JP2012062360A - Propylene-based resin composition and molding thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a propylene-based resin composition and a molding excellent in impact resistance, tensile elongation, weld strength, surface hardness, scratch resistance, whitening resistance, glossiness, and transparency.SOLUTION: The propylene-based resin composition includes: 30-98 pts.wt of a propylene polymer; 1-40 pts.wt of an ethylenic polymer; 1-30 pts.wt of a propylene-ethylene block copolymer which satisfies the following requirements (i)-(v), (the sum total is 100 pts.wt): (i) a metallocene catalyst is sequentially polymerized with 30-95 wt.% of a propylene-ethylene random copolymer component (A) having content of independent propylene or an ethylene of 7 wt.% or lower at a first step, and with 70-5 wt.% of a propylene-ethylene random copolymer (B) of an ethylene content more than that of the component (A) by 3-20 wt.% at a second step; (ii) MFR is 0.5-100 g/10 minutes; (iii) melting peak temperature (Tm) is 110-150°C; (iv) Mw/Mn is 1.5-4; and (v) tan δ curve has a single peak at 0°C or lower.

Description

  The present invention relates to a propylene-based resin composition and a molded article thereof, and in particular, a propylene-based resin composition excellent in impact resistance, tensile elongation, weld strength, surface hardness, scratch resistance, whitening resistance, gloss, and transparency, and It relates to the molded product.

  Propylene polymers are excellent in moldability, rigidity, recyclability and heat resistance, so they are molded and processed by various methods to produce food containers, caps, medical instruments, medical containers, and packaging. Widely used in various applications such as film, stationery sheet, costume case, daily necessities, automobile parts, electrical parts. In these applications, more excellent impact resistance, rigidity, transparency, molding processability and the like are strongly demanded for the propylene polymer or the composition thereof.

  Propylene polymers are propylene homopolymers in terms of rigidity, heat resistance, gas barrier properties, and random copolymers of propylene polymers with ethylene, butene, etc. in terms of transparency, in terms of heat resistance and impact resistance. Is preferably a block copolymer of ethylene, butene or the like and propylene, and is appropriately and selectively used depending on the situation.

However, the propylene polymer may not be sufficient in terms of impact resistance. In such a case, the impact resistance is improved by adding another polymer as a modifier to the propylene-based polymer. Among the modifiers, ethylene polymers are the most widely used because they are relatively inexpensive and have a high impact resistance improving effect. For example, Patent Document 1 attempts to improve impact strength by blending crystalline polypropylene with an ethylene copolymer having a density of 0.93 to 0.88 g / cm ³ . However, when a propylene polymer and an ethylene polymer are used in combination, the compatibility between the two is insufficient, and the two polymers do not disperse finely and uniformly. However, not only the tensile elongation is not sufficiently improved, but also the occurrence of various problems such as impact whitening, reduced weld strength, reduced transparency and gloss, scratch resistance, and scratch resistance is suppressed. The current situation was difficult.

JP 2000-72938 A

  The object of the present invention is to solve the above-mentioned problems and to provide a propylene-based resin composition excellent in impact resistance, tensile elongation, weld strength, surface hardness, scratch resistance, whitening resistance, gloss, and transparency, and the resin composition An object of the present invention is to provide a molded product formed from

  As a result of intensive studies to solve the above problems, the present inventors have used a specific modifier in combination with the propylene-based polymer, whereby each component is finely and uniformly dispersed with each other. As a result, the object of the present invention is to provide a resin excellent in impact resistance, tensile elongation, weld strength, surface hardness, scratch resistance, whitening resistance, gloss, and transparency by dispersing each component minutely and uniformly. It discovered that it could become a composition and a molded article, and came to complete this invention.

That is, according to 1st invention of this invention, propylene type | system | group (a) 30-98 weight part, the ethylene-type polymer (ii) 1-40 weight part, and the propylene which satisfy | fills following (i)-(v) -A propylene-based resin composition comprising 1 to 30 parts by weight of an ethylene block copolymer (U) (however, the sum of (A), (I) and (U) is 100 parts by weight) Things are provided.
(I) Using a metallocene-based catalyst, 30 to 95 wt% of propylene-ethylene random copolymer component (A) having propylene homopolymer or ethylene content of 7 wt% or less in the first step, and from component (A) in the second step (Ii) Melt flow rate (MFR: 230 ° C. 2.16 kg) is obtained by sequential polymerization of 70 to 5 wt% of propylene-ethylene random copolymer component (B) containing 3 to 20 wt% of ethylene. (Iii) that the melting peak temperature (Tm) measured by the DSC method is in the range of 110 to 150 ° C. (iv) the molecular weight measured by the GPC method Distribution (Mw / Mn) is in the range of 1.5 to 4 (v) In the temperature-loss tangent curve obtained by solid viscoelasticity measurement, the tan δ curve is 0 ° C. It has a single peak under

  According to the second invention of the present invention, in the first invention, the propylene copolymer (a) is a propylene homopolymer, or propylene and ethylene and / or an α-olefin having 4 to 12 carbon atoms. The propylene-based resin composition is characterized in that the content of ethylene and / or α-olefin having 4 to 12 carbon atoms is 0 to 7 wt%.

  According to the third invention of the present invention, there is provided a propylene-based resin composition characterized in that, in the first or second invention, the ethylene polymer (a) is polymerized using a metallocene catalyst. Provided.

  Furthermore, according to 4th invention of this invention, the molded article using the propylene-type resin composition of any one of 1st-3rd invention is provided.

  In the propylene-based resin composition of the present invention, a specific amount of the ethylene-based polymer (A) and the propylene-ethylene block copolymer (U) as a modifier is blended with the propylene-based polymer (a). It is characterized by. By using a specific amount of such modifiers in combination, the polymers are finely and uniformly dispersed with each other, and have excellent impact resistance and tensile elongation that could not be realized with conventional propylene resin compositions. , A material having a balance of weld strength, surface hardness, scratch resistance, whitening resistance, gloss and transparency can be obtained.

It is a figure which shows the elution amount and elution amount integration | accumulation of the components (A1) and (A2) by TREF. It is a flow sheet figure of the superposition | polymerization apparatus used by manufacture example 1 and 2 of an Example.

The present invention is a propylene-ethylene block copolymer satisfying the above conditions (i) to (v), with 30 to 98 parts by weight of the propylene polymer (a) and 1 to 40 parts by weight of the ethylene polymer (a). The propylene-based resin composition is characterized by containing 1 to 30 parts by weight of the union (U) (wherein (A), (I) and (U) are the total of 100 parts by weight).
The propylene polymer (a) needs to be in the range of at least 30 parts by weight and 98 parts by weight in order to maintain the properties of the polymer. On the other hand, the ethylene-based polymer (A) needs to be in the range of at least 1 part by weight and 40 parts by weight in order to impart appropriate impact resistance to the resin composition of the present invention.
Furthermore, the propylene-ethylene block copolymer (c) is a component that improves the compatibility between the propylene polymer (A) and the ethylene copolymer (I). It is necessary to be at least 1 part by weight and 30 parts by weight or less.
Hereinafter, the component which comprises a propylene-type resin composition, the manufacturing method of a resin composition, and a molded article are demonstrated in detail.

[1] Propylene polymer (A)
The propylene polymer (a) used in the propylene resin composition of the present invention may be a propylene homopolymer or a propylene copolymer (random copolymer, block copolymer), Alternatively, a mixture thereof may be used.
However, in order to exhibit excellent transparency, a propylene homopolymer, or a random copolymer of ethylene and / or an α-olefin having 4 to 12 carbon atoms and propylene is preferable. Among them, propylene-ethylene copolymer, propylene-ethylene-butene-1 copolymer, propylene-butene-1 copolymer, propylene-pentene-1 copolymer, propylene-hexene-1 copolymer, propylene Preferred examples include binary or ternary copolymers such as -4-methylpentene-1 copolymer.
When the copolymer is used, the comonomer content is preferably 7 wt% or less, and more preferably 1 to 5 wt%. This is because if the amount of the comonomer is too large, the melting point is lowered and the heat resistance is greatly lowered, the low crystalline component is increased, the stickiness performance is deteriorated, and the productivity is greatly deteriorated.

  In the propylene polymer (a), the melt flow rate based on JIS K7210 (230 ° C., 2.16 kg load) is preferably 0.3 to 200 g / 10 minutes. If the melt flow rate is significantly less than 0.3 g / 10 min, the extrusion load during extrusion molding increases, the surface smoothness is impaired, and the appearance of the molded product may be deteriorated. On the other hand, if it is significantly higher than 200 g / 10 min, the dispersibility with the ethylene-based polymer (ii) and the propylene-ethylene block copolymer (iii) may be deteriorated, and impact resistance and transparency may be hardly exhibited. There is. A more preferable melt flow rate is 0.5 to 100 g / 10 minutes, and further 1 to 50 g / 10 minutes.

The catalyst used for obtaining the propylene-based polymer (a) used in the present invention is not particularly limited, and a known catalyst can be used. For example, a so-called Ziegler-Natta catalyst or a metallocene catalyst (for example, those described in JP-A-5-295022), which is a combination of a titanium compound and organic aluminum, can be used.
The polymerization process used for obtaining the propylene polymer (a) used in the present invention is not particularly limited, and a known polymerization process can be used. For example, a slurry polymerization method, a bulk polymerization method, a gas phase polymerization method and the like can be used. Moreover, it can also superpose | polymerize by performing multistage polymerization combining the 1 type (s) or 2 or more types of these polymerization methods. Further, it can also be produced by mechanically mixing or melt-kneading two or more propylene polymers.

The amount of the propylene polymer (a) in the propylene resin composition is in the range of 30 to 98 parts by weight with respect to 100 parts by weight of the total amount of the component (a), the component (b) and the component (c). It is necessary to be, preferably 50 to 98 parts by weight.
If the content of the propylene polymer (a) is too small, desired mechanical properties such as flexural modulus cannot be obtained. On the other hand, if it exceeds 98 parts by weight, impact resistance, tensile elongation and the like are deteriorated.

[2] Ethylene polymer (a)
The ethylene polymer (A) used in the propylene resin composition of the present invention is a high density polyethylene (HDPE), a low density polyethylene (LDPE), or a very low density polyethylene (VLDPE). It may be linear low density polyethylene (LLDPE) or a mixture thereof. Moreover, the copolymer with various comonomers may be sufficient. In the case of a copolymer, it is a copolymer obtained by copolymerizing ethylene and preferably an α-olefin having 3 to 20 carbon atoms, and the α-olefin is one having 3 to 20 carbon atoms, For example, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-heptene and the like can be preferably exemplified.
Among these, in order to give excellent impact resistance, low density such as low density polyethylene, ultra-low density polyethylene, and linear low density polyethylene is preferable. Specifically, the density is 0. About .93 or less is preferable from the viewpoint of improving impact resistance, and more preferably 0.86 to 0.92.

  In addition, in the ethylene polymer (A), the melt flow rate based on JIS K7210 (190 ° C., 2.16 kg load) is preferably 0.3 to 50 g / 10 min. When the melt flow rate is significantly lower than 0.3 g / 10 min, the compatibility with the propylene polymer (a) in the composition is remarkably lowered and it becomes difficult to disperse finely and uniformly in the composition. May cause the appearance of the molded product to be impaired, and it may be difficult to develop various physical properties such as impact resistance and tensile elongation. On the other hand, if it greatly exceeds 50 g / 10 min, the impact resistance improving effect may be reduced. A more preferable melt flow rate is 0.5 to 30 g / 10 minutes, and further 1 to 20 g / 10 minutes.

The catalyst used for obtaining the ethylene-based polymer (i) used in the present invention is not particularly limited, and a known catalyst can be used. For example, a radical initiator, a metal oxide catalyst, a Ziegler catalyst, or a metallocene catalyst can be used.
The polymerization process used to obtain the ethylene copolymer (a) is not particularly limited, and a known polymerization process can be used. For example, an autoclave polymerization method, a tubular polymerization method, a solution polymerization method, a slurry polymerization method, a gas phase polymerization method and the like can be used. Moreover, it can also superpose | polymerize by performing multistage polymerization combining the 1 type (s) or 2 or more types of these polymerization methods. Furthermore, it can also be produced by mechanically mixing or melt-kneading two or more kinds of ethylene polymers.

  When a metallocene catalyst is used as the ethylene copolymer (a), the molecular weight and crystallinity distribution is narrow, so low molecular weight and low crystallinity components are present at the interface with other polymers in the composition. Therefore, it is more preferable because there is little risk of lowering the interfacial adhesive strength and various physical properties such as tensile elongation.

As the metallocene catalyst, various known catalysts used for polymerization of ethylene-α-olefin copolymers and the like can be used. Specific examples include metallocene catalysts described in JP-A-58-19309, JP-A-59-95292, JP-A-60-35006, and JP-A-3-16388. .
Specific polymerization methods using a metallocene catalyst include a slurry method, a gas phase fluidized bed method and a solution method in the presence of these catalysts, or a high-pressure bulk at a pressure of 200 kg / cm ² or higher and a polymerization temperature of 100 ° C. or higher. Examples thereof include a polymerization method. A preferable production method includes high-pressure bulk polymerization.
In addition, ethylene copolymer (I) can also be suitably selected from what is marketed as metallocene polyethylene, and can also be used. Examples of commercially available products include DuPont Dow's trade name affinity (AFFINITY) and Engage (ENGAGE), Nippon Polyethylene's trade name kernel (KERNEL), ExxonMobil's trade name Exact (EXACT), and the like.

The amount of the ethylene copolymer (I) in the propylene-based resin composition is in the range of 1 to 40 parts by weight with respect to 100 parts by weight of the total amount of the component (A), the component (I) and the component (U). It is necessary to be 3 to 40 parts by weight.
If the content of the ethylene copolymer (I) is too small, the impact resistance improving effect is not sufficient, and if it exceeds 40 parts by weight, the rigidity and heat resistance are lowered.

[3] Propylene-ethylene block copolymer (c)
The propylene-ethylene block copolymer (c) used in the present invention is obtained by sequential polymerization, and in the first step, propylene alone or a propylene-ethylene random copolymer component (A) having an ethylene content of 7 wt% or less is added. Propylene-ethylene obtained by sequential polymerization of 70 to 5 wt% of propylene-ethylene random copolymer component (B) containing 30 to 95 wt% of ethylene in the second step and 3 to 20 wt% higher than that of the first step It is a block copolymer and satisfies the conditions (i) to (v) described below.
The propylene-ethylene block copolymer (c) referred to here is a propylene-ethylene random copolymer component (A) (hereinafter referred to as component (A)) and a propylene-ethylene random copolymer component ( B) (hereinafter referred to as “component (B)”) is a block copolymer as a general name obtained by sequential polymerization, and the component (A) and the component (B) are not necessarily combined in a block form. It does not have to be.
The propylene-ethylene block copolymer (c) is a component characterized in that both the propylene polymer (a) and the ethylene polymer (a) are easily dispersed. It has a very important function in order to obtain a uniform dispersion.

(I) Ethylene content in component / component (A) of propylene-ethylene block copolymer (c): [E] A
The component (A) produced in the first step is a component for expressing a compatibilizing effect on the propylene polymer (a). Therefore, it is preferable to have crystallinity close to that of the propylene polymer (a). Since the propylene polymer (a) is a propylene homopolymer or random copolymer having a comonomer content of 0 to 7 wt%, the ethylene content of the component (A) in the propylene-ethylene block copolymer (c) [ E] A is also preferably about 0 to 7 wt%. [E] If A exceeds 7 wt%, the compatibility with the propylene copolymer (a) deteriorates and the dispersibility deteriorates, and the crystallinity of the propylene copolymer (a) decreases. Therefore, there is a concern that rigidity and heat resistance may be significantly reduced, which is not preferable.

-Ethylene content in component (B): [E] B
The component (B) produced in the second step is a component for developing compatibility with the ethylene copolymer (a). In order to increase the compatibility with the ethylene-based copolymer (a), [E] B is preferably higher and closer to the ethylene-based copolymer (a), but if it is too high, the propylene-ethylene block copolymer is preferred. In component (C), component (A) and component (B) are phase-separated, and as a result, in the entire composition, a phase composed of propylene polymer (a) and ethylene polymer It separates into a phase consisting of (a). As a result, the entire composition does not become a uniform and fine dispersion, which is not preferable because mechanical properties and transparency are greatly reduced.

In order to cope with such a problem, the range of the ethylene content of component (B) is the difference [E] B- [E] A (hereinafter also referred to as “[E] gap”) from the ethylene content of component (A). )). [E] B- [E] A needs to be in the range of 3 to 20 wt%, preferably 6 to 18 wt%, and more preferably 8 to 16 wt%.
[E] When the gap is less than 3 wt%, the effect of compatibilization with the ethylene polymer (ii) is not sufficient, which is not preferable. On the other hand, if it exceeds 20 wt%, the compatibility with the component (A) produced in the first step is deteriorated and the entire composition becomes a non-uniform dispersion. This is not preferable because the physical properties are significantly lowered and the transparency is also deteriorated.

-Ratio of component (A): W (A) and ratio of component (B): W (B)
The content ratio of W (A), which is the proportion of the component (A) constituting the propylene-ethylene block copolymer, and W (B), which is the proportion of the component (B), is 30 to 95 wt% for W (A). And W (B) needs to be in the range of 70 to 5 wt%.
When the proportion of W (A) is less than 30 wt%, the compatibility with the propylene-based resin (a) is deteriorated. On the other hand, when the proportion of W (A) exceeds 95 wt%, the compatibility with the ethylene-based resin (A) becomes insufficient. In any case, since the entire composition does not become a uniform and fine dispersion, various physical properties are greatly reduced. Preferably, the ratio of W (A) is in the range of 40 to 80 wt%, more preferably 50 to 70 wt%.

[E] A and [E] B and specific amounts of each component W (A) and W (B) Each ethylene content ([E] A and [E] B) and amount of each component (A) and (B) (W (A) and W (B)) can be specified by the material balance (material balance) at the time of manufacture, but in order to specify these more accurately, the following analysis should be used. desirable.

・ Specification of each component amount W (A) and W (B) by temperature rising elution fractionation (TREF) The technique for evaluating the crystallinity distribution of propylene-ethylene random copolymer by TREF is well known to those skilled in the art. For example, a detailed measurement method is shown in the following document.
G. Glockner, J. et al. Appl. Polym. Sci. : Appl. Polym. Symp. 45, 1-24 (1990)
L. Wild, Adv. Polym. Sci. 98, 1-47 (1990)
J. et al. B. P. Soares, A .; E. Hamielec, Polymer; 36, 8, 1639-1654 (1995)

The propylene-ethylene block copolymer (c) in the present invention is greatly different in the crystallinity of each of the components (A) and (B), and each crystallinity distribution is produced by being produced using a metallocene catalyst. Therefore, the intermediate component between the two is extremely small, and it is possible to determine both with high accuracy by TREF.
A specific method will be described with reference to the figure showing the elution amount and the elution amount integration by TREF in FIG.
In the TREF elution curve (plot of elution amount versus temperature), components (A) and (B) show their elution peaks at elution peak temperatures T (A) and T (B), respectively, due to the difference in crystallinity. Since it is sufficiently large, separation is possible at an intermediate temperature T (C) (= {T (A) + T (B)} / 2).

In addition, the lower limit of the TREF measurement temperature is −15 ° C. in the apparatus used for this measurement, but when the crystallinity of the component (B) is very low or an amorphous component, There may be no peak in the temperature range. In this case, the concentration of the component (B) dissolved in the solvent at the measurement temperature lower limit (that is, −15 ° C.) is detected.
At this time, T (B) is considered to exist below the measurement temperature lower limit, but the value cannot be measured. In such a case, T (B) is the measurement temperature lower limit − It is defined as 15 ° C.
Here, if the integrated amount of the component eluted before T (C) is defined as W (B) wt%, and the integrated amount of the component eluted at T (C) or higher is defined as W (A) wt%, W (B) Almost corresponds to the amount of the component (B) having low crystallinity or amorphousness, and the integrated amount W (A) of the component eluted at T (C) or higher is the component (A) having relatively high crystallinity. Almost corresponds to the amount of. The elution amount curve obtained by TREF and the calculation method of the various temperatures and amounts obtained from the elution amount curve are performed as illustrated in FIG.

-TREF measuring method In the present invention, the TREF is specifically measured as follows.
A sample is dissolved in o-dichlorobenzene (containing 0.5 mg / mL BHT) at 140 ° C. to obtain a solution. This is introduced into a 140 ° C. TREF column, cooled to 100 ° C. at a rate of 8 ° C./min, subsequently cooled to −15 ° C. at a rate of 4 ° C./min, and held for 60 minutes. Thereafter, o-dichlorobenzene (containing 0.5 mg / mL BHT) as a solvent is flowed through the column at a flow rate of 1 mL / min, and components dissolved in o-dichlorobenzene at −15 ° C. are eluted in the TREF column for 10 minutes. Next, the column is linearly heated to 140 ° C. at a heating rate of 100 ° C./hour to obtain an elution curve.

・ Ethylene content [E] A and [E] B in each component ・ ・ Separation of component (A) and component (B) Preparative separation based on T (C) determined by TREF measurement Using a temperature rising column fractionation method using an apparatus, the soluble component (B) in T (C) and the insoluble component (A) in T (C) are fractionated, and the ethylene content of each component is determined by NMR.
The temperature rising column fractionation method refers to a measurement method disclosed in, for example, Macromolecules, 21 314 to 319 (1988). Specifically, the following method was used in the present invention.

.. Fractionation condition A cylindrical column having a diameter of 50 mm and a height of 500 mm is filled with a glass bead carrier (80 to 100 mesh) and maintained at 140 ° C. Next, 200 mL of the o-dichlorobenzene solution (10 mg / mL) of the sample dissolved at 140 ° C. is introduced into the column. Thereafter, the temperature of the column is cooled to 0 ° C. at a rate of temperature decrease of 10 ° C./hour. After holding at 0 ° C. for 1 hour, the column temperature is heated to T (C) at a heating rate of 10 ° C./hour and held for 1 hour. Note that the temperature control accuracy of the column through a series of operations is ± 1 ° C.
Next, while maintaining the column temperature at T (C), 800 mL of o (dichlorobenzene) of T (C) is allowed to flow at a flow rate of 20 mL / min, whereby components soluble in T (C) existing in the column are obtained. Elute and collect.
Next, the column temperature is increased to 140 ° C. at a temperature rising rate of 10 ° C./min, and after leaving still at 140 ° C. for 1 hour, by flowing 800 mL of a 140 ° C. solvent (o-dichlorobenzene) at a flow rate of 20 mL / min, Elute insoluble components with T (C) and collect.
The solution containing the polymer obtained by fractionation is concentrated to 20 mL using an evaporator and then precipitated in 5 times the amount of methanol. The precipitated polymer is recovered by filtration and then dried overnight in a vacuum dryer.

· · ¹³ C-NMR according to the measurement the fractionated by components obtained ethylene content (A) (B) an ethylene content of each is by proton complete decoupling method, the following ¹³ were measured according to the conditions of C-NMR Obtained by analyzing the spectrum.
Model: GSX-400 manufactured by JEOL Ltd. or equivalent equipment (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 attribution of the spectrum may be performed with reference to, for example, Macromolecules, 17 1950 (1984). The attribution of spectra measured under the above conditions is as shown in the table below. In the table, symbols such as S _αα represent Carman et al. (Macromolecules, 10 536 (1977)), P represents a methyl carbon, S represents a methylene carbon, and T represents a methine carbon.

Hereinafter, when “P” is a propylene unit in a copolymer chain and “E” is an ethylene unit, six kinds 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 random copolymer of the present invention contains a small amount of a propylene hetero bond (2,1-bond and / or 1,3-bond), thereby producing the following minute peak.

In order to obtain an accurate ethylene content, it is necessary to include these peaks derived from heterogeneous bonds in the calculation, but it is difficult to completely separate and identify the peaks derived from heterogeneous bonds, and the amount of heterogeneous bonds is small. Therefore, the ethylene content of the present invention is determined using the relational expressions (1) to (7) as in the analysis of the copolymer produced with the Ziegler catalyst that does not substantially contain heterogeneous bonds. .
Conversion from mol% to wt% of ethylene content 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%.
Further, the ethylene content [E] W of the entire propylene-ethylene block copolymer is calculated from the ethylene contents [E] A, [E] B and TREF of the components (A) and (B) measured from the above. From the weight ratios W (A) and W (B) wt% of each component, the following formula is used.
[E] W = {[E] A × W (A) + [E] B × W (B) / 100 (wt%)

(Ii) Melt flow rate (MFR)
The melt flow rate (MFR) of the propylene-ethylene block copolymer (c) used in the present invention is 0.5 to 100 g / 10 minutes, preferably 1 to 50 g / 10 minutes, more preferably 2 to 2. 35 g / 10 min. If the MFR is less than 0.5 g / 10 min, molding becomes difficult, and if it exceeds 100 g / 10 min, impact resistance cannot be expected.
The melt flow rate (MFR) is adjusted by adjusting the temperature and pressure, which are the polymerization conditions of the propylene-ethylene block copolymer, or by controlling the amount of hydrogen added during polymerization of a chain transfer agent such as hydrogen. Adjustments can be made easily.
Here, MFR is a value measured at a heating temperature of 230 ° C. and a load of 2.16 kg in accordance with JIS K7210.

(Iii) Melting peak temperature (Tm)
The melting peak temperature (Tm) measured by the differential scanning calorimeter (DSC) of the propylene-ethylene block copolymer (c) used in the present invention needs to be in the range of 110 to 150 ° C., and 120 to It is preferable that it is 140 degreeC. When Tm is less than 110 ° C., the rate at which the composition cools and solidifies from the molten state is delayed, and the moldability may be deteriorated. On the other hand, if it exceeds 150 ° C., the impact resistance improving effect may be reduced. In order to adjust the melting peak temperature (Tm), it can be easily adjusted by controlling the amount of ethylene supplied to the polymerization reaction system.
Here, the specific measurement of Tm is performed using a differential scanning calorimeter (DSC), taking a sample amount of 5 mg, holding at 200 ° C. for 5 minutes, and then crystallizing to 40 ° C. at a rate of temperature decrease of 10 ° C./min. Further, the peak position of the curve drawn when the film is melted at a temperature rising rate of 10 ° C./min is defined as a melting peak temperature Tm (° C.).

(Iv) Molecular weight distribution (Mw / Mn)
The molecular weight distribution (Mw / Mn) measured by the gel permeation (GPC) method of the propylene-ethylene block copolymer (c) needs to be in the range of 1.5 to 4, and is 1.8 to 3 It is preferable that If Mw / Mn is less than 1.5, it is difficult to obtain with the current polymerization technique, and if it exceeds 4, the product (composition) may become sticky. To narrow the molecular weight distribution of the propylene-ethylene block copolymer, use a metallocene catalyst described later, or polymerize the propylene-ethylene block copolymer, and then melt knead using an organic peroxide. It can be adjusted by doing. To broaden, it can be adjusted by polymerization using a catalyst system in which two or more metallocene catalyst components are used in combination or a catalyst system in which two or more metallocene complexes are used in combination.

Here, the molecular weight distribution is obtained by the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn), and is obtained by measurement by a gel permeation chromatography (GPC) method.
Conversion from the retention volume to the molecular weight is performed using a calibration curve prepared in advance with standard polystyrene.
The standard polystyrenes used are all the following brands manufactured by Tosoh Corporation.
F380, F288, F128, F80, F40, F20, F10, F4, F1, A5000, A2500, A1000
A calibration curve is prepared by injecting 0.2 ml of a solution dissolved in o-dichlorobenzene (containing 0.5 mg / ml BHT) so that each is 0.5 mg / ml.
The calibration curve uses a cubic equation obtained by approximation by the least square method. The following numerical value is used for [η] = K × Mα in the viscosity formula 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: GPC manufactured by WATERS (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 o-dichlorobenzene (containing 0.5 mg / ml BHT) and dissolve it at 140 ° C. for about 1 hour.

(V) Regulation by peak of tan δ curve In the present invention, it is the biggest problem to make the entire propylene-based resin composition uniform and fine dispersion by compatibilization. For this purpose, the propylene-ethylene block copolymer (c) is compatible with each of the propylene polymer (a) and the ethylene polymer (b), and the propylene-ethylene block copolymer (c) It is extremely important that the component (A) and the component (B) constituting the phase are not phase-separated. The phase separation conditions are affected not only by the ethylene content but also by the molecular weight and composition. Therefore, in addition to the above-mentioned regulations regarding the ethylene content, a temperature-loss tangent (tan δ) curve obtained by solid viscoelasticity measurement (DMA) Therefore, it is necessary to define the tan δ curve peak.
When the propylene-ethylene block copolymer has a phase separation structure, the glass transition temperature of the amorphous part contained in the component (A) is different from the glass transition temperature of the amorphous part contained in the component (B). , There will be multiple peaks. Conversely, when they are compatible, both components are mixed in the order of molecules and have a single peak at a temperature intermediate between the glass transition temperatures of both components. That is, whether or not the phase separation structure is taken can be determined in the temperature-tan δ curve in the solid viscoelasticity measurement, and in order to maintain transparency, the tan δ curve has a single peak at 0 ° C. or lower. is required.

  Specifically, solid viscoelasticity measurement is performed by applying a sinusoidal strain of a specific frequency to a strip-shaped sample piece and detecting the generated stress. Here, the frequency is 1 Hz and the measurement temperature is raised stepwise from −60 ° C. until the sample is melted and cannot be measured. Moreover, the magnitude of the strain is recommended to be 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. In the temperature range of 0 ° C. or lower, a sharp peak is generally observed.The peak of the tan δ curve below 0 ° C. is for observing the glass transition of the amorphous part, and in the present invention, this peak temperature is the glass transition temperature. Defined as Tg (° C).

(4) Propylene-ethylene block copolymer production method / metallocene catalyst The method for producing the propylene-ethylene block copolymer (c) used in the present invention requires the use of a metallocene catalyst. .
In the propylene-ethylene random copolymer (c), when the molecular weight and crystallinity distribution are wide, when mixed with the propylene polymer (a) and the ethylene polymer (a), the interface with these polymers As a result, the compatibilizing effect may be hindered. In order to prevent such a phenomenon, the propylene-ethylene block copolymer (c) used in the present invention needs to be polymerized using a metallocene catalyst that has a narrow molecular weight and crystallinity distribution.

The type of the metallocene-based catalyst is not particularly limited as long as it can produce a copolymer having the performance of the present invention. However, in order to satisfy the requirements of the present invention, for example, the following components ( It is preferable to use a metallocene catalyst comprising a), (b), and component (c) used as necessary.
Component (a): At least one metallocene transition metal compound selected from transition metal compounds represented by the following general formula Component (b): At least one selected from the following (b-1) to (b-4) (B-1) a particulate carrier on which an organoaluminoxy compound is supported,
(B-2) Particulate carrier carrying an ionic compound or Lewis acid capable of reacting with component (A) to convert component (A) into a cation (b-3) Solid acid fine particles (b- 4) Ion exchange layered silicate Component (c): Organoaluminum compound

..Ingredient (a)
As the component (a), at least one metallocene transition metal compound selected from transition metal compounds represented by the following general formula can be used.
^{_{Q (C 5 H 4 -aR 1}} ) (C 5 H 4 -bR 2) MeXY
[Wherein Q represents a divalent linking group that bridges two conjugated five-membered ring ligands, Me represents a metal atom selected from titanium, zirconium, and hafnium, and X and Y represent a hydrogen atom, a halogen atom, An atom, a hydrocarbon group, an alkoxy group, an amino group, a nitrogen-containing hydrocarbon group, a phosphorus-containing hydrocarbon group or a silicon-containing hydrocarbon group is shown, and X and Y may be independently, that is, the same or different. R ¹ and R ² are hydrogen, hydrocarbon group, halogenated hydrocarbon group, silicon-containing hydrocarbon group, nitrogen-containing hydrocarbon group, oxygen-containing hydrocarbon group, boron-containing hydrocarbon group, or phosphorus-containing hydrocarbon group. Show. a and b are the number of substituents. ]

Specifically, Q represents a divalent linking group that bridges two conjugated five-membered ring ligands, and has, for example, a divalent hydrocarbon group, a silylene group, an oligosilylene group, or a hydrocarbon group as a substituent. Examples include a silylene group, an oligosilylene group, or a germylene group having a hydrocarbon group as a substituent. Among these, preferred is a silylene group having a divalent hydrocarbon group and a hydrocarbon group as a substituent.
X and Y represent a hydrogen atom, a halogen atom, a hydrocarbon group, an alkoxy group, an amino group, a nitrogen-containing hydrocarbon group, a phosphorus-containing hydrocarbon group, or a silicon-containing hydrocarbon group. Among these, hydrogen is preferable , Chlorine, methyl, isobutyl, phenyl, dimethylamide, diethylamide group and the like. X and Y may be independent, that is, may be the same or different.
R ¹ and R ² are hydrogen, hydrocarbon group, halogenated hydrocarbon group, silicon-containing hydrocarbon group, nitrogen-containing hydrocarbon group, oxygen-containing hydrocarbon group, boron-containing hydrocarbon group, or phosphorus-containing hydrocarbon group. Represents. Specific examples of the hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a phenyl group, a naphthyl group, a butenyl group, and a butadienyl group. In addition, as halogenated hydrocarbon group, silicon-containing hydrocarbon group, nitrogen-containing hydrocarbon group, oxygen-containing hydrocarbon group, boron-containing hydrocarbon group, or phosphorus-containing hydrocarbon group, methoxy group, ethoxy group, phenoxy group Typical examples include trimethylsilyl group, diethylamino group, diphenylamino group, pyrazolyl group, indolyl group, dimethylphosphino group, diphenylphosphino group, diphenylboron group, and dimethoxyboron group. In these, it is preferable that it is a C1-C20 hydrocarbon group, and it is especially preferable that they are a methyl group, an ethyl group, a propyl group, and a butyl group. By the way, adjacent R ¹ and R ² may combine to form a ring, on which a hydrocarbon group, halogenated hydrocarbon group, silicon-containing hydrocarbon group, nitrogen-containing hydrocarbon group, oxygen-containing You may have a substituent which consists of a hydrocarbon group, a boron containing hydrocarbon group, or a phosphorus containing hydrocarbon group.
Me is a metal atom selected from titanium, zirconium and hafnium, preferably zirconium and hafnium.

Among the components (a) described above, those preferable for the production of the propylene-ethylene random block copolymer (c) used in the present invention are a silylene group, a germylene group or an alkylene group having a hydrocarbon substituent. It is a transition metal compound comprising a ligand having a bridged substituted cyclopentadienyl group, substituted indenyl group, substituted fluorenyl group, substituted azulenyl group, particularly preferably a silylene group having a hydrocarbon substituent or a germylene group It is a transition metal compound comprising a ligand having a 2,4-position-substituted indenyl group and a 2,4-position-substituted azulenyl group which are cross-linked by
Non-limiting specific examples include dimethylsilylene bis (2-methyl-4-phenylindenyl) zirconium dichloride, diphenylsilylene bis (2-methyl-4-phenylindenyl) zirconium dichloride, dimethylsilylene bis (2-methyl). Benzoindenyl) zirconium dichloride, dimethylsilylenebis {2-isopropyl-4- (3,5-diisopropylphenyl) indenyl} zirconium dichloride, dimethylsilylenebis (2-propyl-4-phenanthrylindenyl) zirconium dichloride, dimethyl Silylene bis (2-methyl-4-phenylazurenyl) zirconium dichloride, dimethylsilylene bis {2-methyl-4- (4-chlorophenyl) azurenyl} zirconium dichloride, dimethylsilylene bi (2-Ethyl-4-phenylazurenyl) zirconium dichloride, dimethylsilylenebis (2-isopropyl-4-phenylazurenyl) zirconium dichloride, dimethylsilylenebis {2-ethyl-4- (2-fluorobiphenyl) azurenyl} zirconium Dichloride, dimethylsilylenebis {2-ethyl-4- (4-t-butyl-3-chlorophenyl) azurenyl} zirconium dichloride, and the like can be given. A compound in which the silylene group of these specific examples is replaced with a germylene group and zirconium is replaced with hafnium is also exemplified as a suitable compound. In addition, since the catalyst component is not an important element of the present invention, it avoids complicated listing and is limited to representative examples, but it is obvious that the effective range of the present invention is not limited thereby. It is.

..Ingredient (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 known component, and can be appropriately selected from known technologies and used. 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, JP-A No. 2003-105015, and the like.
Here, as the particulate carrier used for the component (b-1) and the component (b-2), inorganic oxides such as silica, alumina, magnesia, silica alumina, silica magnesia, magnesium chloride, magnesium oxychloride, chloride Examples thereof include inorganic halides such as aluminum and lanthanum chloride, and porous organic carriers such as polypropylene, polyethylene, polystyrene, styrene divinyl benzene copolymer, and acrylic acid copolymer.
Further, as a non-limiting specific example of the component (b), as the component (b-1), a particulate carrier on which methylalumoxane, isobutylalumoxane, methylisobutylalumoxane, aluminum butylboronate tetraisobutyl and the like are supported As component (b-2), triphenylborane, tris (3,5-difluorophenyl) borane, tris (pentafluorophenyl) borane, triphenylcarbonium tetrakis (pentafluorophenyl) borate, N, N-dimethyl Particulate carrier carrying anilinium tetrakis (pentafluorophenyl) borate, etc., component (b-3), alumina, silica alumina, magnesium chloride, etc., component (b-4), montmorillonite, zakonite, beidellite , Nontronic , Saponite, hectorite, stevensite, bentonite, smectite group such as taeniolite, vermiculite, and the like mica group. These may form a mixed layer.
Particularly preferred among the above components (B) is the ion-exchange layered silicate of component (b-4), and more preferred are chemical treatments such as acid treatment, alkali treatment, salt treatment, and organic matter treatment. It is an ion exchange layered silicate applied.

..Ingredient (c)
Examples of organoaluminum compounds used as component (c) as needed are:
General formula AlR _a P _3-a
(Wherein R is a hydrocarbon group having 1 to 20 carbon atoms, P is hydrogen, halogen, alkoxy group, a is a number of 0 <a ≦ 3), trimethylaluminum, triethylaluminum, tripropylaluminum, tri Trialkylaluminum such as isobutylaluminum or halogen or alkoxy-containing alkylaluminum such as diethylaluminum monochloride, diethylaluminum monomethoxide. In addition, aluminoxanes such as methylaluminoxane can also be used. Of these, trialkylaluminum is particularly preferred.

-Formation of a catalyst A component (a), a component (b), and a component (c) as needed are made to contact, and it is set as a catalyst. The contact method is not particularly limited, but the contact can be made in the following order. Moreover, this contact may be performed not only at the time of catalyst preparation but also at the time of prepolymerization with olefin or at the time of polymerization of olefin.
1) Contact component (a) and component (b) 2) Add component (c) after contacting component (a) and component (b) 3) Contact component (a) and component (c) 4) Add component (b) after contact 4) Add component (a) after contacting component (b) and component (c), or contact 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 1,000 μmol, particularly preferably 0.5 μmol to 500 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 to 100 μmol, particularly preferably 0.005 to 50 μmol, relative to 1 g of component (b). Therefore, the amount of the component (c) to the component (a) is preferably in the range of 10 ⁻⁵ to 50, particularly preferably 10 ^{−4 to} 5 in terms of the molar ratio of the transition metal.

The catalyst used in the propylene-ethylene block copolymer (c) of the present invention is preferably subjected to a prepolymerization treatment comprising a small amount of polymerization by contacting 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.

-Polymerization method-Sequential polymerization In producing and carrying out the propylene-ethylene block copolymer (c) used in the present invention, it is necessary to sequentially polymerize the component (A) and the component (B). By sequential polymerization, the component (A) and the component (B) having different ethylene contents are finely dispersed at the molecular level. By using the thus-obtained propylene-ethylene block copolymer (c), the propylene-based copolymer (a) and the ethylene-based polymer (b) are very uniformly and finely dispersed. A polymer can be obtained. This is an effect that cannot be obtained if the component (A) and the component (B) are separately polymerized and then melt-kneaded.
In the present invention, since a copolymer having a low molecular weight and easily sticking alone may be used as the component (B), the component (A) is polymerized in order to prevent problems such as adhesion to the reactor. It is necessary to use a method of polymerizing component (B).
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 a batch method, it is possible to polymerize component (A) and component (B) separately using a single reactor by changing the polymerization conditions with time. As long as the effects of the present invention are not impaired, a plurality of reactors may be connected in parallel.
In the case of a continuous process, it is necessary to use a production facility in which two or more reactors are connected in series because it is necessary to individually polymerize the component (A) and the component (B), but the effect of the present invention is not impaired. As long as each of the component (A) and the component (B) is used, a plurality of reactors may be connected in series and / or in parallel.

..Polymerization process As the polymerization process, an arbitrary polymerization method such as a slurry method, a bulk method, or a gas phase method can be used. 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.
Since component (B) is readily soluble in organic solvents such as hydrocarbons and liquefied propylene, it is desirable to use a gas phase method for the production of component (B). The production of component (A) is not particularly problematic regardless of which process is used, but when producing component (A) having relatively low crystallinity, a vapor phase method is used to avoid problems such as adhesion. It is desirable.
Therefore, it is most desirable to polymerize component (A) first by the bulk method or gas phase method and then polymerize component (B) by the gas phase method using the continuous method.

.. Other polymerization conditions The polymerization temperature can be used without any particular problem as long as it is within the usual temperature range. Specifically, a range of 0 ° C. to 200 ° C., more preferably 40 ° C. to 100 ° C. can be used.
The polymerization pressure varies depending on the process to be selected, but 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, more preferably 0.1 MPa to 50 MPa can be used. At this time, an inert gas such as nitrogen may coexist.
When the sequential polymerization of the component (A) in the first step and the component (B) in the second step is performed, it is desirable to add a polymerization inhibitor into the system in the second step. In the case of producing a propylene-ethylene block copolymer, if a polymerization inhibitor is added to the reactor for carrying out the ethylene-propylene random copolymerization in the second step, the particle properties (fluidity, etc.) of the resulting powder, gel, etc. Product quality can be improved. Various technical studies have been made on this method, and examples thereof include Japanese Patent Publication No. 63-54296, Japanese Patent Application Laid-Open No. 7-25960, and Japanese Patent Application Laid-Open No. 2003-2939. It is desirable to apply the method to the present invention.

(5) Method for Controlling Components of Propylene-Ethylene Block Copolymer (C) Each component of propylene-ethylene block copolymer (C) used in the present invention is controlled as follows. It can be manufactured to meet the structural requirements required for the polymer.

・ Ingredient (A)
For component (A), it is necessary to control the ethylene content [E] A and the elution peak temperature T (A).
In the present invention, in order to control [E] A within a predetermined range, the amount ratio of propylene and ethylene supplied to the polymerization tank in the first step may be appropriately adjusted. The relationship between the supply ratio and the ethylene content in the resulting propylene-ethylene random copolymer varies depending on the type of metallocene catalyst used, but the component (A) having the ethylene content [E] A required by adjusting the supply ratio is selected. Can be manufactured.
For example, when [E] A is controlled to be less than 7 wt%, the supply weight ratio of ethylene to propylene may be in the range of 0.3 or less, preferably in the range of 0.2 or less.
At this time, the component (A) has a narrow crystallinity distribution, and T (A) decreases as [E] A increases.
Therefore, in order for T (A) to satisfy the scope of the present invention, [E] A and their relationship are grasped and adjusted so as to take a target range.

・ Ingredient (B)
For component (B), it is necessary to control ethylene content [E] B and elution peak temperature T (B).
In the present invention, in order to control [E] B within a predetermined range, the ratio of ethylene supply to propylene in the second step may be controlled as in [E] A. For example, when [E] B is controlled to 3 to 27 wt%, the supply weight ratio of ethylene to propylene may be in the range of 0.005 to 6, preferably in the range of 0.01 to 3.
At this time, although the crystallinity distribution of the component (B) is slightly increased with the increase of the ethylene content, T (B) is decreased with the increase of [E] B, similarly to the component (A).
Therefore, in order to satisfy T (B) within the scope of the present invention, the relationship between [E] B and T (B) is grasped, and [E] B is controlled to be within a predetermined range. That's fine.

・ W (A) and W (B)
The amount W (A) of the component (A) and the amount W (B) of the component (B) change the ratio of the production amount of the first step for producing the component (A) and the production amount of the component (B). Can be controlled. For example, in order to increase W (A) and decrease W (B), it is only necessary to reduce the production amount of the second step while maintaining the production amount of the first step, which shortens the residence time of the second step. It can be easily controlled by lowering the polymerization temperature or increasing the amount of the polymerization inhibitor. The reverse is also true.
When actually setting the conditions, it is necessary to consider the activity decay. That is, in the range of the ethylene content [E] A and [E] B carried out in the present invention, generally, when the ratio of ethylene supply to propylene is increased in order to increase the ethylene content, the polymerization activity increases. The activity decay tends to increase. Therefore, in order to maintain the activity of the second step, it is necessary to suppress the polymerization activity of the first step. Specifically, in the first step, the ethylene content [E] A is lowered and the production amount W (A ), And if necessary, lower the polymerization temperature and / or shorten the polymerization time (residence time), or increase the ethylene content [E] B in the second step and increase the production W (B). If necessary, the conditions may be set by a method that raises the polymerization temperature and / or lengthens the polymerization time (residence time).

Single peak of tan δ curve The propylene-ethylene block copolymer (c) has a glass transition temperature Tg of 0 at which the tan δ curve obtained in the temperature-loss tangent curve obtained by solid viscoelasticity measurement shows a peak. Must have a single peak below ℃. In order for Tg to have a single peak, the difference between the ethylene content [E] A in component (A) and the ethylene content [E] B in component (B) [E] gap (= [E ] B- [E] A) may be 20 wt% or less, preferably 16 wt% or less, and [E] gap may be reduced to a range where Tg becomes a single peak in actual measurement.

According to the ethylene content [E] A in the component (A), the supply amount of ethylene to propylene during the polymerization of the component (B) so that the ethylene content [E] B in the component (B) falls within an appropriate range. By setting the ratio, a propylene-ethylene block copolymer (c) having a predetermined [E] gap can be obtained.
The Tg of the propylene-ethylene block copolymer (c) that does not have a phase separation structure as used in the present invention is the ethylene content [E] A in the component (A) and the ethylene in the component (B). It is affected by the content [E] B and the quantity ratio of both components. In the present invention, the amount of the component (B) is 5 to 70 wt%, but in this range, Tg is more strongly affected by the ethylene content [E] B in the component (B).
That is, Tg reflects the glass transition of the amorphous part. In the propylene-ethylene block copolymer (c) used in the present invention, the component (A) has crystallinity and a relatively amorphous part. This is because the component (B) is low crystalline or amorphous, and most of it is an amorphous part. Therefore, the value of Tg is almost controlled by [E] B, and the control method of [E] B is as described above.

(6) Content of Propylene-Ethylene Block Copolymer (U) The amount of propylene-ethylene block copolymer (U) in the propylene-based resin composition is determined based on the components (A), (I) and ( The total amount of c) must be in the range of 1 to 30 parts by weight, preferably 3 to 30 parts by weight.
If the content of the propylene-ethylene block copolymer (c) is too small, the compatibilizing effect is reduced, so that the effect of improving impact resistance and tensile elongation is reduced. If the content is more than 40 parts by weight, rigidity, heat resistance, etc. Becomes worse.

(7) Additives In the present invention, additives such as various antioxidants, nucleating agents, neutralizing agents, lubricants, ultraviolet absorbers, light stabilizers and the like used as stabilizers for propylene polymers are added. Can be blended.

  Specifically, as the antioxidant, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol-di-phosphite, di-stearyl-pentaerythritol-di-phosphite, bis ( 2,4-di-t-butylphenyl) pentaerythritol-diphosphite, tris (2,4-di-t-butylphenyl) phosphite, tetrakis (2,4-di-t-butylphenyl) -4 Phosphorous antioxidants such as 4,4'-biphenylene-diphosphonite, tetrakis (2,4-di-t-butyl-5-methylphenyl) -4,4'-biphenylene-diphosphonite, 2,6-di-t-butyl-p-cresol, tetrakis [methylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate)] methane, 1 3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate Phenolic antioxidants such as di-stearyl-ββ'-thio-di-propionate, di-myristyl-ββ'-thio-di-propionate, di-lauryl-ββ'-thio-di-propionate An antioxidant etc. are mentioned.

  As a specific example of the nucleating agent, a known nucleating agent can be used. For example, known nucleating agents such as sorbitol-based nucleating agent, octanol-based nucleating agent, amide-based nucleating agent, organic phosphate-based nucleating agent, aromatic phosphate esters, and talc can be used.

Specific examples of the neutralizer include calcium fatty acid stearate, zinc stearate, magnesium stearate, aluminum stearate, lithium stearate and other metal fatty acid salts, hydrotalcite (trade name: Kyowa Chemical Industry Co., Ltd. (A magnesium aluminum composite hydroxide salt represented by (1)), Mizukarak (a lithium aluminum composite hydroxide salt represented by the following general formula (2)), and the like.
Mg _1-x Al _x (OH) ₂ (CO ₃ ) _{x / 2} · mH ₂ O (1)
[Wherein x is 0 <x ≦ 0.5, and m is a number of 3 or less. ]
[Al ₂ Li (OH) ₆ ] _n X · mH ₂ O (2)
[Wherein, X is an inorganic or organic anion, n is the valence of the anion (X), and m is 3 or less. ]

  Specific examples of the lubricant include known lubricants, and examples thereof include fatty acid amides such as oleic acid amide, stearic acid amide, erucic acid amide, and behenic acid amide, butyl stearate, and silicone oil.

  Examples of the ultraviolet absorber include 2-hydroxy-4-n-octoxybenzophenone, 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2 And ultraviolet absorbers such as' -hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole.

  Examples of the light stabilizer include n-hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate, 2,4-di-t-butylphenyl-3 ′, 5′-di-t-butyl-4 ′. -Hydroxybenzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, dimethyl-2- (4-hydroxy-2,2,6,6-tetramethyl-1-piperidyl) ethanol succinate Condensate, poly {[6-[(1,1,3,3-tetramethylbutyl) amino] -1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetra Methyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]}, N, N′-bis (3-aminopropyl) ethylenediamine-2,4-bis [N-butyl-N- 1,2,2,6,6-pentamethyl-4-piperidyl) amino] -6-chloro-1,3,5-triazine condensate, and the like of the light stabilizer.

  Further, an amine-based antioxidant represented by the following formula (3) or the following general formula (4), 5,7-di-t-butyl-3- (3,4-di-methyl-phenyl) -3H- Examples include lactone antioxidants such as benzofuran-2-one, and vitamin E antioxidants such as the following general formula (5).

［式中のＲ^１とＲ^２は、炭素数１４〜２２のアルキル基］

[Wherein R ¹ and R ² are alkyl groups having 14 to 22 carbon atoms]

In addition, an antistatic agent, a dispersant such as a fatty acid metal salt, an antiblocking agent, an organic peroxide, and the like can be blended within a range that does not impair the object of the present invention.
The propylene-based resin composition comprising the propylene-based polymer (a), the ethylene-based polymer (I), and the propylene-ethylene block copolymer (c) of the present invention maintains the characteristics of this composition to the maximum. However, in order to impart other characteristics or functions, other polymers, copolymers, and elastomers can be arbitrarily blended. Specifically, ethylene-acrylate copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylonitrile copolymer, ethylene-propylene copolymer elastomer, ethylene-propylene-diene copolymer elastomer, ethylene-butene copolymer Combined elastomer, ethylene-hexene copolymer elastomer, ethylene-octene copolymer elastomer, propylene-ethylene copolymer elastomer or plastomer, styrene rubber, natural rubber, diene rubber, chloroprene rubber, nitrile rubber, polysaccharide, natural Various resins such as resins, elastomers, or plastomers can be arbitrarily blended in an amount of about 1 to 30 parts by weight with respect to 100 parts by weight of the propylene-based resin composition.
Similarly, 1-30 parts by weight of various inorganic fillers such as alumina, carbon black, calcium carbonate, silica, gypsum, talc, mica, kaolin, clay, titanium oxide, and alumina as fillers, preferably 1-10 parts by weight. A part can also be added arbitrarily.

(8) Propylene resin composition production method The propylene resin composition of the present invention comprises a propylene polymer (A), an ethylene polymer (I), a propylene-ethylene block copolymer (U), and Other additives and the like used as necessary can be obtained by putting them into a Henschel mixer, a super mixer, a ribbon blender or the like and mixing (dry blending). Alternatively, after dry blending, it is obtained by further melt-kneading (melt blending) in a temperature range of about 180 to 280 ° C. with a normal single screw extruder, twin screw extruder, Banbury mixer, plastic bender, roll or the like. You can also. In addition, dry blend and melt blend are individually added by adding necessary additives to propylene polymer (a), ethylene polymer (b), and propylene-ethylene block copolymer (c). It can also be obtained by dry blending each polymer after the above.

(9) Molded product The molded product of the present invention is obtained by molding the propylene-based resin composition by various molding machines such as a known injection molding machine, extrusion molding machine, film molding machine, blow molding machine, and fiber molding machine. It is obtained by this. It is particularly suitable for applications that require impact resistance and at the same time require tensile elongation, weld strength, surface hardness, scratch resistance, whitening resistance, gloss, and transparency.

  Specifically, food containers (pudding containers, jelly containers, yogurt containers, other dessert containers, side dish containers, tea bowl steamers, instant noodle containers, cooked rice containers, retort containers, lunch boxes, etc.), beverage containers (drink bottles, chilled containers, etc.) Coffee containers, one-hand cup containers, other beverage containers, etc.), caps (plastic bottle caps, 1-piece caps, 2-piece caps, instant coffee caps, seasoning caps, cosmetic container caps, etc.), pharmaceutical containers (infusion bags, blood) Bags, prefilled syringes, kit formulations, eye drops containers, drug containers, drug containers, liquid long-term storage containers, press-through packages, strip packages, sachets, plastic vials, etc., and other various containers (ink containers, cosmetic containers, shampoo containers) , Detergent containers, etc.) Medical devices (Disposable syringes and parts thereof, catheters and tubes, vacuum blood collection tubes, surgical nonwovens, blood filters, disposable devices such as blood circuits, parts of artificial organs such as artificial lungs and colostomy, dialyzers, test tubes , Inspection kits, sutures, poultice base materials, parts for dental materials, parts for orthopedic materials, contact lens cases, etc., daily necessities (costume cases, buckets, washbasins, bath / toiletries, writing utensils, stationery, etc. , Containers, toys, cooking utensils, other cases, etc.), automotive parts (instruments, bumpers, lamps, etc.), electrical / electronic parts (members / housing for various electrical equipment, semiconductor transport containers, optical parts, various information media) Cases, solar cell encapsulants, etc.), building materials, industrial materials, films, fibers, sheets, etc. are preferred.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited at all by these description.
In each of the examples and comparative examples, the physical properties used were measured by the following methods: propylene polymer (A), ethylene polymer (I), propylene-ethylene block copolymer (U), and others. As additives, the following were used.

[1. Measurement method]
(1) TREF
The TREF measurement method is as described above, and the apparatus and conditions are as follows.
<Device>
(TREF part)
TREF column: 4.3 mmφ × 150 mm stainless steel column Column packing material: 100 μm Surface inactive glass beads Heating method: Aluminum heat block Cooling method: Peltier element (Peltier element is cooled by water)
Temperature distribution: ± 0.5 ° C
Temperature controller: Digital program controller KP1000 (valve oven) manufactured by Chino Co., Ltd.
Heating method: Air bath oven Measurement temperature: 140 ° C
Temperature distribution: ± 1 ° C
Valve: 6-way valve 4-way valve (Sample injection part)
Injection method: Loop injection method Injection volume: Loop size 0.1ml
Inlet heating method: Aluminum heat block measurement temperature: 140 ° C
(Detection unit)
Detector: Infrared detector with fixed wavelength MIRAN 1A manufactured by FOXBORO
Detection wavelength: 3.42 μm
High-temperature flow cell: Micro flow cell for LC-IR Optical path length: 1.5 mm Window shape: 2φ x 4 mm long circle Synthetic sapphire window measurement temperature: 140 ° C
(Pump part)
Liquid feed pump: SSC-3461 pump manufactured by Senshu Scientific Co., Ltd. <Measurement conditions>
Solvent: o-dichlorobenzene (containing 0.5 mg / mL BHT)
Sample concentration: 5 mg / mL
Sample injection volume: 0.1 mL
Solvent flow rate: 1 mL / min

(2) Preparation of test pieces Various test pieces were molded by a Toshiba Machine EC-100 injection molding machine at a molding temperature of 220 ° C and a mold temperature of 40 ° C, using JIS family molds.
(3) Solid Viscoelasticity Measurement A 10 mm × 18 mm × 2 mmt strip cut out from a molded sheet obtained by injection molding was used as a test piece. The apparatus used was ARES manufactured by Rheometric Scientific. The frequency is 1 Hz. The measurement temperature was raised stepwise from −60 ° C., and the measurement was performed until the sample melted and became impossible to measure. The strain was performed in the range of 0.1 to 0.5%.

(4) Calculation of amount of each component It calculated by the method mentioned above using TREF.
(5) Calculation of ethylene content
The ethylene content in the random copolymer was measured by infrared spectroscopy using a characteristic absorber of 733 cm ⁻¹ with an ethylene / propylene random copolymer whose composition was verified by ¹³ C-NMR as a reference substance. The test piece used was a pellet made into a film having a thickness of about 500 microns by press molding.

(6) Peak of tan δ curve The sample used was a 10 mm width × 18 mm length × 2 mm thickness strip cut out from a 2 mm thick sheet injection molded under the following conditions. The apparatus used was ARES manufactured by Rheometric Scientific. The frequency is 1 Hz. The measurement temperature was raised stepwise from −60 ° C., and the measurement was performed until the sample melted and became impossible to measure. The strain was performed in the range of 0.1 to 0.5%.
<Conditions for creating specimens>
Standard number: JIS-K7152 (ISO294-1)
Molding machine: TU-15 injection molding machine manufactured by Toyo Machine Metal Co., Ltd. Molding machine set temperature: 80, 80, 160, 200, 200, 200 ° C. from below the hopper
Mold temperature: 40 ℃
Injection speed: 200 mm / sec (speed in the mold cavity)
Injection pressure: 800 kgf / cm ²
Holding pressure: 800 kgf / cm ²
Holding time: 40 seconds Mold shape: Flat plate (thickness 2 mm, width 30 mm, length 90 mm)

(7) MFR: Measured at a temperature of 230 ° C. and a load of 21.2 N according to JIS K7210. However, the measurement temperature for the polyethylene polymer was 190 ° C.
(8) Melting peak temperature: Using RDC220U manufactured by Seiko Instruments Inc. as a DSC tester, taking 5.0 mg of sample, holding it at 200 ° C. for 5 minutes, and then crystallizing to 40 ° C. at a rate of temperature decrease of 10 ° C./min Further, the melting peak temperature when melted at a heating rate of 10 ° C./min was measured.

(9) Molecular weight distribution: measured by the method described above.
(10) Density: Measured by a density gradient tube method in accordance with JIS K7112-1980 “Method for measuring density and specific gravity of plastic”.
(11) Flexural modulus: measured at 23 ° C. according to JIS K7203-1982 “Bending test method of hard plastic”. This value is an indicator of the hardness or flexibility of the plastic.

(12) Izod (IZOD) impact strength: Measured at 23 ° C. using a notched test piece according to JIS K7110-1984 “Izod impact test method for hard plastic”. The higher this value is, the stronger the strength when giving an impact and the harder it is to break.
(13) Tensile properties: Based on JIS K7113-1981 “Plastic Tensile Test Method”, measurement was performed at 23 ° C. and a tensile rate of 50 mm / min using a No. 2 test piece punched from a sheet having a thickness of 2 mm. In general, the larger the tensile elongation, the harder it is to break even if it is deformed.

(14) Weld strength: Using the tensile test piece formed by using a mold having a shape in which resin flows in from two-way gates and the resin from both sides abuts at the center of the test piece, the tensile strength is as described above. A test was conducted. When the tensile elongation when this test piece is used is significantly smaller than the normal tensile elongation, it indicates that the strength at the butt portion (weld portion) is reduced.
(15) Rockwell hardness: Measured at 23 ° C. using an R scale according to JIS K7202-1982 “Plastic Rockwell hardness test method”. It shows that the surface of a molded article is so hard that this value is high, and it is hard to be damaged.

(16) Scratch resistance:
A movement in which a 2 mm-thick flat test piece is loaded on a scratch tester (HEIDON Tribogear TYPE18L) with a tip radii of 150 μm and a conical sapphire scratch needle applied to it. By moving the table at a constant speed (600 mm / min), the scratching needle in contact with the surface of the test piece was slid linearly to scratch the surface of the test piece. Thereafter, the test piece was observed using a confocal laser microscope (Keyence V9700), and the minimum load at which scaly traces were observed on the test piece was recorded as the load at which scratches started to be applied. Larger values indicate that scratches are less likely to occur even under strong pressure.

(17) Whitening resistance: A load having a different weight was dropped from a height of 30 cm on a test piece having a thickness of 2 mm using a DuPont impact drop tester. At that time, the minimum weight load at which the test piece was broken or whitened was recorded and used as an index of whitening resistance. Larger values indicate that it is more difficult to whiten even when subjected to a strong impact.
(18) Gloss: According to JIS K7105-1981 “Testing method for optical properties of plastics”, the glossiness was measured at a 60 ° incident angle and reflection angle using a test piece having a thickness of 2 mm. The larger this value is, the more glossy the molded product is, and the better the design.
(19) Haze: Haze (cloudiness value) was measured using a test piece having a thickness of 2 mm in accordance with JIS K7105-1981 “Testing methods for optical properties of plastics”. The smaller this value, the clearer the molded product and the better the design.

[2. Materials used]
(1) Propylene polymer (A)
Propylene-ethylene random copolymer (hereinafter referred to as “RPP1”):
Product name "Novatec MG03BQ" manufactured by Nippon Polypro Co., Ltd. MFR with Ziegler-Natta catalyst: 30 g / 10 min, ethylene content = 2.3 wt%

(2) Ethylene polymer (I)
-Ethylene-hexene copolymer (hereinafter referred to as “PE1”):
Product name “Kernel KS571” manufactured by Nippon Polyethylene Co., Ltd. MFR (190 ° C) 12 with metallocene catalyst, density 0.907
-Ethylene-hexene copolymer (hereinafter referred to as “PE2”):
Product name "Kernel KS340T" manufactured by Nippon Polyethylene Co., Ltd. MFR (190 ° C) 3.5 with metallocene catalyst, density 0.880

(3) Propylene-ethylene block copolymer (c)
Propylene-ethylene block copolymers (PP-1) and (PP-2) satisfying the requirements of the present invention were obtained by the following Production Examples 1 and 2. Further, according to Production Example 3 below, a propylene-ethylene block copolymer (PP-3) was obtained. PP-3 does not satisfy the requirements of the present invention.

(Production Example 1: Production of PP-1)
・ Manufacture of 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 montmorillonite (Mizusawa Chemical Co., Ltd. Benclay SL; average particle size = 50 μm) was further 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 liquid (filtrate) exceeded 3.5. The collected cake was dried at 110 ° C. overnight under a nitrogen atmosphere. The weight after drying was 707 g. The chemically treated silicate was dried by a kiln dryer.

Catalyst preparation:
200 g of the dry silicate obtained above was introduced into a glass reactor with an internal volume of 3 liters, and 1160 ml of mixed heptane and 840 ml of a heptane solution of triethylaluminum (0.60 M) were added and stirred at room temperature. . After 1 hour, the mixture was washed with mixed heptane to prepare 2.0 l of silicate slurry. Next, 9.6 ml of a heptane solution of triisobutylaluminum (0.71 M / L) was added to the prepared silicate slurry and reacted at 25 ° C. for 1 hour. In parallel, [(r) -dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4H-azurenyl}] zirconium] (according to Examples in JP-A-10-226712) 33.1 ml of a triisobutylaluminum heptane solution (0.71 M) was added to 2180 mg (3 mmol) and 870 ml of mixed heptane, and the mixture reacted at room temperature for 1 hour was added to the silicate slurry. Stir for hours.

Prepolymerization:
Subsequently, 2.1 liters of normal heptane was introduced into a stirring autoclave having an internal volume of 10 liters that had been sufficiently substituted with nitrogen, and maintained at 40 ° C. The previously prepared silicate / metallocene complex slurry was introduced therein. When the temperature was stabilized at 40 ° C., propylene was supplied at a rate of 100 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 remaining monomer was purged, stirring was stopped and the mixture was allowed to stand for about 10 minutes, and then about 3 liters of the supernatant was decanted. Subsequently, 9.5 ml of a heptane solution of triisobutylaluminum (0.71 M / L) and 5.6 liters of mixed heptane were added, and the mixture was stirred at 40 ° C. for 30 minutes and allowed to stand for 10 minutes. Removed liters. This operation was further repeated 3 times. When the component analysis of the final supernatant was performed, the concentration of the organoaluminum component was 1.23 mmol / L and 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. By this operation, a prepolymerized catalyst containing 2.1 g of polypropylene per 1 g of catalyst was obtained.

-Polymerization (i) 1st superposition | polymerization process The superposition | polymerization apparatus of the flow sheet shown in FIG. 2 was used.
After introducing 35 kg of seed polymer in advance into a horizontal polymerization vessel 1 (L / D = 3.7, internal volume 100 L) having a stirring blade, nitrogen gas was circulated for 3 hours. Thereafter, the temperature was raised to 65 ° C. while introducing propylene, ethylene and hydrogen. The pressure of the reactor was set to 2.2 MPaG, and the conditions were adjusted so that ethylene / propylene (molar ratio) = 0.06 and hydrogen / propylene (molar ratio) = 0.0002 in the gas, and then the prepolymerized catalyst 0.9 g / hr (amount including the prepolymerized polymer) and triisobutylaluminum as an organoaluminum compound were fed so as to be constant at 15 mmol / hr. Propylene-ethylene random copolymer (A) was produced while maintaining the reaction temperature of 65 ° C., the reaction pressure of 2.2 MPaG, and the above conditions of ethylene / propylene and hydrogen / propylene.
The reaction heat was removed by the heat of vaporization of the raw material propylene supplied from the pipe 3. The unreacted gas discharged from the polymerization reactor was cooled and condensed outside the reactor system through the pipe 4 and refluxed to the polymerization reactor 1. The propylene-ethylene random copolymer (A) obtained by the main polymerization is intermittently withdrawn from the polymerization vessel 1 through the pipe 5 so that the retained level of the polymer is 65% by volume of the reaction volume. The polymerization vessel 10 was supplied to the process. At this time, the production amount of the propylene-ethylene random copolymer (A) was 7 kg / hr. A part of the propylene-ethylene random copolymer (A) was extracted from the pipe 5 and used as a sample for analysis.

(Ii) Second polymerization step The propylene-ethylene random copolymer (A) from the first polymerization step is intermittently added to a horizontal polymerization vessel 10 (L / D = 3.7, internal volume 100 L) having a stirring blade. Then, propylene and ethylene were copolymerized. The reaction conditions are a stirring speed of 18 rpm, a reaction temperature of 70 ° C., a reaction pressure of 2.1 MPaG, and gas ethylene / propylene (molar ratio) = 0.43, hydrogen / propylene + ethylene (molar ratio) = 0.0003. Adjusted. Oxygen gas was supplied from the piping 7 as a polymerization activity inhibitor for adjusting the polymerization amount of the propylene-ethylene random copolymer (B).
The reaction heat was removed by the heat of vaporization of the raw material propylene supplied from the pipe 6. The unreacted gas discharged from the polymerization reactor was cooled and condensed outside the reactor system through the pipe 8 and refluxed to the polymerization vessel 10. The propylene-based block copolymer (PP-1) produced in the second doubling process is intermittently withdrawn from the polymerizer 10 through the pipe 9 so that the retained level of the polymer is 50% by volume of the reaction volume. It was.

(Iii) Analytical result of propylene-based block copolymer (PP-1) The propylene-based block copolymer (PP-1) obtained above has an MFR of 6 g / 10 min, a melting peak temperature Tm of 133 ° C., a component The content of (A) is 56 wt%, the content of component (B) is 44 wt%, the MFR of component (A) is 6 g / 10 min, the ethylene content is 1.8 wt%, ethylene in component (B) The content was 11% by weight. Production conditions and physical properties of PP-1 are shown in Table 3.

(Production Example 2: Production of PP-2)
In Production Example 1, hydrogen / propylene (molar ratio) in the first polymerization step was 0.0005, the feed amount of the prepolymerization catalyst was 0.6 g / hr, and ethylene / propylene (molar ratio) in the second polymerization step was 0.00. A propylene-based block copolymer (PP-2) was produced in the same manner as in Production Example 1 except that it was changed to 4.
The propylene-based block copolymer (PP-2) obtained above has an MFR of 20 g / 10 min, a component (A) content of 56 wt%, a component (B) content of 44 wt%, and a Tm of 133%. The MFR of component (A) was 42 g / 10 minutes, the ethylene content was 1.8 wt%, and the ethylene content in component (B) was 10 wt%. Production conditions and physical properties of PP-2 are shown in Table 3.

(Production Example 3: Production of PP-3)
In Production Example 1, hydrogen / propylene (molar ratio) in the first polymerization step was 0.0005, the feed amount of the prepolymerization catalyst was 0.6 g / hr, and ethylene / propylene (molar ratio) in the second polymerization step was 0.00. A propylene-based block copolymer (PP-3) was produced in the same manner as in Production Example 1 except that 85.
The propylene-based block copolymer (PP-3) obtained above has an MFR of 20 g / 10 min, a content of component (A) of 56 wt%, a Tm of 133 ° C., and a content of component (B) of 44 wt. %, The MFR of component (A) was 42 g / 10 min, the ethylene content was 1.8 wt%, and the ethylene content in component (B) was 20 wt%. In the temperature-loss tangent curve obtained by solid viscoelasticity measurement, the tan δ curve had two peaks at 0 ° C. or lower. Production conditions and physical properties of PP-3 are shown in Table 3.

(3) Nucleator / Organic Phosphate Metal Salt Compound Nucleator ADEKA product name “ADK STAB NA-21” (hereinafter referred to as “NA11”)
(4) Neutralizing agent / calcium stearate (hereinafter referred to as “CaSt”)

(5) Antioxidants and hindered phenolic antioxidants:
Tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxylphenyl) propionate] methane Product name “Irganox 1010” (hereinafter referred to as “IR1010”) manufactured by BASF Corporation.
・ Phosphorus antioxidants:
Tris (2,4-di-tert-butylphenol) phosphite BASF's trade name “Irgaphos 168” (hereinafter referred to as “IF168”)

(Examples 1-4, Comparative Examples 1-5)
Each of the components described above was prepared at a blending ratio (all parts by weight) shown in Table 4, and after dry blending with a super mixer, it was melt-kneaded using a 35 mm diameter twin screw extruder. Extruded pellets from the die at a die outlet temperature of 230 ° C. The obtained pellets were injection molded by an injection molding machine at a resin temperature of 230 ° C., an injection pressure of 600 kg / cm ^2, and a mold temperature of 40 ° C. to prepare test pieces. The physical properties were measured using the obtained test pieces. The results are shown in Table 4.

As is apparent from Table 4, in Examples 1 and 2, two types of the propylene-ethylene block copolymer (c) of the present invention were added to the propylene polymer (a) and the ethylene polymer (b). It is a blended part by weight. It can be seen that, compared with Comparative Example 1 containing only the propylene-based polymer (A), impact resistance is improved while maintaining transparency, and an excellent physical property balance is obtained.
In Comparative Example 2, the propylene-ethylene block copolymer (U) was not used, but only two types of propylene polymer (A) and ethylene polymer (I) were blended. Compared to the system, Examples 1 and 2 have substantially the same impact resistance, but the tensile elongation at break is good, and it is understood that there is no decrease in tensile elongation at break even with welded test pieces. Furthermore, it is greatly superior in terms of surface hardness, scratch resistance, whitening resistance, gloss, and transparency. The propylene-ethylene block copolymer (c) makes the entire composition a fine and uniform dispersion. It can be seen that the physical property balance is greatly improved.
In Comparative Example 3, a propylene-ethylene block copolymer (PP-3) that does not satisfy the requirements of this patent was used in place of the propylene-ethylene block copolymer (c). It can be seen that the effects of improving the strength, surface hardness, scratch resistance, whitening resistance, gloss and transparency are inferior to those of Examples 1 and 2.
In Examples 3 and 4, and Comparative Examples 4 and 5, the type of the ethylene polymer (A) in the systems of Examples 1, 2 and Comparative Example 2 was changed. Since the ethylene polymer (A) used here has a low MFR, the dispersibility with respect to the propylene polymer (A) is further deteriorated. As a result, in Comparative Examples 4 and 5, the tensile elongation, weld strength, surface hardness, scratch resistance, whitening resistance, gloss, and transparency were further reduced as compared with Comparative Examples 3 and 4. 4, it can be seen that there is a considerable improvement in all these items.

  The propylene-based resin composition of the present invention and a molded product thereof are excellent in impact resistance, and need to have impact resistance easily by a known molding method. At the same time, tensile elongation, weld strength, surface hardness, A molded product having excellent scratch resistance, whitening resistance, gloss, and transparency can be provided. In addition, the propylene-based resin composition of the present invention and the molded product thereof are food containers, caps, medical instruments, medical containers, packaging films, stationery sheets, costume cases, daily necessities, automobiles, due to their excellent balance of physical properties. It is extremely useful for applications such as parts and electrical parts.

Claims (4)

30 to 98 parts by weight of propylene polymer (a), 1 to 40 parts by weight of ethylene polymer (a) and 1 to 30 parts by weight of propylene-ethylene block copolymer (c) satisfying the following (i) to (v) Part (however, the sum of (A), (I) and (U) is 100 parts by weight).
(I) Using a metallocene-based catalyst, 30 to 95 wt% of propylene-ethylene random copolymer component (A) having propylene homopolymer or ethylene content of 7 wt% or less in the first step, and from component (A) in the second step (Ii) Melt flow rate (MFR: 230 ° C. 2.16 kg) is obtained by sequential polymerization of 70 to 5 wt% of propylene-ethylene random copolymer component (B) containing 3 to 20 wt% of ethylene. (Iii) that the melting peak temperature (Tm) measured by the DSC method is in the range of 110 to 150 ° C. (iv) the molecular weight measured by the GPC method Distribution (Mw / Mn) is in the range of 1.5 to 4 (v) In the temperature-loss tangent curve obtained by solid viscoelasticity measurement, the tan δ curve is 0 ° C. It has a single peak under   The propylene-based copolymer (a) is a propylene homopolymer or a random copolymer of propylene and ethylene and / or an α-olefin having 4 to 12 carbon atoms, and ethylene and / or 4 to 12 carbon atoms. The propylene-based resin composition according to claim 1, wherein the α-olefin content is 0 to 7 wt%.   The propylene-based resin composition according to claim 1 or 2, wherein the ethylene-based polymer (I) is polymerized using a metallocene catalyst.   The molded article using the propylene-type resin composition in any one of Claims 1-3.

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