JP2022102668A - Propylene-based resin composition and film using the same - Google Patents

Abstract

To provide a propylene-based resin composition which is excellent in an effect for suppressing a blocking phenomenon generated at the time of high temperature heating treatment while maintaining excellent flexibility, transparency and low temperature impact resistance, and a film using the same.SOLUTION: A propylene-based resin composition contains 35-88 wt.% of a propylene-based resin (A) satisfying conditions (A-i) to (A-iii), 10-35 wt.% of an ethylene-α-olefin copolymer (B) satisfying conditions (B-i) to (B-ii), 1-15 wt.% of a propylene homopolymer (C) satisfying condition (C-i), and 1-15 wt.% of a propylene homopolymer (D) satisfying condition (D-i), in which the total of the propylene-based resin (A), the ethylene-α-olefin copolymer (B), the propylene homopolymer (C) and the propylene homopolymer (D) is 100 wt.%.SELECTED DRAWING: None

Description

The present invention relates to a propylene-based resin composition and a film using the same, and more specifically, it is excellent in flexibility, transparency and low-temperature impact resistance, and has an effect of suppressing a blocking phenomenon generated during high-temperature heat treatment. The present invention relates to a propylene-based resin composition capable of obtaining a film having excellent strength and appearance because of its superiority, and a film using the same.

Films obtained from propylene-based resins have excellent heat resistance and optical properties such as flexibility, transparency, and gloss, and are therefore widely used as various packaging films and containers. .. However, in recent years, in addition to these characteristics, retorts and high-temperature and high-humidity (high-pressure steam) sterilization fields that require blocking resistance have been developed.
In response to these requirements, the applicant has long been excellent in flexibility, transparency, and strength (drop resistance, low temperature impact resistance), and at the time of multilayer molding, appearance defects such as surface roughness and thickness variation occur. Contains a specific propylene-ethylene random copolymer component obtained by step-growth polymerization, which is highly moldable and difficult to mold, and has an excellent effect of suppressing the phenomenon of molten resin flowing and thinning during secondary processing such as heat sealing. A propylene-based resin containing a specific proportion of an ethylene-α-olefin copolymer having a specific density and MFR, and a propylene-based (co) polymer having a specific melting peak temperature. We have made inventions and applications for resin compositions (see, for example, Patent Document 1).

However, it has been found that the propylene-based resin composition causes a problem that blocking resistance is difficult to be exhibited when a bag made from the obtained film is used next in a retort or a high-temperature and high-humidity sterilization step. ..

In particular, when products are stacked and subjected to high-temperature and high-humidity treatment, there is a tendency that the bags tend to block each other.
As described above, there has been a demand for a film that does not cause the above-mentioned problems even under high temperature and high humidity treatment conditions.

Japanese Unexamined Patent Publication No. 2010-138211

A film made of a propylene-based resin composition has excellent flexibility, transparency, and low-temperature impact resistance, and is rich in formability such as poor appearance such as surface roughness and thickness variation during multilayer molding, and heat. In order to sufficiently suppress the phenomenon that the molten resin flows and becomes thin during secondary processing such as sealing, a propylene-based resin containing a specific propylene-ethylene random copolymer component obtained by step-growth polymerization is specified. It is effective to use an ethylene-α-olefin copolymer having a density of, an ethylene-α-olefin copolymer having an MFR, and a propylene-based (co) polymer having a specific melting peak temperature. However, when the films containing the propylene-based (co) polymer are layered and subjected to high-temperature and high-humidity treatment, there tends to be a problem that the bags are easily blocked from each other.
Therefore, an object of the present invention is to provide a propylene-based resin composition having an excellent effect of suppressing a blocking phenomenon generated during a high-temperature heat treatment while maintaining excellent flexibility, transparency and low-temperature impact resistance, and a film using the same. To provide.

The present inventor has conducted various studies and analyzes to solve the above problems, and these problems are caused by the fact that the propylene-based resin composition has a low MFR and an extremely small amount of high crystal components. It was found that a film having a high surface roughness could not be formed during film forming, and a blocking phenomenon occurred between the films during high temperature and high humidity treatment. Then, it was found that a low MFR and a high crystalline component are required to solve this problem. On the other hand, since the flexibility is impaired when a high crystal component is added, it is said that the balance between transparency and flexibility can be maintained by imparting flexibility by adding a specific ethylene-α-olefin copolymer. The present invention was reached based on the above findings.

That is, according to the first invention of the present invention, the propylene-based resin (A) 35 to 88% by weight satisfying the following conditions (Ai) to (A-iii), and the following conditions (Bi) to (B). The ethylene-α-olefin copolymer (B) satisfying -ii) is 10 to 35% by weight, the propylene homopolymer (C) satisfying the following condition (C-i) is 1 to 15% by weight, and the following condition (D-) is satisfied. Contains 1 to 15% by weight of the propylene homopolymer (D) satisfying i) (provided that the propylene resin (A), the ethylene-α-olefin copolymer (B), the propylene homopolymer (C) and the propylene. A propylene-based resin composition, wherein the total of the homopolymers (D) is 100% by weight).
(A) Propylene resin (Ai) Propylene-α having a melting peak temperature Tm (A1) of 125 to 135 ° C. and an α-olefin content E (A1) of 1.5 to 3.0% by weight in DSC measurement. -The olefin random copolymer component (A1) is 50 to 60% by weight, and the propylene-ethylene random copolymer component (A2) having an ethylene content E (A2) of 8 to 14% by weight is 50 to 40% by weight. Being a metallocene-based propylene-α-olefin block copolymer (A) which is a multi-stage polymer composed of.
(A-ii) The melt flow rate (MFR (A): 230 ° C., 2.16 kg) is in the range of 4 to 10 g / 10 minutes.
(A-iii) In the temperature-loss tangent (tanδ) curve obtained by solid viscoelasticity measurement (DMA), the peak of the tanδ curve representing the glass transition observed in the range of -60 to 20 ° C is simply below 0 ° C. Show one peak.
(B) The density of the ethylene-α-olefin copolymer (Bi) is in the range of 0.860 to 0.900 g / cm ³ .
(B-ii) Melt flow rate (MFR (B): 190 ° C., 2.16 kg) is 2.0 g / 10 minutes or more.
(C) The melt flow rate of the propylene homopolymer (C-i) (MFR (C): 230 ° C., 2.16 kg) is in the range of 1.9 to 100 g / 10 minutes.
(D) The melt flow rate of the propylene homopolymer (Di) (MFR (D): 230 ° C., 2.16 kg) is less than 1.9 g / 10 minutes.

Further, according to the second invention of the present invention, in the first invention, the propylene homopolymer (C) and the propylene homopolymer (D) further have a melt flow rate ratio (MFR (C) / MFR (D). )) Is a propylene-based resin composition characterized by satisfying 5 to 300.
Further, according to the third aspect of the present invention, there is provided a film characterized by using the propylene-based resin composition of the first or second invention.

The basic requirements for the propylene-based resin composition of the present invention and the film using the same are a specific propylene-based resin (A), a specific ethylene-α-olefin copolymer (B), and a specific propylene homopolymer. (C) and the specific propylene homopolymer (D) are used.
The propylene-based resin (A) is a propylene-ethylene block copolymer obtained by using a metallocene catalyst, which is the main component of the propylene-based resin composition of the present invention, and has a good balance of transparency and flexibility in the obtained film. Can be granted.
The propylene resin (A) contains a propylene-ethylene random copolymer component (A1) that exhibits a melting peak temperature in a specific range controlled by the ethylene content in the first step, and a specific ethylene content in the second step. By having It is a propylene-ethylene block copolymer (A) obtained by sequentially polymerizing a propylene-ethylene random copolymer component (A2) that does not deteriorate the transparency, which is specified not to be taken.
The ethylene-α-olefin copolymer (B) is specified by the density and the melt flow rate, and can impart flexibility to the obtained film without impairing the transparency.
The propylene homopolymer (C) has a melt flow rate (MFR (C): 230 ° C., 2.16 kg) in the range of 1.9 to 100 g / 10 minutes, so that the fluidity adjustment performance during film molding can be improved. Can be granted.
The propylene homopolymer (D) has a melt flow rate (MFR (D): 230 ° C., 2.16 kg) of less than 1.9 g / 10 minutes, and thus has a function of increasing the film surface roughness during film molding. Can be granted.

Therefore, the propylene-based resin composition of the present invention is excellent in strength and appearance because it is excellent in flexibility, transparency and low-temperature impact resistance, and also has an excellent effect of suppressing the blocking phenomenon generated during high-temperature heat treatment. It can be suitably used as a film.

The present invention is obtained from a propylene-based resin composition containing a propylene-based resin (A), an ethylene-α-olefin copolymer (B), a propylene homopolymer (C) and a propylene homopolymer (D). It is a film. Hereinafter, the constituent components of the propylene-based resin composition of the present invention, the method for producing the propylene-based resin composition, and the film will be described in detail.

[I] Components of the propylene-based resin composition 1. Propylene resin (A)
The propylene-based resin (A) (hereinafter, also referred to as component (A)) used as the main component of the propylene-based resin composition of the present invention has high transparency, flexibility, and impact resistance. is required. In order to meet these requirements at a high level, the component (A) needs to meet the following requirements (A-i) to (A-iii).
Characteristics of Component (A) (A-i) Basic Regulations The component (A) used in the present invention uses a polymer-based catalyst and has a melting peak temperature Tm (A1) of 125 to 135 ° C. in DSC measurement, α-olefin. The propylene-α-olefin random copolymer component (A1) having a content E (A1) of 1.5 to 3.0% by weight is 50 to 60% by weight, and the ethylene content E (A2) is 8 to 14% by weight. Being a metallocene-based propylene-α-olefin block copolymer (A) which is a multi-stage polymer composed of 50 to 40% by weight of a propylene-ethylene random copolymer component (A2).

(I) Melting peak temperature Tm (A1) of component (A1)
The component (A1) produced in the first step is a component that determines crystallinity in the component (A) used in the present invention. In order to improve the heat resistance of the component (A), it is necessary that the melting peak temperature Tm (A1) (hereinafter, also referred to as Tm (A1)) of the component (A1) is high. When Tm (A1) is 135 ° C. or lower, flexibility and transparency are good. Further, when Tm (A1) is 125 ° C. or higher, the heat resistance becomes good and thinning is suppressed at the time of heat sealing. Tm (A1) needs to be in the range of 125 to 135 ° C, preferably 128 to 133 ° C.
Here, the melting peak temperature Tm is a value obtained by a differential scanning calorimeter (DSC manufactured by Seiko Instruments Co., Ltd.). Specifically, a sample amount of 5.0 mg was taken and held at 200 ° C. for 5 minutes. After that, it is a value obtained as the melting peak temperature when crystallized to 40 ° C. at a temperature lowering speed of 10 ° C./min and further melted at a temperature rising speed of 10 ° C./min.

(Ii) Ethylene content E (A1) of component (A1)
The melting peak temperature Tm (A1) of the component (A1) is controlled by the ethylene content, and the ethylene content E (A1) (hereinafter, also referred to as E (A1)) of the component (A1) in the present invention is. , 1.5 to 3.0% by weight. When E (A1) is 1.5% by weight or more, Tm (A1) is low and flexibility and transparency are good, and when E (A1) is 3.0% by weight or less, Tm (A1) is high. Therefore, thinning is suppressed during heat sealing.

(Iii) Percentage of component (A1) in component (A) Ratio of component (A1) in component (A) W (A1) is a component that imparts heat resistance to component (A). When W (A1) is 60% by weight or less, flexibility, impact resistance and transparency can be sufficiently exhibited. Therefore, the ratio of the component (A1) needs to be 60% by weight or less.
On the other hand, when the ratio of the component (A1) is 50% by weight or more, Tm (A1) is sufficient, the heat resistance is improved, and thinning is suppressed during heat sealing, so that the ratio of the component (A1) is Must be at least 50% by weight.

(Iv) Ethylene content E (A2) in component (A2)
The component (A2) produced in the second step is a component necessary for improving the flexibility, impact resistance and transparency of the component (A). In general, as the ethylene content of a propylene-ethylene random copolymer increases, the crystallinity decreases and the effect of improving flexibility increases. Therefore, the ethylene content E (A2) in the component (A2) (hereinafter, E) (A2) is also required to be 8% by weight or more. When E (A2) is 8% by weight or more, sufficient flexibility can be exhibited, preferably 10% by weight or more.
On the other hand, if E (A2) is 14% by weight or less in order to reduce the crystallinity of the component (A2), the compatibility is improved and the phase separation structure is not formed. If E (A2) is increased too much, the compatibility between the component (A1) and the component (A2) decreases, and the component (A2) forms a domain without being compatible with the component (A1). In such a phase-separated structure, if the refractive index of the matrix and the domain are different, the transparency is sharply lowered. Therefore, the E (A2) of the component (A2) in the component (A) used in the present invention needs to be 14% by weight or less, preferably 12% by weight or less.

(V) Percentage of component (A2) in component (A) Ratio of component (A2) in component (A) W (A2) is W (A2) because heat resistance is improved when it is 50% by weight or less. (A2) needs to be suppressed to 50% by weight or less.
On the other hand, when W (A2) is 40% by weight or more, the effect of improving flexibility and impact resistance can be obtained. Therefore, W (A2) needs to be 40% by weight or more.

Here, W (A1) and W (A2) are values obtained by the temperature temperature rise elution separation method (TREF), and ethylene contents E (A1) and E (A2) are values obtained by ¹³ C-NMR. Is.
Specifically, the following method is used.
Identification of W (A1) and W (A2) by the temperature temperature rise elution fractionation method (TREF) A method for evaluating the crystallinity distribution of a propylene-ethylene random copolymer by the temperature temperature rise elution fractionation method (TREF) is a method for those skilled in the art. For example, the following documents show detailed measurement methods.
・ G. Glockner, J. Mol. Apple. Polym. Sci. : Apple. Polym. Symp. 45, 1-24 (1990)
・ L. Wild, Adv. Polym. Sci. 98,1-47 (1990)
・ J. B. P. Soares, A. E. Hamielec, Polymer; 36,8,1639-1654 (1995)

The component (A) used in the present invention has a large difference in crystallinity between the component (A1) and the component (A2), and since it is produced using a metallocene-based catalyst, the crystallinity distribution of each is narrow. Therefore, there are very few intermediate components between the two, and it is possible to accurately separate both by TREF.
Specifically, in the present invention, the measurement is performed as follows. The sample is dissolved in o-dichlorobenzene (with 0.5 mg / ml BHT) at 140 ° C. to prepare a solution. After introducing this into a TREF column at 140 ° C., it is cooled to 100 ° C. at a temperature lowering rate of 8 ° C./min, followed by cooling to −15 ° C. at a temperature lowering rate of 4 ° C./min, and held for 60 minutes. Then, the solvent -15 ° C. o-dichlorobenzene (containing 0.5 mg / mlBHT) was flowed through the column at a flow rate of 1 ml / min, and the component dissolved in -15 ° C. o-dichlorobenzene in the TREF column. Is eluted for 10 minutes, then the column is linearly heated to 140 ° C. at a heating rate of 100 ° C./hour to obtain an elution curve.
In the obtained elution curve, the elution peaks of the component (A1) and the component (A2) are shown at the respective temperatures T (A1) and T (A2) due to the difference in crystallinity, and the difference is sufficiently large, so that it is in the middle. Almost separation is possible at the temperature T (A3) (= {T (A1) + T (A2)} / 2).
Here, if the integrated amount of the components eluted by T (A3) is defined as W (A2) by weight%, and the integrated amount of the portion eluted by T (A3) or higher is defined as W (A1) by weight%, W (A2). Corresponds to the amount of the component (A2), and the integrated amount W (A1) of the components eluted above T (A3) corresponds to the amount of the component (A1) having a relatively high crystallinity.
The equipment and specifications used for the measurement are shown below.
(TREF section)
TREF column: 4.3 mmφ x 150 mm Stainless steel column Column filler: 100 μm Surface-inactivated glass beads Heating method: Aluminum heat block Cooling method: Pelche element (Cooling of Pelche element is water cooling)
Temperature distribution: ± 0.5 ° C
Temperature controller: Chino Digital Program Controller KP1000 (valve oven)
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 amount: Loop size 0.1 ml
Injection inlet heating method: Aluminum heat block measurement temperature: 140 ° C
(Detection unit)
Detector: Fixed wavelength infrared detector FOXBORO MIRAN 1A
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 Oval synthetic sapphire Window plate Measurement temperature: 140 ° C
(Pump section)
Liquid feed pump: SSC-3461 pump manufactured by Senshu Kagaku Co., Ltd. [Measurement conditions]
Solvent: o-dichlorobenzene (containing 0.5 mg / ml BHT)
Sample concentration: 5 mg / ml
Sample injection amount: 0.1 ml
Solvent flow rate: 1 ml / min

Identification of ethylene contents E (A1) and E (A2) For the ethylene contents E (A1) and E (A2) of each component, each component is separated by a temperature rise column sorting method using a preparative type sorting device. ¹³ Ethylene content of each component is determined by C-NMR.
The temperature-increasing column separation method refers to, for example, a measuring method as disclosed in Macromolecukes 21 314-319 (1988). Specifically, the following method was used in the present invention.

Separated by heating column 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 kept at 140 ° C. Next, 200 ml of an o-dichlorobenzene solution (10 mg / ml) of the sample dissolved at 140 ° C. is introduced into the column. Then, the temperature of the column is cooled to 0 ° C. at a temperature lowering rate of 10 ° C./hour. After holding at 0 ° C. for 1 hour, the column temperature is heated to T (A3) (obtained in the TREF measurement) at a heating rate of 10 ° C./hour and held for 1 hour. The temperature control accuracy of the column through a series of operations shall be ± 1 ° C.
Then, while maintaining the column temperature at T (A3), 800 ml of T (A3) o-dichlorobenzene was flowed at a flow rate of 20 ml / min to remove the T (A3) soluble component present in the column. Elute and collect.
Next, the column temperature was raised to 140 ° C. at a heating rate of 10 ° C./min, allowed to stand at 140 ° C. for 1 hour, and then 800 ml of o-dichlorobenzene as a solvent at 140 ° C. was flowed at a flow rate of 20 ml / min. , T (A3) elutes and recovers insoluble components.
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 filtered and recovered, and then dried in a vacuum dryer overnight.

¹³ Measurement of ethylene content by C-NMR The ethylene content of each of the components (A1) and (A2) obtained by the above separation was measured by the proton complete decoupling method according to the following conditions. ¹³ C-NMR spectrum Is obtained by analyzing.
Model: JEOL Ltd. GSX-400 or equivalent device (carbon nuclear resonance frequency 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 Total number of integrations: 5,000 times or more Spectrum attribution may be performed with reference to, for example, Macromolecules 17 1950 (1984). Table 1 shows the attribution of the spectra measured under the above conditions. Symbols such as Sαα in the table follow the notation of Carman et al. (Macromolecules 10 536 (1977)), where P represents methyl carbon, S represents methylene carbon, and T represents methine carbon.

Hereinafter, assuming that "P" is a propylene unit in the copolymer chain and "E" is an ethylene unit, there may be six types of triads in the chain: PPP, PPE, EPE, PEP, PEE, and EEE. As described in Macromolecules 15 1150 (1982) and the like, 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 (Tββ)… (1)
[PPE] = k × I (Tβδ)… (2)
[EPE] = k × I (Tδδ)… (3)
[PEP] = k × I (Sββ)… (4)
[PEE] = k × I (Sβδ)… (5)
[EEE] = k × {I (Sδδ) / 2 + I (Sγδ) / 4} ... (6)
Here, [] indicates a fraction of triad, for example, [PPP] is a fraction of PPP triad in all triads.
therefore,
[PPP] + [PPE] + [EPE] + [PEP] + [PEE] + [EEE] = 1 ... (7)
Is. Further, k is a constant, I indicates the spectral intensity, and for example, I (Tββ) means the intensity of the peak of 28.7 ppm attributed to Tββ.
By using the relational expressions (1) to (7) above, the fraction of each triad can be obtained, and further, the ethylene content can be obtained by the following formula.
Ethylene content (mol%) = ([PEP] + [PEE] + [EEE]) x 100
The propylene-ethylene random copolymer of the present invention contains a small amount of propylene heterogeneous bonds (2,1-bonds and / or 1,3-bonds), which causes minute peaks shown in Table 2. ..

In order to obtain an accurate ethylene content, it is necessary to consider the peaks derived from these heterogeneous bonds and include them in the calculation, but it is difficult to completely separate and identify the peaks derived from the heterologous bonds, and the amount of heterologous bonds is small. Therefore, the ethylene content of the present invention is determined by using the relational expressions (1) to (7) as in the analysis of the copolymer produced by the Ziegler-Natta catalyst which does not substantially contain heterogeneous bonds. I will do it.
The conversion of ethylene content from mol% to weight% is performed using the following formula.
Ethylene content (% by weight) = (28 x X / 100) / {28 x X / 100 + 42 x (1-X / 100)} x 100
(Here, X is the ethylene content in mol% representation.)

(A-ii) Melt flow rate of component (A) MFR (A)
The melt flow rate MFR (A) (hereinafter, also referred to as MFR (A)) of the component (A) used in the present invention needs to be in the range of 4 to 10 g / 10 minutes.
The MFR (A) is determined by the ratio of the component (A1) and the respective MFR corresponding to the component (A2) (hereinafter, may be referred to as MFR (A1) and MFR (A2)), but in the present invention. Is MFR (A1) and MFR (A2) are arbitrary as long as the MFR (A) is in the range of 4 to 10 g / 10 minutes, as long as the object of the present invention is not impaired. However, when the difference between the two MFRs is small, the appearance is good, so it is desirable that both MFR (A1) and MFR (A2) are in the range of 4 to 10 g / 10 minutes.
When the MFR (A) is 4 g / 10 minutes or more, the resistance to the rotation of the screw becomes small, so that the motor load and the tip pressure decrease, and the surface of the film becomes rough, which causes a problem that the appearance is deteriorated. Therefore, the MFR (A) needs to be 4 g / 10 minutes or more, preferably 5 g / 10 minutes or more.
On the other hand, when MFR (A) is 10 g / 10 minutes or less, molding is stable and it becomes easy to obtain a uniform film. Therefore, MFR (A) is 10 g / 10 minutes or less, preferably 8 g / 10 minutes. Must be less than a minute.
Here, MFR is a value measured according to JIS K7210.

(A-iii) tanδ curve peak The component (A) used in the present invention is observed in the temperature-loss tangent (tanδ) curve obtained by solid viscoelasticity measurement (DMA) in the range of -60 to 20 ° C. It is necessary that the peak of the tan δ curve representing the glass transition shows a single peak below 0 ° C.
When the component (A) has a phase-separated structure, the peak is because the glass transition temperature of the amorphous portion contained in the component (A1) and the glass transition temperature of the amorphous portion contained in the component (A2) are different from each other. There will be multiple. In this case, there arises a problem that transparency is significantly deteriorated.
Normally, the glass transition temperature in the propylene-ethylene random copolymer is observed in the range of -60 to 20 ° C, and whether or not it has a phase-separated structure is determined by the tan δ curve obtained by solid viscoelasticity measurement in this range. The avoidance of the phase-separated structure, which is possible and affects the transparency of the film, is brought about by having a single peak below 0 ° C.

Here, the solid viscoelasticity measurement is specifically performed by applying a sine and cosine strain of a specific frequency to a strip-shaped sample piece and detecting the generated stress. The frequency is 1 Hz and the measurement temperature is gradually increased from -60 ° C until the sample melts and becomes unmeasurable. The size 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 positive contact (= loss modulus / storage modulus) defined by the ratio of these is plotted against the temperature. A sharp peak is shown in the temperature range of 0 ° C. or lower. Generally, the peak of the tan δ curve at 0 ° C. or lower observes the glass transition of the amorphous part. In the present invention, the peak temperature is the glass transition temperature Tg (° C.). ).

Method for Producing Component (A) As the method for producing component (A) used in the present invention, the method described in JP-A-2005-132979 can be used.

The ratio of the component (A) in the propylene-based composition The ratio of the component (A) in the propylene-based composition needs to be in the range of 35 to 88% by weight, preferably 45 to 85% by weight. Yes, more preferably 40-80% by weight.
When the content of the component (A) is 35% by weight or more, good flexibility and transparency can be obtained. On the other hand, when the content of the component (A) is 88% by weight or less, thinning during secondary processing such as heat sealing is suppressed.

2. 2. Ethylene-α-olefin copolymer (B)
Characteristics of Component (B) The ethylene-α-olefin copolymer (B) (hereinafter, also referred to as component (B)) used in the propylene-based resin composition of the present invention contains ethylene and has 3 to 20 carbon atoms. A copolymer obtained by copolymerizing the α-olefin of the above, wherein the α-olefin has 3 to 20 carbon atoms, for example, propylene, 1-butene, 1-pentene, 1-hexene, 1 -Exemplifications include octene and 1-heptene. The component (B) is a component that works to improve the transparency and flexibility of the propylene-based resin composition, and it is necessary to satisfy the following requirements (B-i) to (B-ii). ..
The propylene-based resin composition of the present invention is required to have flexibility and transparency. Regarding the transparency, if the refractive index of the component (B) is significantly different from that of the component (A), the transparency of the obtained film deteriorates, so it is also important to match the refractive index. The index of refraction can be controlled by the density, and it is important to keep the density in a specific range in order to obtain the transparency required in the present invention.
Further, although the component (A) is excellent in flexibility, the flexibility is impaired by the addition of the component (C). Therefore, it is necessary to add the component (B) that can improve the flexibility.

(B-i) Density The component (B) used in the present invention needs to have a density in the range of 0.860 to 0.900 g / cm ³ .
When the density is 0.860 g / cm ³ or more, the difference in refractive index becomes small and the transparency becomes good. Therefore, when the density is 0.860 g / cm ³ or more, the transparency required for the present invention is ensured. Can be done.
On the other hand, when the density is 0.900 g / cm ³ or less, the crystallinity becomes low and the flexibility becomes sufficient. Therefore, it is necessary to be 0.900 g / cm ³ or less, preferably 0.885 g / cm / cm. It is cm ³ or less.
Here, the density is a value measured according to JIS K7112.

(B-ii) Melt flow rate MFR (B) of component (B)
The propylene-based resin composition of the present invention needs to have appropriate fluidity in order to ensure moldability.
Therefore, when the melt flow rate MFR (B) (hereinafter, also referred to as MFR (B)) of the component (B) is 2.0 g / 10 minutes or more, the fluidity becomes sufficient and the dispersibility becomes good. This improves transparency. Therefore, the MFR (B) needs to be 2.0 g / 10 minutes or more, preferably 2.5 g / 10 minutes or more.
On the other hand, when the MFR (B) is 20 g / 10 minutes or less, the molding is stable and the film thickness does not fluctuate. Therefore, the MFR (B) is preferably 20 g / 10 minutes or less, and particularly preferably 15 g / 10 minutes or less.
Here, MFR is a value measured according to JIS K7210.

Method for Producing Component (B) The component (B) used in the present invention needs to have a small density difference from the component (A) in order to reduce the difference in refractive index from the component (A). Further, in order to suppress stickiness and bleed-out, it is desirable that the crystallinity and the molecular weight distribution are narrow. Therefore, it is desirable to use a metallocene-based catalyst capable of narrowing the crystallinity and molecular weight distribution for the production of the component (B).

(I) Metallocene-based catalyst As the metallocene catalyst, various known catalysts used for the polymerization of ethylene-α-olefin copolymers can be used.
Specifically, the metallocene catalysts described in JP-A-58-19309, JP-A-59-95292, JP-A-60-35006, JP-A-3-163088 and the like can be exemplified. ..

(Ii) Polymerization method Specific polymerization methods include a slurry method in the presence of these catalysts, a gas phase flow bed method or a solution method, a pressure of 200 kg / cm ² (19.6 MPa) or more, and a polymerization temperature of 200 kg / cm 2 (19.6 MPa) or more. Examples thereof include a high-pressure bulk polymerization method at 100 ° C. or higher. A high pressure bulk polymerization method is mentioned as a preferable production method.
The component (B) can also be appropriately selected and used from those commercially available as metallocene-based polyethylene. Examples of commercially available products include Affinity and Engage, which are traded by DuPontau, Kernel, which is traded by Japan Polyethylene Corporation, and EXACT, which is traded by Exxon.
In these uses, a grade that satisfies the density and MFR required by the present invention may be appropriately selected.

Ratio of the component (B) in the propylene-based resin composition The ratio of the component (B) in the propylene-based resin composition needs to be in the range of 10 to 35% by weight.
When the content of the component (B) is 10% by weight or more, the flexibility is sufficiently imparted, and the sacrifice of the flexibility due to the addition of the component (C) can be regained. On the other hand, when the content of the component (B) is 35% by weight or less, the moldability becomes sufficient, the thickness of the film becomes uniform, and a film having a good appearance can be obtained. Therefore, the proportion of the component (B) in the composition needs to be in the range of 10 to 35% by weight, preferably 20 to 30% by weight.

3. 3. Propylene homopolymer (C)
(1) Characteristics of Component (C) The propylene homopolymer (C) used in the propylene-based resin composition of the present invention (hereinafter, also referred to as component (C)) has fluidity for ensuring moldability. Used as a conditioning component.
In the present invention, the component (A) used as the main component is extremely effective for imparting high flexibility and transparency to the film, but since it is produced by a metallocene-based catalyst, the molecular weight distribution is narrow. It has problems such as poor flowability during molding due to this.
Therefore, if the molecular weight distribution of the component (A) is expanded, the number of low-crystal and low-molecular-weight components is inevitably increased, and as a result, problems such as stickiness due to bleed-out to the surface of the molded product film and poor appearance occur. It is not suitable for applications that require transparency.
Therefore, by adding a specific amount of the component (C) to the component (A) having a narrow molecular weight distribution, it is possible to increase the high crystal and low molecular weight components without increasing the low crystal and low molecular weight components. As a result, it is possible to suppress poor flowability during molding without causing poor appearance such as bleed-out.
(C-i) Melt flow rate of component (C) MFR (C)
The melt flow rate MFR (C) (hereinafter, also referred to as MFR (C)) of the propylene homopolymer (C) is 1.9 to 100 g / 10 minutes, preferably 2.0 to 90 g / 10 minutes. More preferably, it is 4.0 to 80 g / 10 minutes. When the MFR (C) is 1.9 g / 10 minutes or more, good fluidity is obtained, and extrusion defects during film formation can be reduced. On the other hand, when the MFR (C) is 100 g / 10 minutes or less, the dispersibility of the propylene-based resin (A) in the propylene homopolymer (C) is enhanced, so that the appearance of the film is excellent.
Here, MFR is a value measured according to JIS K7210.
The MFR (C) of the propylene homopolymer (C) is easily adjusted by changing the conditions of the polymerization temperature and the polymerization pressure, or by adding a chain transfer agent such as hydrogen at the time of polymerization.

(2) Method for Producing Component (C) The propylene homopolymer (C) is not particularly limited in terms of production method as long as the above-mentioned characteristics are satisfied, but a preferred production method is to use propylene and necessary comonomer in Ziegler. -It is a method of polymerizing with a Natta-based catalyst.
The Ziegler-Natta catalyst is, for example, "Polypropylene Handbook" Edward P. Moore Jr. It is a catalytic system as outlined in Section 2.3.1 (pages 20-57) of the Industrial Research Council (1998), edited by Tetsuo Yasuda and supervised by Nobu Sakuma. For example, titanium trichloride and halogen. For titanium trichloride catalysts made of organic aluminum, solid catalyst components containing magnesium chloride, titanium halide, and electron donating compounds as essential, magnesium-supporting catalysts made of organic aluminum and organic silicon compounds, and solid catalyst components. It refers to a catalyst in which an organic aluminum compound component is combined with an organic silicon-treated solid catalyst component formed by contacting organic aluminum and an organic silicon compound.
The method for producing the propylene homopolymer (C) is not particularly limited, and any conventionally known slurry polymerization method, bulk polymerization method, gas phase polymerization method, or the like can be used, and the propylene homopolymer (C) can be produced within the range of the above-mentioned characteristics. If this is the case, it is also possible to produce a propylene homopolymer of the multi-stage polymer by using the multi-stage polymerization method.

(3) Ratio of the component (C) in the propylene-based resin composition The ratio of the component (C) in the propylene-based resin composition needs to be in the range of 1 to 15% by weight.
When the amount of the component (C) is 1% by weight or more, the high crystal and low molecular weight components are sufficient, and sufficient moldability can be obtained. Therefore, it is necessary and preferably 1% by weight or more. 5% by weight or more. On the contrary, when the amount of the component (C) is 15% by weight or less, the physical properties such as flexibility and transparency are significantly improved, and the quality required for the resin composition of the present invention can be satisfied. It is necessary to be 15% by weight or less, preferably 13% by weight or less.

4. Propylene homopolymer (D)
(1) Characteristics of Component (D) The propylene homopolymer (D) used in the propylene-based resin composition of the present invention (hereinafter, also referred to as component (D)) exhibits a blocking phenomenon that occurs during high-temperature heat treatment. It is used as a component that can improve the surface roughness during film formation in order to suppress it.
In the present invention, the component (A) used as the main component is extremely effective for imparting high flexibility and transparency to the film, but has a narrow molecular weight distribution and is extremely flexible, so that a film was formed. It has a problem of blocking phenomenon during high temperature heat treatment of the film.
Therefore, if the molecular weight distribution of the component (A) is expanded, the number of low-crystal and low-molecular-weight components is inevitably increased, and as a result, problems such as stickiness due to bleed-out to the surface of the molded product film and poor appearance occur. It is not suitable for applications that require transparency.
Therefore, by adding a specific amount of the component (D) to the component (A) having a narrow molecular weight distribution, it is possible to increase the high crystal and high molecular weight components without increasing the low crystal and low molecular weight components. As a result, the surface of the film at the time of molding can be roughened without causing an appearance defect such as bleed-out, and the blocking phenomenon generated at the time of high temperature heat treatment can be suppressed.
(Di) Melt flow rate of component (D) MFR (D)
The melt flow rate MFR (D) (hereinafter, also referred to as MFR (D)) of the propylene homopolymer (D) is less than 1.9 g / 10 minutes, preferably 1.5 g / 10 minutes or less, more preferably. Is 1.0 g / 10 minutes or less. When the MFR (D) is less than 1.9 g / 10 minutes, the surface roughness of the film at the time of film formation can be improved.
On the other hand, when the MFR (D) is 0.01 g / 10 minutes or more, the dispersibility is good and fish eyes (FE) are less likely to occur. Therefore, the MFR (D) is preferably 0.01 g / 10 minutes or more, more preferably 0.05 g / 10 minutes or more, and particularly preferably 0.1 g / 10 minutes or more.
Here, MFR is a value measured according to JIS K7210.
The MFR of the propylene homopolymer (D) is easily adjusted by changing the conditions of the polymerization temperature and the polymerization pressure, or by adding a chain transfer agent such as hydrogen at the time of polymerization.

(2) Method for Producing Component (D) The propylene homopolymer (D) is not particularly limited in terms of production method as long as the above-mentioned characteristics are satisfied, but a preferred production method is to use propylene and necessary comonomer in Ziegler. -It is a method of polymerizing with a Natta-based catalyst.
The Ziegler-Natta catalyst is, for example, "Polypropylene Handbook" Edward P. Moore Jr. It is a catalytic system as outlined in Section 2.3.1 (pages 20-57) of the Industrial Research Council (1998), edited by Tetsuo Yasuda and supervised by Nobu Sakuma. For example, titanium trichloride and halogen. For titanium trichloride catalysts made of organic aluminum, solid catalyst components containing magnesium chloride, titanium halide, and electron donating compounds as essential, magnesium-supporting catalysts made of organic aluminum and organic silicon compounds, and solid catalyst components. It refers to a catalyst in which an organic aluminum compound component is combined with an organic silicon-treated solid catalyst component formed by contacting organic aluminum and an organic silicon compound.
The method for producing the propylene homopolymer (D) is not particularly limited, and any conventionally known slurry polymerization method, bulk polymerization method, gas phase polymerization method, or the like can be used, and the propylene homopolymer (D) can be produced within the range of the above-mentioned characteristics. If this is the case, it is also possible to produce a propylene homopolymer of the multi-stage polymer by using the multi-stage polymerization method.

(3) Ratio of the component (D) in the propylene-based resin composition The ratio of the component (D) in the propylene-based resin composition needs to be in the range of 1 to 15% by weight.
When the amount of the component (D) is 1% by weight or more, the high crystal and high molecular weight components are sufficient, and sufficient surface roughness can be obtained on the film surface, so that the amount needs to be 1% by weight or more. Yes, preferably 2% by weight or more. On the contrary, when the amount of the component (D) is 15% by weight or less, the physical properties such as flexibility and transparency are significantly improved, and the load on the molding machine is also reduced. In order to satisfy the quality required for the resin composition of the present invention, it is necessary to be 15% by weight or less, preferably 13% by weight or less.

(4) Melt flow rate ratio of propylene homopolymer (C) and propylene homopolymer (D) Melt flow rate ratio of propylene homopolymer (C) and propylene homopolymer (D) (MFR (C) / MFR (D)) is preferably in the range of 5 to 300.
When the melt flow rate ratio of the component (C) to the component (D) is 5 or more, the molecular weight distribution can be expanded, the moldability is improved, and the load on the motor of the molding machine is reduced. Therefore, the melt flow rate ratio (MFR (C) / MFR (D)) of the component (C) to the component (D) is preferably 5 or more, and more preferably 8 or more. On the contrary, when the melt flow rate ratio of the component (C) to the component (D) is 300 or less, the compatibility is improved and the physical properties such as transparency are significantly improved, which is required for the resin composition of the present invention. It is preferably 300 or less, more preferably 200 or less, because it can satisfy the above quality.

5. Additional ingredients (additives)
Since the propylene-based resin composition in the present invention is suitably used as a film, any additive can be blended as long as the effects of the present invention such as bleed-out are not significantly impaired. Such optional components include antioxidants, crystal nucleating agents, clearing agents, lubricants, antiblocking agents, antistatic agents, antifogging agents, neutralizing agents, and metal inerts used in ordinary polyolefin resin materials. Examples thereof include agents, colorants, dispersants, peroxides, fillers, fluorescent whitening agents and the like. The various additives are described in detail below.

Antioxidants As antioxidants, specific examples of phenolic antioxidants include tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate and 1,1,3-tris (2-methyl). -4-Hydroxy-5-t-butylphenyl) butane, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, pentaerythrityl-tetrakis {3- (3,5-di) -T-butyl-4-hydroxyphenyl) propionate}, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 3,9- Bis [2- {3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5 ] Undecane, 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanuric acid and the like can be mentioned.

Specific examples of phosphorus-based antioxidants include tris (mixed, mono and dinonylphenyl phosphite), tris (2,4-di-t-butylphenyl) phosphite, and 4,4'-butylidenebis (3-). Methyl-6-t-butylphenyl-di-tridecyl) phosphite, 1,1,3-tris (2-methyl-4-di-tridecylphosphite-5-t-butylphenyl) butane, bis (2, 4-di-t-butylphenyl) pentaerythritol-di-phosphite, bis (2,4-di-cumylphenyl) pentaerythritol-di-phosphite, tetrakis (2,4-di-t-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,4-di-t-butyl-5-methylphenyl) -4,4'-biphenylenediphosphonite, bis (2,6-di-t) -Butyl-4-methylphenyl) pentaerythritol-di-phosphite and the like can be mentioned.
Specific examples of the sulfur-based antioxidant include di-stearyl-thio-di-propionate, di-myristyl-thio-di-propionate, pentaerythritol-tetrakis (3-lauryl-thio-propionate) and the like. ..
These antioxidants can be used alone or in combination of two or more as long as the effects of the present purpose are not impaired.

The amount of the antioxidant to be blended is preferably 0.01 to 1.0 parts by weight, more preferably 0.02 to 0.5 parts by weight, still more preferably 0, with respect to 100 parts by weight of the propylene resin composition. When the amount is 05 to 0.1 parts by weight and the blending amount is 0.01 parts by weight or more, the effect of thermal stability is obtained, deterioration occurs when the resin is manufactured, and it becomes burnt and causes fish eyes. To prevent. Further, when it is 1.0 part by weight or less, it is preferable because it does not become a foreign substance and causes fish eyes.

Anti-blocking agent As the anti-blocking agent, the average particle size is preferably 1 to 7 μm, more preferably 1 to 5 μm, and further preferably 1 to 4 μm. When the average particle size is 1 μm or more, the slipperiness and openness of the obtained film are excellent and preferable. On the other hand, when it is 7 μm or less, transparency and scratch resistance are excellent and preferable. Here, the average particle size is a value measured by a Coulter counter.

Specific examples of the anti-blocking agent include, for example, synthetic or natural silica (silicon dioxide), magnesium silicate, aluminosilicate, talc, zeolite, aluminum borate, calcium carbonate, calcium sulfate, barium sulfate, calcium phosphate. Etc. are used.
Examples of the organic system include polymethylmethacrylate, polymethylsilsesquioxane (silicone), polyamide, polytetrafluoroethylene, epoxy resin, polyester resin, benzoguanamine / formaldehyde condensate (benzoguanamine resin), urea resin, phenol resin and the like. Can be used.
In particular, synthetic silica and polymethylmethacrylate are suitable because of their balance of dispersibility, transparency, blocking resistance, and scratch resistance.
Further, the antiblocking agent may be a surface-treated one, and the surface-treating agent includes a surface active agent, a metal soap, an acrylic acid, an oxalic acid, a citric acid, an organic acid such as tartrate acid, a higher alcohol, an ester, and the like. Condensed phosphates such as silicone, fluororesin, silane coupling agent, sodium hexametaphosphate, sodium pyrophosphate, sodium tripolyphosphate, sodium trimetaphosphate, etc. can be used, especially those treated with citric acid among organic acid treatments. Is preferable. The treatment method is not particularly limited, and known methods such as surface spraying and dipping can be adopted.
The anti-blocking agent may have any shape, such as spherical, square, columnar, needle-shaped, plate-shaped, and irregular-shaped.
These anti-blocking agents can be used alone or in combination of two or more as long as the effects of the present purpose are not impaired.

When the anti-blocking agent is blended, the blending amount is preferably 0.01 to 1.0 parts by weight, more preferably 0.05 to 0.7 parts by weight, still more preferably, with respect to 100 parts by weight of the propylene-based resin composition. Is 0.1 to 0.5 parts by weight. When the blending amount is 0.01 parts by weight or more, the antiblocking property, slipperiness and opening property of the film are excellent. When it is 1.0 part by weight or less, the transparency of the film is not impaired, and the film itself does not become a foreign substance and causes fish eyes, which is preferable.

Slip agent Examples of the slip agent include monoamides, substituted amides, bisamides and the like, and one type or a combination of two or more types can be used.
Specific examples of the monoamides include lauric acid amide, palmitic acid amide, stearic acid amide, behenic acid amide, hydroxystearic acid amide and the like as saturated fatty acid monoamides.
Examples of the unsaturated fatty acid monoamide include oleic acid amide, erucic acid amide, and ricinoleic acid amide.
Specific examples of the substituted amides include N-stearyl stearic acid amide, N-oleyl oleic acid amide, N-stearyl oleic acid amide, N-oleyl stearic acid amide, N-stearyl erucic acid amide, and N-oleyl palmitic acid amide. And so on.
Specific examples of bisamides include methylene bisstearate amide, ethylene biscapric acid amide, ethylene bislauric acid amide, ethylene bisstearic acid amide, ethylene bisisostearic acid amide, and ethylene bishydroxystearic acid amide, as saturated fatty acid bisamides. Ethylene bisbechenic acid amide, hexamethylene bisstearic acid amide, hexamethylene bisstearic acid amide, hexamethylene bishydroxystearic acid amide, N, N'-distealyl adipic acid amide, N, N'-distearyl sevacinate amide, etc. Can be mentioned.
Examples of unsaturated fatty acid bisamides or unsaturated hydrocarbon-substituted saturated fatty acid bisamides include ethylene bisoleic acid amide, hexamethylene bisoleic acid amide, N, N'-diorail adipic acid amide, and N, N'-diorail sevacinic acid amide. And so on.
Examples of the aromatic bisamide include m-xylylene bisstearic acid amide and N, N'-distearylisophthalic acid amide.
Among these, among the fatty acid amides, oleic acid amide, erucic acid amide, and behenic acid amide are particularly preferably used.

When the slip agent is blended, the blending amount is preferably 0.01 to 1.0 parts by weight, more preferably 0.05 to 0.7 parts by weight, and further, with respect to 100 parts by weight of the propylene resin composition. It is preferably 0.1 to 0.4 parts by weight. At 0.01 parts by weight or more, the opening property and slipperiness are excellent. When it is 1.0 part by weight or less, the embossment of the slip agent does not become excessive, and the film surface does not bleed and the transparency does not deteriorate.

Nuclear agent Specific examples of the nuclear agent include 2,2-methylene-bis (4,6-di-t-butylphenyl) sodium phosphate, talc, and 1,3,2,4-di (p-methylbenzylidene) sorbitol. , 1,3,2,4-di (p-propylbenzylidene) sorbitol compounds such as propylsorbitol, hydroxy-di (t-butylbenzoic acid) aluminum, hydroxy-bis [2,2-methylene-bis (4,4) 6-di-t-butylphenyl) phosphate] Aluminum and an aliphatic monocarboxylic acid lithium salt mixture having 8 to 20 carbon atoms (manufactured by ADEKA Co., Ltd., trade name Adecastab NA21), 1,3,5-tris [2 2-Dimethylpropionylamino] benzene and the like can be mentioned.
When the nucleating agent is blended, the blending amount is preferably 0.0005 to 0.5 parts by weight, more preferably 0.001 to 0.1 parts by weight, based on 100 parts by weight of the propylene resin composition. More preferably, it is 0.005 to 0.05 parts by weight. At 0.0005 parts by weight or more, the effect as a nucleating agent can be obtained. When it is 0.5 parts by weight or less, it is preferable because it does not become a foreign substance and causes fish eyes.

In addition, high-density polyethylene resin can be mentioned as a nucleating agent other than the above. The density of the high-density polyethylene resin is preferably 0.94 to 0.98 g / cm ³ , and more preferably 0.95 to 0.97 g / 10 cm ³ . When the density is within this range, the transparency improving effect can be obtained. The melt flow rate (MFR: 190 ° C., 2.16 kg) of the high-density polyethylene resin is preferably 5 g / 10 minutes or more, more preferably 7 to 500 g / 10 minutes, and further preferably 10 to 100 g / 10 minutes. When the MFR is 5 g / 10 minutes or more, the dispersion diameter of the high-density polyethylene resin becomes sufficiently small, and it is preferable that the high-density polyethylene resin itself does not become a foreign substance and cause fish eyes. Further, in order for the high-density polyethylene resin to be finely dispersed, the MFR of the high-density polyethylene resin is preferably larger than the MFR of the propylene-based resin (A) used in the present invention.

The method for producing the high-density polyethylene resin used as a nucleating agent is not particularly limited with respect to the polymerization method and the catalyst as long as the polymer having the desired physical characteristics can be produced. For catalysts, Cheegler-type catalysts (ie, based on a combination of supported or unsupported halogen-containing titanium compounds and organoaluminum compounds), Kaminsky-type catalysts (ie, supported or unsupported metallocene compounds and organoaluminum compounds, especially Armoxane. (Based on combination). The shape of the high-density polyethylene resin is not limited and may be in the form of pellets or powder.

When used as a nucleating agent, the blending amount of the high-density polyethylene is preferably 0.01 to 5 parts by weight, more preferably 0.05 to 3 parts by weight, still more preferably, with respect to 100 parts by weight of the propylene resin composition. Is 0.1 to 1 part by weight. If it is 0.01 parts by weight or more, the effect as a nucleating agent can be obtained. When it is 5 parts by weight or less, it is preferable because it does not become a foreign substance and causes fish eyes.

Neutralizing agent Specific examples of the neutralizing agent include calcium stearate, zinc stearate, hydrotalcite (trade name: DHT-4A, manufactured by Kyowa Chemicals Co., Ltd.), and Mizusawa Industrial Chemicals (manufactured by Mizusawa Industrial Chemicals Co., Ltd.). First name) and so on.
When the neutralizing agent is blended, the blending amount is preferably 0.01 to 1.0 parts by weight, more preferably 0.02 to 0.5 parts by weight, still more preferably, with respect to 100 parts by weight of the propylene resin composition. It is 0.05 to 0.1 parts by weight. When the blending amount is 0.01 or more, the effect as a neutralizing agent is obtained, deterioration occurs during the production of the resin, and it is prevented from becoming discolored and causing fish eyes. Further, when it is 1.0 part by weight or less, it is preferable because it does not become a foreign substance and causes fish eyes.

Light stabilizer As the light stabilizer, a hindered amine-based stabilizer is preferably used, and a compound having a structure in which all the hydrogens bonded to the carbons at the 2- and 6-positions of the conventionally known piperidine are substituted with a methyl group. Is used without particular limitation, but specifically, the following compounds are used.
Specific examples include a polycondensate of dimethyl amber and 1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine, tetrakis (1,2,2,6,6). -Pentamethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, 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, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, poly [{6- (1,1,3,3-tetramethylbutyl) imino-1,3,5-triazine-2,4- Diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {2,2,6,6-tetramethyl-4-piperidyl} imino], poly [(6-morpholino-s) -Triazine-2,4-diyl) [(2,2,6,6-tetramethyl-4-piperidyl) imino] Hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}]] And so on.
These hindered amine-based stabilizers can be used alone or in combination of two or more as long as the effects of the present purpose are not impaired.

When the hindered amine-based stabilizer is blended, the blending amount is preferably 0.005 to 2 parts by weight, more preferably 0.01 to 1 part by weight, still more preferably 0. It is desirable to use 05 to 0.5 parts by weight.
When the content of the hindered amine stabilizer is 0.005 parts by weight or more, there is an effect of improving stability such as heat resistance and aging resistance, and when it is 2 parts by weight or less, the fish itself becomes a foreign substance. It does not cause eye and is preferable.

Antistatic agent As the antistatic agent, any known antistatic agent conventionally used as an antistatic agent or an antistatic agent can be used without particular limitation, and for example, anionic surfactant and cationic surfactant can be used. Agents, nonionic surfactants, amphoteric surfactants and the like can be mentioned.

Examples of the anionic surfactant include fatty acids or carboxylates such as loginate sken, N-acylcarboxylate, ether carboxylate, and fatty acid amine salts; sulfosuccinate, ester sulfonate, and N-acylsulfonic acid. Sulfates such as salts; sulfate ester salts such as sulfated oil, sulfate ester salt, alkyl sulfate, alkyl sulfate polyoxyethylene salt, sulfate ether salt, sulfate amide salt; alkyl phosphate, alkyl polyoxyethylene phosphate Examples thereof include phosphate ester salts such as salts, phosphate ether salts and phosphate amide salts.

Examples of the cationic surfactant include amine salts such as alkylamine salts; alkyltrimethylammonium chloride, alkylbenzyldimethylammonium chloride, alkyldihydroxyethylmethylammonium chloride, dialkyldimethylammonium chloride, tetraalkylammonium salt, N, N-di. (Polyoxyethylene) quaternary ammonium salts such as dialkylammonium salts and salts of N-alkylalcanamideammonium; 1-hydroxyethyl-2-alkyl-2-imidazoline, 1-hydroxyethyl-1-alkyl-2-alkyl -2-Alkyl imidazoline derivatives such as imidazoline; imidazolinium salt, pyridinium salt, isoquinolinium salt and the like can be mentioned.

Examples of the nonionic surfactant include ether forms such as alkylpolyoxyethylene ether and p-alkylphenylpolyoxyethylene ether; fatty acid sorbitan polyoxyethylene ether, fatty acid sorbitol polyoxyethylene ether, fatty acid glycerin polyoxyethylene ether and the like. Ether form: fatty acid polyoxyethylene ester, monoglyceride, diglyceride, sorbitan ester, sucrose ester, divalent alcohol ester, borate ester, etc. ester form; dialcohol alkylamine, dialcohol alkylamine ester, fatty acid alkanolamide, Examples thereof include nitrogen-containing forms such as N, N-di (polyoxyethylene) alkaneamide, alkanolamine ester, N, N-di (polyoxyethylene) alkaneamine, amine oxide, and alkylpolyethyleneimine.

Examples of the amphoteric surfactant include amino acid forms such as monoaminocarboxylic acid and polyaminocarboxylic acid; N-alkyl-β-alanine such as N-alkylaminopropionate and N, N-di (carboxyethyl) alkylamine salts. Form; betaine form such as N-alkylbetaine, N-alkylamide betaine, N-alkylsulfobetaine, N, N-di (polyoxyethylene) alkylbetaine, imidazolinium betaine; 1-carboxymethyl-1-hydroxy- Examples thereof include alkyl imidazoline derivatives such as 1-hydroxyethyl-2-alkyl-2-imidazoline and 1-sulfoethyl-2-alkyl-2-imidazoline.

Among these, nonionic surfactants and amphoteric surfactants are preferable, and among them, ester-type or nitrogen-containing non-forms such as monoglycerides, diglycerides, borate esters, dialcohol alkylamines, dialcohol alkylamine esters, and amides are preferable. Ionic surfactants; betaine-type amphoteric surfactants are preferred.

As the antistatic agent, a commercially available product can be used, for example, electrostripper TS5 (manufactured by Kao Co., Ltd., trade name, glycerin monostearate), electrostripper TS6 (manufactured by Kao Co., Ltd., trade name). , Stearic acid diethanolamine), Electro stripper EA (manufactured by Kao Co., Ltd., trade name, lauryl diethanolamine), Electro stripper EA-7 (manufactured by Kao Co., Ltd., trade name, polyoxyethylene laurylamine capryl ester), Denon 331P (maru) Ryoyu Kagaku Co., Ltd., trade name, stearyldiethanolamine monostearate), Denon 310 (Maruhishi Yuka Co., Ltd., trade name, alkyldiethanolamine fatty acid monoester), Register PE-139 (Daiichi Kogyo Seiyaku Co., Ltd.) Made by Sanyo Kasei Co., Ltd., trade name, stearic acid mono & diglyceride borate ester), Chemistat 4700 (manufactured by Sanyo Kasei Co., Ltd., trade name, alkyldimethylbetaine), Leostat S (manufactured by Lion Co., Ltd., trade name, alkyldiethanolami Do) and so on.

When the antistatic agent is blended, the blending amount is preferably 0.01 to 2 parts by weight, more preferably 0.05 to 1 part by weight, still more preferably 0.1 to 100 parts by weight with respect to 100 parts by weight of the propylene resin composition. It is 0.8 parts by weight, most preferably 0.2 to 0.5 parts by weight. These antistatic agents can be used alone or in combination of two or more as long as the effects of the present purpose are not impaired. When the amount of the antistatic agent compounded is 0.01 parts by weight or more, the surface intrinsic resistance can be reduced and damage due to antistatic can be prevented. When it is 2 parts by weight or less, powder blowing is less likely to occur on the film surface due to bleeding.

[II] Method for Producing Propylene-based Resin Composition The propylene-based resin composition of the present invention comprises the above-mentioned propylene-based resin (A), ethylene-α-olefin copolymer (B), propylene homopolymer (C), and the like. After mixing the propylene homopolymer (D) and other additives as necessary with a Henshell mixer (trade name), v-blender, ribbon blender, tumbler blender, etc., a single-screw extruder, multi-screw extruder, kneader, bumper, etc. It is obtained by a method of kneading with a kneading machine such as a remixer.

[III] Film The film of the present invention can be produced by a known method using the above propylene-based resin composition. For example, it is manufactured by a known technique such as extrusion molding using a T die or a circular die.
The film of the present invention has excellent flexibility, can suppress deterioration of transparency due to poor appearance such as uneven thickness and rough interface, and can suppress thinning in secondary processing such as deep drawing, so that it has mechanical strength. It can be retained, and it can maintain a good appearance because it can suppress thinning due to overflow of the resin caused by heat sealing and the consequent unevenness, and it has an excellent effect of suppressing the blocking phenomenon that occurs during high temperature heat treatment.

The film of the present invention is characterized by having excellent flexibility, and it is desirable that the tensile elastic modulus, which is a measure of flexibility, is 250 MPa or less. When the tensile elastic modulus is 230 MPa or less, preferably 210 MPa or less, the tactile sensation is good and it is very excellent in that a high-class feeling can be produced.

The method of using the film of the present invention is not limited, but is limited to a container obtained by deep drawing molding that is exposed to a semi-melted state for a certain period of time, and high strength obtained by high temperature, high pressure, and long-term heat sealing. As a container or bag that requires a seal, it is suitable for, for example, water packaging such as a standing pouch with a spout, liquid packaging, and heavy packaging. Highly transparent as a container and uniform in wall thickness, highly transparent as a bag, thinning by heat sealing, suppressing printing blur by not causing unevenness associated with it, and blocking that occurs during high temperature heat treatment It is characterized by being able to take advantage of its excellent appearance, such as suppressing the phenomenon. In addition, it is characterized by having extremely high peel strength (high-strength seal) by being able to suppress thinning.

The film of the present invention can clearly show the contents when Haze, which is a measure of transparency, is 10% or less, preferably 8.0% or less, particularly preferably 7.0% or less, and the film. When the surface roughness of 1 or more, preferably 1.5 or more, more preferably 2 or more, the blocking phenomenon that occurs during the high temperature heat treatment can be prevented, so that the line speed in the manufacturing process can be improved. Very good in terms.

In the following, in order to explain the present invention more concretely and clearly, the present invention will be described in comparison with Examples and Comparative Examples, and the rationality and significance of the requirements of the constitution of the present invention will be demonstrated. The present invention is not limited to these examples. The physical property measurement method, characteristic evaluation method, and resin material used in Examples and Comparative Examples are as follows.

1. 1. Measurement method of physical properties (1) MFR: The propylene-based resin (A), the propylene angstrom (C) and the propylene angstrom (D) are subjected to the JIS K7210 A method condition M, test temperature: 230 ° C., nominal load: 2.16 kg, die shape: 2.095 mm in diameter and 8.00 mm in length. The ethylene-α-olefin copolymer (B) was measured according to JIS K7210 A method condition D at a test temperature of 190 ° C., a nominal load of 2.16 kg, and a die shape: diameter of 2.095 mm and length of 8.00 mm. (Unit: g / 10 minutes)
(2) Density: Using the extruded strand obtained at the time of MFR measurement, the measurement was performed by the density gradient tube method according to the JIS K7112 D method.
(3) Melting peak temperature: Using DSC of Seiko Instruments Co., Ltd., take 5.0 mg of a sample, hold it at 200 ° C. for 5 minutes, crystallize it to 40 ° C. at a temperature lowering rate of 10 ° C./min, and further 10 The melting peak temperature when melted at a heating rate of ° C./min was measured. (Unit: ° C)
(4) Solid viscoelasticity measurement:
As the sample, a sheet having a thickness of 2 mm, which was injection-molded under the following conditions, was cut into strips having a width of 10 mm, a length of 18 mm, and a thickness of 2 mm. The device used was ARES manufactured by Leometric Scientific. The frequency is 1 Hz. The measurement temperature rises from -60 ° C to 20 ° C at a rate of 3 ° C / 30 seconds, and gradually rises at a rate of 3 ° C / 40 seconds above 20 ° C, causing the sample to melt and become unmeasurable. The measurement was carried out until it became. The strain was in the range of 0.1 to 0.5%. Then, in the temperature-loss tangent (tanδ) curve obtained by the measurement, it was confirmed whether the peaks of the tanδ curve at 0 ° C. or lower were single or separated.
[Preparation of test piece]
Standard number: JIS-7152 (ISO294-1)
Molding machine: EC-20 injection molding machine manufactured by Toshiba Machine Co., Ltd. Molding machine Set temperature: 80 ° C, 80 ° C, 160 ° C, 200 ° C, 200 ° C, 200 ° C from under the hopper
Mold temperature: 40 ° C
Injection speed: 200 mm / sec (speed in the mold cavity)
Holding pressure: 20MPa
Holding time: 40 seconds Mold shape: Flat plate (thickness 2 mm, width 40 mm, length 80 mm)

(5) W (A1), W (A2), E (A1), E (A2) of the component (A): Measured by the above-mentioned method.
(6) Weight average molecular weight:
It was measured by gel permeation chromatography (GPC) method.
The conversion from the retained capacity to the molecular weight in the GPC measurement is performed using a calibration curve using standard polystyrene prepared in advance.
The standard polystyrenes used are all the following brands manufactured by Tosoh Corporation.
F380, F288, F128, F80, F40, F20, F10, F4, F1, A5000, A2500, A1000
A calibration curve is created by injecting 0.2 ml of a solution dissolved in 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 approximating with the least squares method. The following numerical values are used for [η] = K × M ^α in the viscosity formula used for conversion to the molecular weight.
PS: K = 1.38 × 10 ^-4 α = 0.7
PE: K = 3.92 × 10 ^-4 α = 0.733
PP: K = 1.03 × 10 ^-4 α = 0.78
The measurement conditions of GPC are as follows.
Equipment: GPC manufactured by WATERS (ALC / GPC 150C)
Detector: FOXBORO MIRAN 1A IR detector (measurement wavelength: 3.42 μm)
Column: Showa Denko Corporation AD806M / S (3 series)
Mobile phase solvent: o-dichlorobenzene Measurement temperature: 140 ° C
Flow velocity: 1.0 ml / min
Injection amount: 0.2 ml
Preparation of sample As a sample, prepare a 1 mg / ml solution using o-dichlorobenzene (containing 0.5 mg / ml BHT) and dissolve it at 140 ° C. in about 1 hour.

Evaluation method Transparency (HAZE):
The transparency of the obtained laminated film was measured with a haze meter according to JIS-K7136-2000. The smaller the obtained value (unit:%), the better the transparency, and if this value is 10% or less, it is easy to check the contents and it is excellent in obtaining a display effect, and it is 8% or less. Is preferable, and 7% or less is particularly preferable.
Tension modulus:
According to JIS K-7127-1989, the tensile elastic modulus in the flow direction (MD) of the laminated film was measured under the following conditions. The smaller the obtained value (unit: MPa) is, the more excellent the flexibility is. When this value is 250 MPa or less, it is excellent in that a high-class feeling is obtained with a good touch, and 230 MPa or less is preferable. , 210 MPa or less is particularly preferable.
Sample length: 150 mm
Sample width: 15 mm
Distance between chucks: 100 mm
Crosshead speed: 1mm / min

Surface roughness:
After adjusting the condition of the film in an atmosphere of 23 ° C. and 50% RH for 24 hours or more, there is no cutoff value for the contact surface with the cooling roll immediately after the die during film forming in accordance with JIS B-0601. The average value (Ra) of the central surface of the film was measured and used as an index of the film surface roughness. The larger the obtained value, the larger the unevenness of the film surface.
(4) 0 ° C impact:
A device compliant with JIS P8134 was used under the condition of an atmospheric temperature of 0 ° C. The film test piece was fixed to a holder having a diameter of 50 mm, hit by a hemispherical metal penetrating portion of 25.4 mm, and the work amount (kJ) required for penetrating fracture was measured and divided by the film thickness to obtain the film (kJ). Unit: kJ / m). Those in which the film test piece did not break were described as NB.
Blocking resistance:
Two films are set, a weight of 10 kg is placed on the film, and the film is stored in an atmosphere of 120 ° C. for 0.5 hours. After 0.5 hours, the films are returned to room temperature and the adhesion between the films is checked. The blocking resistance was evaluated according to the following criteria according to the adhesive condition. If it is not sticky at all, it has excellent blocking resistance.
◯: Not sticky at all.
×: Adhesive.

Resins used, additives (1) Additives Antioxidants Phenolic antioxidants "IR1010" Tetrakis [methylene-3- (3', 5'-di-t-butyl-4'-hydroxylphenyl) propionate] Methane. Product name "IRGANOX1010" manufactured by BASF Japan Ltd.
Phosphorus-based antioxidant "IF168" Tris (2,4-di-t-butylphenyl) phosphite. Product name "IRGAFOS168" manufactured by BASF Japan Ltd.
Neutralizer "DHT4A" hydrotalcite. Product name "DHT-4A" manufactured by Kyowa Chemical Industry Co., Ltd.
Neutralizer "CAST" Calcium stearate. Made by Nitto Kasei Kogyo Co., Ltd., trade name "Ca-St".
Organic peroxide "LP101" 2,5-dimethyl-2,5-di (t-butylperoxy) hexane. Product name "LUPEROX 101" manufactured by Atchem Yoshitomi Co., Ltd.
(2) Propylene resin (A)
The resin obtained in the following production example (A-1) was used.

(Manufacturing Example A-1)
(I) Preparation of prepolymerization catalyst (chemical treatment of silicate)
3.75 liters of distilled water followed by 2.5 kg of concentrated sulfuric acid (96%) was slowly added to a glass separable flask with a 10 liter stirring blade. At 50 ° C, 1 kg of montmorillonite (trade name Benclay SL manufactured by Mizusawa Industrial Chemicals Co., Ltd .; average particle size = 25 μm particle size distribution = 10-60 μm) was dispersed, the temperature was raised to 90 ° C, and the temperature was raised for 6.5 hours. Maintained. After cooling to 50 ° C., the slurry was filtered under reduced pressure to collect the cake. 7 liters of distilled water was added to this cake to reslurry it, and then the cake was filtered. This washing operation was carried out until the pH of the washing liquid (filtrate) exceeded 3.5. The recovered cake was dried overnight at 110 ° C. under a nitrogen atmosphere. The weight after drying was 707 g.
(Drying silicate)
The previously chemically treated silicate was dried by a kiln dryer. The specifications and drying conditions are as follows.
Rotating cylinder: Cylindrical inner diameter 50 mm Heating zone 550 mm (electric furnace) With hoisting wings Rotation speed: 2 rpm Inclined angle: 20/520 Silicate supply speed: 2.5 g / min Gas flow rate: Nitrogen 96 liters / hour Diverted drying Temperature: 200 ° C (powder temperature)
(Catalyst preparation)
An autoclave with an internal volume of 16 liters with agitation and temperature control was sufficiently replaced with nitrogen. 200 g of dry silicate was introduced, 1160 ml of mixed heptane and 840 ml of a heptane solution of triethylaluminum (0.60 M) were added, and the mixture was stirred at room temperature. After 1 hour, the mixture was washed with mixed heptane to adjust the silicate slurry to 2,000 ml. Next, 9.6 ml of a heptane solution of triisobutylaluminum (0.71 M) was added to the silicate slurry prepared above, and the mixture was reacted at 25 ° C. for 1 hour. In parallel, (r) -dichloro [1,1'-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4H-azurenyl}] zirconium (synthesized in Japanese Patent Laid-Open No. 10-226712, Example). To 870 ml of mixed heptane with 2,177 mg (0.3 mmol) was added, 33.1 ml of a heptane solution of triisobutylaluminum (0.71 M) was added, and the mixture was reacted at room temperature for 1 hour. The obtained reaction mixture was added to the silicate slurry, stirred for 1 hour, and then mixed heptane was added to adjust the volume to 5,000 ml.
(Prepolymerization / cleaning)
Subsequently, the temperature inside the tank was raised to 40 ° C., and when the temperature became stable, 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 residual monomer was purged, stirring was stopped, and the mixture was allowed to stand for about 10 minutes, and then the supernatant was decanted by 2,400 ml. Subsequently, 9.5 ml of a heptane solution of triisobutylaluminum (0.71 M) and 5,600 ml of mixed heptane were added, the mixture was stirred at 40 ° C. for 30 minutes, allowed to stand for 10 minutes, and then 5,600 ml of the supernatant was removed. Further, this operation was repeated three times. When the component analysis of the final supernatant was carried out, the concentration of the organic aluminum component was 1.23 mM, the Zr concentration was 8.6 × 10 ^-6 g / L, and the amount of Zr present in the supernatant with respect to the charged amount (weight). The ratio) was 0.018% by weight. Subsequently, 170 ml of a heptane solution of triisobutylaluminum (0.71 M) was added, and then drying under reduced pressure was carried out at 45 ° C. A prepolymerization catalyst containing 2.0 g of polypropylene per 1 g of the catalyst was obtained.
Using this prepolymerization catalyst, a propylene-ethylene block copolymer was produced according to the following procedure.

(Ii) First Polymerization Step A horizontal reactor (L / D = 6, internal volume 100 liters) having a stirring blade was sufficiently dried, and the inside was sufficiently replaced with nitrogen gas. In the presence of a polypropylene powder bed, while stirring at a rotation speed of 30 rpm, a prepolymerized catalyst prepared by the above method was added to the upstream portion of the reactor (as a solid catalyst amount excluding the prepolymerized powder) at 0.568 g / hr. Triisobutylaluminum was continuously supplied at 15.0 mmol / hr. Continuously use the monomer mixed gas so that the temperature of the reactor is maintained at 65 ° C., the pressure is maintained at 2.1 MPaG, the ethylene / propylene molar ratio in the gas phase inside the reactor is 0.07, and the hydrogen concentration is 100% by volume ppm. Was circulated in the reactor and gas phase polymerization was performed. The polymer powder produced by the reaction was continuously withdrawn from the downstream part of the reactor so that the amount of powder bed in the reactor was constant. At this time, the amount of polymer extracted when the steady state was reached was 10.0 kg / hr.
Analysis of the propylene-ethylene random copolymer obtained in the first polymerization step revealed that the MFR was 6.0 g / 10 minutes (MFR: 230 ° C., 2.16 kg) and the ethylene content was 2.2% by weight. rice field.

(Iii) Second Polymerization Step The propylene-ethylene copolymer extracted from the first step was continuously supplied to a horizontal reactor (L / D = 6, internal volume 100 liters) having a stirring blade. While stirring at a rotation speed of 25 rpm, keep the temperature of the reactor at 70 ° C. and the pressure at 2.0 MPaG, and make the ethylene / propylene molar ratio of the gas phase inside the reactor 0.453 and the hydrogen concentration 330 volume ppm. , The monomer mixed gas was continuously circulated in the reactor, and gas phase polymerization was performed. The polymer powder produced by the reaction was continuously withdrawn from the downstream part of the reactor so that the amount of powder bed in the reactor was constant. At this time, oxygen was supplied as an activity inhibitor so that the amount of polymer extracted was 17.9 kg / hr, and the amount of polymerization reaction in the second polymerization step was controlled. The activity was 31.4 kg / g-catalyst.
Table 3 shows various analysis results of the propylene-based resin (A-1) thus obtained.

(3) Ethylene-α-olefin copolymer (B)
The following resins were used.

(B-1)
An ethylene-α-olefin copolymer, a trade name "kernel" manufactured by Japan Polyethylene Corporation, and a grade name "KS340T" were used. The melt flow rate (MFR: 190 ° C., 2.16 kg) is 3.5 g / 10 minutes, and the density is 0.880 g / cm ³ .
(B-2)
An ethylene-α-olefin copolymer, a trade name "kernel" manufactured by Japan Polyethylene Corporation, and a grade name "KF360T" were used. The melt flow rate (MFR: 190 ° C., 2.16 kg) is 3.5 g / 10 minutes, and the density is 0.898 g / cm ³ .
(B-3)
An ethylene-α-olefin copolymer, a trade name "Toughmer" manufactured by Mitsui Chemicals, Inc., and a grade name "P0280" were used. The melt flow rate (MFR: 190 ° C., 2.16 kg) is 3.0 g / 10 minutes, and the density is 0.869 g / cm ³ .

(4) Propylene homopolymer (C)
The resins obtained in the following production examples (C-1) to (C-3) were used.

(Manufacturing Example C-1)
(1) First Polymerization Step The first polymerizer of a horizontal polymerizer (L / D = 5.2, internal volume 50 m ³ ) having stirring blades rotating around the horizontal axis, stirring rotation speed 19.5 rpm, reaction pressure 2 The propylene homopolymer in the first polymerization step was produced at .25 MPaG and a polymerization temperature of 60 to 70 ° C. However, regarding the supply of the catalyst, the production rate of the Cheegler-based polymerization catalyst prepared according to Example 1 described in JP-A-2008-150466 so as to be the target production amount in the first polymerization step after the second polymerization step. Was fed to 8t / h. Triethylaluminum was fed so that the Al / Mg molar ratio was 10 with respect to Mg in the catalyst after the prepolymerization. Further, hydrogen and propylene were fed after adjusting the hydrogen / propylene molar ratio to 0.010 to produce a propylene homopolymer component.
(2) Second Polymerization Step The propylene homopolymer from the first polymerization step is applied to the second polymerizer of the horizontal polymerizer (L / D = 5.2, internal volume 50 m ³ ) having stirring blades rotating around the horizontal axis. The components were accepted and a propylene homopolymer component similar to that in the first polymerization step was produced. At this time, the stirring speed was 18 rpm, the reaction pressure was 2.20 MPaG, the polymerization temperature was 70 ° C., hydrogen and propylene were fed so as to be the target MFR of the propylene homopolymer component, and the hydrogen / propylene molar ratio = 0.010. To produce a propylene homopolymer component.
0.02 parts by weight of the antioxidant IR1010, 0.1 part by weight of IR168, and 0.05 parts by weight of the neutralizing agent DHT4A were added to 100 parts by weight of the obtained propylene homopolymer powder, and the mixture was used in an extruder. It was melt-kneaded at a die outlet temperature of 190 to 230 ° C. and pelletized. The MFR of this pellet was 4.2 g / 10 minutes (MFR: 230 ° C., 2.16 kg). This was used as a C-1 pellet.
(Production Example C-2): Antioxidant IR1010 is added to 100 parts by weight of a propylene homopolymer powder produced so that the molar ratio of hydrogen / propylene is 0.040 by the same polymerization method as in (C-1) above. .05 parts by weight, IF168 by 0.05 parts, and neutralizer CAST by 0.05 parts by weight were blended, dry blended with a super mixer, and then melted at a die outlet temperature of 190 to 230 ° C. using an extruder. It was kneaded and pelletized. The MFR of this pellet was 40 g / 10 min (MFR: 230 ° C., 2.16 kg). This was used as a C-2 pellet.
(Production Example C-3): Antioxidant IR1010 is added to 100 parts by weight of a propylene homopolymer powder produced so that the molar ratio of hydrogen / propylene is 0.025 by the same polymerization method as in (C-1) above. A mixture of 0.01 parts by weight, 0.05 parts by weight of the neutralizing agent CAST, and 0.03 parts by weight of the organic peroxide LP101 was melt-kneaded at a die outlet temperature of 190 to 230 ° C. using an extruder, and pelleted. It became. The MFR of this pellet was 75 g / 10 min (MFR: 230 ° C., 2.16 kg). This was designated as C-3 pellet.

(5) Propylene homopolymer, etc. (D)
The resins obtained in the following production examples (D-1) to (D-4) were used. The ethylene content of (Production Example D-2) was measured according to the method for measuring the ethylene contents E (A1) and E (A2) of the component (A) described above.
(Manufacturing Example D-1)
(1) First Polymerization Step The first polymerizer of a horizontal polymerizer (L / D = 5.6, internal volume 100 m ³ ) having stirring blades rotating around the horizontal axis, stirring rotation speed 13 rpm, reaction pressure 2.45 MPaG. , The propylene homopolymer of the first polymerization step was produced at a polymerization temperature of 63 to 70 ° C. However, regarding the supply of the catalyst, the Ziegler-based polymerization catalyst prepared according to Example 1 described in JP-A-2008-150466 was fed so as to have a production rate of 30 t / h after the second polymerization step. The triisobutylaluminum was fed so that the Al / Mg molar ratio was 5 with respect to Mg in the catalyst after the prepolymerization. Further, hydrogen and propylene were adjusted to a hydrogen / propylene molar ratio of 0.002 to produce a propylene homopolymer component.
(2) Second Polymerization Step The propylene homopolymer from the first polymerization step is applied to the second polymerizer of the horizontal polymerizer (L / D = 5.6, internal volume 100 m ³ ) having stirring blades rotating around the horizontal axis. The components were accepted and a propylene homopolymer component similar to that in the first polymerization step was produced. At this time, the stirring speed was 16 rpm, the reaction pressure was 2.40 MPaG, the polymerization temperature was 70 ° C., and hydrogen and propylene were adjusted to a hydrogen / propylene molar ratio = 0.002 to produce a propylene homopolymer component.
0.1 part by weight of the antioxidant IR1010, 0.2 part by weight of IF168, and 0.05 part by weight of the neutralizing agent CAST are added to the obtained propylene homopolymer powder, and the mixture is dry-blended with a super mixer and then extruded. Using a machine, the product was melt-kneaded at a die outlet temperature of 190 to 230 ° C. and pelletized. The MFR of this pellet was 0.4 g / 10 min (MFR: 230 ° C., 2.16 kg). This was used as a D-1 pellet.
(Manufacturing Example D-2)
Propylene-ethylene produced by feeding hydrogen, ethylene, and propylene so that the molar ratio of hydrogen / propylene is 0.002 and the molar ratio of ethylene / propylene is 0.004 by the same polymerization method as in (D-1). 0.10 parts by weight of antioxidant IR1010, 0.10 parts by weight of IF168, and 0.10 parts by weight of neutralizer CAST are mixed with 100 parts by weight of random copolymer powder, and a die outlet is used using an extruder. It was melt-kneaded at a temperature of 190 to 230 ° C. and pelletized. The MFR of this pellet was 0.5 g / 10 min (MFR: 230 ° C., 2.16 kg), and the ethylene content was 0.4% by weight. This was used as a D-2 pellet.
(Manufacturing Example D-3)
In the same polymerization method as in (D-1), 0.05 parts by weight of the antioxidant IR1010 was added to the propylene homopolymer powder produced while feeding hydrogen and propylene so that the molar ratio of hydrogen / propylene was 0.006. , IF168 by 0.10 part by weight and the neutralizing agent CAST by 0.05 part by weight were melt-kneaded at a die outlet temperature of 190 to 230 ° C. using an extruder to pelletize. The MFR of this pellet was 1.9 g / 10 minutes (MFR: 230 ° C., 2.16 kg). This was designated as D-3 pellet.
(D-4)
Instead of the propylene homopolymer, low-density polyethylene, trade name "Novatec LD" manufactured by Japan Polyethylene Corporation, and grade name "LM360" were used. The melt flow rate (MFR: 190 ° C., 2.16 kg) is 0.9 g / 10 minutes, and the density is 0.928 g / cm ³ .

(6) Propylene-ethylene block copolymer (CD)
The resin obtained in the following production example (CD-1), that is, a propylene-ethylene block which is a multi-stage polymer composed of a propylene homopolymer component (first stage) and a propylene-ethylene random copolymer component (second stage). A copolymer (CD) was used.
The propylene homopolymer component in the first stage corresponds to the propylene homopolymer (C). The ethylene content of (Production Example CD-1) was measured according to the method for measuring the ethylene contents E (A1) and E (A2) of the component (A) described above.
(Manufacturing Example CD-1)
(1) First Polymerization Step The first polymerizer of a horizontal polymerizer (L / D = 5.2, internal volume 50 m ³ ) having stirring blades rotating around the horizontal axis, stirring rotation speed 19.5 rpm, reaction pressure 2 The propylene homopolymer in the first polymerization step was produced at .25 MPaG and a polymerization temperature of 60 to 70 ° C. However, regarding the supply of the catalyst, the Ziegler-based polymerization catalyst prepared according to Example 1 described in JP-A-2008-150466 was fed so that the production rate after the second polymerization step would be 8 t / h. Triethylaluminum was fed so that the Al / Mg molar ratio was 10 with respect to Mg in the catalyst after the prepolymerization. Further, hydrogen and propylene were fed by adjusting the hydrogen / propylene molar ratio to 0.012 to produce a propylene homopolymer component.
Analysis of the propylene homopolymer obtained in the first polymerization step revealed that the MFR was 5.4 g / 10 minutes (MFR: 230 ° C., 2.16 kg).
(2) Second Polymerization Step The propylene homopolymer from the first polymerization step is applied to the second polymerizer of the horizontal polymerizer (L / D = 5.2, internal volume 50 m ³ ) having stirring blades rotating around the horizontal axis. Ingredients were accepted to produce a propylene-ethylene random copolymer component. At this time, the stirring speed was 18 rpm, the reaction pressure was 2.20 MPaG, the polymerization temperature was 60 ° C., and hydrogen, propylene, and ethylene were adjusted to hydrogen / propylene molar ratio = 0.009 and ethylene / propylenemol ratio = 0.450. A propylene-based polymer component was produced by feeding and feeding 1.0 mol / h of oxygen in order to control the reaction amount in the second polymerization step.
Add 0.05 parts by weight of the antioxidant IR1010, 0.10 parts by weight of IF168, and 0.05 parts by weight of the neutralizing agent CAST to 100 parts by weight of the obtained propylene-ethylene block copolymer powder. It was melt-kneaded and pelletized at a die outlet temperature of 190 to 230 ° C. The MFR of this pellet was 2.5 g / 10 minutes (MFR: 230 ° C., 2.16 kg), and the ethylene content was 10.1% by weight. Here, when the index for the propylene-ethylene random copolymer component produced in the second stage (second polymerization step) was calculated, the production amount was 21.5% by weight with respect to the total polymer weight, and MFR. Was 0.15 g / 10 minutes (MFR: 230 ° C., 2.16 kg), and the ethylene content was 47.0% by weight.
(Example 1)
(1) Blending The propylene-based resin (A-1) obtained in Production Example A-1 as the component (A), the ethylene-α-olefin copolymer (B-1) as the component (B), and the component (C). The propylene homopolymer (C-1) obtained in Production Example C-1 and the propylene homopolymer (D-1) obtained in Production Example D-1 as the component (D) were added in an amount of 57% by weight, respectively. The propylene-based resin composition obtained by weighing to 30% by weight, 10% by weight, and 3% by weight is put into a Henshell mixer (trade name), and then oxidized with respect to 100 parts by weight of the propylene-based resin composition. 0.07 parts by weight of the inhibitor IR1010, 0.07 parts by weight of the antioxidant IF168 and 0.01 part by weight of the neutralizing agent CAST were added, and the mixture was sufficiently stirred and mixed to obtain a compound.

(2) Granulation The obtained compound is melt-kneaded in a single-screw extruder or a twin-screw extruder at a screw rotation speed of 200 rpm, a discharge rate of 10 to 25 kg / hr, and an extruder temperature of 190 to 230 ° C., and a strand die. The molten resin extruded from the above was taken up while being cooled and solidified in a cooling water tank, and the strands were cut into a diameter of about 2 mm and a length of about 3 mm using a strand cutter to obtain raw material pellets.

(3) Evaluation of physical properties of the film The obtained raw material pellets were used as an extruder for an intermediate layer, a single-screw extruder with a diameter of 30 mm and L / D = 28, and an extruder for a skin layer, a diameter of 18 mm, L / D = 28. Extruded from a circular die with a mandrel diameter of 50 mm and a Lip width of 0.6 mm at a set temperature of 167 ° C., cooled with water, molded at a speed of 2 m / min, and formed into a tubular shape with a thickness of 300 μm. A molded body was obtained. Next, one side of the obtained tubular molded product was cut with a cutter to form a film, and then the film was adjusted for 24 hours or more in an atmosphere of 23 ° C. and 50% RH.
The epidermis layer uses the same raw material pellets as above and is laminated on the intermediate layer.
The physical characteristics of the obtained three-layer structure laminated film were evaluated. The evaluation results are shown in Table 4.
The film satisfying the constitution of the present invention maintains excellent transparency, flexibility and low temperature impact resistance, and has sufficient surface roughness, so that it has excellent blocking resistance.

(Example 2)
The propylene resin (A-1) obtained in Production Example A-1 is used as the component (A), the ethylene-α-olefin copolymer (B-1) is used as the component (B), and Production Example C is used as the component (C). The propylene homopolymer (C-2) obtained in -2 and the propylene homopolymer (D-1) obtained in Production Example D-1 as the component (D) were used in 63% by weight and 27% by weight, respectively. After putting the propylene-based resin composition obtained by weighing so as to be 5.4% by weight% and 4.6% by weight into a Henshell mixer (trade name), the additive compounding, granulation, and the like in Example 1 are carried out. A film was obtained and its physical properties were evaluated. The evaluation results are shown in Table 4.
The film satisfying the constitution of the present invention maintains excellent transparency, flexibility and low temperature impact resistance, and has sufficient surface roughness, so that it has excellent blocking resistance.

(Example 3)
The propylene resin (A-1) obtained in Production Example A-1 is used as the component (A), the ethylene-α-olefin copolymer (B-1) is used as the component (B), and Production Example C is used as the component (C). The propylene homopolymer (C-3) obtained in -3 and the propylene homopolymer (D-1) obtained in Production Example D-1 as the component (D) were added in an amount of 58% by weight and 27% by weight, respectively. The propylene-based resin composition obtained by weighing to 7% by weight and 8% by weight was put into a Henshell mixer (trade name), and then the additive compounding, granulation, and film were obtained in the same manner as in Example 1. The physical properties were evaluated. The evaluation results are shown in Table 4.
The film satisfying the constitution of the present invention maintains excellent transparency, flexibility and low temperature impact resistance, and has sufficient surface roughness, so that it has excellent blocking resistance.

(Example 4)
The propylene resin (A-1) obtained in Production Example A-1 is used as the component (A), the ethylene-α-olefin copolymer (B-1) is used as the component (B), and Production Example C is used as the component (C). The propylene homopolymer (C-3) obtained in -3 and the propylene homopolymer (D-1) obtained in Production Example D-1 as the component (D) were added in an amount of 60% by weight and 25% by weight, respectively. The propylene-based resin composition obtained by weighing to 5% by weight and 10% by weight was put into a Henshell mixer (trade name), and then the additive compounding, granulation, and film were obtained in the same manner as in Example 1. The physical properties were evaluated. The evaluation results are shown in Table 4.
The film satisfying the constitution of the present invention maintains excellent transparency, flexibility and low temperature impact resistance, and has sufficient surface roughness, so that it has excellent blocking resistance.

(Example 5)
The propylene resin (A-1) obtained in Production Example A-1 is used as the component (A), the ethylene-α-olefin copolymer (B-2) is used as the component (B), and Production Example C is used as the component (C). The propylene homopolymer (C-2) obtained in -2 and the propylene homopolymer (D-1) obtained in Production Example D-1 as the component (D) were used in 63% by weight and 27% by weight, respectively. After putting the propylene-based resin composition obtained by weighing so as to be 5.4% by weight% and 4.6% by weight into a Henshell mixer (trade name), the additive compounding, granulation, and the like in Example 1 are carried out. A film was obtained and its physical properties were evaluated. The evaluation results are shown in Table 4.
The film satisfying the constitution of the present invention maintains excellent transparency, flexibility and low temperature impact resistance, and has sufficient surface roughness, so that it has excellent blocking resistance.

(Example 6)
The propylene resin (A-1) obtained in Production Example A-1 is used as the component (A), the ethylene-α-olefin copolymer (B-3) is used as the component (B), and Production Example C is used as the component (C). The propylene homopolymer (C-2) obtained in -2 and the propylene homopolymer (D-1) obtained in Production Example D-1 as the component (D) were used in 63% by weight and 27% by weight, respectively. After putting the propylene-based resin composition obtained by weighing so as to be 5.4% by weight% and 4.6% by weight into a Henshell mixer (trade name), the additive compounding, granulation, and the like in Example 1 are carried out. A film was obtained and its physical properties were evaluated. The evaluation results are shown in Table 4.
The film satisfying the constitution of the present invention maintains excellent transparency, flexibility and low temperature impact resistance, and has sufficient surface roughness, so that it has excellent blocking resistance.

(Comparative Example 1)
The propylene resin (A-1) obtained in Production Example A-1 is used as the component (A), the ethylene-α-olefin copolymer (B-1) is used as the component (B), and Production Example C is used as the component (C). A propylene-based resin composition obtained by weighing the propylene homopolymer (C-1) obtained in -1 so as to be 63% by weight, 27% by weight, and 10% by weight, respectively, is a henschel mixer (trade name). In the same manner as in Example 1, additive compounding, granulation, and a film were obtained, and their physical properties were evaluated. The evaluation results are shown in Table 4.
Films that do not use the propylene homopolymer (D-1) have insufficient surface roughness, and the films block each other during high-temperature heat treatment, making them unsuitable for applications with high-temperature heat treatment steps. I understand.

(Comparative Example 2)
The propylene resin (A-1) obtained in Production Example A-1 is used as the component (A), the ethylene-α-olefin copolymer (B-1) is used as the component (B), and Production Example C is used as the component (C). The propylene homopolymer (C-1) obtained in -1 and the low-density polyethylene (D-4) as the component (D) were 63.5% by weight, 22.5% by weight, 10% by weight, and 4% by weight, respectively. After putting the propylene-based resin composition obtained by weighing so as to be% into a Henshell mixer (trade name), an additive compounding, granulation, and a film were obtained and their physical properties were evaluated in the same manner as in Example 1. .. The evaluation results are shown in Table 4.
A film using low-density polyethylene (D-4) instead of the propylene homopolymer (D-1) has insufficient surface roughness, and the films block each other during high-temperature heat treatment, resulting in high-temperature heat treatment. It turns out that the process is not suitable for certain applications.

(Comparative Example 3)
The propylene-based resin (A-1) obtained in Production Example A-1 was obtained as the component (A), the ethylene-α-olefin copolymer (B-1) was obtained as the component (B), and Production Example CD-1 was used. The propylene-based resin composition obtained by weighing the propylene-ethylene block copolymer (CD-1) so as to be 63% by weight, 24% by weight, and 13% by weight, respectively, is put into a Henshell mixer (trade name). After that, as in Example 1, additive compounding, granulation, and a film were obtained, and their physical properties were evaluated. The evaluation results are shown in Table 4.
The propylene homopolymer component in the first stage corresponds to the propylene homopolymer (C), and the propylene-ethylene random copolymer component in the second stage does not correspond to the propylene homopolymer (D-1). Since the film of Comparative Example 3 using the polymer (CD-1) does not use the propylene homopolymer (D-1), the surface roughness is insufficient, and the films are blocked from each other during the high temperature heat treatment. Therefore, it turns out that it is not suitable for applications with a high temperature heat treatment process.

(Comparative Example 4)
The propylene resin (A-1) obtained in Production Example A-1 is used as the component (A), the ethylene-α-olefin copolymer (B-1) is used as the component (B), and Production Example C is used as the component (C). The propylene homopolymer (C-2) obtained in -2 and the propylene-ethylene random copolymer (D-2) obtained in Production Example D-2 as the component (D) were 59% by weight and 27, respectively. The propylene-based resin composition obtained by weighing to 10% by weight, 10% by weight, and 4% by weight is put into a Henshell mixer (trade name), and then the additive formulation, granulation, and film are carried out in the same manner as in Example 1. Was obtained, and its physical properties were evaluated. The evaluation results are shown in Table 4.
Films using a propylene-ethylene random copolymer (D-2) instead of the propylene homopolymer (D-1) have insufficient surface roughness, and the films block each other during high-temperature heat treatment. It turns out that it is not suitable for applications with high temperature heat treatment steps.

(Comparative Example 5)
The propylene resin (A-1) obtained in Production Example A-1 is used as the component (A), the ethylene-α-olefin copolymer (B-1) is used as the component (B), and Production Example C is used as the component (C). The propylene homopolymer (C-3) obtained in -3 and the propylene-ethylene random copolymer (D-2) obtained in Production Example D-2 as the component (D) were 59% by weight and 27, respectively. After putting the propylene-based resin composition obtained by weighing so as to be% by weight, 6% by weight, and 8% by weight into a Henshell mixer (trade name), the additive compounding, granulation, and film are carried out in the same manner as in Example 1. Was obtained, and its physical properties were evaluated. The evaluation results are shown in Table 4.
Films with an increased amount of propylene-ethylene random copolymer (D-2) added have insufficient surface roughness, and the films block each other during high-temperature heat treatment, making them suitable for applications with high-temperature heat treatment steps. Turns out to be unsuitable.

(Comparative Example 6)
The propylene resin (A-1) obtained in Production Example A-1 is used as the component (A), the ethylene-α-olefin copolymer (B-1) is used as the component (B), and Production Example C is used as the component (C). The propylene homopolymer (C-3) obtained in -3 and the propylene-ethylene random copolymer (D-2) obtained in Production Example D-2 as the component (D) were added in an amount of 58% by weight and 27, respectively. After putting the propylene-based resin composition obtained by weighing so as to be% by weight, 5% by weight, and 10% by weight into a Henshell mixer (trade name), the additive compounding, granulation, and film are carried out in the same manner as in Example 1. Was obtained, and its physical properties were evaluated. The evaluation results are shown in Table 4.
The film in which the amount of the propylene-ethylene random copolymer (D-2) added is further increased has insufficient surface roughness, and the films are blocked from each other during the high temperature heat treatment, so that the film has a high temperature heat treatment step. It turns out that it is not suitable for.

(Comparative Example 7)
The propylene resin (A-1) obtained in Production Example A-1 is used as the component (A), the ethylene-α-olefin copolymer (B-1) is used as the component (B), and Production Example C is used as the component (C). The propylene homopolymer (C-2) obtained in -2 and the propylene homopolymer (D-3) obtained in Production Example D-3 as the component (D) were added in an amount of 58% by weight and 27% by weight, respectively. The propylene-based resin composition obtained by weighing to 7% by weight and 8% by weight was put into a Henshell mixer (trade name), and then the additive compounding, granulation, and film were obtained in the same manner as in Example 1. The physical properties were evaluated. The evaluation results are shown in Table 4.
The film using the propylene homopolymer (D-3) having an MFR of 1.9 (MFR: 230 ° C., 2.16 kg) has insufficient surface roughness, and the films block each other during the high temperature heat treatment. It turns out that it is not suitable for applications with a high temperature heat treatment process.

In contrast to each of the above Examples and Comparative Examples, the novel propylene-based resin composition of the present invention, which satisfies each of the provisions of the present invention, has excellent flexibility, transparency and low temperature resistance. It is clear that it is possible to obtain a film having an excellent effect of suppressing the blocking phenomenon that occurs during the high temperature heat treatment while maintaining the impact resistance.

A propylene-based resin composition and a propylene-based resin composition that can obtain a film that does not easily cause the blocking phenomenon that occurs during high-temperature heat treatment because it has sufficient surface roughness while maintaining excellent flexibility, transparency, and low-temperature impact resistance. The film used is extremely useful for heavy-weight packaging such as standing pouches and water packaging, and for containers obtained by deep drawing.

Claims (3)

Ethylene-α-olefin copolymer satisfying the following conditions (A-i) to (A-iii), 35 to 88% by weight of the propylene resin (A), and the following conditions (B-i) to (B-ii). (B) 10 to 35% by weight, propylene homopolymer (C) 1 to 15% by weight satisfying the following condition (Ci), and propylene homopolymer (D) 1 to satisfying the following condition (Di). It contains 15% by weight (however, the total of the propylene resin (A), the ethylene-α-olefin copolymer (B), the propylene homopolymer (C) and the propylene homopolymer (D) is 100% by weight. A propylene-based resin composition characterized by the above.
(A) Propylene resin (Ai) Propylene-α having a melting peak temperature Tm (A1) of 125 to 135 ° C. and an α-olefin content E (A1) of 1.5 to 3.0% by weight in DSC measurement. -The olefin random copolymer component (A1) is 50 to 60% by weight, and the propylene-ethylene random copolymer component (A2) having an ethylene content E (A2) of 8 to 14% by weight is 50 to 40% by weight. Being a metallocene-based propylene-α-olefin block copolymer (A) which is a multi-stage polymer composed of.
(A-ii) The melt flow rate (MFR (A): 230 ° C., 2.16 kg) is in the range of 4 to 10 g / 10 minutes.
(A-iii) In the temperature-loss tangent (tanδ) curve obtained by solid viscoelasticity measurement (DMA), the peak of the tanδ curve representing the glass transition observed in the range of -60 to 20 ° C is simply below 0 ° C. Show one peak.
(B) The density of the ethylene-α-olefin copolymer (Bi) is in the range of 0.860 to 0.900 g / cm ³ .
(B-ii) Melt flow rate (MFR (B): 190 ° C., 2.16 kg) is 2.0 g / 10 minutes or more.
(C) The melt flow rate of the propylene homopolymer (C-i) (MFR (C): 230 ° C., 2.16 kg) is in the range of 1.9 to 100 g / 10 minutes.
(D) The melt flow rate of the propylene homopolymer (Di) (MFR (D): 230 ° C., 2.16 kg) is less than 1.9 g / 10 minutes. The propylene-based product according to claim 1, wherein the melt flow rate ratio (MFR (C) / MFR (D)) of the propylene homopolymer (C) and the propylene homopolymer (D) satisfies 5 to 300. Resin composition. A film comprising the propylene-based resin composition according to claim 1 or 2.