production of ethylene / α-olefin copolymer (B-c1)]
In the production (polymerization) of the ethylene / α-olefin copolymer (B-1), the gas composition was 1-hexene / ethylene = 0.04, hydrogen / ethylene = 4.1 × 10 ^-4 , ethylene concentration =. An ethylene / 1-hexene copolymer was obtained in the same manner as in the production of the ethylene / α-olefin copolymer (B-1) except that the content was changed to 38.1%. The yield of the obtained ethylene / 1-hexene copolymer was 6.0 kg / hr, the density was 885 kg / m ³ , and the MFR was 3.8 g / 10 minutes.
The obtained ethylene / 1-hexene copolymer is also referred to as an ethylene / α-olefin copolymer (B-c1).

[Production of ethylene / α-olefin copolymer (B-c2)]
In the production (polymerization) of the ethylene / α-olefin copolymer (B-1), the polymerization temperature was 80 ° C., and the gas composition was 1-hexene / ethylene = 0.02, hydrogen / ethylene = 4.6 ×. An ethylene / 1-hexene copolymer was obtained in the same manner as in the production of the ethylene / α-olefin copolymer (B-1) except that the ethylene concentration was changed to ^10-4 and 70%. The yield of the obtained ethylene / 1-hexene copolymer was 5.8 kg / hr, the density was 924 kg / m ³ , and the MFR (ASTM D-1238, measurement temperature 190 ° C., load 2.16 kg) was 3. It was 0.8 g / 10 minutes.
The obtained ethylene / 1-hexene copolymer is also referred to as an ethylene / α-olefin copolymer (B-c2).

[Examples A1 to A9, Comparative Examples A1 to A10]
In the formulations shown in Table 1 (Examples A1 to A9) and Table 2 (Comparative Examples A1 to A10), the propylene-based polymer (A), the ethylene / α-olefin copolymer (B), and the nucleating agent ( As D), nonitol 1,2,3-trideoxy-4,6: 5,7-bis-O-[(4-propylphenyl) methylene] ("Mirrored NX8000J" (trade name), manufactured by Milliken) is blended. Further, as an additive, 0.15 parts by mass of tris (2,4-di-t-butylphenyl) phosphite, which is a phosphorus-based antioxidant, 0.04 parts by mass of calcium stearate, which is a neutralizing agent, and hydrotalcite. 0.05 parts by mass and 0.07 parts by mass of the lubricant erucic acid amide were stirred and mixed with a Henchel mixer.
The obtained mixture was melt-kneaded under the following conditions using a twin-screw extruder (TEM35BS) manufactured by Toshiba Machine Co., Ltd. to obtain strands.
-Model: TEM35BS (35mm twin-screw extruder)
・ Screw rotation speed: 300 rpm
-Screen mesh: # 200
-Resin temperature: 220 ° C
The obtained strands were cooled with water and then cut with a pelletizer to obtain pellets of the propylene-based resin composition (X).
Using these pellets, the melt flow rate (MFR) (ASTM D-1238, measurement temperature 230 ° C., load 2.16 kg) and melting point of the propylene resin composition (X) were measured by the method shown below. Carried out. The results are shown in Tables 1 and 2.

0.7 mmt dessert cup molding Using pellets of a propylene-based resin composition, a container was molded by the following method.
Using an electric injection molding machine (FANUC Roboshot S-2000i-100B) with a mold clamping force of 100 tons, cylinder temperature 230 ° C, mold temperature 20 ° C, injection primary pressure 120 MPa, injection speed 120 mm / sec, maintenance Pellets of the propylene-based resin composition were injection-molded under the conditions of pressure pressure, 50 MPa, and holding time of 1.0 sec, and a container having a height of 62 mm, a diameter of 86 mm, and a side wall thickness of 0.7 mm was injection-molded.

High-speed moldability In continuous molding under the above molding conditions, the minimum cycle time that enables molding with zero troubles such as 100-shot separation mold failure, container deformation, and container flow direction damage due to L-LDPE orientation was measured.

Mold release property In continuous molding under the above molding conditions, the cycle time was unified to 8 seconds, and the presence or absence of mold release failure and container deformation when 10-shot molding was performed was measured.
Those with no mold release failure or container deformation were marked with "○", and those with mold release failure or container deformation were marked with "x".

Transparency (container haze)
The state of the obtained container was adjusted under the condition of 24 ° C. for 48 to 72 hours, the side surface of the container was cut off, and the haze value was measured using NDH2000 manufactured by Nippon Denshoku Kogyo Co., Ltd. according to the haze test method specified in JIS K 7136. ..

The condition of the container obtained with impact resistance was adjusted under the condition of 24 ° C. for 48 to 72 hours, and further the condition was adjusted for 24 hours or more under the environment of 5 ° C.
The container after adjusting the condition was placed on a flat iron plate in an environment of 5 ° C. so that the bottom surface of the container was facing up, and a 6.8 kg iron plate was dropped from a height of 100 cm from the top.
At this time, those in which the container was crushed and no cracks or breakage occurred were marked with "○", and those in which the container was cracked or broken like glass were marked with "x".

MFR (melt flow rate)
Measurements were made according to ASTM D-1238 (measurement temperature 230 ° C., load 2.16 kg). The ethylene / α-olefin copolymer (B) was measured according to ASTM D-1238 (measurement temperature 190 ° C., load 2.16 kg).

Melting point (Tm)
Measurements were performed using a differential scanning calorimeter (DSC, manufactured by PerkinElmer (Diamond DSC)) according to JIS-K7121. The apex of the endothermic peak in the third step measured here was defined as the crystal melting point (Tm). When there are a plurality of endothermic peaks, the apex of the maximum endothermic peak is defined as the crystal melting point (Tm).

(Measurement condition)
Measurement environment: Nitrogen gas atmosphere Sample amount: 5 mg
Sample shape: Press film (molded at 230 ° C, thickness 200-400 μm)
1st step: The temperature is raised from 30 ° C. to 240 ° C. at 10 ° C./min and maintained for 10 min.
2nd step: The temperature is lowered to 60 ° C. at 10 ° C./min.
3rd step: The temperature is raised to 240 ° C. at 10 ° C./min.

Amount of D _insol and D _sol The ratio of D _insol and D _sol of the propylene-based polymer (A) was determined by the following method.
200 ml of n-decane is added to 5 g of a sample of the propylene-based polymer (A), and the mixture is heated and dissolved at 145 ° C. for 30 minutes to obtain a solution (1).
Next, the solution is cooled to room temperature of 25 ° C. over about 2 hours and left at 25 ° C. for 30 minutes to obtain a solution (2) containing the precipitate (α).
Then, the precipitate (α) is filtered off from the solution (2) with a filter cloth having an opening of about 15 μm, the precipitate (α) is dried, and then the mass of the precipitate (α) is measured. The mass of the precipitate (α) divided by the sample mass (5 g) is defined as the ratio of the n-decane insoluble portion (D _insol ).
Further, the solution (2) obtained by filtering the precipitate (α) was placed in about 3 times the amount of acetone of the solution (2) to precipitate the components dissolved in n-decane, and the precipitate (β) was deposited. ).
Then, the precipitate (β) is filtered by a glass filter (G2, opening of about 100 to 160 μm), dried, and then the mass of the precipitate (β) is measured.
The mass of the precipitate (β) at this time divided by the sample mass (5 g) is defined as the ratio of the n-decane soluble portion (D _sol ).
In the above-mentioned examples, no residue was observed even when the filtrate side from which the precipitate (β) was filtered off was concentrated to dryness.

Extreme viscosity of D _sol measured at 135 ° C. in decalin [η _sol ]
The ultimate viscosity [η _sol ] of the D _sol of the propylene-based polymer (A) measured at 135 ° C. in decalin was determined as follows.
As the sample, the precipitate (β) obtained when the ratio of D _insol and D _sol was determined was used.
About 25 mg of this sample is dissolved in 25 ml of decalin and the specific viscosity ηsp is measured in an oil bath at 135 ° C.
After adding 5 ml of a decalin solvent to this decalin solution and diluting it, the specific viscosity ηsp is measured in the same manner.
This dilution operation was repeated twice more, and the value of ηsp / C when the concentration (C) was extrapolated to 0 was obtained as the ultimate viscosity, and this value was measured at 135 ° C. in Decalin of D _sol . _sol ].

Ethylene-derived skeleton content in D _insol and D _sol The content of the ethylene-derived skeleton in the D _insol and D _sol of the propylene-based polymer (A) is as follows based on the measurement of ¹³ CNMR. Measured, calculated and decided.
As the sample, the precipitates (α) and (β) obtained when the ratios of D _insol and D _sol were determined were used.
Using the precipitates (α) and (β) as samples, ¹³ C-NMR measurements were carried out under the following conditions, respectively.

¹³ C-NMR measurement condition Measuring device: LA400 type nuclear magnetic resonance device manufactured by JEOL Ltd. Measurement mode: BCM (Bilevel Complete decoupling)
Observation frequency: 100.4MHz
Observation range: 1706.8Hz
Pulse width: C nucleus 45 ° (7.8 μsec)
Pulse repetition time: 5 seconds Sample tube: 5 mmφ
Sample tube rotation speed: 12 Hz
Number of integrations: 20000 times Measurement temperature: 125 ° C
Solvent: 1,2,4-trichlorobenzene: 0.35 ml / heavy benzene: 0.2 ml
Sample amount: Approximately 40 mg

From the spectrum obtained by the measurement, the ratio of the monomer chain distribution (triad (triplet) distribution) was determined according to the following document (1), and the constituent units derived from ethylene in the above-mentioned D _insol and D _sol . The mole fraction (mol%) (hereinafter referred to as E (mol%)) and the mole fraction (mol%) of the constituent unit derived from propylene (hereinafter referred to as P (mol%)) were calculated. Converting the obtained E (mol%) and P (mol%) into mass% according to the following (formula 1), the content of the structural unit derived from ethylene in the above-mentioned D _insol and D _sol of the propylene-based polymer ( Mass%) (hereinafter referred to as E (wt%)) was calculated.
Reference (1): Kakugo, M .; Naito, Y .; Mizunuma, K .; Miyatake, T., Carbon-13 NMR determination of monomer sequence distribution in ethylene-propylene copolymers prepared with delta-titanium trichloride-diethylaluminum chloride. Macromolecules 1982, 15, (4), 1150-1152
E (wt%) = E (mol%) × 28 × 100 / [P (mol%) × 42 + E (mol%) × 28] (Equation 1)

Ethylene / α-olefin copolymer (B) density The density of the ethylene / α-olefin copolymer (B) can be determined as follows.
The strands of the ethylene / α-olefin copolymer (B) obtained at the time of measuring the melt flow rate (ASTM D-1238) at a measurement temperature of 190 ° C. under a load of 2.16 kg are heat-treated at 120 ° C. for 1 hour, and 1 A sample slowly cooled to room temperature over time was used, and the density was measured by a density gradient tube method to determine the density of the ethylene / α-olefin copolymer (B).

Ethylene / α-olefin copolymer (E)
As the ethylene / α-olefin copolymer (E), the following three types were used from the commercially available L-LDPE "Evolu" (registered trademark) series.
SP 1540 (MFR = 3.8 g / 10 min (ASTM D-1238, measurement temperature 190 ° C., load 2.16 kg), density DE = 914 kg / m ³ )
SP 2040 (MFR = 3.8 g / 10 min (ASTM D-1238, measurement temperature 190 ° C., load 2.16 kg), density DE = 918 kg / m ³ )
SP 2540 (MFR = 3.8 g / 10 min (ASTM D-1238, measurement temperature 190 ° C., load 2.16 kg), density DE = 924 kg / m ³ )

[Examples B1 to B3, Comparative Examples B1 to B3]
In the formulation shown in Table 1, the propylene polymer (A), ethylene / α-olefin copolymer (B), and nonitol 1,2,3-trideoxy-4,6: 5,7 as the nucleating agent (D) -Bis-O- [(4-propylphenyl) methylene] ("Mirrored NX8000J" (trade name), manufactured by Milliken), ethylene / α-olefin copolymer (E) is blended, and phosphorus is added as an additive. 0.15 parts by mass of antioxidative agent [Tris (2,4-di-t-butylphenyl) phosphite], 0.04 parts by mass of calcium stearate as neutralizing agent, 0.07 parts of erucate amide as lubricant. The parts by mass were stirred and mixed with a Henshell mixer.
The obtained mixture was melt-kneaded under the following conditions using a twin-screw extruder (TEM35BS) manufactured by Toshiba Machine Co., Ltd. to obtain strands.
-Model: TEM35BS (35mm twin-screw extruder)
・ Screw rotation speed: 300 rpm
-Screen mesh: # 200
-Resin temperature: 220 ° C

The obtained strands were cooled with water and then cut with a pelletizer to obtain pellets of the propylene-based resin composition (Y).
Using these pellets, the melt flow rate (MFR) (ASTM D-1238, measurement temperature 230 ° C., load 2.16 kg) and melting point of the propylene resin composition (Y) are used in the same manner as in the composition (X). Was measured. The results are shown in Table 3.
Further, a 0.7 mmt dessert cup was molded in the same manner as in the composition (X), and high-speed moldability, mold releasability, transparency, and impact resistance were evaluated in the same manner. The results are shown in Table 3.

Claims (7)

82 to 92 parts by mass of the propylene-based polymer (A) satisfying the following requirements (A1) to (A5), and 8 to 18 parts by mass of the ethylene / α-olefin copolymer (B) satisfying the following requirements (B1) to (B2). Parts (however, the total of the propylene-based polymer (A) and the ethylene / α-olefin copolymer (B) is 100 parts by mass), and 0.1 to 0.6 parts by mass of the nucleating agent (D). A propylene-based resin composition having a melt flow rate (MFR) of 20 to 60 g / 10 minutes measured at a measurement temperature of 230 ° C. and a load of 2.16 kg in accordance with ASTM D-1238 .
(A1): The melt flow rate (MFR) of the propylene-based polymer (A) measured at a measurement temperature of 230 ° C. and a load of 2.16 kg according to ASTM D-1238 is 1 to 100 g / 10 minutes.
(A2): The room temperature n-decane-insoluble portion (D _insol ) of the propylene-based polymer (A) is 88 to 96% by mass, and the room temperature n-decane-soluble portion (D _sol ) is 4 to 12% by mass. % (However, the total of D in _sol and D _sol is 100% by mass).
(A3): The content of the skeleton derived from ethylene in the D _insol is 0.2 to 6% by mass.
(A4): The content of the skeleton derived from ethylene in the D _sol is 20 to 30% by mass.
(A5): The ultimate viscosity [η] of the D _sol in 135 ° C. decalin is 1.0 to 2.5 dl / g.
(B1): The melt flow rate (MFR) of the ethylene / α-olefin copolymer (B) measured at a measurement temperature of 190 ° C. and a load of 2.16 kg according to ASTM D-1238 is 0.5 to 50 g. / 10 minutes.
(B2): The density of the ethylene / α-olefin copolymer (B) is 886 to 920 kg / m ³ . 86 to 92 parts by mass of the propylene-based polymer (A) satisfying the following requirements (A1) to (A5), and the ethylene / α-olefin copolymer (B') 8 satisfying the following requirements (B1') to (B2'). ~ 14 parts by mass (however, the total of the propylene-based polymer (A) and the ethylene / α-olefin copolymer (B') is 100 parts by mass), and the total of (A) and (B') is 100. A propylene-based resin composition containing 2 to 15 parts by mass of an ethylene / α-olefin copolymer (E) that satisfies the following requirements (E1) and (E2) with respect to a mass portion of the nucleating agent (D).
(A1): The melt flow rate (MFR) of the propylene-based polymer (A) measured at a measurement temperature of 230 ° C. and a load of 2.16 kg according to ASTM D-1238 is 1 to 100 g / 10 minutes.
(A2): The room temperature n-decane-insoluble portion (D _insol ) of the propylene-based polymer (A) is 88 to 96% by mass, and the room temperature n-decane-soluble portion (D _sol ) is 4 to 12% by mass. % (However, the total of D _insol and D _sol is 100% by mass).
(A3): The content of the skeleton derived from ethylene in the D _insol is 0.2 to 6% by mass.
(A4): The content of the skeleton derived from ethylene in the D _sol is 20 to 30% by mass.
(A5): The ultimate viscosity [η] of the D _sol in 135 ° C. decalin is 1.0 to 2.5 dl / g.
(B1'): The melt flow rate (MFR) of the ethylene / α-olefin copolymer (B') measured at a measurement temperature of 190 ° C. and a load of 2.16 kg according to ASTM D-1238 is 0.5. ~ 50 g / 10 minutes.
(B2'): The density DB of the ethylene / α-olefin copolymer ( _B ') is 886 to 915 kg / m ³ .
(E1): The melt flow rate (MFR) of the ethylene / α-olefin copolymer (E) measured at a measurement temperature of 190 ° C. and a load of 2.16 kg according to ASTM D-1238 is 0.5 to 50 g. / 10 minutes.
(E2): The density DE of the ethylene / α _- olefin copolymer ( _E ) is 900 to 920 kg / m ³ , and the density _DE is 5 kg / m ³ or more higher than the density DB. A molded product containing the propylene-based resin composition according to claim 1 or 2. A container containing the propylene-based resin composition according to claim 1 or 2. The container according to claim 4, wherein the container is a dessert cup. The container according to claim 4 or 5, wherein the thinnest portion of the container has a wall thickness in the range of 0.3 to 2.0 mm. A method for producing a container, which comprises a step of injection molding or injection stretching blow molding of the propylene-based resin composition according to claim 1 or 2.