JP2007084806A - Propylene resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a propylene resin composition having excellent impact resistance and heat resistance. <P>SOLUTION: The propylene resin composition contains (A) 1-99 wt.% specific propylene polymer and (B) 99-1 wt.% olefin block copolymer composed of specific polymer segments (B1), (B1') and (B2) (the sum of the propylene polymer (A) and the olefin block copolymer (B) is 100 wt.%). <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a propylene-based resin composition. More specifically, the present invention relates to a propylene-based resin composition that is suitably used for extrusion molded articles or inflation molded articles such as films and sheets.

  Conventionally, for the purpose of improving the impact resistance of a polypropylene resin, a technique in which an elastomer such as an ethylene / propylene copolymer or an ethylene / butene copolymer is blended with the polypropylene resin as a modifier is often used.

  However, in addition to impact resistance, polypropylene resin molded products are often required to have heat resistance such that the molded product does not deform or change its appearance even at high temperatures. Depending on the application, excellent transparency may be required even at high temperatures. Conventionally, the method of blending an elastomer as a modifier improves impact resistance, but it has been difficult to obtain excellent heat resistance and transparency.

For example, when a soft resin composition containing a polypropylene resin is produced, a large amount of rubber may be blended with the polypropylene resin.
However, by simply blending a large amount of known elastomers such as ethylene / propylene copolymers and ethylene / butene copolymers, excellent rubber elasticity cannot be obtained, and there is room for improvement in terms of heat resistance. It was.

  On the other hand, in Patent Document 1, in order to obtain a propylene-based resin composition excellent in the balance between rigidity and tensile elongation at break and the balance between rigidity and impact resistance, a polypropylene resin, a specific block copolymer, A propylene resin composition composed of an ethylene copolymer and an inorganic filler is disclosed.

However, the composition described in Patent Document 1 cannot provide excellent transparency and is insufficient in terms of heat resistance. Further, no soft resin is disclosed.
JP 2004-204057 A

  An object of the present invention is to provide a polypropylene resin composition excellent in impact resistance and heat resistance. Another object of the present invention is to provide a polypropylene resin composition which is excellent in transparency as well as impact resistance and heat resistance and hardly changes in appearance even at high temperatures. Another object of the present invention is to provide a composition excellent in heat resistance, flexibility and rubber elasticity.

The present inventors diligently studied to solve the above problems. As a result, a propylene resin composition comprising a specific propylene polymer (A) and an olefin block copolymer (B) containing specific polymer segments (B1), (B1 ′) and (B2) is obtained. The present inventors have found that they are excellent in impact resistance and heat resistance.

The propylene-based resin composition according to the present invention is
[A] (i) Melt flow rate (MFR: 230 ° C., under 2.16 kg load) 0.1 to 400 g
/ 10 minutes,
(ii) containing a normal temperature n-decane soluble component in an amount of 0.01 to 30% by weight,
The intrinsic viscosity [η] measured in 135 ° C. decalin of the room temperature n-decane soluble component is 0.2 to 0.2.
10 dl / g,
(iii) The pentad isotacticity (I ₅ ) determined by the ¹³ C-NMR method of the room temperature n-decane insoluble component is 0.95 or more.
Propylene polymer (A) in an amount of 1 to 99% by weight,
[B] An olefin block copolymer composed of polymer segments (B1), (B1 ′) and (B2),
(B1) and (B1 ′) are each independently at least one polymer selected from ethylene and an α-olefin having 3 to 20 carbon atoms,
(i) the ethylene content is 95-100 mol%,
(ii) an ethylene polymer polymer segment having a weight average molecular weight (Mw) measured by high temperature GPC of 2,000 to 100,000;
(B2) is a copolymer of ethylene and at least one selected from C3-C20 α-olefins,
(iii) the ethylene content is 50-80 mol%,
(iv) an ethylene / α-olefin copolymer polymer segment having a weight average molecular weight (Mw) measured by high temperature GPC of 10,000 to 300,000,
The olefin block copolymer is a block copolymer containing a linear triblock structure of (B1)-(B2)-(B1 ′),
(v) has a peak attributed to ββ methylene in the ¹³ C-NMR spectrum,
(vi) The glass transition temperature (Tg) measured with a differential scanning calorimeter (DSC) is −50 ° C. or lower,
(vii) an endothermic peak due to melting point (Tm) is present at 105 ° C. or higher,
(viii) the heat of fusion determined from the melting peak area is in the range of 20-60 J / g,
(ix) the density is in the range of 0.870-0.910 g / cm ³ ;
(x) The melt flow rate (MFR: 190 ° C., under 2.16 kg load) is in the range of 0.3 to 50 g / 10 min,
(xi) Storage elastic modulus at room temperature (G _'50 ° C) and storage elastic modulus at 100 ° C by solid viscoelasticity measurement (
G ′ ₁₀₀ ° C.) (G ′ ₅₀ ° C./G ′ ₁₀₀ ° C.) is 1.0 to 2.0,
The olefinic block copolymer (B) is included in an amount of 99 to 1% by weight (here, the total of the propylene polymer (A) and the olefinic block copolymer (B) is 100% by weight). It is characterized by that. This resin composition may be referred to as a “first composition”.

  The propylene-based resin composition according to the present invention includes the propylene-based polymer (A) in an amount of 40 to 99% by weight and the olefinic block copolymer (B) in an amount of 60 to 1% by weight. (Here, the total of the propylene polymer (A) and the olefin block copolymer (B) is 100% by weight) and it is preferable that the inorganic filler (D) is substantially not contained.

  Further, the propylene-based resin composition according to the present invention is the propylene-based polymer (A) in an amount of less than 40% by weight and 1% by weight or more, and the block copolymer (B) exceeds 60% by weight and exceeds 99% by weight. It is preferable to include the following amounts (here, the total of the propylene-based polymer (A) and the olefin-based block copolymer (B) is 100% by weight).

The polymer segments (B1), (B1 ′) and (B2) are preferably obtained by polymerization in the presence of an olefin polymerization catalyst containing a transition metal compound represented by the following general formula (1).

(In the formula, M ¹ represents a transition metal atom selected from Groups 4 to 5 of the periodic table, and m represents 1 or 2)
R ¹ is an aromatic hydrocarbon group, an aliphatic hydrocarbon group or an alicyclic hydrocarbon group, and when R ¹ is a phenyl group, the position of the carbon atom bonded to nitrogen is the 1st position 2
Has at least one substituent selected from a heteroatom or a heteroatom-containing group at at least one position in the position and the 6-position, or a fluorine atom at at least one position in the 3-position, 4-position and 5-position A fluorine-containing group containing 1 or more carbon atoms and 2 or less fluorine atoms, a fluorine-containing group containing 2 or more carbon atoms, or a group containing a heteroatom excluding fluorine atoms When it has at least one atom or substituent and R ¹ is an aromatic hydrocarbon group other than a phenyl group, an aliphatic hydrocarbon group or an alicyclic hydrocarbon group, it contains heteroatoms and heteroatoms Having at least one substituent selected from a group, and R ^{2 to} R ⁵ are each independently a hydrogen atom, a halogen atom, a halogen-containing group, a hydrocarbon group, or a hydrocarbon-substituted silyl group. Group, oxygen-containing group, nitrogen-containing group or sulfur-containing group, which may be the same or different from each other, and R ⁶ represents a halogen atom, a halogen-containing group, a hydrocarbon group or a hydrocarbon-substituted silyl group , N is a number satisfying the valence of M, and X is an oxygen atom, hydrogen atom, halogen atom, hydrocarbon group, oxygen-containing group, sulfur-containing group, nitrogen-containing group, boron-containing group, aluminum-containing group, A phosphorus-containing group, a halogen-containing group, a heterocyclic compound residue, a silicon-containing group, a germanium-containing group, or a tin-containing group. When n is 2 or more, a plurality of groups represented by X are the same as each other And a plurality of groups represented by X may be bonded to each other to form a ring. )
The molded body according to the present invention is preferably composed of the above-mentioned propylene-based resin composition.

The molded body is preferably an extrusion molded body or an inflation molded body, and the molded body is preferably a film or a sheet.
More preferably, the molded body is a medical molded body or a food packaging molded body.

The propylene-based resin composition ("second composition") according to the present invention is
[A] (i) Melt flow rate (MFR: 230 ° C., under 2.16 kg load) is 0.1 to 400 g / 10 minutes,
(ii) containing a normal temperature n-decane soluble component in an amount of 0.01 to 30% by weight,
The intrinsic viscosity [η] measured in 135 ° C. decalin of the room temperature n-decane soluble component is 0.2 to 0.2.
10 dl / g,
(iii) The pentad isotacticity (I ₅ ) determined by the ¹³ C-NMR method of the room temperature n-decane insoluble component is 0.95 or more.
Propylene polymer (A) in an amount of 1 to 99% by weight,
[BB] an olefin block copolymer containing polymer segments (B1), (B1 ′) and (B2),
(B1) and (B1 ′) are each independently at least one polymer selected from ethylene and an α-olefin having 3 to 20 carbon atoms,
(i) the ethylene content is 95-100 mol%,
(ii) an ethylene polymer polymer segment having a weight average molecular weight (Mw) measured by high temperature GPC of 2,000 to 100,000;
(B2) is a copolymer of ethylene and at least one selected from C3-C20 α-olefins,
(iii) the ethylene content is 50-80 mol%,
(iv) an ethylene / α-olefin copolymer polymer segment having a weight average molecular weight (Mw) measured by high temperature GPC of 10,000 to 300,000,
The olefin block copolymer is
(v) has a peak attributed to ββ methylene in the ¹³ C-NMR spectrum,
(vi) The glass transition temperature (Tg) measured with a differential scanning calorimeter (DSC) is −50 ° C. or lower,
(vii) an endothermic peak due to melting point (Tm) is present at 105 ° C. or higher,
(viii) the heat of fusion determined from the melting peak area is in the range of 20-60 J / g,
(ix) the density is in the range of 0.870-0.910 g / cm ³ ;
(x) The melt flow rate (MFR: 190 ° C., under 2.16 kg load) is in the range of 0.3 to 50 g / 10 min,
(xi) Storage elastic modulus at room temperature (G _'50 ° C) and storage elastic modulus at 100 ° C by solid viscoelasticity measurement (
G ′ ₁₀₀ ° C.) (G ′ ₅₀ ° C./G ′ ₁₀₀ ° C.) is 1.0 to 2.0,
The olefin block copolymer (BB) is included in an amount of 99 to 1% by weight (here, the total of the propylene polymer (A) and the olefin block copolymer (BB) is 100% by weight). It is characterized by that.

  The molded body according to the present invention is preferably composed of the above-mentioned propylene-based resin composition (“second composition”).

  According to the polypropylene resin composition of the present invention, excellent impact resistance and heat resistance can be obtained. In addition, according to the polypropylene resin composition of the present invention, excellent transparency is obtained in addition to impact resistance and heat resistance, and appearance changes hardly occur even at high temperatures. Moreover, according to the polypropylene-type resin composition which concerns on this invention, the outstanding softness | flexibility and rubber elasticity are obtained with heat resistance.

  The polypropylene resin composition is suitably used for various molded articles, and particularly suitably used for various applications as an extruded molded article and an inflation molded article.

Hereinafter, the present invention will be specifically described.
<Propylene polymer (A)>
In the present invention, a propylene polymer (A) having the following characteristics is used. The propylene polymer (A) may be any of homopolypropylene, propylene block copolymer, and propylene random copolymer as long as it has the following characteristics. A block copolymer is preferable.

Melt flow rate (MFR; ASTM D1238 of this propylene polymer (A)
, 230 ° C., under 2.16 kg load) is 0.1 to 400 g / 10 min, preferably 0.8.
It is desirable to be 1 to 200 g / 10 minutes. When the MFR value is in the above range, a propylene-based resin composition having excellent fluidity and capable of molding a large product can be obtained. If the MFR value exceeds 400 g / 10 min, the molded article may have inferior impact resistance (IZ impact strength).

  The propylene polymer (A) contains a normal temperature (23 ° C.) n-decane insoluble component and a normal temperature (23 ° C.) n-decane soluble component. The former is a highly crystalline polypropylene component (isotactic polypropylene) of a propylene polymer. The latter is a rubber component, and is preferably an atactic polypropylene or an ethylene / propylene polymer. When the propylene polymer (A) is a propylene block copolymer, it is preferably formed from a highly crystalline polypropylene component (crystal component) and an ethylene / propylene copolymer (rubber component).

The propylene-based polymer (A) used in the present invention has a normal temperature n-decane soluble component (rubber part) of 0.01 to 30% by weight, preferably 0.1 to 30% by weight, more preferably 0.1. It is desirable to contain it in an amount of ˜20% by weight. The propylene-based polymer (A) has a normal temperature n-decane insoluble component (crystal component) of 99.99 to 70% by weight, preferably 99.9 to 70% by weight, more preferably 99.9 to 80% by weight. It is desirable to contain in the amount of%. Normal temperature n-
If the content of the decane-soluble component is less than 0.01% by weight, the impact resistance improving effect may not be sufficiently exhibited, whereas if it exceeds 30% by weight, the rigidity may not be sufficient.

The intrinsic viscosity [η] (measured in decalin at 135 ° C.) of this room-temperature n-decane soluble component is 0.00.
It is desirable that it is 2 to 10 dl / g, preferably 0.2 to 8 dl / g.
The room temperature n-decane soluble component preferably contains units derived from ethylene in an amount of 30 to 50 mol%, preferably 30 to 45 mol%.

The room temperature n-decane soluble component of the propylene polymer (A) may contain a unit derived from a polymerizable compound other than ethylene and propylene as long as the object of the present invention is not impaired. Specific examples of such other polymerizable compounds include 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-hexadodecene, 4- Α-olefins such as methyl-1-pentene; vinyl compounds such as vinylcyclopentene, vinylcyclohexane and vinylnorbornane; vinyl esters such as vinyl acetate; unsaturated organic acids such as maleic anhydride or derivatives thereof.

  The room temperature n-decane soluble component content of the propylene polymer (A) is measured as follows. First, 5 g of a sample (propylene polymer (A)) was dissolved by being immersed in 200 cc of boiling n-decane for 5 hours, and then cooled to room temperature (23 ° C.). The precipitated solid phase is filtered through a G4 glass filter, dried, and then calculated by back calculation from the measured solid phase weight.

As described above, the room temperature n-decane insoluble component is a highly crystalline polypropylene component (isotactic polypropylene) of the propylene polymer (A). The pentad isotacticity (I ₅ ) obtained by the ¹³ C-NMR method of the room temperature n-decane insoluble component is 0.95 or more, preferably 0.97 or more. When the pentad isotacticity (I ₅ ) is in the above range, a composition having excellent rigidity can be obtained.

Pentad isotacticity (I ₅ ) is determined by the ¹³ C-NMR method (nuclear magnetic resonance method) (A. Zambelli et al., Macromolecules 6, 925 (1973)). It is an isotactic fraction in pentad units, and is a fraction of propylene monomer units in which five propylene units are isotactically bonded in succession.

The assignment of peaks in the above NMR measurement is performed based on the description of Macromolecules 8, 687 (1975). In addition, ¹³ C-NMR can improve the signal detection limit to 0.001 by performing an integrated measurement of 20000 times at a frequency of 125 MHz using a Fourier transform NMR (500 MHz (when measuring hydrogen nuclei)).

Further, the propylene polymer (A) used in the present invention is 3-methyl-1-butene, 3,3-dimethyl-1-butene, 3-methyl-1-pentene, 3-methyl-1-hexene, When it contains a homopolymer or copolymer such as 3,5,5-trimethyl-1-hexene, vinylcyclopentene, vinylcyclohexane, vinylnorbornane, for example, as a prepolymer formed by prepolymerization, The crystallization rate of the propylene polymer (A) is large.

  The propylene polymer (A) can be produced by various methods, and can be produced using, for example, a known stereoregular catalyst. Specifically, it is produced using a catalyst formed from a solid titanium catalyst component, an organometallic compound catalyst component, and, if necessary, an electron donor.

Specific examples of the solid titanium catalyst component include, for example, a solid titanium catalyst component in which titanium trichloride or a titanium trichloride composition is supported on a carrier having a specific surface area of 100 m ² / g or more; magnesium, A solid titanium catalyst having halogen, an electron donor (preferably an aromatic carboxylic acid ester or an alkyl group-containing ether) and titanium as essential components, and these essential components supported on a support having a specific surface area of 100 m ² / g or more. Ingredients and the like. Of these, the latter solid titanium catalyst component is preferred.

  The organometallic compound catalyst component is preferably an organoaluminum compound, and specific examples of the organoaluminum compound include trialkylaluminum, dialkylaluminum halide, alkylaluminum sesquihalide, alkylaluminum dihalide, and the like. In addition, what is necessary is just to select this organoaluminum compound suitably according to the kind of titanium catalyst component to be used.

  Examples of the electron donor include organic compounds having a nitrogen atom, a phosphorus atom, a sulfur atom, a silicon atom, a boron atom, etc., and specifically, ester compounds and ether compounds having the above atoms. Etc. are preferably used.

Such a catalyst may be further activated by a technique such as co-grinding, and an olefin as described above may be prepolymerized.
<Olefin Block Copolymer (B)>
Next, the olefin type block copolymer (B) used for this invention is demonstrated. Here, the block copolymer refers to two types of polymer chains (polymer segments) having different primary structures of the polymer such as monomer type, comonomer type, comonomer composition, comonomer content, comonomer sequence, and stereoregularity in one molecular chain. This refers to a copolymer in a connected form. The olefinic block copolymer (B) used in the present invention is an ethylene polymer polymer segment (B1) obtained by polymerizing at least one selected from ethylene and an α-olefin having 3 to 20 carbon atoms, (B1 ′) and a polymer segment (B2) of an ethylene / α-olefin copolymer obtained by polymerizing ethylene and at least one selected from α-olefins having 3 to 20 carbon atoms. The polymer segments (B1) and (B1 ′) may be the same as or different from each other.

The ethylene polymer polymer segment (B1), (B1 ′) may be an ethylene homopolymer or a homopolymer of a monomer selected from α-olefins having 3 to 20 carbon atoms,
The copolymer obtained by superposing | polymerizing ethylene and 1 type, or 2 or more types chosen from a C3-C20 alpha olefin may be sufficient.

  Even if the ethylene / α-olefin copolymer polymer segment (B2) is a copolymer obtained by polymerizing ethylene and one kind selected from α-olefins having 3 to 20 carbon atoms, ethylene, The copolymer obtained by superposing | polymerizing with 2 or more types chosen from C3-C20 alpha olefin may be sufficient.

Examples of the α-olefin having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, and 3-ethyl-1- Penten, 4-
Methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene 1-octene, 3-ethyl-1-hexene, 1-octene, 1-decene 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and the like.

Among these, the polymer segments (B1) and (B1 ′) include an ethylene homopolymer, a copolymer of ethylene and one selected from propylene, 1-butene, 1-hexene and 1-octene. And ethylene homopolymers are more preferably used. As the polymer segment (B2), a copolymer of ethylene and one kind selected from propylene, 1-butene, 1-hexene and 1-octene is preferably used.

  Hereinafter, the composition and molecular weight of each polymer segment, the physical properties of the olefin block copolymer (B) composed of these polymer segments, and the production method will be specifically described.

(i) Ethylene content of polymer segments (B1) and (B1 ′) The ethylene content of polymer segments (B1) and (B1 ′) is 95 to 100 mol%,
Preferably it is 97-100 mol%. If the ethylene content is less than 95 mol%, the rigidity when blended with the propylene polymer may be lowered.

(ii) Molecular weight of polymer segments (B1) and (B1 ′) The polymer segments (B1) and (B1 ′) have a weight average molecular weight (polystyrene equivalent) measured by high-temperature GPC in the range of 2,000 to 100,000. Yes, preferably in the range of 5,000 to 80,000, more preferably 10,000 to 60,000.

(iii) Ethylene content of polymer segment (B2) The ethylene content of the polymer segment (B2) is 50 to 80 mol%, preferably 55 to 70 mol%. When the ethylene content is less than 50 mol%, the rigidity when blended with the propylene polymer (A) may be reduced. When the ethylene content exceeds 80 mol%, the rigidity when blended with the propylene polymer (A) may be reduced. Impact resistance may be greatly reduced.

(iv) Molecular Weight of Polymer Segment (B2) The polymer segment (B2) has a weight average molecular weight (polystyrene conversion) measured by high temperature GPC in the range of 10,000 to 300,000, preferably 50,000 to 250, 000, more preferably in the range of 100,000 to 200,000.

(v) ββ methylene in the olefin block copolymer (B) The olefin block copolymer (B) has a peak attributed to ββ methylene in the ¹³ C-NMR spectrum. Here, ββ methylene in the ¹³ C-NMR spectrum means a methylene carbon at the β-position of two tertiary carbons as shown in the following formula (2).

The ¹³ C-NMR spectrum of the olefin block copolymer (B) was measured with an NMR measuring device (
For example, measurement is performed using JEOL-GX270 manufactured by JEOL Ltd. The measurement was performed using a mixed solution of hexachlorobutadiene / d ₆ -benzene = 2/1 (volume ratio) adjusted to a sample concentration of 5% by weight, 67.8 MHz, 25 ° C., d ₆ -benzene ( 128ppm) standard. The measured ¹³ C-NMR spectrum is analyzed according to the proposal of Lindeman Adams (Analysis Chemistry, 43, p. 1245 (1971), JCRandall (Review Macromolecular Chemistry Physics, C29, 201 (1989)).

  When the peak attributed to ββ methylene is not observed, it means that the block chain of ethylene and α-olefin becomes large. Therefore, the distribution of ethylene and α-olefin is not uniform, indicating that the composition distribution is wide.

(vi) Glass Transition Temperature of Olefin Block Copolymer (B) The olefin block copolymer (B) has a glass transition temperature measured by a differential scanning calorimeter (DSC) of −50 ° C. or less, preferably Is desirably −55 ° C. or lower, more preferably −60 ° C. or lower.

(vii) Melting point of olefinic block copolymer (B) The olefinic block copolymer (B) has an endothermic peak due to the melting point measured by a differential scanning calorimeter (DSC) at 105 ° C or higher, Preferably, it exists at 110 ° C. or higher, more preferably 115 ° C. or higher.

(viii) Heat of fusion of olefinic block copolymer (B) The olefinic block copolymer (B) has a heat of fusion of 20-80 J / s determined from the melting peak area measured with a differential scanning calorimeter (DSC). g, preferably 20 to 60 J / g, more preferably 30 to 50 J / g.

(ix) Density of Olefin Block Copolymer (B) The olefin block copolymer (B) has a density in the range of 0.870 to 0.910 g / cm ³ , preferably 0.875 to 0.005. It is desirable to be in the range of 900 g / cm ³ .

(x) Melt flow rate of olefin block copolymer (B) Melt flow rate (MFR; ASTM D1) of olefin block copolymer (B)
238, 190 ° C., under 2.16 kg load) is in the range of 0.3 to 50 g / 10 min, and preferably in the range of 0.8 to 20 g / 10 min.

For viscoelastic behavior olefin block copolymer of (xi) an olefin based block copolymer (B) (B), by solid viscoelasticity measurement, the storage elastic and 100 ° C. storage elastic modulus at room temperature (G _'50 ℃) 'ratio of ₍₁₀₀ ° C. (G rate _{G)' 50. / G '100} ℃) is 1
. 0-2.0.

The olefin block copolymer (B) is composed of polymer segments (B1) and (B1 ′).
And an olefinic block copolymer composed of (B2). Examples of the structure possessed by the olefin block copolymer (B) include (B1)-(B2), (B1)-(B2)-(
B1 ′), (B1)-(B2)-(B1 ′)-(B2)-(B1), and the like. Where (B1)
, (B1 ′) may be the same or different. Olefin block copolymer (B
) Is an olefin block copolymer composed of polymer segments (B1), (B1 ′) and (B2), and includes a triblock structure of (B1)-(B2)-(B1 ′) The triblock structure is more preferably (B1)-(B2)-(B1 ′).

  The olefin-based block copolymer (B) used in the present invention preferably has a uniform monomer composition in the same polymer segment, but the comonomer composition has a tapered shape as long as the physical characteristics of the polymer segment are not significantly altered. It may be a tapered polymer that is continuously changing.

  The olefin block copolymer (B) preferably has a value of Mw / Mn, which is a ratio of the weight average molecular weight Mw and the number average molecular weight Mn obtained by high temperature GPC measurement, of 3.0 or less. It is more preferably 2.0 or less, and further preferably 1.5 or less. If the molecular weight distribution is wide, the modification performance may be reduced due to gelation of the high molecular weight body.

  The olefin block copolymer (B) used in the present invention may have a functional group at the end of the main chain. Moreover, if the olefin block copolymer (B) has the above-mentioned structure, it may be combined with a portion having a structure other than the above structure within the range not impairing the object of the present invention. Good. The olefin block copolymer (B) may be graft-modified.

As the functional group, an aromatic hydrocarbon group, a halogen atom, an oxygen-containing group, a nitrogen-containing group, a sulfur-containing group, a phosphorus-containing group, a metal atom-containing group, or the like is preferably used.
Examples of the aromatic hydrocarbon group include phenyl, naphthyl, tolyl, biphenylyl, and anthryl, and examples of the halogen atom include fluorine, chlorine, bromine, and iodine.

  The oxygen-containing group is, for example, a group containing 1 to 5 oxygen atoms in the group, and does not include a heterocyclic compound residue as described later. Further, the oxygen-containing group does not include a group containing a nitrogen atom, a sulfur atom, a phosphorus atom or a halogen atom, and a group in which these atoms and oxygen atom are directly bonded. Specific examples of the oxygen-containing group include hydroxy groups; alkoxy groups such as methoxy, ethoxy, propoxy, and butoxy; aryloxy groups such as phenoxy, methylphenoxy, dimethylphenoxy, and naphthoxy; arylalkoxy groups such as phenylmethoxy and phenylethoxy Group; acetoxy group; carbonyl group; carboxyl group; ester group; acetyl group and the like. When the oxygen-containing group contains a carbon atom, the number of carbon atoms is preferably in the range of 1 to 30, more preferably 1 to 20.

  The nitrogen-containing group is, for example, a group containing 1 to 5 nitrogen atoms in the group, and does not include a heterocyclic compound residue as described later. Specific examples of the nitrogen-containing group include amino groups; alkylamino groups such as methylamino, dimethylamino, ethylamino, propylamino, butylamino, and cyclohexylamino; arylamino groups such as phenylamino, tolylamino, and naphthylamino. Etc.

The sulfur-containing group is, for example, a group containing 1 to 5 sulfur atoms in the group, and does not include a heterocyclic compound residue as described later. Specific examples of the sulfur-containing group include methyl sulfonate, trifluoromethane sulfonate, phenyl sulfonate, benzyl sulfonate, p-toluene sulfonate, trimethyl benzene sulfonate, triisobutyl benzene sulfonate. Sulfonate groups such as phonate, p-chlorobenzene sulfonate, pentafluorobenzene sulfonate; methyl sulfinate, phenyl sulfinate, benzyl sulfinate, p-toluene sulfinate, trimethylbenzene sulfinate, Examples thereof include a sulfinate group such as pentafluorobenzene sulfinate; an alkylthio group; an arylthio group. When the sulfur-containing group contains a carbon atom, the number of carbon atoms is preferably in the range of 1 to 30, more preferably 1 to 20.

  The phosphorus-containing group is, for example, a group containing 1 to 5 phosphorus atoms in the group. Specific examples of the phosphorus-containing group include trialkylphosphine groups such as trimethylphosphine, tributylphosphine, and tricyclohexylphosphine; triarylphosphine groups such as triphenylphosphine and tolylphosphine; methyl phosphite, ethyl phosphite, Examples thereof include phosphite groups (phosphide groups) such as phenyl phosphite; phosphonic acid groups; phosphinic acid groups.

  Examples of the metal atom-containing group include groups containing atoms such as silicon, aluminum, boron, zinc and magnesium, and metal atoms such as lithium. Specifically, silicon-containing groups, aluminum-containing groups, Examples thereof include a boron-containing group, a zinc-containing group, a magnesium-containing group, and a lithium atom.

  The silicon-containing group is, for example, a group containing 1 to 5 silicon atoms in the group. Specific examples of the silicon-containing group include hydrocarbon substitution such as phenylsilyl, diphenylsilyl, trimethylsilyl, triethylsilyl, tripropylsilyl, tricyclohexylsilyl, triphenylsilyl, tritolylsilyl, trinaphthylsilyl, and methyldiphenylsilyl. Examples include silyl groups; alkyl-substituted silyl ether groups such as trimethylsilyl ether; silicon-substituted alkyl groups such as trimethylsilylmethyl; silicon-substituted aryl groups such as trimethylsilylphenyl; hydrocarbon-substituted siloxy groups such as trimethylsiloxy. More specifically, the hydrocarbon-substituted silyl group is preferably a trialkylsilyl group such as trimethylsilyl, triethylsilyl, tripropylsilyl, or tricyclohexylsilyl.

The aluminum-containing group is, for example, a group containing 1 to 5 aluminum atoms in the group. Specific examples of the aluminum-containing group include —AlR ₂ group (R represents hydrogen, an alkyl group, an aryl group which may have a substituent, a halogen atom, etc.).

The boron-containing group is, for example, a group containing 1 to 5 boron atoms in the group. Specific examples of the boron-containing group include a —BR ₂ group (R represents hydrogen, an alkyl group, an aryl group which may have a substituent, a halogen atom, etc.).

  The zinc-containing group is, for example, a group containing 1 to 3 zinc atoms in the group. Specific examples of the zinc-containing group include a -ZnR group (R represents hydrogen, an alkyl group, an aryl group which may have a substituent, a halogen atom, or the like).

  The magnesium-containing group is a group containing 1 to 3 magnesium atoms in the group. Specific examples of the magnesium-containing group include a -MgR group (R represents hydrogen, an alkyl group, an aryl group which may have a substituent, a halogen atom, or the like).

  Such an olefin block copolymer (B) having a functional group at the end of the main chain is suitable for various additives such as compatibilizers, paints and adhesives in addition to resin modifiers. Used for.

Next, the manufacturing method of an olefin type block copolymer (B) is demonstrated.
In the production of the olefin block copolymer (B), the transition metal compound (Q) represented by the general formula (1) may be used alone as an olefin polymerization catalyst, or
A transition metal compound (Q);
(R) (R-1) organometallic compound,
(R-2) an organoaluminum oxy compound, and
(R-3) At least one compound selected from compounds that react with the transition metal compound (Q) to form an ion pair may be used in combination as an olefin polymerization catalyst.

In the above formula (1), M ¹ represents a transition metal atom selected from Groups 4 to 5 of the periodic table,
m represents 1 or 2, and R ¹ is an aromatic hydrocarbon group, an aliphatic hydrocarbon group or an alicyclic hydrocarbon group, and when R ¹ is a phenyl group, carbon bonded to nitrogen When the position of the atom is the 1st position, it has at least one atom or substituent selected from a heteroatom and a heteroatom-containing group in at least one position of the 2nd and 6th positions (in this case) Furthermore, it may have an atom or group selected from a heteroatom and a heteroatom-containing group at a position other than the position selected from the 2-position and the 6-position), or at least one of the 3-position, 4-position and 5-position A heteroatom excluding a fluorine atom, a fluorine-containing group containing 1 carbon atom and 2 or less fluorine atoms, a fluorine-containing group containing 2 or more carbon atoms, and a heteroatom excluding a fluorine atom Select from the group to At least one atom or substituent (in this case, a heteroatom (may be a fluorine atom) and a heteroatom (fluorine) at a position other than the position selected from the 3-position, the 4-position, and the 5-position R ¹ may be an aromatic hydrocarbon group other than a phenyl group, an aliphatic hydrocarbon group or an alicyclic hydrocarbon group. In the case, it has at least one atom or substituent selected from a heteroatom and a heteroatom-containing group, and R ^{2 to} R ⁵ each independently represents a hydrogen atom, a halogen atom, a halogen-containing group, carbonization hydrogen group, a hydrocarbon-substituted silyl group, an oxygen-containing group, a nitrogen-containing group or a sulfur-containing group, may be the being the same or different, R ⁶ is a halogen atom, a halogen-containing group, a hydrocarbon group or Represents a hydrocarbon-substituted silyl group, n is a number satisfying the valence of M, and X is an oxygen atom, hydrogen atom, halogen atom, hydrocarbon group, oxygen-containing group, sulfur-containing group, nitrogen-containing group, boron A containing group, an aluminum containing group, a phosphorus containing group, a halogen containing group, a heterocyclic compound residue, a silicon containing group, a germanium containing group or a tin containing group, and when n is 2 or more, a plurality of The groups may be the same as or different from each other, and a plurality of groups represented by X may be bonded to each other to form a ring.

Of these, M ¹ is more preferably a Ti atom. R ¹ is more preferably an aromatic hydrocarbon group, and even more preferably a phenyl group. In the case where R ¹ is a phenyl group, it is more preferable that each of the 2- to 6-positions has a hetero atom when the position of the carbon atom bonded to nitrogen is the 1-position, The hetero atom is more preferably a fluorine atom. R ^{2 to} R ⁵ are more preferably each independently a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 4 carbon atoms. R ⁶ is preferably a halogen atom or a hydrocarbon group having 1 to 4 carbon atoms. X is more preferably a halogen atom.

  As such a transition metal compound, for example, a corresponding compound among the compounds described on pages 104 to 107 of WO 2001/55231 pamphlet can be mentioned.

  When the transition metal compound (Q) and the component (R) are used in combination, the transition metal compound (Q) forms a compound represented by the following general formula (3) in the polymerization system.

In the formula ^{(3), R 1 ~R 6} , M 1, m, n and X are each located at ^{R 1 ~R 6, M 1,} m, n and X as defined in the formula (1) , Y represents a so-called weakly coordinating anion. In the above formula (3), the bond between the metal M and Y may be a covalent bond or an ionic bond.

As Y, for example,
(1) Chemical Review, Vol. 88, page 1405 (1988),
(2) Chemical Review, Vol. 93, p. 927 (1993), and
(3) The weakly coordinating anion described in WO98 / 30612, page 6, etc.
In particular,
AlR ₄ ^-
(R may be the same as or different from each other, and may be an oxygen atom, a nitrogen atom, a phosphorus atom, a hydrogen atom, a halogen atom or a substituent containing them; an aliphatic hydrocarbon group, an aromatic hydrocarbon group or An alicyclic hydrocarbon group; an aliphatic hydrocarbon group, an aromatic hydrocarbon group or an alicyclic hydrocarbon group substituted with an oxygen atom, a nitrogen atom, a phosphorus atom or a halogen atom; or an aliphatic hydrocarbon group And a group in which an aromatic hydrocarbon group or an alicyclic hydrocarbon group is substituted with a substituent having an oxygen atom, a nitrogen atom, a phosphorus atom or a halogen atom.)
BR ₄ ^-
(Rs may be the same as or different from each other, and may be an oxygen atom, a nitrogen atom, a phosphorus atom, a halogen atom or a substituent containing them; an aliphatic hydrocarbon group, an aromatic hydrocarbon group or an alicyclic group. A hydrocarbon group; an aliphatic hydrocarbon group, an aromatic hydrocarbon group or an alicyclic hydrocarbon group substituted with an oxygen atom, a nitrogen atom, a phosphorus atom or a halogen atom; or an aliphatic hydrocarbon group or an aromatic group A hydrocarbon group or an alicyclic hydrocarbon group substituted with a substituent having an oxygen atom, a nitrogen atom, a phosphorus atom or a halogen atom).
Examples thereof include PF ₆ ⁻ , SbF ₅ ⁻ , trifluoromethane sulfonate, and p-toluene sulfonate.

  In the polymerization of the olefin block copolymer (B), a polymer is obtained by copolymerizing ethylene and an α-olefin having 3 to 20 carbon atoms in the presence of the olefin polymerization catalyst as described above. Examples of the olefin having 3 to 20 carbon atoms include the same ones as described above.

In the polymerization of the olefin block copolymer (B), either a liquid phase polymerization method such as solution polymerization or suspension polymerization, or a gas phase polymerization method may be used.
Specific examples of the inert hydrocarbon medium used in the liquid phase polymerization method include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane, Alicyclic hydrocarbons such as methylcyclopentane; Aromatic hydrocarbons such as benzene, toluene and xylene; Halogenated hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane; and mixtures thereof, and the olefin itself as a solvent It may be used.

When polymerizing an olefin having 2 to 20 carbon atoms using the above olefin polymerization catalyst, the transition metal compound (Q) is usually in an amount of 10 ⁻¹² to 1 mol per liter of reaction volume, It is desirable to use it in an amount of 10 ⁻¹⁰ to 10 ⁻² mol.

When component (R-1) is used, the molar ratio [(R-1) / M] between component (R-1) and transition metal atom (M) in transition metal compound (Q) is usually It is desirable to use it in an amount of 0.01 to 100,000, preferably 0.05 to 50,000. When the component (R-2) is used, the molar ratio of the aluminum atom in the component (R-2) and the transition metal atom (M) in the transition metal compound (Q) [(R-2) / M ] Is usually used in an amount of 10 to 500,000, preferably 20 to 100,000. When component (R-3) is used, the molar ratio [(R-3) / M] between component (R-3) and transition metal atom (M) in transition metal compound (Q) is usually 1-10, preferably 1
It is desirable to use in an amount of 5.

  In the presence of an olefin polymerization catalyst containing a transition metal compound (Q), ethylene and at least one α-olefin having a different polymerization reactivity selected from α-olefins having 3 to 20 carbon atoms are allowed to coexist. If polymerization is performed, an olefin block copolymer (B) containing a polymer segment in which two or more kinds of monomer compositions continuously change can be produced.

  Here, as described above, the olefin block copolymer (B) is a polymer chain (polymer segment) having a different primary structure of the polymer, such as monomer species, comonomer species, comonomer composition, comonomer content, comonomer arrangement, and stereoregularity. ) Refers to a copolymer in a form in which two or more types are connected in one molecular chain. This copolymer is synthesized by sequentially adding different monomer species or monomers having different monomer compositions in a living polymerization system in which chain transfer reaction does not substantially occur.

  Specifically, the olefin block copolymer (B) used in the present invention is produced, for example, by repeating the step (3) as many times as necessary after the following step (1) and step (2). Is done. Thereby, the olefin type block copolymer (B) which consists of a some polymer segment is manufactured.

  In step (1), in the presence of the olefin polymerization catalyst, ethylene alone or ethylene and at least one α-olefin selected from α-olefins having 3 to 20 carbon atoms are polymerized. To produce a polymer segment as described above. The α-olefin having 3 to 20 carbon atoms may be used alone or in combination of two or more.

In the step (1), the polymerization temperature is usually in the range of −40 to + 200 ° C., preferably 0 to + 150 ° C. The polymerization pressure is usually normal pressure to 100 kg / cm ² , preferably normal pressure to 50 k.
g / cm ² .

  In step (2), in the presence of the polymer segment produced in step (1), ethylene and at least one α-olefin selected from α-olefins having 3 to 20 carbon atoms are polymerized, A polymer segment as described above, which is different from the polymer segment produced in the step (1), is produced. The α-olefin having 3 to 20 carbon atoms may be used alone or in combination of two or more.

  Here, the different polymer segments indicate those in which at least one of the primary structure of the polymer is different, such as monomer type, comonomer type, comonomer composition, comonomer content, comonomer sequence, and stereoregularity.

In the step (2), the polymerization temperature is usually in the range of −40 to + 200 ° C., preferably 0 to + 150 ° C. The polymerization pressure is usually normal pressure to 100 kg / cm ² , preferably normal pressure to 50 k.
g / cm ² .

  In the step (3), in the presence of the polymer segment obtained in the steps (1) and (2), at least 1 selected from ethylene alone or ethylene and an α-olefin having 3 to 20 carbon atoms. A polymer segment as described above, which is different from the polymer segment produced in step (2), is polymerized with a seed α-olefin. The α-olefin having 3 to 20 carbon atoms may be used alone or in combination of two or more.

In the step (3), the polymerization temperature is usually in the range of −40 to + 200 ° C., preferably 0 to + 150 ° C. The polymerization pressure is usually normal pressure to 100 kg / cm ² , preferably normal pressure to 50 k.
The condition is g / cm ² .

This step (3) may be repeated any number of times by changing the type, combination or polymerization conditions of the α-olefin.
According to the above production method, an olefin block copolymer (B) having a high polymerization activity, a large molecular weight, and a narrow molecular weight distribution can be obtained at a high polymerization temperature.

Moreover, this olefin type block copolymer and a functional group containing compound may be contacted, and the olefin type block copolymer (B) which has a functional group at the terminal may be obtained.
Furthermore, in this production method, a catalyst obtained by polymerizing an olefin in the presence of a catalyst that promotes living polymerization of the olefin, and cleaving the bond between the catalyst generated in the system and the generated polymer chain by a chain transfer reaction is obtained. Can be used for polymerization.

  The progress of the living polymerization can be confirmed by the narrow molecular weight distribution of the obtained polymer and the increase in the molecular weight of the resulting polymer with the polymerization time. According to this, for example, the monodisperse polyolefin, olefin copolymer, tapered polymer, or olefin block copolymer can be produced.

  About progress of the said living polymerization, it is preferable to superpose | polymerize and confirm an olefin on the conditions except a chain transfer agent, for example. The molecular weight of the resulting polymer is adjusted by controlling the monomer / catalyst ratio, polymerization time, and the like.

According to the production method as described above, an olefin block copolymer (B) having a high polymerization activity, a large molecular weight, a narrow molecular weight distribution, and a precisely controlled structure can be obtained at a high polymerization temperature.

The block copolymer (B) of the present invention may be graft-modified with at least one compound selected from unsaturated carboxylic acids and derivatives thereof. Examples of the unsaturated carboxylic acid include maleic anhydride. Graft modification can be performed by a usual method.
<Inorganic filler (D)>
Specific examples of the inorganic filler (D) include natural silicates or silicates such as finely powdered talc, kaolinite, calcined clay, virophilite, sericite, wollastonite; precipitated calcium carbonate, heavy calcium carbonate Carbonates such as magnesium carbonate; hydroxides such as aluminum hydroxide and magnesium hydroxide; oxides such as zinc oxide, zinc white and magnesium oxide; synthesis of hydrous calcium silicate, hydrous aluminum silicate, hydrous silicic acid, anhydrous silicic acid, etc. Powder fillers such as silicic acid or silicates;
Flaky filler such as mica;
Basic magnesium sulfate whisker, calcium titanate whisker, aluminum borate whisker, sepiolite, PMF (Processed Mineral Fiber), zonotlite,
Fibrous fillers such as potassium titanate and elestadite;
Examples include balun fillers such as glass balun and fly ash balun.

Among these, when used in the present invention, talc is preferable, and an average particle size of 0.01 to
10 μm fine powder talc is more preferable. The average particle size of talc can be measured by a liquid phase precipitation method.

  Further, the inorganic filler used in the present invention, particularly talc, may be untreated or may be surface-treated in advance. Specific examples of the surface treatment include chemical or physical treatment using a silane coupling agent, a higher fatty acid, a fatty acid metal salt, an unsaturated organic acid, an organic titanate, a resin acid, polyethylene glycol, or the like. It is done. When a talc subjected to such a surface treatment is used, a molded body having excellent mechanical properties and molding processability can be obtained.

When the inorganic filler as described above is used in the present invention, it may be used alone or in combination of two or more. Moreover, you may use together organic fillers, such as high styrenes, lignin, a re-rubber, with such an inorganic filler.
<Other copolymers>
The propylene-based polymer composition according to the present invention (herein, the above-mentioned composition means “first composition” and “second composition” described later), if necessary, “other components”. "Polymer" (elastomer, resin for elastomer) may be contained.

  Such “other copolymer” is not particularly limited, and examples thereof include an ethylene / α-olefin random copolymer (C). These copolymers are used alone or in combination of two or more.

  “Other copolymer” means a total of 100 parts by weight of the propylene polymer (A) and the olefin block copolymer (B), or the propylene polymer (A) and the olefin block copolymer (BB). ) And 100 parts by weight in total, usually 1 to 80 parts by weight, preferably 10 to 70 parts by weight.

As also good ethylene · alpha-olefin random copolymer used in the present invention (C), is not particularly limited, for example, density of 0.855 g / cm ³ or more 0.895 g / cm less than ^3, preferably 0 860 to 0.890 g / cm ³ , and melt flow rate (MFR; ASTM D 1238, 190 ° C., load 2.16 kg) is, for example, 0.001 to 30 g / 10 minutes, preferably 1 to 20 g / 10 A soft ethylene / α-olefin copolymer is preferred.

The α-olefin copolymerized with ethylene is an α-olefin having 3 to 20 carbon atoms, specifically, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, Examples include 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-hexadedecene, 1-octadecene, 1-nonadecene, 1-eicocene, 4-methyl-1-pentene, and the like. Of these, α-olefins having 3 to 10 carbon atoms are preferable. These α-olefins may be used alone or in combination of two or more.

  The ethylene / α-olefin random copolymer (C) is an amount of 60 to 90 mol% of units derived from ethylene and 10 to 40 mol% of units derived from an α-olefin having 3 to 20 carbon atoms. It is desirable to contain in an amount (here, the total of units derived from ethylene and units derived from an α-olefin having 3 to 20 carbon atoms is 100 mol%).

  Further, the ethylene / α-olefin random copolymer (C) may contain units derived from other polymerizable monomers in addition to these units as long as the object of the present invention is not impaired.

As the other polymerizable monomer, for example,
Vinyl compounds such as styrene, vinylcyclopentene, vinylcyclohexane, vinylnorbornane;
Vinyl esters such as vinyl acetate;
Unsaturated organic acids such as maleic anhydride or derivatives thereof;
Conjugated dienes such as butadiene, isoprene, pentadiene, 2,3-dimethylbutadiene;
1,4-hexadiene, 1,6-octadiene, 2-methyl-1,5-hexadiene, 6-methyl-1,5-
Heptadiene, 7-methyl-1,6-octadiene, dicyclopentadiene, cyclohexadiene, dicyclooctadiene, methylene norbornene, 5-vinyl norbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5- Isopropylidene-2-norbornene, 6-chloromethyl-5-isopropylene-2-norbornene, 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2 Non-conjugated polyenes such as 2-norbornadiene.

  In the ethylene / α-olefin random copolymer (C), units derived from such other polymerizable monomers are composed of units derived from ethylene and units derived from an α-olefin having 3 to 20 carbon atoms. You may contain in the quantity of 10 mol% or less further with respect to a total of 100 mol%, Preferably it is 5 mol% or less, More preferably, it is 3 mol% or less.

  As the ethylene / α-olefin random copolymer (C), specifically, an ethylene / propylene random copolymer, an ethylene / 1-butene random copolymer, an ethylene / propylene / 1-butene random copolymer, Examples thereof include an ethylene / propylene / ethylidene norbornene random copolymer, an ethylene / propylene / dicyclopentadiene random copolymer, an ethylene / 1-hexene random copolymer, and an ethylene / 1-octene random copolymer. Among these, ethylene / propylene random copolymer, ethylene / 1-butene random copolymer, ethylene / 1-hexene random copolymer, ethylene / 1-octene random copolymer, ethylene / propylene / ethylidene norbornene random A copolymer and an ethylene / propylene / dicyclopentadiene random copolymer are particularly preferably used. Two or more of these copolymers may be used in combination.

The ethylene / α-olefin random copolymer (C) used in the present invention is X
The degree of crystallinity measured by a line diffraction method is usually 40% or less, preferably 0 to 39%, more preferably 0 to 35%.

In addition, the propylene-based resin composition according to the present invention may contain a crosslinked ethylene / α-olefin random copolymer (C).
The ethylene / α-olefin random copolymer (C) as described above can be produced by a conventionally known method using a vanadium catalyst, a titanium catalyst or a metallocene catalyst.
<Propylene-based resin composition>
The olefin block copolymer (B) produced as described above is useful as a modifier, and a propylene resin composition having desired characteristics can be obtained by blending with the propylene polymer (A). It is done. A propylene-based resin composition containing a propylene-based polymer (A) in an amount of 1 to 99% by weight and an olefinic block copolymer (B) in an amount of 99 to 1% by weight (wherein the propylene-based polymer ( The sum of A) and the olefinic block copolymer (B) is 100% by weight) and is excellent in impact resistance and heat resistance.

  The propylene polymer (A) is 40 to 99% by weight, preferably 50 to 90% by weight, and the olefin block copolymer (B) is 60 to 1% by weight, preferably 50 to 10% by weight. (Wherein the total of the propylene-based polymer (A) and the olefin-based block copolymer (B) is 100% by weight), and is substantially free of the inorganic filler (D). The propylene-based resin composition (I) is excellent in transparency as well as impact resistance and heat resistance, and hardly changes in appearance even at high temperatures.

  Further, the propylene polymer (A) is less than 40% by weight in an amount of 1% by weight or more, preferably 30 to 1% by weight, and the olefin block copolymer (B) is more than 60% by weight and 99% by weight or less, Propylene resin composition (II) preferably contained in an amount of 70 to 99% by weight (wherein the total of propylene polymer (A) and olefin block copolymer (B) is 100% by weight) Is excellent in heat resistance, flexibility and rubber elasticity.

Here, the inorganic filler (D) is substantially free of the inorganic filler (D) with respect to a total of 100 parts by weight of the propylene polymer (A) and the olefin block copolymer (B). Is 1 part by weight or less, preferably 0.5 part by weight or less, more preferably 0.1 part by weight or less.

  Further, the composition (II) may contain an inorganic filler (D) such as talc in order to improve flame retardancy, and the inorganic filling with respect to 100 parts by weight of the composition (II). The material (D) is preferably contained in an amount of 10 to 800 parts by weight, more preferably 100 to 500 parts by weight.

When such a propylene-based resin composition measures and plots the temperature dependence of the elastic modulus every 2 ° C., the peak of the decay rate (tan δ) due to the glass transition temperature of the propylene-based polymer (A) , Decay rate due to glass transition temperature of olefin block copolymer (B) (tan
It is preferable that there is a peak of δ) and that both peaks are separated. When two peaks clearly appear, that is, when a ridge exists between the highest points of the two peaks, it is determined as “separated”. The propylene-based resin composition having two “separated” peaks is excellent in impact resistance and rigidity.

  The propylene-based resin composition according to the present invention is a method in which a propylene-based polymer (A) and an olefin-based block copolymer (B) are mixed with an internal mixer such as a Banbury mixer, a kneader, or an intermix. It is produced by kneading by a conventionally known method.

Further, in the resin modification as described above, an apparatus for continuously kneading and discharging such as an extruder is preferably used. The kneading is desirably performed at a temperature equal to or higher than the melting point or softening point of the discharged resin and not higher than 400 ° C.
<Additives>
The propylene-based resin composition according to the present invention (herein, the above-mentioned composition means a “first composition” and a “second composition” described later) is added to the above components. As long as the object of the present invention is not impaired, the nucleating agent, antioxidant, hydrochloric acid absorbent, heat stabilizer, light stabilizer, ultraviolet absorbent, lubricant, antistatic agent, flame retardant, pigment, dye, dispersant Contains additives such as copper damage inhibitors, neutralizers, foaming agents, plasticizers, anti-bubble agents, crosslinking agents, crosslinking aids, silane coupling agents, peroxides, weld strength improvers, etc. Also good.

Examples of the antioxidant include a phenol-based antioxidant, a sulfur-based antioxidant, and a phosphorus-based antioxidant.
Examples of the phenol-based antioxidant include 2,6-di-tert-butyl-p-cresol,
Stearyl (3,3-dimethyl-4-hydroxybenzyl) thioglycolate, stearyl-β-
(4-hydroxy-3,5-di-tert-butylphenol) propionate, distearyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 2,4,6-tris (3 ', 5'- Di-tert-butyl-4'-hydroxybenzylthio) -1,3,5-triazine, distearyl (4-hydroxy-3-methyl-5-tert-butylbenzyl) malonate, 2,2'-methylenebis (4 -Methyl-6-tert-butylphenol), 4,4'-methylenebis (2,6-di-tert-butylphenol), 2,2'-methylenebis [6- (1-methylcyclohexyl) p-cresol], bis [ 3,5-bis [4-hydroxy-3-tert-butylphenyl) butyric acid] glycol ester, 4,4′-butylidenebis (6-tert-butyl-m-cresol), 1,1,3-tris ( 2-methyl-4-hydroxy-5-tert-butylphenyl) butane, bis [2-tert-butyl-4-methyl-6- (2-hydroxy-3-tert-butyl-5-methylben) Dil) phenyl] terephthalate, 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-tert-butyl) benzyl isocyanurate, 1,3,5-tris (3,5-di-tert- Butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris [(3,5-di-tert-
Butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, 2-octylthio-4,6-di (4-hydroxy-3,5-di-tert-butyl) phenoxy-1,3,5-triazine, 4, Phenols such as 4'-thiobis (6-tert-butyl-m-cresol), carbonic acid oligoesters of 4,4'-butylidenebis (2-tert-butyl-5-methylphenol) (eg, degree of polymerization 2 to 10) And polyhydric phenol carbonic acid oligoesters.

  Examples of the sulfur-based antioxidant include dialkylthiodipropionates such as dilauryl-, dimyristyl-, and distearyl-, and polyhydric alcohols of alkylthiopropionic acids such as butyl-, octyl-, lauryl-, stearyl- , Ester of glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, trishydroxyethyl isocyanurate) (for example, pentaerythritol tetralaurylthiopropionate).

Examples of the phosphorus antioxidant include trioctyl phosphite, trilauryl phosphite, tridecyl phosphite, octyl-diphenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tri Phenyl phosphite, tris (butoxyethyl) phosphite, tris (nonylphenyl) phosphite, distearyl pentaerythritol diphosphite, tetra (tridecyl) -1,1,3-tris (2-methyl-5-tert-butyl 4-hydroxyphenyl) butane diphosphite, tetra (C ₁₂ -C ₁₅ mixed alkyl) -4,4'-isopropylidene diphenyl diphosphite, tetra (tridecyl) -4,4'-butylidene bis (3-methyl - 6-tert-butylphenol) diphosphite, tris (3,5-di-t
ert-butyl-4-hydroxyphenyl) phosphite, tris (mono-dimixed nonylphenyl) phosphite, hydrogenated-4,4'-isopropylidenediphenol polyphosphite, bis (octylphenyl) bis [4, 4'-butylidenebis (3-methyl-6-tert-butylphenol)], 1,6-hexanediol diphosphite, phenyl, 4,4'-isopropylidenediphenol, pentaerythritol diphosphite, bis (2,4 -Di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl)
Pentaerythritol diphosphite, tris [4,4'-isopropylidenebis (2-tert-butylphenol)] phosphite, phenyl diisodecyl phosphite, di (nonylphenyl) pentaerythritol diphosphite), tris (1,3 -Di-stearoyloxyisopropyl) phosphite, 4,4'-isopropylidenebis (2-tert-butylphenol) di (nonylphenyl) phosphite, 9,10-di-hydro-9-oxa-9-oxa- Examples include 10-phosphaphenanthrene-10-oxide, tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite.

Further, other antioxidants include 6-hydroxychroman derivatives such as α, β, γ, δ various tocopherols and mixtures thereof, 2- (4-methyl-pent-3-enyl) -6-
Hydroxychroman 2,5-dimethyl substituted, 2,5,8-trimethyl substituted, 2,5,7,8-tetramethyl substituted, 2,2,7-trimethyl-5-tert-butyl-6- Hydroxychroman, 2,2,5-trimethyl-7-tert-butyl-6-hydroxychroman, 2,2,5-trimethyl-6-tert-butyl-6-hydroxychroman, 2,2-dimethyl-5-tert -Butyl-6-hydroxychroman and the like are used.

Further, the following general formula _{M x Al y (OH) 2x} + 3y-2z (A) z · aH 2 O
(M is Mg, Ca, or Zn, A is an anion other than a hydroxyl group, x, y, and z are positive numbers, and a is 0 or a positive number.) For example,
Mg ₆ Al ₂ (OH) ₁₆ CO ₃ .4H ₂ O,
Mg ₆ Al ₂ (OH) ₂₀ CO ₃ .5H ₂ O,
Mg ₅ Al ₂ (OH) ₁₄ CO ₃ .4H ₂ O,
_{Mg 10 Al 2 (OH) 22} (CO 3) 2 · 4H 2 O,
Mg ₆ Al ₂ (OH) ₁₆ HPO ₄ · 4H ₂ O,
Ca ₆ Al ₂ (OH) ₁₆ CO ₃ .4H ₂ O,
Zn ₆ Al ₂ (OH) ₁₆ CO ₃ .4H ₂ O,
Zn ₆ Al ₂ (OH) ₁₆ SO ₄ .4H ₂ O,
Mg ₆ Al ₂ (OH) ₁₆ SO ₃ .4H ₂ O,
Mg ₆ Al ₂ (OH) ₁₂ CO ₃ · 3H ₂ O
Etc. may be used as hydrochloric acid absorbents.

Examples of the light stabilizer include 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone-2,2′-di-hydroxy-4-methoxybenzophenone, and 2,4-dihydroxybenzophenone. Hydroxybenzophenones such as 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di- tert-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-amylphenyl) Benzotriazoles such as benzotriazole, phenyl salicylate, p-tert-butylphenyl salicylate, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl-3,5 -Di-tert-butyl-4-hydroxybenzoe Benzoates such as To, 2,2'-thiobis (4-tert-octylphenol) Ni salt, [2,2'-thiobis (4-tert-octylphenolate)]-n-butylamine Ni, (3,5- Di-tert-butyl-4-hydroxybenzyl) phosphonic acid monoethyl ester nickel compounds such as Ni salt, substituted acrylonitriles such as methyl α-cyano-β-methyl-β- (p-methoxyphenyl) acrylate, N Oxalic acid dianilides such as' -2-ethylphenyl-N-ethoxy-5-tert-butylphenyloxalic acid diamide, N-2-ethylphenyl-N'-2-ethoxyphenyloxalic acid diamide, bis (2,2 , 6,6-tetramethyl-4-piperidine) sebacate, poly [{(6- (1,1,3,3-tetramethylbutyl) imino} -1,3,5-triazine-2,4-diyl { 4- (2,2,6,6-tetramethylpiperidyl) imino} hexamethylene], 2- (4-hydroxy-2,2,6,6-teto Methyl-1-piperidyl) hindered amine compound condensation products of ethanol and dimethyl succinate, and the like.

  Examples of the lubricant include aliphatic hydrocarbons such as paraffin wax, polyethylene wax and polypropylene wax, capric acids, higher fatty acids such as lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, arachidic acid and behenic acid. And metal salts thereof (for example, lithium salt, calcium salt, sodium salt, magnesium salt, potassium salt), aliphatic alcohols such as palmityl alcohol, cetyl alcohol, stearyl alcohol, capron amide, caprylic amide, caprin Aliphatic amides such as acid amides, lauric acid amides, myristic acid amides, palmitic acid amides, stearic acid amides, esters of aliphatic and alcohols, fluoroalkylcarboxylic acids and metal salts thereof, fluoroalkyls And fluorine compounds such as acid metal salts.

The additive as described above is a total of 100 parts by weight of the propylene polymer (A) and the olefin block copolymer (B), or the propylene polymer (A) and an olefin block copolymer (described later). BB) with respect to a total of 100 parts by weight, preferably 0.00
Used in an amount of 01 to 10 parts by weight. The propylene-based resin composition contains the additives as described above, thereby forming a molded body having further improved physical property balance, durability, paintability, printability, scratch resistance, and moldability. it can.

  Moreover, the propylene-based resin composition according to the present invention may contain a nucleating agent. The nucleating agent is not particularly limited, and various conventionally known nucleating agents are used. Among these, nucleating agents such as aromatic phosphate ester salts represented by the following general formulas (4) and (5) and dibenzylidene sorbitol represented by the following general formula (6) are preferably used.

Wherein R ¹ is oxygen, sulfur or a hydrocarbon group having 1 to 10 carbon atoms, R ² and R ³ are each independently hydrogen or a hydrocarbon group having 1 to 10 carbon atoms; ² and R ³ may be the same or different, and R ² , R ^3, or R ² and R ³ may be bonded to form a ring. (It is a trivalent metal atom, and n is an integer of 1 to 3.)

(In the formula, R ¹ is hydrogen or a hydrocarbon group having 1 to 10 carbon atoms, M is a 1 to 3 valent metal atom, and n is an integer of 1 to 3).

(In the formula, R ¹ is hydrogen or a hydrocarbon group having 1 to 10 carbon atoms.)
Specific examples of the nucleating agent represented by the above formula (4) include sodium-2,2′-methylene-bis (4,6-di-t-butylphenyl) phosphate, sodium-2,2 ′. -Ethylidene-bis (4,6-di-t-butylphenyl) phosphate, lithium-2,2'-methylene-bis- (4,6-di-t-butylphenyl) phosphate, lithium-2,2 '-Ethylidene-bis (4,6-di-t-butylphenyl) phosphate, sodium-2,2'-ethylidene-bis (4-i-propyl-6-t-butylphenyl) phosphate, lithium-2 , 2'-methylene-bis (4-methyl-6-t-butylphenyl) phosphate, lithium-2,2'-methylene-bis (4-ethyl-6-t-butylphenyl) phosphate, calcium-bis [2,2'-thiobis (4-methyl-6-t-butylphenyl) phosphate], calcium-bis [2,2'-thiobis (4-ethyl-6-t-butylphenyl) phosphate , Calcium-bis [2,2'-thiobis- (4,6-di-t-butylphenyl) phosphate], magnesium-bis [2,2'-thiobis (4,6-di-t- Butylphenyl) phosphate], magnesium-bis [2,2'-thiobis- (4-t-octylphenyl) phosphate], sodium-2,2'-butylidene-bis (4,6-di-methylphenyl) Phosphate, sodium-2,2'-butylidene-bis (4,6-di-t-butylphenyl) phosphate, sodium-2,2'-t-octylmethylene-bis (4,6-di-methylphenyl) ) Phosphate, sodium-2,2′-t-octylmethylene-bis (4,6-di-t-butylphenyl) phosphate, calcium-bis- (2,2′-methylene-bis (4,6- Di-t-butylphenyl) phosphate), magnesium-bis [2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate], barium-bis [2,2'-me Tylene-bis (4,6-di-t-butylphenyl) phosphate], sodium-2,2'-methylene-bis (4-methyl-6-t-butylphenyl) phosphate, sodium-2,2 ' -Methylene-bis (4-ethyl-6-t-butylphenyl) phosphate, sodium (4,4'-dimethyl-5,6'-di-t-butyl-2,2'-biphenyl) phosphate, calcium -Bis [(4,4'-dimethyl-6,6'-di-t-butyl-2,2'-biphenyl) phosphate], sodium-2,2'-ethylidene-bis (4-m-butyl- 6-t-butylphenyl) phosphate, sodium-2,2'-methylene-bis (4,6-di-methylphenyl) phosphate, sodium-2,2'-methylene-bis (4,6-di- Ethylphenyl) phosphate, potassium-2,2'-ethylidene-bis (4,6-di-t-butylphenyl) phosphate, calcium-bis [2,2'-ethylidene-bis (4,6-di-) t-Butylphenyl) Huo Fate], magnesium-bis [2,2'-ethylidene-bis (4,6-di-t-butylphenyl) phosphate], barium-bis [2,2'-ethylidene-bis (4,6-di-) t-butylphenyl) phosphate], aluminum-tris [2,2'-methylene-bis (4,6-di-t-butylfell) phosphate], aluminum-tris [2,2'-ethylidene-bis (4 , 6-Di-t-butylphenyl)
Phosphate] and the like. These may be used singly or in combination of two or more. Of these, sodium-2,2′-methylene-bis (4,6-di-t-butylphenyl) phosphate is preferred.

Specific examples of the nucleating agent represented by the above formula (5) include sodium-bis (4-t-butylphenyl) phosphate, sodium-bis (4-methylphenyl) phosphate, sodium-bis (4 -Ethylphenyl) phosphate, sodium-bis (4-i-propylphenyl) phosphate, sodium-bis (4-t-octylphenyl) phosphate, potassium-bis (4-t-butylphenyl) phosphate, calcium -Bis (4-t-butylphenyl) phosphate, magnesium-bis (4-t-butylphenyl) phosphate, lithium-bis (4-t-butylphenyl) phosphate, aluminum-bis (4-t-butyl) Phenyl) phosphate and the like. These may be used singly or in combination of two or more. Of these, sodium-bis (4-t-butylphenyl) phosphate is preferred.

Specific examples of the nucleating agent represented by the above formula (6) include 1,3,2,4-dibenzylidene sorbitol, 1,3-benzylidene-2,4-p-methylbenzylidene sorbitol, 1,3 -Benzylidene-2,4-p-ethylbenzylidenesorbitol, 1,3-p-methylbenzylidene-2,4-benzylidenesorbitol, 1,3-p-ethylbenzylidene-2,4-benzylidenesorbitol, 1,3-p -Methylbenzylidene-2,4-p-ethylbenzylidenesorbitol, 1,3-p-ethylbenzylidene-2,4-p-methylbenzylidenesorbitol, 1,3,2,4-di (p-methylbenzylidene) sorbitol, 1,3,2,4-di (p-ethylbenzylidene) sorbitol, 1,3,2,4-di (pn-propylbenzylidene) sorbitol, 1,3,2,4-di (pi-propylbenzylidene) sorbitol 1,3,2,4-di (pn-butylbenzylidene) sorbitol, 1,3,2,4-di (ps-butylbenzylidene) so Rubitol, 1,3,2,4-di (pt-butylbenzylidene) sorbitol, 1,3,2,4-di (2 ', 4'-dimethylbenzylidene) sorbitol, 1,3,2,4-di ( p-methoxybenzylidene) sorbitol, 1,3,2,4-di (p-ethoxybenzylidene) sorbitol, 1,3-benzylidene-2-4-p-chlorobenzylidenesorbitol, 1,3-p-chlorobenzylidene-2 , 4-Benzylidenesorbitol, 1,3-p-chlorobenzylidene-2,4-p-methylbenzylidenesorbitol, 1,3-p-chlorobenzylidene-2,4-p-ethylbenzylidenesorbitol, 1,3-p- Methylbenzylidene-2,4-p-chlorobenzylidenesorbitol, 1,3-p-ethylbenzylidene-2,4-p-chlorobenzylidenesorbitol and 1,3,2,4-di (p-chlorbenzylidene) sorbitol and these Can be exemplified. Among these, 1,3,2,4-dibenzylidene sorbitol, 1,3,2,4-di (p-methylbenzylidene) sorbitol, 1,3,2,4-di (p-ethylbenzylidene) sorbitol 1,3-p-chlorobenzylidene-2,4-p-methylbenzylidene sorbitol, 1,3,2,4-di (p-chlorobenzylidene) sorbitol and the like. These may be used singly or in combination of two or more.

  Furthermore, as a nucleating agent, a metal salt of an aromatic carboxylic acid or a metal salt of an aliphatic carboxylic acid may be used. Specifically, an aluminum benzoate, an aluminum pt-butylbenzoate, a sodium adipate, Examples include sodium thiophenecarboxylate and sodium pyrolelecarboxylate. In addition, an inorganic compound such as talc may be used as a nucleating agent.

The nucleating agent is a total of 100 parts by weight of the propylene-based polymer (A) and the olefin-based block copolymer (B), or the propylene-based polymer (A) and the olefin-based block copolymer (BB) described later. Is preferably contained in the composition in an amount of 0.001 to 10 parts by weight, more preferably 0.01 to 5 parts by weight, still more preferably 0.1 to 3 parts by weight with respect to a total of 100 parts by weight. It is desirable. When the nucleating agent is contained, the crystallization speed of the propylene-based resin composition is improved, the crystal particles can be refined during crystallization, and molding can be performed at a higher speed.
<Molded body made of propylene-based resin composition>
The propylene-based resin composition according to the present invention is widely used for conventionally known polyolefin applications. For example, the propylene-based resin composition is suitably used for molded articles having various shapes such as a sheet, an unstretched film, and a stretched film. Moreover, even if the molded object which consists of the said propylene-type resin composition, this composition may be used for all the molded objects, even if this composition is used for a part of molded object. Examples of the former include a multilayer laminate including at least one layer containing a propylene polymer composition, and more specifically, a multilayer film, a multilayer sheet, a multilayer container, a multilayer tube, and the like. And a multilayer coating film laminate included as a constituent component of the water-based paint.

  The propylene-based resin composition according to the present invention is used as various molded articles such as films, sheets, and pipes by a known thermoforming method such as extrusion molding, inflation molding, and calendar molding. Among these, it is suitably used as a molded product obtained by extrusion molding or inflation molding. Thereby, the molded object excellent in distortion recovery property etc. is obtained.

  When the molded body according to the present invention is an extruded molded body, its shape and product type are not particularly limited, and examples thereof include a sheet, an unstretched or stretched film, a pipe, a hose, a wire coating, a tube, and a catheter. Among these, a sheet (skin material), an unstretched or stretched film, a tube, and a catheter are preferable.

  When extruding the propylene-based resin composition, a conventionally known extrusion apparatus and molding conditions can be employed. For example, the melted composition can be extruded from a specific die or the like using a single screw extruder, a kneading extruder, a ram extruder, a gear extruder, or the like, and formed into a desired shape.

  For the stretched film, a known stretching method such as a tenter method (longitudinal and transverse stretching or transverse and longitudinal stretching), a simultaneous biaxial stretching method, a uniaxial stretching method, or the like is applied to the above-described extruded sheet or extruded film (unstretched). Use it to get it.

  The stretching ratio when stretching the sheet or film (unstretched) is usually about 20 to 70 times in the case of biaxial stretching, and is usually about 2 to 10 times in the case of uniaxial stretching. Thereby, it is desirable to obtain a stretched film having a thickness of about 5 to 200 μm.

Moreover, you may manufacture an inflation film as a film-form molded object. Drawdown is less likely to occur during inflation molding.
Films and sheets comprising the above propylene-based resin composition are difficult to be charged and have rigidity such as tensile modulus, heat resistance, stretchability, impact resistance, aging resistance, transparency, gloss, rigidity, moisture resistance and gas barrier. And is widely used as a packaging film, a sealing sheet, and the like. In this case, the film and sheet may be a multilayer laminate containing at least one layer composed of a propylene-based polymer composition.

  The molded body according to the present invention is suitably used for food packaging and medical use, for example. Specifically, examples of the food packaging molded body include food containers such as retort pouches, bottle containers, and the like, and examples of the medical molded body include medical containers and infusion bags. Further, containers and packaging materials other than those exemplified above may be used. When the molded product of the present invention is used for a molded product for food packaging, a molded product for medical use, or other containers, a molded product made of the propylene-based resin composition (I) is preferably used. In particular, such a composition is preferable because it is excellent in impact resistance, heat resistance, and transparency and hardly changes in appearance even at high temperatures.

Moreover, when the molded object which concerns on this invention consists of the said propylene polymer composition (II), it is excellent in rubber elasticity and heat resistance.
Another resin composition according to the present invention is:
[A] (i) Melt flow rate (MFR: 230 ° C., under 2.16 kg load) is 0.1 to 400 g / 10 minutes,
(ii) containing a normal temperature n-decane soluble component in an amount of 0.01 to 30% by weight,
The intrinsic viscosity [η] measured in 135 ° C. decalin of the room temperature n-decane soluble component is 0.2 to 0.2.
10 dl / g,
(iii) The pentad isotacticity (I ₅ ) determined by the ¹³ C-NMR method of the room temperature n-decane insoluble component is 0.95 or more.
Propylene polymer (A) in an amount of 1 to 99% by weight,
[BB] an olefin block copolymer containing polymer segments (B1), (B1 ′) and (B2),
(B1) and (B1 ′) are each independently at least one polymer selected from ethylene and an α-olefin having 3 to 20 carbon atoms,
(i) the ethylene content is 95-100 mol%,
(ii) an ethylene polymer polymer segment having a weight average molecular weight (Mw) measured by high temperature GPC of 2,000 to 100,000;
(B2) is a copolymer of ethylene and at least one selected from C3-C20 α-olefins,
(iii) the ethylene content is 50-80 mol%,
(iv) an ethylene / α-olefin copolymer polymer segment having a weight average molecular weight (Mw) measured by high temperature GPC of 10,000 to 300,000,
The olefin block copolymer is
(v) has a peak attributed to ββ methylene in the ¹³ C-NMR spectrum,
(vi) The glass transition temperature (Tg) measured with a differential scanning calorimeter (DSC) is −50 ° C. or lower,
(vii) an endothermic peak due to melting point (Tm) is present at 105 ° C. or higher,
(viii) the heat of fusion determined from the melting peak area is in the range of 20-60 J / g,
(ix) the density is in the range of 0.870-0.910 g / cm ³ ;
(x) The melt flow rate (MFR: 190 ° C., under 2.16 kg load) is in the range of 0.3 to 50 g / 10 min,
(xi) Storage elastic modulus at room temperature (G _'50 ° C) and storage elastic modulus at 100 ° C by solid viscoelasticity measurement (
G ′ ₁₀₀ ° C.) (G ′ ₅₀ ° C./G ′ ₁₀₀ ° C.) is 1.0 to 2.0,
The olefin block copolymer (BB) is included in an amount of 99 to 1% by weight (here, the total of the propylene polymer (A) and the olefin block copolymer (BB) is 100% by weight). This is a propylene-based resin composition. This resin composition may be referred to as a “second composition”.

Examples of the propylene polymer (A) include the same propylene polymer as that of the first composition. The olefin block copolymer (BB) is an olefin block copolymer containing polymer segments (B1), (B1 ′) and (B2). Examples of the structure of the olefin block copolymer (BB) include (B1)-(B2), (B1)-(B2)-(B1 ′), (B1)-(B2)-(B1 ′). -(B2)-(B1) etc. are mentioned. Here, (B1) and (B1 ′) may be the same or different. The olefin block copolymer (BB) may be any olefin block copolymer containing the polymer segments (B1), (B1 ′) and (B2), that is, the polymer segments (B1), (B1 It may be a copolymer containing other polymer segments other than ') and (B2). Among these, the olefin block copolymer (BB) is composed of the polymer segment (B1), (
B1 ′) and (B2) are olefinic block copolymers comprising (B1)-(
It is preferable that it is the said olefin type block copolymer (B) containing the triblock structure which is B2)-(B1 '), and is a triblock structure which is (B1)-(B2)-(B1'). It is more preferable.

  Such a second composition contains the propylene polymer (A) in an amount of 40 to 99% by weight and the olefinic block copolymer (BB) in an amount of 60 to 1% by weight (where, It is preferable that the total of the propylene polymer (A) and the olefin block copolymer (BB) is 100% by weight) and the inorganic filler (D) is not substantially contained.

  The second composition contains the propylene polymer (A) in an amount of less than 40% by weight and 1% by weight or more, and the block copolymer (BB) in an amount of more than 60% by weight and 99% by weight or less. (Here, the total of the propylene polymer (A) and the olefin block copolymer (BB) is 100% by weight).

  In such a second composition, the ratio of the amount of the propylene polymer (A) and the olefin block copolymer (BB), the preferred propylene polymer (A) and the olefin block copolymer ( Examples of the property of BB), the kind and amount of the additive that may be added, and the like are the same as those in the first composition.

  The 2nd molded object of this invention consists of the above 2nd compositions, It is characterized by the above-mentioned. The same thing as what was demonstrated about the said 1st composition is mentioned for the use etc. of the molded object of this invention.

EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples.
[Example]
The physical properties of each resin component were evaluated as follows.

1. Physical properties of olefin block copolymer (B) <Density>
The strand after MFR measurement at 190 ° C. and a 2.16 kg load was heat-treated at 120 ° C. for 1 hour, gradually cooled to room temperature over 1 hour, and then measured by a density gradient tube method.

<Α-olefin content, ββ methylene>
Determined by ¹³ C-NMR spectrum.
<Molecular weight measurement>
GPC (gel permeation chromatography) was used and measured at 140 ° C. with an orthodichlorobenzene solvent. The obtained value is a standard polystyrene equivalent value.

<MFR>
Based on ASTM D-1238, the MFR at 2.16 kg load at 190 ° C. was measured.

<Tm, glass transition temperature>
The temperature was raised from normal temperature to 200 ° C. at 30 ° C./minute, held for 5 minutes, then lowered to −100 ° C. at 10 ° C./minute, and then obtained from an endothermic curve when the temperature was raised at 10 ° C./minute.

<Crystallinity>
The heat of fusion per unit weight was determined from the endothermic peak at the time of DSC measurement, and this was determined by dividing the heat of fusion by 70 cal / g of polyethylene crystals.

<Solid viscoelasticity>
The temperature dependence of dynamic viscoelasticity from −80 to 150 ° C. was measured at a frequency of 62.5 rad / sec using RDSII manufactured by Rheometrics, and the storage elastic modulus at ₅₀ ° C. (G ′ ₅₀ ° C.) and The storage elastic modulus at 100 ° C. (G ′ ₁₀₀ ° C.) was determined, and the ratio of storage elastic modulus (G ′ _{50 ./G} ′ ₁₀₀ ° C.) was calculated.

2. Physical properties of propylene polymer (A) and ethylene copolymer (C) <Density>
The strand after MFR measurement at 190 ° C. and a 2.16 kg load was heat-treated at 120 ° C. for 1 hour, gradually cooled to room temperature over 1 hour, and then measured by a density gradient tube method.

<Α-olefin content>
Determined by ¹³ C-NMR spectrum.
<Melting tension (MT)>
It is determined by measuring the stress when the molten polymer is stretched at a constant speed. A polymer granulated pellet was used as a measurement sample, using a MT measuring device manufactured by Toyo Seiki Seisakusho, resin temperature 190 ° C., extrusion speed 15 mm / min, winding speed 10-20 m / min, nozzle diameter 2.09 m.
Measurement was performed under the conditions of mφ and nozzle length of 8 mm.

<MFR>
Based on ASTM D-1238, MFR under a 2.16 kg load at a predetermined temperature was measured.

<Tm>
An endothermic curve of DSC is obtained, and the temperature at the maximum peak position is Tm. In the measurement, a sample is packed in an aluminum pan, heated to 200 ° C. at 10 ° C./min, held at 200 ° C. for 5 minutes, then cooled to room temperature at 20 ° C./min, and then heated at 10 ° C./min. It was determined from the endothermic curve.

3. Physical properties of propylene-based resin composition <tensile modulus (YM)>
In accordance with JIS K6301, a JIS No. 3 dumbbell was used, and measurement was performed at 23 ° C. with a span interval of 30 mm and a pulling speed of 30 mm / min.
<Izod impact strength (IZ)>
According to ASTM D256, using a test piece (rear notch) with a thickness of 6 mm, temperature 0 ° C.
The measurement was performed under the following conditions.
<Transparency (Haze)>
Using a test piece having a thickness of 1 mm, measurement was performed with a digital turbidimeter “NDH-20D” manufactured by Nippon Denshoku Industries Co., Ltd.
<Whitening resistance>
Using a test piece having a thickness of 1 mm, Haze after heating at 121 ° C. for 20 minutes was measured with a digital turbidimeter “NDH-20D” manufactured by Nippon Denshoku Industries Co., Ltd.
<Permanent elongation>
A dumbbell piece having a length of 50 mm, a length between marked lines (L0) of 30 mm, and a width of 5 mm and a thickness of 1 mmt applied with a load of 30 mm between chucks and a pulling speed of 30 mm / min, 100% (60 mm between chucks) The strain was applied and held for 10 minutes, and then the length (L) mm between the marked lines 10 minutes after unloading (excluding the load) was measured. Permanent elongation was determined as follows.

Permanent elongation (%) = [(L−L0) / L0] × 100
<Heat resistance (TMA)>
In accordance with JIS K7196, a pressure of ² kg / cm ² was applied to a flat indenter of 1.8 mmφ at a heating rate of 5 ° C./min using a test piece having a thickness of 1 mm. )
[Production Example 1] Olefin-based block copolymer (B)
<Production of Olefin Block Copolymer (b-2)>
800 mL of toluene was inserted into a glass autoclave having an internal volume of 1000 mL that had been sufficiently purged with nitrogen, and the liquid phase and gas phase were saturated with an ethylene / nitrogen mixed gas (ethylene 30 L / h, nitrogen 70 L / h). While ethylene and nitrogen were stopped and nitrogen was allowed to flow in the gas phase, 15 mmol of methylaluminoxane in terms of aluminum atom and then 0.15 mmol of titanium compound (1) were added to initiate polymerization. After reacting at 25 ° C. for 5 minutes, the temperature is 25
While being kept at ° C., an ethylene / butene mixed gas (ethylene 5 L / h, butene 95 L / h) was allowed to flow through the liquid phase for 50 minutes. Nitrogen gas (100 L / h) was circulated in the liquid phase for 30 minutes, and after purging ethylene and propylene in the liquid phase, ethylene gas (100 L / h) was circulated again for 2.5 minutes, and then 25 ml of methanol was added. The polymerization was stopped by adding. After completion of the polymerization, 5.0 ml of concentrated hydrochloric acid and a large amount of methanol were added to the reaction product to precipitate a total amount of the polymer, followed by filtration. After drying the polymer under reduced pressure at 80 ° C. for 10 hours, 11.2 g of a block copolymer (b-2) (PE-EBR-PE) was obtained. The weight average molecular weight (Mw) of the obtained polymer was 185,200 in terms of PS, Mw / Mn was 1.25, and the ethylene content in the polymer was 72 mol%.

Next, the weight average molecular weight of the PE segment was calculated as follows. A glass autoclave with an internal volume of 1000 ml that was sufficiently purged with nitrogen was charged with 800 ml of toluene, and the liquid phase and gas phase were saturated with an ethylene / nitrogen mixed gas (ethylene 30 L / h, nitrogen 70 L / h). While stopping ethylene and nitrogen and circulating nitrogen in the gas phase, methylaluminoxane was converted to 15 mmol in terms of aluminum atom, and subsequently titanium compound (1) was added to 0.15 mmol.
l was added to initiate polymerization. After reacting at 25 ° C. for 5 minutes, the polymerization was terminated by adding 25 ml of methanol. After completion of the polymerization, 5.0 ml of concentrated hydrochloric acid and a large amount of methanol were added to the reaction product to precipitate a total amount of the polymer, followed by filtration. As a result of drying the polymer under reduced pressure at 80 ° C. for 10 hours, the Mw of the obtained PE was 20,000.

Therefore, in the olefin block copolymer (b-2), the Mw of the PE segment was 20,000 each, the Mw of the EBR segment was 145,200, and the butene content was 36 mol%.
<Production of Olefin Block Copolymer (b-4)>
800 mL of toluene was inserted into a glass autoclave having an internal volume of 1000 mL sufficiently purged with nitrogen, and the liquid phase and gas phase were saturated with an ethylene / nitrogen mixed gas (ethylene 50 L / h, nitrogen 50 L / h). While ethylene and nitrogen were stopped and nitrogen was allowed to flow in the gas phase, 15 mmol of methylaluminoxane in terms of aluminum atom and then 0.15 mmol of titanium compound (1) were added to initiate polymerization. After reacting at 25 ° C. for 5 minutes, hexene 40
mL was added and ethylene (3 L / h) was passed through the liquid phase for 90 minutes while maintaining the temperature at 25 ° C. Nitrogen gas (100 L / h) is circulated in the liquid phase for 30 minutes, the monomer in the liquid phase is purged, ethylene gas (100 L / h) is circulated again for 3.0 minutes, and then 25 mL of methanol is added. This stopped the polymerization. After completion of the polymerization, 5.0 mL of concentrated hydrochloric acid and a large amount of methanol were added to the reaction product to precipitate a total amount of the polymer, followed by filtration. After the polymer was dried under reduced pressure at 80 ° C. for 10 hours, 11.5 g of a block copolymer (b-4) (PE-EHR-PE) was obtained. The weight average molecular weight (Mw) of the obtained polymer was 196,000 in terms of PS, Mw / Mn was 1.30, and the ethylene content in the polymer was 79 mol%.

Next, the weight average molecular weight of the PE segment was calculated as follows. To a glass autoclave with an internal volume of 1000 mL sufficiently purged with nitrogen, 800 mL of toluene was charged, and the liquid phase and gas phase were saturated with an ethylene / nitrogen mixed gas (ethylene 50 L / h, nitrogen 50 L / h). While stopping ethylene and nitrogen and circulating nitrogen in the gas phase, methylaluminoxane was converted to 15 mmol in terms of aluminum atom, and subsequently titanium compound (1) was added to 0.15 mmol.
l was added to initiate polymerization. After reacting at 25 ° C. for 5 minutes, the polymerization was terminated by adding 25 ml of methanol. After completion of the polymerization, 5.0 ml of concentrated hydrochloric acid and a large amount of methanol were added to the reaction product to precipitate a total amount of the polymer, followed by filtration. As a result of drying the polymer under reduced pressure at 80 ° C. for 10 hours, the Mw of the obtained PE was 28,000.

  Therefore, the Mw of the PE segment of the block copolymer b-4 was 28,000 each, the Mw of EHR was 140,000, and the 1-hexene content was 30 mol%.

  Table 1 shows the properties of the obtained olefinic block copolymers (b-2) and (b-4).

[Production Example 2] Ethylene copolymer (C)
845 mL of hexane was inserted at 23 ° C. into a SUS autoclave equipped with a stirrer having a capacity of 2 liters and sufficiently purged with nitrogen. In this autoclave, 30 mL of 1-butene was inserted while rotating a stirrer and cooling with ice water. Next, the autoclave was heated to an internal temperature of 60 ° C., and further pressurized with ethylene so that the total pressure was 8 kg / cm ² (0.8 MPa). When the internal pressure of the autoclave reaches 8 kg, 1.0 mM of triisobutylaluminum (TIBA)
A 1.0 mL / ml decane solution was pressurized with nitrogen. Subsequently, methylaluminoxane prepared in advance in an amount of 0.3 mM in terms of Al, and rac-dimethylsilylene-bis [1- (2-methyl-4-phenyl-indenyl)] zirconium dichloride in an amount of 0.001 mM. Containing toluene solution 0.
3 mL was pressed into the autoclave with nitrogen to initiate polymerization.

Thereafter, the temperature of the autoclave was adjusted to 60 ° C. for 30 minutes, and ethylene was directly supplied so that the pressure was 8 kg / cm ² (0.8 MPa). 30 minutes after the start of polymerization, 5 mL of methanol was inserted into the autoclave by a pump to stop the polymerization, and the autoclave was depressurized to atmospheric pressure. 2 l of acetone was poured into the reaction solution with stirring.

The obtained rubber-like polymer containing the solvent was dried at 130 ° C. for 13 hours at 600 torr to obtain 58 g of an ethylene / 1-butene copolymer containing 16 mol% of 1-butene.
The properties of the obtained ethylene / 1-butene copolymer (c-1) are shown in Table 2.

<Propylene polymer (A)>
The following polymers were used as the propylene polymer (A).
Propylene polymer (a-1): F327D (MFR = 7 g / 10 min, Tm = 139 ° C., amount of n-decane soluble component = 4.7% by weight, [η] = 1.4 dl / g, n-decane insoluble component I ₅ = 0.95)
Propylene polymer (a-2): manufactured by Mitsui Chemicals, J104W (MFR = 6 g / 10 min, Tm = 162 ° C., amount of n-decane soluble component = 1.7 wt%, [η] = 1.2 dl / g, I _{5 of} the n-decane insoluble part = 0.95)
[Example 1]
70% by weight of the propylene polymer (a-1) was added to 30% by weight of the olefin block copolymer (b-2), and the mixture was melt-kneaded at 200 ° C. and pelletized using a twin screw extruder. The obtained pellets were injection-molded at a cylinder temperature of 200 ° C. and a mold temperature of 40 ° C. using a Toshiba machine 55t injection molding machine, and the physical properties were evaluated. The results are shown in Table 3.
[Examples 2 to 5, Comparative Examples 1 to 3]
Pellets were molded and evaluated in the same manner as in Example 1 except that the type and ratio of the polymer used were changed as shown in Table 3. The results are shown in Table 3.

Claims (11)

[A] (i) Melt flow rate (MFR: 230 ° C., under 2.16 kg load) is 0.1 to 400 g / 10 minutes,
(ii) containing a normal temperature n-decane soluble component in an amount of 0.01 to 30% by weight,
The intrinsic viscosity [η] measured in 135 ° C. decalin of the room temperature n-decane soluble component is 0.2 to 0.2.
10 dl / g,
(iii) The pentad isotacticity (I ₅ ) determined by the ¹³ C-NMR method of the room temperature n-decane insoluble component is 0.95 or more.
Propylene polymer (A) in an amount of 1 to 99% by weight,
[B] An olefin block copolymer composed of polymer segments (B1), (B1 ′) and (B2),
(B1) and (B1 ′) are each independently at least one polymer selected from ethylene and an α-olefin having 3 to 20 carbon atoms,
(i) the ethylene content is 95-100 mol%,
(ii) an ethylene polymer polymer segment having a weight average molecular weight (Mw) measured by high temperature GPC of 2,000 to 100,000;
(B2) is a copolymer of ethylene and at least one selected from C3-C20 α-olefins,
(iii) the ethylene content is 50-80 mol%,
(iv) an ethylene / α-olefin copolymer polymer segment having a weight average molecular weight (Mw) measured by high temperature GPC of 10,000 to 300,000,
The olefin block copolymer is a block copolymer comprising a linear triblock structure of (B1)-(B2)-(B1 ′),
(v) has a peak attributed to ββ methylene in the ¹³ C-NMR spectrum,
(vi) The glass transition temperature (Tg) measured with a differential scanning calorimeter (DSC) is −50 ° C. or lower,
(vii) an endothermic peak due to melting point (Tm) is present at 105 ° C. or higher,
(viii) the heat of fusion determined from the melting peak area is in the range of 20-60 J / g,
(ix) the density is in the range of 0.870-0.910 g / cm ³ ;
(x) The melt flow rate (MFR: 190 ° C., under 2.16 kg load) is in the range of 0.3 to 50 g / 10 min,
(xi) Storage elastic modulus at room temperature (G _'50 ° C) and storage elastic modulus at 100 ° C by solid viscoelasticity measurement (
G ′ ₁₀₀ ° C.) (G ′ ₅₀ ° C./G ′ ₁₀₀ ° C.) is 1.0 to 2.0,
The olefinic block copolymer (B) is included in an amount of 99 to 1% by weight (here, the total of the propylene polymer (A) and the olefinic block copolymer (B) is 100% by weight). A propylene-based resin composition characterized by that. The propylene polymer (A) is contained in an amount of 40 to 99% by weight, and the olefin block copolymer (B) is contained in an amount of 60 to 1% by weight (here, the propylene polymer (A) and The total amount with the olefin block copolymer (B) is 100% by weight), and
The propylene-based resin composition according to claim 1, which is substantially free of an inorganic filler (D).   The propylene polymer (A) is contained in an amount of less than 40% by weight and 1% by weight or more, and the block copolymer (B) is contained in an amount of more than 60% by weight and 99% by weight or less (wherein the propylene polymer 2. The propylene-based resin composition according to claim 1, wherein the total of the combination (A) and the olefin-based block copolymer (B) is 100 wt%. The polymer segments (B1), (B1 ′) and (B2) are obtained by polymerization in the presence of an olefin polymerization catalyst containing a transition metal compound represented by the following general formula (1). The propylene-based resin composition according to claim 1.

(In the formula, M ¹ represents a transition metal atom selected from Groups 4 to 5 of the periodic table, and m represents 1 or 2)
R ¹ is an aromatic hydrocarbon group, an aliphatic hydrocarbon group or an alicyclic hydrocarbon group, and when R ¹ is a phenyl group, the position of the carbon atom bonded to nitrogen is the 1st position 2
Has at least one substituent selected from a heteroatom or a heteroatom-containing group at at least one position in the position and the 6-position, or a fluorine atom at at least one position in the 3-position, 4-position and 5-position A fluorine-containing group containing 1 or more carbon atoms and 2 or less fluorine atoms, a fluorine-containing group containing 2 or more carbon atoms, or a group containing a heteroatom excluding fluorine atoms When it has at least one atom or substituent and R ¹ is an aromatic hydrocarbon group other than a phenyl group, an aliphatic hydrocarbon group or an alicyclic hydrocarbon group, it contains heteroatoms and heteroatoms Having at least one substituent selected from a group, and R ^{2 to} R ⁵ are each independently a hydrogen atom, a halogen atom, a halogen-containing group, a hydrocarbon group, or a hydrocarbon-substituted silyl group. Group, oxygen-containing group, nitrogen-containing group or sulfur-containing group, which may be the same or different from each other, and R ⁶ represents a halogen atom, a halogen-containing group, a hydrocarbon group or a hydrocarbon-substituted silyl group , N is a number satisfying the valence of M, and X is an oxygen atom, hydrogen atom, halogen atom, hydrocarbon group, oxygen-containing group, sulfur-containing group, nitrogen-containing group, boron-containing group, aluminum-containing group, A phosphorus-containing group, a halogen-containing group, a heterocyclic compound residue, a silicon-containing group, a germanium-containing group, or a tin-containing group. When n is 2 or more, a plurality of groups represented by X are the same as each other And a plurality of groups represented by X may be bonded to each other to form a ring. )   The molded object which consists of a propylene-type resin composition of any one of Claims 1-4.   The molded body according to claim 5, wherein the molded body is an extruded molded body or an inflation molded body.   The molded body according to claim 5 or 6, wherein the molded body is a film or a sheet.   The molded body according to any one of claims 5 to 7, wherein the molded body is a medical molded body.   The said molded object is a molded object for food packaging, The molded object in any one of Claims 5-7 characterized by the above-mentioned. [A] (i) Melt flow rate (MFR: 230 ° C., under 2.16 kg load) is 0.1 to 400 g / 10 minutes,
(ii) containing a normal temperature n-decane soluble component in an amount of 0.01 to 30% by weight,
The intrinsic viscosity [η] measured in 135 ° C. decalin of the room temperature n-decane soluble component is 0.2 to 0.2.
10 dl / g,
(iii) The pentad isotacticity (I ₅ ) determined by the ¹³ C-NMR method of the room temperature n-decane insoluble component is 0.95 or more.
Propylene polymer (A) in an amount of 1 to 99% by weight,
[BB] an olefin block copolymer containing polymer segments (B1), (B1 ′) and (B2),
(B1) and (B1 ′) are each independently at least one polymer selected from ethylene and an α-olefin having 3 to 20 carbon atoms,
(i) the ethylene content is 95-100 mol%,
(ii) an ethylene polymer polymer segment having a weight average molecular weight (Mw) measured by high temperature GPC of 2,000 to 100,000;
(B2) is a copolymer of ethylene and at least one selected from C3-C20 α-olefins,
(iii) the ethylene content is 50-80 mol%,
(iv) an ethylene / α-olefin copolymer polymer segment having a weight average molecular weight (Mw) measured by high temperature GPC of 10,000 to 300,000,
The olefin block copolymer is
(v) has a peak attributed to ββ methylene in the ¹³ C-NMR spectrum,
(vi) The glass transition temperature (Tg) measured with a differential scanning calorimeter (DSC) is −50 ° C. or lower,
(vii) an endothermic peak due to melting point (Tm) is present at 105 ° C. or higher,
(viii) the heat of fusion determined from the melting peak area is in the range of 20-60 J / g,
(ix) the density is in the range of 0.870-0.910 g / cm ³ ;
(x) The melt flow rate (MFR: 190 ° C., under 2.16 kg load) is in the range of 0.3 to 50 g / 10 min,
(xi) Storage elastic modulus at room temperature (G _'50 ° C) and storage elastic modulus at 100 ° C by solid viscoelasticity measurement (
G ′ ₁₀₀ ° C.) (G ′ ₅₀ ° C./G ′ ₁₀₀ ° C.) is 1.0 to 2.0,
The olefin block copolymer (BB) is included in an amount of 99 to 1% by weight (here, the total of the propylene polymer (A) and the olefin block copolymer (BB) is 100% by weight). A propylene-based resin composition characterized by that. The molded object which consists of a propylene-type resin composition of Claim 10.