JP2001049060A - Propylenic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a propylenic resin composition excellent in the balance between rigidity and heat resistance as well as in impact resistance. SOLUTION: This resin composition comprises a polypropylene component and a propylene/ethylene copolymer component, and gives, by the temperature- rising elution fractionation method, fractionated eluted components consisting of 5-25 wt.% of an eluted component (component A) below 20 deg.C, 8-45 wt.% of an eluted component (component B) at a temperature of not lower than 20 and lower than 90 deg.C and more than 40 wt.% and not more than 85 wt.% of an eluted component (component C) above 90 deg.C, the ratio of the component B to the component A (B/A) being at least 0.5, and has a mol.wt. distribution (Mw/Mn) and a melt flow rate(MFR) satisfying the equation: 0.4<=log(Mw/ Mn)×MFR0.33<=1.5.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a novel propylene-based resin composition. More specifically, the present invention relates to a propylene-based resin composition having excellent rigidity and impact resistance, excellent heat resistance, and good moldability.

[0002]

2. Description of the Related Art Conventionally, as means for improving the impact resistance of a propylene-based resin, amorphous ethylene-propylene rubber (hereinafter, referred to as amorphous rubber) has been used.
A method of adding a soft material such as EPR) is generally used.

However, since the propylene-based resin and EPR have poor compatibility, a small amount of addition does not provide a sufficient effect of improving the impact resistance. However, there was a problem that was reduced.

[0004] In order to solve the above problems, there has been proposed means for producing a soft material having good compatibility with a propylene-based resin and mixing the same with the propylene-based resin. Specifically, a method of mixing a soft material obtained by a method of producing a crystalline polyolefin component and a low-crystalline ethylene-propylene copolymer component by continuous polymerization (hereinafter abbreviated as polymerization method) with a propylene-based resin. It is.

The present inventors have also disclosed in Japanese Patent Application Laid-Open No. 5-331328 that a soft material comprising a specific propylene block copolymer obtained by the above polymerization method is mixed with a propylene resin to obtain good compatibility. A propylene-based resin composition having excellent rigidity and impact resistance that achieves the above was proposed.

[0006]

However, a conventional composition obtained by mixing a propylene-based block copolymer obtained by a polymerization method with a propylene-based resin has a disadvantage in that the composition of the copolymer and the propylene-based resin is mixed. Because of the good solubility, the improvement of impact resistance by the propylene-based block copolymer can be achieved without lowering the rigidity, but on the other hand, there is a problem that the heat resistance decreases. Further, the propylene-based block copolymer of the present invention has a narrow molecular weight distribution due to its production method, and causes a decrease in moldability when mixed with a propylene-based resin having a low melt flow rate, and an improvement is desired. Was.

Accordingly, an object of the present invention is to provide a propylene-based resin composition having excellent rigidity and impact resistance, excellent heat resistance, and good moldability.

[0008]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the object, and as a result, the achievement of the object has been achieved not only by improving the compatibility of a soft material with a propylene resin but also by improving the compatibility thereof. It has been found that it is necessary to adjust all factors such as the crystallinity distribution and molecular weight distribution of the resin composition. As a result of further research based on the above findings, we succeeded in developing a new propylene-based resin composition having a specific crystallinity distribution and molecular weight distribution, and the propylene-based resin composition has excellent rigidity and impact resistance. It was confirmed that the composition also had excellent heat resistance and good moldability, and completed the present invention.

That is, the present invention is a propylene resin composition comprising a polypropylene component and a propylene-ethylene copolymer component and having the following characteristics. (1) 5 to 25% by weight of the eluted component (component A) having a temperature of less than 20 ° C., from 20 ° C. to less than 90 ° C., of the eluted components separated by the temperature-increasing elution fractionation method using an O-dichlorobenzene solvent The amount of the eluted component (component B) is 8 to 45% by weight, and the amount of the eluted component (component C) at 90 ° C. or higher is 50 to 85%.
% By weight, and the total of the components A, B and C is 10
0% by weight. (2) The weight ratio (B / A) of the component B and the component A is 0.5 or more. (3) Weight average molecular weight (Mw) and number average molecular weight (Mn)
And the molecular weight distribution (Mw / Mn) is 4 or more, and the molecular weight distribution and the melt flow rate (MF
R) satisfy the following formula (I).

0.40 ≦ log ((Mw / Mn) × MFR ^0.33 ) ≦ 1.5 (I)

[0011]

DESCRIPTION OF THE PREFERRED EMBODIMENTS In the present invention, the temperature-elevating elution fractionation method is, for example, a Journal of Applier.
d Polymer Science; Applied
Polymer Symposium 45, 1-2
4 (1990). First, a high-temperature polymer solution is introduced into a column filled with diatomaceous earth filler, and the column temperature is gradually lowered to crystallize the filler surface in order from the component with the highest melting point, and then the column temperature is gradually increased. This is a method in which the components are eluted in order from the component having the lowest melting point by raising the temperature, and the eluted polymer component is collected. In the present invention, as shown in detail in the examples, SSC-7300 type manufactured by Senshu Kagaku Co., Ltd. was used as a measuring device, solvent: O-dichlorobenzene, flow rate: 2.5 ml /
min, heating rate: 4 ° C./Hr, column: φ30 mm ×
The values measured under the condition of 300 mm are shown.

In the propylene-based resin composition comprising the polypropylene component and the propylene-ethylene copolymer component of the present invention, the elution component (component A) at a temperature lower than 20 ° C., which is fractionated by the above-mentioned temperature raising elution fractionation method, 20 ° C
The amount of all eluted components on the low temperature side up to 5 to 25% by weight. When the amount of the component A is less than 5% by weight, the impact resistance of the obtained polypropylene-based resin composition is reduced, and 25% by weight.
If it exceeds, rigidity and heat resistance are reduced. Impact resistance, rigidity,
Considering the balance of heat resistance, the amount of the component A is preferably 8 to 23% by weight.

In the propylene resin composition of the present invention, the amount of the eluted component at 20 ° C. or more and less than 90 ° C. (hereinafter abbreviated as B component) is 8 to 45% by weight. When the amount of the component B is less than 8% by weight, the polypropylene component and the propylene-
The compatibility of the ethylene copolymer component is reduced, and the impact resistance of the resulting polypropylene resin composition is reduced. Also,
If it exceeds 45% by weight, excellent rigidity and heat resistance cannot be satisfied. Regarding impact resistance, rigidity and heat resistance, B
The component amount is preferably from 10 to 40% by weight.

Further, in the propylene resin composition of the present invention, the weight ratio of the B component and the A component (B component amount / A component amount) is preferably 0.5 or more. B component and A
If the weight ratio of the components (B component amount / A component amount) is less than 0.5, the rigidity and heat resistance characteristic of the polypropylene resin composition of the present invention tend to decrease, which is not preferable. In order to have better heat resistance and surface hardness, B
The weight ratio of the component to the component A (B component amount / A component amount) is preferably 0.55 or more, and more preferably 0.60 or more.

In the propylene resin composition of the present invention, the amount of the eluted component at 90 ° C. or higher (hereinafter abbreviated as C component) is 50 to 85% by weight or less. When the amount of the C component is 50% by weight or less, rigidity and heat resistance are reduced, and when it exceeds 85% by weight, impact resistance is poor. In order to satisfy excellent rigidity, heat resistance and impact resistance, the amount of the C component is preferably 50 to 83% by weight, more preferably 5 to 83% by weight.
0 to 80% by weight.

In the present invention, the components A, B and C, which are the elution components obtained by the temperature rising elution fractionation method, are crystals of the propylene resin composition of the present invention comprising a polypropylene component and a propylene-ethylene copolymer component. Each component has a crystallinity that sequentially decreases from the C component to the A component. Such crystallinity is generally approximately proportional to the ethylene content in the propylene-ethylene copolymer component, which is a random copolymer.

That is, the component C is a fraction in which propylene monomer units occupy almost the entire proportion, and usually 100 to 95 mol% of propylene monomer units and 0 to 100% of other α-olefin monomer units. Propylene-α-
It consists of an olefin copolymer. Examples of the α-olefin include ethylene, 1-butene, 1-pentene, 1-hexene, 4-methylpentene-1, 1-octene and the like.

The component B is a fraction in which the ethylene monomer unit is present in a relatively small amount with respect to the propylene monomer unit.
The copolymer composition has a mol% of 5 to 20 mol% of ethylene monomer units.

The component A is a propylene-ethylene random copolymer component containing an amorphous polypropylene component, and generally has a relatively large number of ethylene monomer units relative to propylene monomer units. Fraction present in quantity. Usually, the propylene monomer unit has a copolymer composition of not more than 80 mol% and the ethylene monomer unit of not less than 20 mol%, but in the propylene resin composition of the present invention,
Considering the compatibility with the component B and the component C, the propylene monomer unit is 80 to 50 mol% and the ethylene monomer unit is 20%.
Those having a copolymer composition of ５０50 mol% are preferred.

The propylene-based resin composition of the present invention has a molecular weight distribution (Mw / Mn) represented by a ratio of a weight average molecular weight (Mw) to a number average molecular weight (Mn) and a melt flow rate (MFR) represented by the following formula (MFR). I) must be satisfied.

0.40 ≦ log ((Mw / Mn) × MFR ^0.33 ) ≦ 1.5 (I) That is, when the melt flow rate of the propylene-based resin composition is low, if the molecular weight distribution is narrow, the moldability is reduced. When the melt flow rate is high, the bleeding of low molecular weight substances increases if the molecular weight distribution is wide, which adversely affects the surface hardness of the molded article.

Therefore, when the propylene-based resin composition of the present invention does not satisfy the condition of the above formula (I), the moldability is deteriorated and the physical properties such as the surface hardness of the molded product are deteriorated. In consideration of the above moldability and physical properties, the value of the formula (I) is 0.45
-1.3 is preferred.

The molecular weight distribution (Mw / Mn) of the propylene resin composition of the present invention is 4 or more, preferably 4 to 15.
It is. That is, when the molecular weight distribution is less than 4, the melt viscosity increases and the moldability decreases, whereby the appearance of a molded article obtained using the propylene-based resin composition decreases.

The melt flow rate of the propylene resin composition of the present invention is not particularly limited, but is generally 0.1 to 100 g / 10 min, preferably 0.1 to 80 g / 10 min, and more preferably. 0.1 ~
It is 50 g / 10 min. Melt flow rate is 0.
If it is less than 1 g / 10 min, the moldability tends to decrease, which is not preferable. On the other hand, if the melt flow rate exceeds 100 g / 10 min, physical properties may be deteriorated, which is not preferable.

The method for producing the propylene resin composition used in the present invention is not particularly limited as long as the requirements of the present invention are satisfied.
Considering the compatibility with the ethylene copolymer, a method for producing the A to C components by a polymerization method can be mentioned.

However, when it is intended to adjust the components A to C by a polymerization method in an amount ratio that matches the composition of the propylene-based resin composition of the present invention, the obtained polymer becomes viscous and is difficult to manufacture or handle. May cause trouble. In order to avoid such a problem, a method of obtaining a polymer having a high molecular weight can be considered.However, in order to improve the moldability of the obtained polymer, it is necessary to perform thermal decomposition and adjust a melt flow rate. There is. And
In this case, there is a possibility that the polypropylene component constituting the C component is decomposed more than necessary and strength such as rigidity is reduced.

Accordingly, a preferred method for producing the propylene-based resin composition of the present invention is a propylene-ethylene block having the following components a to c in which a part of the polypropylene component is reduced from the composition of the propylene resin composition. This is a method in which a copolymer is produced by a polymerization method, and a polypropylene-based polymer obtained by separate polymerization is mainly mixed as a polypropylene component.

That is, the present invention relates to a preferred method for producing the propylene resin composition, which comprises mixing a propylene-ethylene block copolymer obtained by a polymerization method and having the following characteristics with a propylene polymer. A method for producing a resin composition is also provided.

(1) With respect to the eluted components separated by the temperature-increasing elution fractionation method using an O-dichlorobenzene solvent, the amount of the eluted component (component a) at a temperature lower than 20 ° C. is 10 to 60.
The amount of the eluted component (component b) at 20 ° C. or more and less than 90 ° C. is 10 to 70% by weight, the amount of the eluted component (component c) at 90 ° C. or more is 1 to 40% by weight, and a component b Component and c
The sum of the components is 100% by weight.

(2) The weight ratio of the component b to the component a (b /
a) is 0.6 or more.

(3) Molecular weight distribution (Mw / Mw) expressed by the ratio of weight average molecular weight (Mw) to number average molecular weight (Mn)
n) is 2 to 8, and the molecular weight distribution (Mw / Mn) and the melt flow rate (MFR) satisfy the following formula (II).

0.5 ≦ log ((Mw / Mn) × MFR ^0.33 ) ≦ 1.0 (II) In the present invention, the propylene-ethylene block copolymer obtained by the polymerization method comprises a polypropylene component and a propylene-ethylene random Because the molecular chains of the so-called block copolymer in which the copolymer components are arranged in one molecular chain and / or the molecular chains of the polypropylene component and the propylene-ethylene random copolymer component alone are mixed microscopically. Compatibility with the propylene-based polymer.

In the present invention, the propylene-ethylene block copolymer comprising the above (a) to (c) obtained by the polymerization method has excellent heat resistance and is compatible with the propylene-based polymer. Therefore, a propylene-based resin composition having excellent heat resistance, impact resistance, and rigidity can be obtained by mixing with this.

In the present invention, in the above-mentioned production method, 20 ° C., which is a total eluting component of the propylene-ethylene block copolymer obtained by the polymerization method, which is fractionated up to 20 ° C. by a temperature rising elution fractionation method, The elution component (a component) in less than is a component necessary for imparting excellent impact resistance to a propylene-based resin composition obtained by mixing with a propylene-based polymer, and a balance between rigidity and heat resistance. In consideration of the above, the amount is preferably 20 to 60% by weight. In particular, considering the balance of impact resistance, rigidity and heat resistance of the obtained propylene-based resin composition, the amount of the component a is 20
Preferably, it is about 55% by weight.

In the present invention, all the eluting components (component (b)) of less than 20 ° C. and less than 90 ° C., which are fractionated by the temperature raising elution fractionation method of the propylene-ethylene block copolymer obtained by the polymerization method, are as described above. It is also a component that is compatible with the propylene-based polymer together with its function, and its amount is preferably 20 to 70% by weight. b component amount is 2
If the amount is less than 0% by weight, the compatibility with the propylene-based polymer is reduced, the impact resistance is reduced, and the amount of the component b is 70% by weight.
If it exceeds, the rigidity and heat resistance decrease, which is not preferable. Considering the balance of impact resistance, rigidity and heat resistance of the obtained propylene resin composition, the amount of the component b is 2
It is preferably from 5 to 65% by weight, more preferably from 30 to 60% by weight.
% By weight.

The weight ratio (b component amount / a component amount) of the propylene-ethylene block copolymer b component and a component used in the present invention is preferably 0.6 or more. In order to obtain a propylene-based resin composition having better heat resistance and rigidity when mixed with a propylene-based polymer, the weight ratio of the b-component and the a-component (b-component amount / a-component amount) is preferably 0.65 or more, more preferably 0.
It is desirable that the number be 7 or more.

The low crystalline component consisting of the component a and the component b of the propylene-ethylene block copolymer used in the present invention is not particularly limited. 1 monomer unit
Desirably, it is 0 to 50 mol%. When the ethylene monomer unit is less than 10 mol%, the flexibility of the obtained propylene-based resin composition is reduced, and when the ethylene monomer unit exceeds 50 mol%, the obtained propylene-based resin composition is The heat resistance of the composition decreases. In consideration of the balance between flexibility and heat resistance, the ethylene content of the low crystalline component is preferably 12 to 48 mol%, more preferably 15 to 45 mol%.
Mol%.

In the present invention, the amount of all the eluted components (component (c)) at 90 ° C. or higher, which is separated by the temperature-raising elution fractionation method, of the propylene-ethylene block copolymer obtained by the polymerization method is from 1 to 40 weight%. %. c
When the amount of the component is less than 1% by weight, the production of the propylene-ethylene block copolymer becomes difficult, and when the amount of the component c exceeds 40% by weight, it is preferable to mix with the propylene-based polymer. It is not preferable because the impact resistance of the obtained propylene-based resin composition is reduced.

In the present invention, the propylene-ethylene block copolymer obtained by the polymerization method has a molecular weight distribution (Mw / Mn) represented by the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of from 2 to 8. And the molecular weight distribution (M
w / Mn) and the melt flow rate (MFR) preferably satisfy the following formula (II).

0.5 ≦ log ((Mw / Mn) × MFR ^0.33 ) ≦ 1.0 (II) When the molecular weight distribution (Mw / Mn) is less than 2 and the condition of the formula (II) is not satisfied, propylene The propylene-based resin composition obtained when mixed with a styrene-based polymer, the molecular weight distribution (Mw / Mn) exceeds 8, and the formula (II)
If the above condition is not satisfied, it is not preferable because low molecular weight substances increase and affect the surface hardness of the obtained propylene-based resin composition. For this reason, the molecular weight distribution (Mw /
Mn) is preferably from 2 to 6, and the formula (II)
Is preferably 0.6 to 1.

The melt flow rate of the propylene-ethylene block copolymer is not particularly limited, but is generally preferably 0.1 to 50 g / 10 min. Melt flow rate is 0.1g / 10
If it is less than min, the moldability of the resulting propylene-based resin composition will be reduced, and if it is more than 50 g / 10 min, low molecular weight substances will increase and physical properties will be reduced. Considering moldability and physical properties, the melt flow rate is preferably 0.1 to 40 g / 10 min, and more preferably 0.1 to 40 g / 10 min.
It is 1 to 30 g / 10 min.

The propylene-ethylene block copolymer used in the present invention has the above-mentioned crystalline distribution,
Molecular weight distribution, and excellent rigidity and heat resistance to have a relationship between the specific molecular weight distribution and melt flow rate, and,
Excellent in impact resistance and moldability. On the other hand, in JP-A-5-331328, it is difficult to satisfy the crystallinity distribution of the propylene-ethylene copolymer within the range of the present invention, and even when the melt flow rate is low, Since the molecular weight distribution is narrow, the moldability may be deteriorated, and an improvement has been desired.

In the present invention, the process for producing a propylene-ethylene block copolymer comprising the above components (a) to (c) is carried out in the presence of the following catalyst components [a], [b] and [c]. After the above polymerization, a method of successively increasing the ethylene supply ratio and performing random copolymerization of propylene and ethylene is preferred. [A] Titanium compound [b] Organoaluminum compound [c] Electron donor As the titanium compound [a], a titanium compound known to be used for olefin polymerization may be used without any limitation. In particular, when the propylene-based resin composition of the present invention is obtained, a titanium trichloride compound that can obtain a highly stereoregular polymer in a high yield when used for the polymerization of propylene is preferable.

Next, the organoaluminum compound [b] is
Compounds known to be used for the polymerization of olefins are employed without any limitation, and trialkylaluminums are used as essential components, and as necessary, dialkylaluminum monohydrides, alkoxyaluminums, and the like are used in combination. Preferably, one is used.

As the electron donor [c], a compound known to be used for improving the stereoregularity of an olefin is employed without any limitation. For example, ester compounds, ether compounds, and organosilicon compounds are used. Among them, an organosilicon compound is preferable, and an organosilicon compound having a bulky substituent such as a chain hydrocarbon in which an atom directly bonded to a silicon atom is tertiary carbon or a cyclic hydrocarbon in which tertiary carbon is used, It is preferable because the stereoregularity of the obtained polypropylene component is further increased and good heat resistance is exhibited.

The titanium compound [A] used in the present invention,
The combination of the organoaluminum compound [b] and the electron donor [c] is as follows: (1) titanium trichloride compound-trialkylaluminum-electron donor (2) titanium trichloride compound-trialkylaluminum / diethylaluminum monochloride-electron When the combination of the donor and the other production conditions is changed, (a)
The propylene-ethylene block copolymer that satisfies the above ranges for the amounts of the components (c) to (c) can be easily produced, which is preferable.

In the present invention, prior to the main polymerization in the presence of each of the above components, the titanium compound (i) is preliminarily polymerized with an α-olefin in the presence of the above (ii) and (iii). However, it is preferable because the amount of low molecular weight components generated in the obtained polypropylene resin composition can be reduced and stickiness in the case of a molded article can be suppressed. Further, if necessary, in addition to the respective combination systems using the above [b] and [c], an iodine compound [d] RI represented by the following general formula (where R is an iodine atom or a group having 1 to 1 carbon atoms) Pre-polymerizing the α-olefin in the presence of an alkyl group or a phenyl group of formula (7) to further reduce the amount of low molecular weight components produced in the resulting propylene-ethylene block copolymer, This is a more preferable embodiment because stickiness in the case of (1) can be further suppressed.

The catalysts (a) and (b) used in the prepolymerization of the present invention, (c) used as needed, and (d) further used as needed Since the amount of the component varies depending on the type of the catalyst component and the polymerization conditions, the optimum use amount may be determined in advance according to each of these conditions. An example of a range preferably used is as follows.

The ratio of the organoaluminum compound [b] used in the prepolymerization is A to the titanium compound [a].
0.1 / 100 (preferably 0.1 / 100) in 1 / Ti (molar ratio).
The proportion of the organosilicon compound [c] used in the range of 1 to 20, and if necessary, is 0.01 to 100 as [c] / Ti (molar ratio) with respect to the titanium compound [a], preferably. Is preferably in the range of 0.01 to 10.
The proportion of the iodine compound [d] used as necessary is in the range of 0.1 to 100, preferably 0.5 to 50 in I / Ti (molar ratio) with respect to the titanium compound [a]. It is suitable.

Specific examples of the iodine compound that can be suitably used in the prepolymerization of the present invention are as follows. For example, iodine, methyl iodide, ethyl iodide, propyl iodide,
Butyl iodide, iodobenzene, p-iodine toluene and the like. Particularly, methyl iodide and ethyl iodide are preferred.

The amount of prepolymerization for polymerizing an α-olefin in the presence of the catalyst component varies depending on the prepolymerization conditions.
Generally, a range of 0.1 to 500 g / g · Ti compound, preferably 1 to 100 g / g · Ti compound, is sufficient. The α-olefin used in the prepolymerization may be propylene alone, and 5 mol% or less of other α-olefin, for example, ethylene or 1-butene, as long as the physical properties of the propylene-based resin composition are not adversely affected. Mixing 1-pentene, 1-hexene, 4-methylpentene-11-octene and the like with propylene is acceptable. Also,
The prepolymerization can be performed in multiple stages, and different α-olefin monomers can be prepolymerized in each stage. In particular, as a prepolymerization method for obtaining the propylene-ethylene block copolymer of the present invention, a multi-stage method of polymerizing propylene in the first step and subsequently polymerizing another α-olefin is preferable, and among them, The preliminary polymerization is performed so that the polymerization ratio of the other α-olefin and propylene is in the range of 0.1 / 1 to 10/1 in terms of the polyα-olefin / polypropylene ratio. This is preferable because it can be further suppressed.

In the above case, it is also possible to make hydrogen coexist at each prepolymerization stage. It is preferable to apply slurry polymerization for the pre-polymerization in general.Saturated aliphatic or aromatic hydrocarbons such as hexane, heptane, cyclohexane, benzene and toluene are used alone or as a mixed solvent. Can be. The prepolymerization temperature is preferably in the range of -20 to 100C, particularly preferably 0 to 60C. The pre-polymerization time may be appropriately determined according to the pre-polymerization temperature and the amount of polymerization in the pre-polymerization. The pressure in the pre-polymerization is not limited, but in the case of slurry polymerization, it is generally from atmospheric pressure to about 5 kg / cm ² G. The prepolymerization may be performed in any of batch, semi-batch, and continuous methods.

The main polymerization is carried out after the preliminary polymerization. In the main polymerization, propylene is firstly polymerized and then propylene-ethylene random copolymerization is performed in the presence of the catalyst-containing prepolymer obtained by the above prepolymerization. The catalyst components added during the prepolymerization can be used as they are, but it is preferable to add and adjust the components other than the titanium compound during the main polymerization.

The above [A] used in the main polymerization of the present invention,
Since the amounts and polymerization conditions of each of the catalyst components (b) and (c) differ depending on the type of the catalyst components, the optimum use amount and polymerization conditions may be determined in advance according to the types of these catalyst components. . Examples of the amount of the catalyst component and the polymerization conditions suitably used are as follows.

The amount of the organoaluminum compound [b] used in the main polymerization is 1 to 1000, preferably 2 to 500, in terms of Al / Ti (molar ratio), based on the titanium atoms in the catalyst-containing prepolymer. .

The amount of the electron donor [c] used in the main polymerization is determined based on the amount of S based on the titanium atom in the catalyst-containing prepolymer.
i / Ti (molar ratio) is 0.001 to 1000, preferably 0.1 to 500.

In the above main polymerization, propylene is firstly polymerized. The polymerization of propylene may be carried out by supplying propylene alone or a mixture of propylene and another α-olefin within a range satisfying the requirements of the present invention. Taking typical conditions for propylene polymerization as an example, it is preferable to employ a polymerization temperature of 80 ° C. or less, and more preferably in the range of 20 to 70 ° C. If necessary, hydrogen can also be allowed to coexist as a molecular weight regulator. Furthermore, the polymerization may be any method such as slurry polymerization using propylene itself as a solvent, gas-phase polymerization, and solution polymerization. Considering the simplicity of the process, the reaction rate, and the particle properties of the produced copolymer, slurry polymerization using propylene itself as a solvent is a preferred embodiment. The polymerization system may be any of a batch system, a semi-batch system, and a continuous system. Further, the polymerization can be performed in two or more stages having different conditions such as hydrogen concentration and polymerization temperature.

Next, random copolymerization of propylene and ethylene is performed. In the random copolymerization of propylene and ethylene, in the case of slurry polymerization using propylene itself as a solvent, ethylene gas is supplied following the propylene polymerization, and in the case of gas phase polymerization, a mixed gas of propylene and ethylene is supplied. It is implemented by doing.

The polymerization temperature for the random copolymerization of propylene and ethylene is 80 ° C. or lower, preferably 20 to 70 ° C. If necessary, hydrogen can be used as a molecular weight regulator, and the polymerization can be carried out by changing the hydrogen concentration at this time in multiple stages.

In the random copolymerization of ethylene and propylene following the propylene polymerization, by selecting the above specific catalyst, the desired propylene resin composition having a desired molecular weight distribution, crystallinity distribution, copolymerizability, etc. can be obtained in one step. Although it can be produced, as a method for obtaining the propylene-based resin composition of the present invention, a method in which random copolymerization is performed in multiple stages and polymerization conditions such as hydrogen concentration and ethylene concentration are changed in each stage may be used. In such multi-stage copolymerization,
The copolymerization is carried out by appropriately adjusting the proportions of the components a, b and c according to the polymerization conditions.

The random copolymerization of propylene and ethylene may be any of a batch system, a semi-batch system and a continuous system, and the polymerization may be carried out in multiple stages. Further, for the polymerization in this step, any method of slurry polymerization, gas-phase polymerization, and solution polymerization may be adopted, and in particular, (a) to (d) of the present invention are used.
(C) The weight ratio of the component, the weight ratio of the b component and the a component (b /
In order to satisfy a), it is preferable to carry out a random copolymerization of propylene and ethylene by slurry polymerization in which ethylene gas is supplied in the same polymerization tank after polymerization of propylene.

After completion of the main polymerization, the monomer is evaporated from the polymerization system to obtain the propylene block copolymer of the present invention. This propylene-ethylene block copolymer can be subjected to known washing or countercurrent washing with a hydrocarbon having 7 or less carbon atoms.

The polymer powder of the propylene-ethylene block copolymer used in the present invention preferably has a low melt flow rate from the viewpoint of production. The polymer powder may be decomposed to adjust the melt flow rate to the above range. it can. In the case of adjusting the melt flow rate with an organic peroxide, known organic peroxides can be used without any limitation.
Ketone peroxides such as methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide and cyclohexanone peroxide; diacyl peroxides such as isobutyryl peroxide, lauroyl peroxide and benzoyl peroxide; hydroperoxides such as diisopropylbenzene hydroperoxide; dicumyl Peroxide, 2,5-dimethyl-
2,5-di- (t-butylperoxy) hexane, 1,
3-bis- (t-butylperoxy-isopropyl)-
Dialkyl peroxides such as benzene, di-t-butyl peroxide, and 2,5-dimethyl-2,5-di- (t-butylperoxy) -hexane-3; 1,1-di-
peroxy ketals such as t-butylperoxy-3,3,5-trimethylcyclohexane and 2,2-di- (t-butylperoxy) -butane; t-butylperoxy-
Alkyl peresters such as pivalate and t-butylperoxybenzoate; and percarbonates such as t-butylperoxyisopropyl carbonate.

The kneading of the polymerization powder of the propylene-ethylene block copolymer and the organic peroxide is generally carried out at a melting point of the propylene-ethylene block copolymer,
The kneading is performed at a temperature equal to or higher than the decomposition temperature of the organic peroxide using a known kneading apparatus. For example, screw extruders,
1 using a Banbury mixer, mixing rolls, etc.
A method of kneading at 60 to 330 ° C, preferably 170 to 300 ° C can be adopted. Also, melt kneading is
It can also be performed under a stream of an inert gas such as nitrogen gas.
Prior to melt-kneading, preliminary kneading can also be performed using a known mixing device, for example, a tumbler or Henschel mixer.

The propylene-based polymer used in the present invention improves the strength such as rigidity and heat resistance of the propylene-based resin composition obtained by mixing with the propylene-ethylene block copolymer. It is a polymer having high crystallinity and having a propylene monomer unit as a main component.

Specifically, propylene homopolymer, propylene-ethylene random copolymer, propylene-ethylene block copolymer, 90 mol% or more of propylene,
Preferably, 95 mol% or more of α-olefin other than propylene, for example, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-methyl-1-pentene, etc.
It can be selected from a random copolymer of not less than 10 mol%, preferably not more than 5 mol%, a propylene-ethylene-α-olefin terpolymer and the like within a range satisfying the requirements of the present invention. .

In the propylene-based polymer, the amount of the eluting component having a temperature lower than 20 ° C. is 1 to 20% by weight and the amount of the eluting component having a temperature higher than or equal to 20 ° C. and lower than 90 ° C. It is preferable that the amount of the eluted component at 1 to 25% by weight and 90 ° C or higher is in the range of 70 to 98% by weight (however, the total amount of each component is 100% by weight).

The molecular weight distribution (Mw / Mn) is 5 to 5.
8. Melt flow rate (MFR) is 0.01 to 100
Those in the range of g / 10 min are generally used.

In the present invention, the mixing ratio of the propylene-ethylene block copolymer and the propylene-based polymer satisfies the above-mentioned properties of the propylene-based resin composition of the present invention by mixing with the propylene-ethylene block copolymer. Is determined as follows. Generally, the propylene-ethylene block copolymer accounts for about 1 to 40% by weight, and the propylene-based polymer accounts for about 99 to 60% by weight.

In the present invention, mixing of the propylene-ethylene block copolymer and the propylene-based polymer is not particularly limited. Examples of typical methods include a tumbler, a method of directly molding with a molding machine after mixing with a known mixing device such as a Henschel mixer, a screw extruder,
Examples of the method include melting and kneading using a Banbury mixer, a mixing roll, and the like, followed by molding with a molding machine.

In the propylene resin composition of the present invention, the polypropylene component and / or propylene
The ethylene random copolymer component may contain other α-olefins in a small amount, for example, 5 mol% or less as long as the physical properties of the propylene-based resin composition are not impaired.

The propylene resin composition used in the present invention contains an antioxidant, a heat stabilizer, a chlorine scavenger, a lubricant, an ultraviolet absorber, a light stabilizer, an antistatic agent, an antifogging agent, an antiblocking agent, Commercially available additives such as a flame retardant and a crystal nucleating agent, and fillers such as talc, magnesium hydroxide, calcium carbonate, glass, mica, and wood powder may be added. After mixing these additives, they may be pelletized by an extruder and used.

Further, other resins can be added to the propylene resin composition of the present invention as long as the characteristics of the present invention are not significantly affected. For example, high-density polyethylene (HDPE), low-density polyethylene (LDPE), linear polyethylene (LLDPE) obtained by copolymerizing ethylene and C4 to C10, ethylene-vinyl acetate copolymer (E
VA), polyethylene resins such as ethylene methyl methacrylate (EMMA), ethylene / propylene copolymers (EPR, EPDM), ethylene / butene-1 copolymer (EBM), propylene / butene-1 copolymer (PB
Known materials such as olefin-based soft resins such as M), styrene / butadiene block copolymer (SBR), petroleum resins / terpene resins, and hydrogenated products thereof can be used without limitation.

In the present invention, the propylene-based resin composition to be used is obtained by mixing and melt-kneading the above raw materials and the like, if necessary. The method of melt kneading is not particularly limited. For example, using a screw extruder, a Banbury mixer, a mixing roll, or the like, 160 to 300 ° C., preferably 180 to 270 ° C.
It is good to carry out under the temperature of. The melt-kneading can also be performed under a stream of an inert gas such as nitrogen gas. Prior to melt-kneading, a known mixing device such as a tumbler or a Henschel mixer can be used without any limitation.

Further, in the present invention, a molded article may be obtained by mixing the respective components of the above resin composition if necessary after mixing the respective components, and then directly charging the mixture into a molding machine and molding. It is possible. In the case of molding a film, a sheet, or the like, it can be molded by a known molding method. For example, molding methods such as T-die molding, calendar molding, and inflation molding are used. In addition to using the propylene resin composition of the present invention in a single layer, propylene resin, high density polyethylene, low density polyethylene, linear Low density polyethylene, ethylene-vinyl acetate copolymer,
It can also be used as a multilayer with an ethylene resin such as an ethylene-methyl methacrylate copolymer.

[0076]

The propylene-based resin composition of the present invention is excellent in rigidity, heat resistance and impact resistance, and can be suitably used in various fields in which conventional thermoplastic elastomers are used. For example, in the field of injection molding, bumpers, mudguards, horn pads, lamp packings for automobile parts, and in the field of home appliances, various packings, wheels such as vacuum cleaners, various molded parts such as bumpers, hoses, and various types of OA equipment. Molded parts and ski shoes, grips, roller skates.

On the other hand, film applications include wrap films, shrink films, stitch films, films for sealants, sizing films, adhesive tapes, masking films, agricultural films, medical films, adhesive substrates, adhesive plaster films, surface protective films , Decorative films, etc., such as stationery sheets, bite sheets, desk mats, agricultural sheets, waterproof sheets, interior skin materials for automobile parts, corrugates, wind moldings, air duct hoses, weather strips, wire covering materials, etc. Wall paper, flooring, etc. as sheets, decorative boxes, decorative bags, packaging boxes, packaging bags, food containers, sundries,
It can be suitably used for toys, tatami mats and the like.

[0078]

The present invention will be described below with reference to examples and comparative examples, but the present invention is not limited to these examples. The measurement method used in the following examples will be described. 1) Measurement of molecular weight distribution (Mw / Mn) P. It was measured by the C (gel permeation chromatography) method. Sensyu Science SSC-7
Using o-dichlorobenzene as solvent, 135
C. was performed. The column used was Shodex UT80.
7, 806M. The calibration curve is a standard sample having a weight average molecular weight of 950, 2900, 10,000, 50,000 and 49.8.
Were prepared using 10,000, 2.7, and 4.9 million polystyrene. 2) Separation method of component A, component B, and component C (temperature-separated elution separation method) SSC-7300 manufactured by Senshu Scientific Co., Ltd. was used under the following measurement conditions.

Solvent: O-dichlorobenzene Flow rate: 2.5 ml / min Heating rate: 4.0 ° C./Hr Sample concentration: 0.7 wt% Sample injection amount: 100 ml Detector: Infrared detector, wavelength 3.14 μm Column; φ30 mm x 300 mm Filler: Chromosorb P 30-6
0 mesh Column cooling rate; 2.0 ° C / Hr 2) Measurement of propylene content and ethylene content.

The measurement was performed by ¹³ C-NMR. 3) Melt flow rate (measurement of MFR) It was based on ASTM D-1238. 4) Evaluation of melt viscosity and surface appearance Using Capillograph 1B of Toyo Seiki Co., Ltd., 230
At ℃ ° C. and a shear rate of 114 s ⁻¹ , the melt viscosity was measured, and the resulting strands were visually evaluated for ○ and ×.

：: No rough skin condition X: Rough skin condition 5) Flexural modulus According to JIS K6758. 6) Measurement of heat deformation temperature Measured under a load of 045 MPa in accordance with JIS K7207. 7) Rockwell hardness Measured on an R scale according to JIS K6758. 8) Izod impact value An example of the polypropylene resin composition of the present invention will be described below, in which a test piece is measured with a notch according to JIS K6758.

Production Example 1 (Preliminary polymerization) A 1-liter glass autoclave reactor equipped with a stirrer was sufficiently replaced with nitrogen gas, and 400 ml of hexane was charged. Reactor temperature 2
Keep at 0 ° C and dicyclopentyldimethoxysilane 4.2
After adding 21.5 mmol, 21.5 mmol of ethyl iodide, 21.5 mmol of triethylaluminum, and 21.5 mmol of titanium trichloride (manufactured by Marubeni Solvay Chemical Co., Ltd.), propylene was added to 3 g per 1 g of titanium trichloride.
It was continuously introduced into the reactor for 0 minutes. The temperature during this period was kept at 20 ° C. After stopping the supply of propylene,
After sufficiently replacing the inside of the reactor with nitrogen gas, 1-
Butene was continuously introduced into the reactor so as to be 10 g per 1 g of the solid catalyst component for 1 hour. After stopping the supply of 1-butene, the inside of the reactor was sufficiently replaced with nitrogen gas, and the obtained titanium-containing polypropylene was washed four times with purified hexane. As a result of analysis, 2.7 g per 1 g of titanium trichloride
Of propylene and 7.7 g of 1-butene were polymerized. (Main Polymerization) In a 2 liter autoclave subjected to N ₂ substitution, 1 liter of liquid propylene, 2.4 mmol of triethylaluminum, 1.2 mmol of dicyclopentyldimethoxysilane, and hydrogen were added at a concentration of 3.0 mol in the gas phase.
1%, and the internal temperature of the autoclave is increased to 70 ° C.
The temperature rose. 0.3 mmol of titanium-containing polypropylene obtained by the preliminary polymerization was added as titanium trichloride, and propylene-ethylene was copolymerized at 70 ° C. for 120 minutes (step 1). Next, the ethylene gas concentration in the gas
The polymerization was carried out for 30 minutes by supplying the solution so as to be maintained at 5.0 mol% (step 2). Unreacted monomer was purged to obtain a polymer. The obtained polymer was dried at 70 ° C. for 1 hour. The resulting polymer has a melt flow rate of 0.7
g / 10 min. (Molecular weight control) 0.2% of an antioxidant was added to the obtained polymer.
After adding 0.07 parts by weight of 1,3-bis- (t-butylperoxyisopropyl) benzene as an organic peroxide and mixing, the mixture was extruded at 230 ° C. using a Brabender to obtain pellets. The results are shown in Table 1.

Production Example 2 The same operation as in Example 1 was carried out except that the polymerization time in Step 1 of Example 1 was set to 100 minutes, the gas concentration of ethylene in Step 2 was set to 12 mol%, and polymerization was carried out for 20 minutes. Was done. The resulting polymer has a melt flow rate of 0.6
g / 10 min. (Molecular weight control) 0.2% of an antioxidant was added to the obtained polymer.
After adding 0.10 parts by weight of 1,3-bis- (t-butylperoxyisopropyl) benzene as an organic peroxide and mixing, the mixture was extruded at 230 ° C. using a Brabender to obtain pellets. The results are shown in Table 1.

Production Example 3 The same operation as in Example 1 was carried out, except that in Step 1 of the main polymerization in Example 1, ethylene was supplied so as to have a gas concentration of 1.5 mol%. The melt flow rate of the obtained polymer was 0.8 g / 10 min. (Molecular weight control) Antioxidant 0.2
The same operation as in Production Example 1 was performed, except that 0.06 parts by weight of 1,3-bis- (t-butylperoxyisopropyl) benzene was added. The results are shown in Table 1.

Production Example 4 In Step 1 of the main polymerization of Production Example 1, the internal temperature of the autoclave was set to 55 ° C., the hydrogen concentration in the gas phase was set to 1.0 mol%, and the polymerization time was set to 30 minutes. The same operation as in Example 1 was performed, except that the ethylene content was supplied so as to be maintained at 13 mol% and polymerization was performed for 120 minutes. The melt flow rate of the obtained polymer was 0.06 g / 1.
0 min. (Molecular weight control) Antioxidant 0.2
The same operation as in Production Example 1 was performed except that a propylene-ethylene copolymer was obtained by adding 0.06 part by weight of 1,3-bis- (t-butylperoxyisopropyl) benzene and 0.06 part by weight. The results are shown in Table 1.

Production Example 5 In Step 1 of the main polymerization of Production Example 4, the hydrogen concentration in the gas phase was 1.5 mol%, the polymerization time was 20 minutes, and the ethylene concentration in the gas phase was 10 mol% in Step 2. , And the same operation as in Example 1 was performed except that the polymerization was carried out for 120 minutes. The melt flow rate of the obtained polymer was 0.08 g / 10 min. (Molecular weight control) Antioxidant 0.2
The same operation as in Production Example 1 was carried out except that propylene-ethylene copolymer was obtained by adding 0.05 parts by weight of 1,3-bis- (t-butylperoxyisopropyl) benzene and 0.05 parts by weight. The results are shown in Table 1.

Production Example 6 In Step 1 of the main polymerization of Production Example 4, the hydrogen concentration was adjusted to 2.0
mol%, the polymerization time was 20 minutes, and in step 2,
The same operation was performed except that the gas concentration of ethylene in the gas phase was 11 mol% and the polymerization time was 140 minutes. The melt flow rate of the obtained polymer is 0.07 g / 10 m
was in. (Molecular weight control) Antioxidant 0.2
The same operation as in Production Example 1 was performed, except that a propylene-ethylene copolymer was obtained by adding 0.07 parts by weight of 1,3-bis- (t-butylperoxyisopropyl) benzene and 0.07 part by weight. The results are shown in Table 1.

Production Example 7 In controlling the molecular weight of Production Example 6, 1,3-bis- (t-
The same operation as in Production Example 6 was performed except that 0.35 part by weight of (butylperoxyisopropyl) benzene was added. Table 1 shows the results.

Production Example 8 (Preliminary polymerization) A 1-liter glass autoclave reactor equipped with a stirrer was sufficiently replaced with nitrogen gas, and 400 ml of hexane was charged. Reactor temperature 2
Keep at 0 ° C and maintain diethylaluminum chloride 18.5
mmol, ethyl iodide 22.7 mmol, diethylene glycol dimethyl ether 0.18 mmol, and titanium trichloride (manufactured by Marubeni Solvay Chemical) 22.7 mmol
After adding propylene, 3 g per 1 g of titanium trichloride
And continuously introduced into the reactor for 30 minutes. The temperature during this period was kept at 20 ° C. After stopping the supply of propylene, the inside of the reactor is sufficiently replaced with nitrogen gas,
The titanium-containing polypropylene thus obtained is purified with purified hexane.
Washed twice. As a result of the analysis, it was found that 2.g per 1 g of titanium trichloride.
9 g of propylene had been polymerized. (Main polymerization) 1 liter of liquid propylene, 0.70 mmol of diethylaluminum chloride, 0.07 of butyl acetate were placed in a 2 liter autoclave subjected to N ₂ substitution.
mmol, cyclopentyldimethoxysilane 0.07 m
mol and hydrogen were added so that the gas concentration in the gas phase became 2 mol%, and the internal temperature of the autoclave was raised to 50 ° C.
0.087 mmol of titanium-containing polypropylene obtained by the preliminary polymerization was added as titanium trichloride, and polymerization was performed at 50 ° C. for 30 minutes (step 1). Next, 4 mol% of ethylene was checked while confirming the gas concentration in the gas phase by gas chromatography.
And polymerized for 60 minutes (step 2). Then, the ethylene gas concentration in the gas phase was supplied so as to be maintained at 9 mol%, and polymerization was carried out for 60 minutes (step 3). Unreacted monomer was purged to obtain a polymer. The obtained polymer was dried at 70 ° C. for 1 hour. The melt flow rate of the obtained polymer was 0.1 g / 10 min. (Molecular weight control) Antioxidant 0.2
The same operation as in Production Example 1 was carried out except that propylene-ethylene copolymer was obtained by adding 0.05 parts by weight of 1,3-bis- (t-butylperoxyisopropyl) benzene and 0.05 parts by weight. Table 1 shows the results.

Comparative Production Example 1 The same procedure was carried out as in Production Example 1, except that no hydrogen was added in Step 1 of the main polymerization. The melt flow rate of the obtained polymer was 0.01 g / 10 min or less. (Molecular weight control) Antioxidant 0.2
The same operation as in Example 1 was performed, except that a propylene-ethylene copolymer was obtained by adding 0.10 part by weight of 1,3-bis- (t-butylperoxyisopropyl) benzene and 0.10 part by weight. The same operation was performed for the measurement of physical properties. Table 1 shows the results.

Comparative Production Example 2 (Main polymerization) 1 liter of liquid propylene, 0.70 mmol of diethylaluminum chloride, 0.07 of butyl acetate were placed in a 2 liter autoclave subjected to N ₂ substitution.
mmol was added and the internal temperature of the autoclave was raised to 50 ° C. After adding 0.087 mmol of titanium-containing polypropylene obtained by the prepolymerization of Example 10 as titanium trichloride, hydrogen was added to a gas concentration of 1.5 mol% in a gas phase, and polymerization was performed at 50 ° C. for 30 minutes. (Step 1). Next, ethylene was supplied at a concentration of 15 mol% while confirming the gas concentration in the gas phase by gas chromatography, and polymerization was carried out for 140 minutes (step 2). Unreacted monomer was purged to obtain a polymer. The obtained polymer was dried at 70 ° C. for 1 hour. The melt flow rate of the obtained polymer was 0.08 g / 10 min or less, and the polymer was partially in a lump state. (Molecular weight control) Antioxidant 0.2
Parts by weight and 0.03 parts by weight of 1,3-bis- (t-butylperoxyisopropyl) benzene were added to obtain a propylene-ethylene copolymer. The melt flow rate of the obtained propylene-ethylene copolymer is 1.6 g / 10 m
was in. Table 1 shows the results.

[0092]

[Table 1]

Example 1 15 g of the propylene resin composition obtained in Production Example 1 was used.
Using an injection molding machine, a test piece for measuring flexural modulus, thermal deformation, and a Rockwell hardness test piece were molded at a cylinder temperature of 230 ° C and a mold temperature of 40 ° C. The results are shown in Tables 3, 4 and 5.

Example 2 Using the propylene-based resin composition obtained in Production Example 2, physical properties were measured in the same manner as in Example 1. The results are shown in Tables 3, 4 and 5.

Example 3 Using the propylene-based resin composition obtained in Production Example 3, physical properties were measured in the same manner as in Example 1. The results are shown in Tables 3, 4 and 5.

Example 4 20% by weight of the propylene-ethylene block copolymer obtained in Production Example 4 was mixed with a propylene-based polymer shown in Table 2 at a mixing ratio of 80% by weight.
Melt kneading was performed at 0 ° C. to obtain a propylene-based resin composition. Using the obtained propylene-based resin composition, physical properties were measured in the same manner as in Example 1. The results are shown in Tables 3, 4 and 5.

Example 5 Example 4 was repeated except that the propylene-based polymer shown in Table 2 was mixed at a blending ratio of 80% by weight with 20% by weight of the propylene-ethylene block copolymer obtained in Production Example 4. The same operation as described above was performed. The results are shown in Tables 3, 4 and 5.

Example 6 Example 4 was repeated except that the propylene-based polymer shown in Table 2 was mixed at a blending ratio of 80% by weight with 20% by weight of the propylene-ethylene block copolymer obtained in Production Example 5. The same operation as described above was performed. The results are shown in Tables 3, 4 and 5.

Example 7 Example 4 was repeated except that the propylene-based polymer shown in Table 2 was mixed in an amount of 80% by weight with 20% by weight of the propylene-ethylene block copolymer obtained in Production Example 5. The same operation as described above was performed. The results are shown in Tables 3, 4 and 5.

Example 8 Example 4 was repeated except that 30% by weight of the propylene-ethylene block copolymer obtained in Production Example 6 was mixed with 70% by weight of the propylene-based polymer shown in Table 2. The same operation as described above was performed. The results are shown in Tables 3, 4 and 5.

Example 9 Example 4 was repeated except that the propylene-based polymer shown in Table 2 was mixed in an amount of 70% by weight with 30% by weight of the propylene-ethylene block copolymer obtained in Production Example 7. The same operation as described above was performed. The results are shown in Tables 3, 4 and 5.

Example 10 Example 4 was repeated except that 30% by weight of the propylene-ethylene block copolymer obtained in Production Example 8 was mixed with 70% by weight of a propylene-based polymer shown in Table 2. The same operation as described above was performed. The results are shown in Tables 3, 4 and 5.

Comparative Example 1 The same operation as in Example 1 was performed except that the propylene-based resin composition obtained in Comparative Production Example 1 was used. The results are shown in Tables 3, 4 and 5.

Comparative Example 2 The procedure of Example 2 was repeated except that the propylene-based polymer shown in Table 2 was mixed in a proportion of 80% by weight with 20% by weight of the propylene-ethylene block copolymer obtained in Comparative Production Example 2. The same operation as in Example 4 was performed. The results are shown in Tables 3, 4 and 5.

Comparative Example 3 The same operation as in Example 1 was performed, except that the propylene resin composition obtained in Production Example 4 was used. The results are shown in Tables 3, 4 and 5.

Comparative Example 4 The same operation as in Example 1 was performed except that the propylene-based polymer shown in Table 2 was used. The results are shown in Tables 3, 4 and 5.

[0107]

[Table 2]

[0108]

[Table 3]

[0109]

[Table 4]

[0110]

[Table 5]

Claims (2)

[Claims] 1. A polypropylene component and propylene-
A propylene-based resin composition comprising an ethylene copolymer component and having the following characteristics. (1) 5 to 25% by weight of the eluted component (component A) having a temperature of less than 20 ° C., from 20 ° C. to less than 90 ° C., of the eluted components separated by the temperature-increasing elution fractionation method using an O-dichlorobenzene solvent The amount of the eluted component (component B) is 8 to 45% by weight, and the amount of the eluted component (component C) at 90 ° C. or higher is 50 to 85%.
% By weight, and the total of the components A, B and C is 10
0% by weight. (2) The weight ratio (B / A) of the component B and the component A is 0.5 or more. (3) Weight average molecular weight (Mw) and number average molecular weight (Mn)
And the molecular weight distribution (Mw / Mn) is 4 or more, and the molecular weight distribution and the melt flow rate (MF
R) satisfy the following formula (I). 0.40 ≦ log ((Mw / Mn) × MFR ^0.33 ) ≦ 1.5 (I) 2. The method for producing a propylene-based resin composition according to claim 1, wherein a propylene-based polymer and a propylene-ethylene block copolymer having the following properties and obtained by a polymerization method are mixed. (1) With respect to the eluted components separated by the temperature-raising elution fractionation method using an O-dichlorobenzene solvent, the amount of the eluted component (a component) less than 20 ° C. is 10 to 60% by weight, and 20 ° C.
The amount of the eluted component (component b) at a temperature of 90 ° C. or less is 10 to 70.
Weight%, the amount of the eluted component (component c) at 90 ° C. or higher is 1 to 4
0% by weight, and the total of component a, component b and component c is 1
00% by weight. (2) The weight ratio (b / a) between the component b and the component a is 0.6 or more. (3) Weight average molecular weight (Mw) and number average molecular weight (Mn)
And the molecular weight distribution (Mw / Mn) and the melt flow rate (MFR) satisfy the following formula (II). 0.57 ≦ log ((Mw / Mn) × MFR ^0.33 ) ≦ 1.0 (II)