JP2000355643A - Flexible syndiotactic polypropylene composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition excellent in transparency, heat sealability, and impact resistance. SOLUTION: This composition comprises (A) a syndiotactic propylene polymer comprising 90-100 mol% propylene units (a), 0-10 mol% ethylene units (b), and 0-9.5 mol% 4-20C α-olefin units (c) and having a limiting viscosity [η] of 0.5-10 dl/g, (B) an α-olefin polymer containing 5-100 mol% units of at least one member selected from among 2-20C α-olefins and having a Young's modulus of elasticity of 150 MPa or below, and (C) a nucleator, and wherein the ratio of (A) to (B) is 99/1 to 1/99 by weight, and 0.05-1 pt.wt. (C) is present per 100 pts.wt. total of components A and B.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a soft syndiotactic polypropylene composition, and more particularly, to a soft syndiotactic polypropylene composition having excellent transparency, flexibility, impact resistance and heat sealability.

[0002]

BACKGROUND OF THE INVENTION A film made of isotactic polypropylene obtained by copolymerizing propylene and ethylene and, if necessary, an α-olefin having 4 to 20 carbon atoms is inexpensive, flexible, moisture-resistant and heat-resistant. It is widely used for various packaging materials because of its excellent properties. However, when the thickness of the film is increased, transparency, flexibility, and heat sealability are deteriorated to prevent breakage of the contents, and when the comonomer content of the isotactic polypropylene is increased to improve this, solid components are increased. And the production of a thick film material having excellent transparency, flexibility and heat sealability was difficult.

On the other hand, it is known that syndiotactic polypropylene can be obtained by low-temperature polymerization in the presence of a catalyst comprising a vanadium compound, ether and organoaluminum. However, the polymer obtained by this method has a low syndiotacticity, and it cannot be said that the polymer exhibits the original syndiotactic property.

In recent years, JA Ewen et al. Have reported that a syndiotactic triad fraction in the presence of a transition metal catalyst having an asymmetric ligand and an aluminoxane catalyst is in the presence of a catalyst.
It has been found that polypropylene having a high tacticity of more than 7 can be obtained (J. Am. Chem. Soc., 198).
8,110,6255-6256). The polymer obtained by the method of JA Ewen et al. Had a high syndiotacticity and an elastic property than isotactic polypropylene, but this was used as a soft molding material, for example, When it is intended to be used in a field where soft vinyl chloride, vulcanized rubber or the like is used, its flexibility, rubber elasticity and mechanical strength are not sufficient.

Conventionally, attempts have been made to improve the flexibility and impact resistance of a propylene-based polymer by blending an ethylene-propylene copolymer rubber or the like in which the stereoregularity of the propylene repeating unit is isotactic. However, a molded article comprising the resin composition obtained by this method is not sufficient, although the flexibility and impact resistance are improved to some extent.

The present inventors have conducted intensive studies in view of such circumstances, and as a result, a soft syndiotactic polypropylene composition comprising a specific syndiotactic propylene polymer, an α-olefin polymer and a crystal nucleating agent has been obtained. The inventors have found that the present invention has an excellent balance among transparency, flexibility, heat sealability, and impact resistance, and have completed the present invention.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems associated with the prior art, and to provide a soft syndiotactic polypropylene having excellent transparency, flexibility, heat sealability and impact resistance. It is intended to provide a system composition.

[0008]

SUMMARY OF THE INVENTION The soft syndiotactic polypropylene-based composition according to the present invention comprises (A) a repeating unit (a) derived from propylene having a substantially syndiotactic structure and, if necessary, ethylene. A repeating unit (b) and / or a repeating unit (c) derived from an α-olefin having 4 to 20 carbon atoms, wherein the repeating unit (a) is contained in a proportion of 90 to 100 mol% with the repeating unit ( b) in a proportion of 0 to 10 mol%, and the repeating unit (c) in a proportion of 0 to 9.5 mol%.
The intrinsic viscosity [η] measured in decalin at 35 ° C. is 0.5
A syndiotactic propylene polymer having a range of from 10 to 10 dl / g, and (B) at least one or more repeating units derived from an α-olefin selected from α-olefins having 2 to 20 carbon atoms, and One of the one or more kinds of repeating units is 50 to 100.
Mol%, Young's modulus is 150MP
a) The weight ratio of the above-mentioned syndiotactic propylene polymer (A) and the above-mentioned α-olefin polymer (B), which contains an α-olefin polymer of not more than a and a crystal nucleating agent (C) 剤 (A) / (B)｝ is 90/10 to 10/90,
And syndiotactic propylene polymer (A) and α
-It is characterized in that the nucleating agent (C) is contained at a ratio of 0.01 to 1 part by weight based on 100 parts by weight in total with the olefin polymer (B).

[0009] In an embodiment of the soft syndiotactic polypropylene composition according to the present invention, the (A) syndiotactic propylene polymer comprises a propylene triad.
The α-olefin polymer (B) has a limiting viscosity [η] of 0.01 to 10 d as measured in decalin at 135 ° C.
1 / g, the molecular weight distribution (Mw / Mn) determined by gel permeation chromatography is 4 or less, the glass transition temperature is -5 ° C or less, and the nucleating agent (C) is sorbitol. Some are nucleating agents for the system.

In the present invention, the (B) α-olefin polymer contains 50 to 99 repeating units derived from ethylene.
A copolymer containing at least 1 mol% of a repeating unit derived from at least one kind of α-olefin selected from α-olefins having 3 to 20 carbon atoms in a proportion of 1 to 50 mol%; Preferably, the (B) α-olefin polymer contains 50 to 99 mol% of repeating units derived from propylene in an amount of at least one kind selected from ethylene and α-olefins having 4 to 20 carbon atoms. 1-5 repeating units derived from α-olefin
It is also preferable that the copolymer is contained at a ratio of 0 mol%.

The (B) α-olefin polymer comprises, for example, (a) a transition metal compound represented by the following general formula (I) or (II), and (b) (b-1) the transition metal compound ( a) a compound that forms an ionic complex by reacting with the transition metal M in a) (hereinafter sometimes referred to as “ionized ionic compound”), (b-2) an organic aluminum oxy compound, and (b-3) an organic Obtained in the presence of a metallocene-based catalyst comprising at least one compound selected from aluminum compounds;

[0012]

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(In the formulas (I) and (II), M is Ti, Z
r, Hf, Rn, Nd, Sm or Ru, and Cp ¹
And Cp ² are a cyclopentadienyl group, an indenyl group, a fluorenyl group or a derivative thereof bonded to M by π, X ¹ and X ² are an anionic ligand or a neutral Lewis base Y is a nitrogen atom,
It is a ligand containing an oxygen atom, a phosphorus atom or a sulfur atom, and Z is a C, O, B, S, Ge, Si or Sn atom or a group containing these atoms. The soft syndiotactic polypropylene composition according to the present invention has an excellent balance of transparency, flexibility, heat sealability, and impact resistance.

[0014]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the soft syndiotactic polypropylene composition of the present invention will be described in detail.

The soft syndiotactic polypropylene composition according to the present invention comprises a specific syndiotactic propylene polymer (A), a specific α-olefin polymer (B) and a crystal nucleating agent (C). Contains.

First, each component contained in the soft syndiotactic polypropylene composition according to the present invention will be described. (A) Syndiotactic propylene polymer The syndiotactic propylene polymer (A) is a propylene homopolymer or a propylene-based random copolymer obtained from propylene and ethylene or an α-olefin having 4 to 20 carbon atoms. A recurring unit (a) derived from propylene and, if necessary, a recurring unit (b) derived from ethylene and / or a recurring unit (c) derived from an α-olefin having 4 to 20 carbon atoms. Wherein the repeating unit (a) is contained in an amount of 90 to 100 mol%, preferably 92 to 10 mol%.
0 mol%, more preferably 92 to 98 mol%, and the repeating unit (b) is contained in an amount of 0 to 10 mol%, preferably 0 to 8 mol%, more preferably 0.2 to 8 mol%. And the repeating unit (c) is contained in an amount of 0 to 9.5.
Mol%, preferably 0 to 8.5 mol%, more preferably 0 to 7 mol%.

The α-olefin having 4 to 20 carbon atoms includes 1-butene, 1-pentene, 1-hexene, 1-octene, 4-methyl-1-pentene, 3-methyl-1-pentene,
Examples thereof include 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosane, among which 1-butene is preferable.

This syndiotactic propylene polymer (A) has an intrinsic viscosity [η] measured in decalin at 135 ° C. of 0.5 to 10 dl / g, preferably 1.0 to 10 dl / g.
6 dl / g, more preferably in the range of 1.0 to 4 dl / g. When the intrinsic viscosity is in such a range, the syndiotactic propylene polymer (A)
Has good fluidity, is easily blended with other components, and tends to give a molded article having excellent mechanical strength from the obtained composition.

The repeating unit derived from propylene constituting the syndiotactic propylene polymer (A) used in the present invention has substantially a syndiotactic structure, and has a syndiotacticity as viewed from a propylene triad chain. Is 0.6 or more, preferably 0.7 or more. When the syndiotacticity is in such a range, the crystallization rate is high and the workability is excellent. In this specification, substantially having a syndiotactic structure means that the syndiotacticity of the propylene in the triad chain is 0.6 or more.

The syndiotactic propylene polymer (A) has a triad syndiotacticity (hereinafter referred to as "r
r fraction ". ) Is ¹³ of the polymer (A).
According to the C-NMR spectrum and the following formula (1),
It is determined as the strength (area) ratio of the side chain methyl group of the second unit of the three propylene units linked by tail.

Rr fraction (%) = PPP (rr) / {PPP (mm) + PPP (mr) + PPP (rr)} (1) (where, PPP (mm), PPP (mr), PPP (rr) ) Is the area of the second-chain methyl group in the three-chain head-to-tail bonded propylene unit observed in the following shift region of the ¹³ C-NMR spectrum.)

[0022]

[Table 1]

Such PPP (mm), PPP (mr), PP
P (rr) represents a head-to-tail bonded propylene 3 unit chain having the following structure.

[0024]

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In the methyl carbon region (19 to 23 pp)
In m), in addition to the side chain methyl groups of the propylene units in the three head-to-tail bonded propylene chains, peaks of the side chain methyl groups of the propylene units in the other chains as described below are observed. When determining the rr fraction, the peak area of such a methyl group that is not based on three chains of propylene units is corrected as follows. P represents a repeating unit derived from propylene, and E represents a repeating unit derived from ethylene.

In the second region, propylenes are head-
A peak derived from the side chain methyl group of the second unit (propylene unit) in the tail-linked PPE 3 chain is observed.
The area of this methyl group peak can be determined from the peak area of the methine group (resonating around 30.6 ppm) of the second unit (propylene unit) in the PPE chain.

In the third area, the second in the EPE3 chain
A peak derived from the side chain methyl group of the unit (propylene unit) is observed. The peak area of this methyl group is
The methine group (3) of the second unit (propylene unit) in the chain
(Resonance around 2.9 ppm).

In the second region and the third region, in the positionally irregular units represented by the following partial structures (i), (ii) and (iii), which are contained in a small amount in the ethylene / ethylene random copolymer: Peaks derived from the methyl groups CE to E ′ are observed.

In the second region, a methyl group C peak, a methyl group D peak and a methyl group D 'peak are observed,
In the region, a methyl group E peak and a methyl group E ′ peak are observed.

The methyl group A peak and the methyl group B peak were observed at 17.3 ppm and 17.0 ppm, respectively, in the methyl groups in the position irregular units (i) to (iii). Is not observed.

[0031]

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The peak area of the methyl group C can be determined from the peak area of the adjacent methine group (resonating at around 31.3 ppm). The peak area of the methyl group D is determined by the peak based on the αβ methylene carbon in the structure (ii) (34.3p
pm and around 34.5 ppm).

The peak area of the methyl group D ′ is determined by the structure (ii)
It can be determined from the area of a peak (around 33.3 ppm) based on the methine group adjacent to the methyl group E ′ in i). The peak area of the methyl group E can be determined from the peak area of the adjacent methine carbon (around 33.7 ppm).

The peak area of the methyl group E ′ can be determined from the peak area of the adjacent methine carbon (around 33.3 ppm). Therefore, these peak areas are
By subtracting from the total peak area of the region and the third region, the peak area of the side chain methyl group of the second propylene unit in the three head-to-tail bonded propylene units can be determined.

Each carbon peak in the spectrum can be assigned by referring to the literature (Polymer, 30, 1350 (1989)). Production of syndiotactic propylene polymer (A) When producing such a syndiotactic propylene polymer (A), α-
The metallocene catalyst used for the production of the olefin polymer (B) is preferably used.

In producing the syndiotactic propylene polymer (A), JP-A-2-41303, JP-A-2-41305, and JP-A-2-274703 are used in place of the above catalyst system. JP-A-2-274704, JP-A-3-179005, JP-A-3-179
006, JP-A-4-69394, JP-A-5-69
The catalyst system described in Japanese Patent No. 17589 or JP-A-8-120127 can also be used.

More specifically, the reference "J. Am. Chem. Soc., 1" by JA Ewen et al.
988, 110, 6255-6256 '' can be used, and even if the compound has a structure different from the compound described in the literature, when a propylene homopolymer is produced, the obtained polymer Syndio-tactic triad fraction (A. Zambelli et al. Macromolecules vol 6 687 (1973); same v
ol 8 925 (1975)) as described above, for example, 0.5
Any catalyst system that provides a polymer having a relatively high tacticity of the above degree can be used, for example, a catalyst system comprising a cross-linked transition metal compound having asymmetrical ligands and a co-catalyst such as organoaluminum. Can be

Examples of the bridged transition metal compound having asymmetrical ligands constituting such a catalyst system include diphenylmethylene (cyclopentadienyl) (fluorenyl) hafnium dichloride and diphenylmethylene described in the above-mentioned literature. Methylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, isopropyl (cyclopentadienyl-1-fluorenyl) hafnium dichloride, or isopropyl (cyclopentadienyl-1-fluorenyl) zirconium dichloride, (t-butylamido) dimethyl (fluorenyl) ) Silane titanium dimethyl, diphenylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride and the like.

As the co-catalyst, α as described later
-An ionized ionic compound, an organic aluminum oxy compound (also referred to as aluminoxane or alumoxane) and an organic aluminum compound similar to those constituting the metallocene-based catalyst used in the production of the olefin polymer (B).

When the syndiotactic propylene polymer (A) used in the present invention is produced in the presence of the above-mentioned catalyst, propylene and, if necessary, ethylene and carbon atoms having 4 to 20 carbon atoms are used. At least one or more α-olefins selected from the above α-olefins are finally polymerized so as to have the above-mentioned properties. The polymerization can be carried out by any of liquid phase polymerization methods such as suspension polymerization and solution polymerization or gas phase polymerization methods.

In the liquid phase polymerization method, as a polymerization medium, aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane and kerosene; alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclopentane and the like. Hydrogen; aromatic hydrocarbons such as benzene, toluene and xylene; inert hydrocarbon solvents such as halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane or mixtures thereof, and propylene as a solvent You can also.

The polymerization is preferably carried out at a temperature of usually -50 to 100 ° C., preferably 0 to 90 ° C. when carrying out the suspension polymerization method.
Usually, it is desirable to carry out at a temperature of 0 to 250 ° C, preferably 20 to 200 ° C. When carrying out the gas phase polymerization, the polymerization is usually carried out at 0 to 120 ° C., preferably at 20 to 1 ° C.
Preferably, it is performed at a temperature of 00 ° C. The polymerization is usually carried out at normal pressure to 100 kg / cm ² , preferably at normal pressure to 50 kg / cm ² .
It is performed under a pressure of kg / cm ² .

The polymerization can be carried out by any of a batch system, a semi-continuous system and a continuous system. Further, the polymerization can be performed in two or more stages having different reaction conditions. The molecular weight of the resulting syndiotactic propylene polymer (A) can be adjusted by allowing hydrogen to exist in the polymerization system or by changing the polymerization temperature and the polymerization pressure.

(B) α-Olefin Polymer The α-olefin polymer (B) is a homopolymer of one kind of α-olefin selected from α-olefins having 2 to 20 carbon atoms, or 2 carbon atoms. A copolymer of two or more α-olefins selected from α-olefins having from 20 to 20 carbon atoms, wherein at least one repeating unit is derived from an α-olefin selected from α-olefins having 2 to 20 carbon atoms.
And at least one of the one or more kinds of repeating units is contained in a proportion of 50 to 100 mol%, preferably 60 to 90 mol%, more preferably 65 to 85 mol%. I have.

The α-olefin polymer (B) containing the α-olefin component in such a ratio has good compatibility with the syndiotactic propylene polymer (A), and the resulting soft syndiotactic polypropylene The system composition tends to exhibit sufficient flexibility, heat sealability, and impact resistance.

The α-olefin polymer (B) is amorphous and has a Young's modulus of 150 MPa or less, preferably 100 MPa or less, more preferably 50 MPa or less. The Young's modulus of the syndiotactic propylene polymer (A) is usually 300 MPa.
That is all.

Examples of such an α-olefin polymer (B) include ethylene / propylene copolymer (the α-olefin described first as a main component, the same applies hereinafter), ethylene / butene copolymer, Ethylene-pentene copolymer, ethylene-4-methyl-1-pentene copolymer,
Ethylene / hexene copolymer, ethylene / heptene copolymer, ethylene / octene copolymer, ethylene / nonene copolymer, ethylene / decene copolymer, ethylene / norbornene copolymer, ethylene / tetracyclododecene copolymer Copolymer, ethylene / butadiene copolymer, ethylene / isoprene copolymer, ethylene / 1,5-hexadiene copolymer, ethylene / acrylic acid copolymer, ethylene / methacrylic acid copolymer, ethylene / acrylic acid ester copolymer Copolymer, binary ethylene copolymers such as ethylene / methacrylic acid ester copolymer, isotactic propylene
Ethylene copolymer, atactic propylene / ethylene copolymer, syndiotactic propylene / ethylene copolymer, isotactic propylene / butene copolymer, atactic propylene / butene copolymer,
Syndiotactic propylene / butene copolymer, isotactic propylene / pentene copolymer, atactic propylene / pentene copolymer, syndiotactic propylene / pentene copolymer, isotactic propylene / hexene copolymer, attack Tic propylene / hexene copolymer, syndiotactic propylene / hexene copolymer, isotactic propylene / heptane copolymer, atactic propylene / heptane copolymer, syndiotactic propylene / heptane copolymer, isotactic Propylene / octene copolymer, atactic propylene / octene copolymer, syndiotactic propylene / octene copolymer, isotactic propylene / decene copolymer, ATA Tic propylene / decene copolymer, syndiotactic propylene / decene copolymer, isotactic propylene / styrene copolymer, atactic propylene / styrene copolymer, syndiotactic propylene / styrene copolymer, isotactic Propylene-norbornene copolymer,
Atactic propylene / norbornene copolymer, syndiotactic propylene / norbornene copolymer, isotactic propylene / tetracyclododecene copolymer, atactic propylene / tetracyclododecene copolymer, syndiotactic propylene / tetra Cyclododecene copolymer, isotactic propylene / butadiene copolymer, atactic propylene / butadiene copolymer, syndiotactic propylene / butadiene copolymer, isotactic propylene / isoprene copolymer, atactic propylene / Isoprene copolymer, syndiotactic propylene / isoprene copolymer, isotactic propylene / 1,5-hexadiene copolymer, atactic propylene / 1,5-hexa Binary propylene copolymers such as ene copolymers, syndiotactic propylene / 1,5-hexadiene copolymers, ethylene / propylene / norbornene copolymers, ethylene / butene / norbornene copolymers, ethylene / octene / Norbornene copolymer, ethylene / propylene / tetracyclododecene copolymer,
Ethylene-butene-tetracyclododecene copolymer, ethylene-octene-tetracyclododecene copolymer, ethylene-propylene-butadiene copolymer, ethylene-
Butene-butadiene copolymer, ethylene-octene-butadiene copolymer, ethylene-propylene-isoprene copolymer, ethylene-butene-isoprene copolymer, ethylene-octene-isoprene copolymer, ethylene-propylene-ethylidene norbornene copolymer Polymers, ethylene-butene-ethylidene norbornene copolymer, ethylene-octene-ethylidene norbornene copolymer, etc.
Primary ethylene copolymer, isotactic propylene / butene / ethylene copolymer, atactic propylene / butene / ethylene copolymer, syndiotactic propylene / butene / ethylene copolymer, isotactic propylene / octene / ethylene Copolymer, atactic propylene / octene / ethylene copolymer,
Syndiotactic propylene / octene / ethylene copolymer, isotactic propylene / octene /
Ethylene copolymer, atactic propylene / octene / ethylene copolymer, syndiotactic propylene / octene / ethylene copolymer, isotactic propylene / norbornene / ethylene copolymer, atactic propylene / norbornene / ethylene copolymer , Syndiotactic Propylene Norbornene
Ethylene copolymer, isotactic propylene / tetracyclododecene / ethylene copolymer, atactic propylene / tetracyclododecene / ethylene copolymer, syndiotactic propylene / tetracyclododecene / ethylene copolymer, iso Tactic propylene / butadiene / ethylene copolymer, atactic propylene / butadiene / ethylene copolymer, syndiotactic propylene / butadiene / ethylene copolymer, isotactic propylene / isoprene / ethylene copolymer, atactic propylene / Ternary propylene copolymers such as isoprene / ethylene copolymer and syndiotactic propylene / isoprene / ethylene copolymer are exemplified.

Such an α-olefin polymer (B)
Is the intrinsic viscosity [η] measured in 135 ° C. decalin,
Usually 0.01 to 10 dl / g, preferably 0.5 to 10 dl / g
dl / g, more preferably in the range of 1 to 8 dl / g. When the intrinsic viscosity [η] of the α-olefin polymer (B) is within the above range, a soft synth having excellent properties such as weather resistance, ozone resistance, heat aging resistance, low temperature properties, and dynamic fatigue resistance. It becomes an tactic polypropylene composition.

The α-olefin polymer (B) has a single glass transition temperature and a differential scanning calorimeter (DS)
It is desirable that the glass transition temperature (Tg) measured by C) is usually -5C or lower, preferably -10C or lower, more preferably -20C or lower. When the glass transition temperature (Tg) of the α-olefin polymer (B) is within the above range, excellent cold resistance and low-temperature properties are obtained.

The molecular weight distribution (Mw / M) measured by gel permeation chromatography (GPC)
n, in terms of polystyrene, Mw: weight average molecular weight, Mn:
(Number average molecular weight) is preferably 4.0 or less, and more preferably 3.5 or less.

Production of α-Olefin Polymer (B) Such α-olefin polymer (B) has a carbon number of 2 to 2 in the presence of, for example, a metallocene catalyst shown below.
It is obtained by (co) polymerizing at least one or more α-olefins selected from 0 α-olefins.

Examples of such a metallocene catalyst include:
(A) a transition metal compound represented by the following general formula (I) or (II), and (b) (b-1) the transition metal compound (a)
A compound which forms an ionic complex by reacting with a transition metal M therein, (b-2) an organic aluminum oxy compound, (b-3)
At least one catalyst system comprising at least one compound selected from organoaluminum compounds is exemplified.

First, the transition metal compound represented by the general formula (I) used in the present invention will be described.

[0054]

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Where M is Ti, Zr, Hf, Rn, N
It represents d, Sm or Ru, and is preferably Ti, Zr or Hf. Cp ¹ and Cp ² are a cyclopentadienyl group, an indenyl group, a fluorenyl group or a derivative group thereof bonded to M by π. More specifically, Cp ¹ and Cp ² are ligands that coordinate to the transition metal, and include cyclopentadienyl group, indenyl group, 4,5,6,
A ligand having a cyclopentadienyl skeleton such as a 7-tetrahydroindenyl group and a fluorenyl group, and the ligand having a cyclopentadienyl skeleton includes an alkyl group, a cycloalkyl group, a trialkylsilyl group, and a halogen atom. It may have a substituent such as an atom.

X ¹ and X ² are anionic ligands or neutral Lewis base ligands, specifically, a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a sulfone Acid-containing group (—SO ₃ R ^a , where R ^a is an alkyl group, an alkyl group substituted with a halogen atom, an aryl group, an aryl group substituted with a halogen atom, or an aryl group substituted with an alkyl group. ), A halogen atom, a hydrogen atom and the like.

Z is C, O, B, S, Ge, Si or
Is Sn or a group containing these atoms, for example, carbon
Divalent hydrocarbon group having 1 to 20 atoms, 1 to 2 carbon atoms
0 divalent halogenated hydrocarbon group, divalent silicon-containing
Group, divalent germanium-containing group, divalent tin-containing group,-
CO-, -SO-, -SO_Two -, -BR^Five -(R
^FiveIs a hydrogen atom, a halogen atom, a carbon atom having 1 to 20 carbon atoms.
Hydrogen groups, halogenated hydrocarbons having 1 to 20 carbon atoms
Group).

Specific examples of the transition metal compound represented by the general formula (I) include diphenylmethylene (cyclopentadienyl) (fluorenyl) hafnium dichloride and diphenylmethylene (cyclopentadienyl) (fluorenyl) zirconium. Dichloride, isopropyl (cyclopentadienyl-1-fluorenyl) hafnium dichloride, isopropyl (cyclopentadienyl-1-fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) fluorenyl zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2,7-dimethyl-4-
Ethylindenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis (1- (2,7-dimethyl-4-n-propylindenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2,7- Dimethyl-4-i-propylindenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2,7-dimethyl-4-n-butylindenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1
-(2,7-dimethyl-4-sec-butylindenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2,7-dimethyl-4-t-butylindenyl)｝ zirconium dichloride, rac- Dimethylsilylene-bis ｛1- (2,7-dimethyl-4-n
-Pentylindenyl) zirconium dichloride, rac-
Dimethylsilylene-bis {1- (2,7-dimethyl-4-n-hexylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-cyclohexylindenyl)} zirconium Dichloride, rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-methylcyclohexylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-phenylethylindene) Nil)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2,7-dimethyl-4-phenyldichloromethylindenyl)｝ zirconium dichloride, rac-
Dimethylsilylene-bis {1- (2,7-dimethyl-4-chloromethylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-trimethylsilylenemethylindenyl)} Zirconium dichloride, r
ac-dimethylsilylene-bis {1- (2,7-dimethyl-4-trimethylsiloxymethylindenyl)} zirconium dichloride, rac-diethylsilylene-bis {1- (2,7-dimethyl-4)
-i-propylindenyl) zirconium dichloride, ra
c-di (i-propyl) silylenebis ｛1- (2,7-dimethyl-4-i-
Propylindenyl) zirconium dichloride, rac-
Di (n-butyl) silylenebis {1- (2,7-dimethyl-4-i-propylindenyl)} zirconium dichloride, rac-di (cyclohexyl) silylenebis {1- (2,7-dimethyl-4-i- (Propylindenyl) zirconium dichloride, rac-methylphenylsilylene bis 1- (2,7-dimethyl-4-i-propylindenyl) zirconium dichloride, rac-methylphenylsilylene bis 1- (2,7- (Dimethyl-4-t-butylindenyl)｝ zirconium dichloride, rac-diphenylsilylenebis ｛1- (2,7-dimethyl-4-t-butylindenyl)｝ zirconium dichloride, rac-diphenylsilylenebis ｛1- ( 2,7-dimethyl-4-i-propylindenyl) デ
Zirconium dichloride, rac-diphenylsilylene bis ｛1- (2,7-dimethyl-4-ethylindenyl)｝ zirconium dichloride, rac-di (p-tolyl) silylenebis ｛1- (2,7
-Dimethyl-4-i-propylindenyl) zirconium dichloride, rac-di (p-chlorophenyl) silylene bis
(2,7-dimethyl-4-i-propylindenyl) zirconium dichloride, rac-dimethylsilylene bis 1- (2-methyl-4-i-propyl-7-ethylindenyl) zirconium dibromide, rac -Dimethylsilylene-bis {1- (2,7-dimethyl-4-i-propyl-1-indenyl)} zirconium dimethyl, rac-dimethylsilylene-bis {1- (2,7-dimethyl-4)
-i-propyl-1-indenyl) デ zirconium methyl chloride, rac-dimethylsilylene-bis ｛1- (2,7-dimethyl-4
-i-propyl-1-indenyl) デ zirconium-bis ｛1-
(Trifluoromethanesulfonato)｝, rac-dimethylsilylene-bis ｛1- (2,7-dimethyl-4-i-propyl-1-indenyl)｝ zirconium-bis ｛1- (p-phenylsulfinato)｝ , Rac-dimethylsilylene-bis ｛1- (2-phenyl-4-
i-propyl-7-methyl-1-indenyl) zirconium dichloride, (cyclopentadienyl) (fluorenyl) hafnium dichloride, (cyclopentadienyl) (fluorenyl) zirconium dichloride, bis {1- (2,7-dimethyl)
4-ethylindenyl) zirconium dichloride, bis
(Cyclopentadienyl) hafnium dichloride, bis
(Cyclopentadienyl) zirconium dichloride, bisindenyl hafnium dichloride, bisindenyl zirconium dichloride, bis ｛1- (2,7-dimethyl-4-n-
(Propylindenyl) zirconium dichloride, bis {1- (2,7-dimethyl-4-i-propylindenyl) zirconium dichloride, bis} 1- (2,7-dimethyl-4-n-butylindenyl) ｝ Zirconium dichloride, bis ｛1- (2,7-
Dimethyl-4-sec-butylindenyl)｝ zirconium dichloride, bis ｛1- (2,7-dimethyl-4-t-butylindenyl)｝ zirconium dichloride, bis ｛1- (2,7-dimethyl
-4-n-pentylindenyl) zirconium dichloride,
Bis ｛1- (2,7-dimethyl-4-n-hexylindenyl)｝ zirconium dichloride, bis ｛1- (2,7-dimethyl-4-cyclohexylindenyl)｝ zirconium dichloride, bis ｛1- (2 , 7-Dimethyl-4-methylcyclohexylindenyl) zirconium dichloride, bis {1- (2,7-dimethyl)
-4-phenylethylindenyl) zirconium dichloride, bis 1- (2,7-dimethyl-4-phenyldichloromethylindenyl) zirconium dichloride, bis 1- (2,7-
Dimethyl-4-chloromethylindenyl)｝ zirconium dichloride, bis ｛1- (2,7-dimethyl-4-trimethylsilylenemethylindenyl)｝ zirconium dichloride, bis ｛1- (2,7-dimethyl-4-trimethyl) (Siloxymethylindenyl)｝ zirconium dichloride, bis ｛1- (2,7-dimethyl-4-ethylindenyl)｝ zirconium dichloride, bis ｛1- (2-methyl-4-i-propyl-7-ethylindenyl) )｝
Zirconium dibromide, bis ｛1- (2,7-dimethyl-4-i-
(Propyl-1-indenyl) コ zirconium dimethyl, bis ｛1- (2,7-dimethyl-4-i-propyl-1-indenyl)｝ zirconium methyl chloride, bis ｛1- (2,7-dimethyl-4-i -
(Propyl-1-indenyl) コ zirconium-bis ｛1- (trifluoromethanesulfonato), bis ｛1- (2,7-dimethyl-4)
-i-propyl-1-indenyl)｝ zirconium-bis ｛1- (p
-Phenylsulfinato)｝, bis ｛1- (2-phenyl-4-i-
Propyl-7-methyl-1-indenyl) zirconium dichloride.

Further, a transition metal compound in which zirconium metal is replaced with titanium metal or hafnium metal in the above compounds can also be exemplified. In the present invention, a transition metal compound represented by the following general formula (II) can also be used as the transition metal compound (a).

[0060]

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In the formula (II), M is a transition metal of Group 4 of the periodic table or a lanthanide series, and specifically, Ti, Z
r, Hf, Rn, Nd, Sm or Ru, preferably Ti, Zr, Hf.

Cp ¹ is a cyclopentadienyl group, an indenyl group, a fluorenyl group or a derivative thereof bonded to M by π. More specifically, Cp ¹ is a ligand that coordinates to a transition metal, and is a ligand having a cyclopentadienyl skeleton such as a cyclopentadienyl group, an indenyl group, a fluorenyl group, or a derivative group thereof, The ligand having a cyclopentadienyl skeleton may have a substituent such as an alkyl group, a cycloalkyl group, a trialkylsilyl group, and a halogen atom.

X ¹ and X ² are anionic ligands or neutral Lewis base ligands, which may be the same or different from each other, are hydrogen atoms or halogen atoms, or have up to 20 carbon atoms. A hydrocarbon group containing atoms, a silyl group containing not more than 20 silicon atoms, or a germyl group containing not more than 20 germanium atoms.

Z is carbon, oxygen, sulfur, boron or an element of group 14 of the periodic table (for example, silicon, germanium or tin), preferably any of carbon, oxygen and silicon, and Z is an alkyl group, It may have a substituent such as an alkoxy group, and these substituents may be bonded to each other to form a ring. Further, Z and Y may form a condensed ring.

Specific examples of the transition metal complex represented by the formula (II) include (t-butylamido) dimethyl (fluorenyl) silanetitaniumdimethyl, (t-butylamido) dimethyl (fluorenyl) silanetitaniumdichloride, (t-butylamido) dimethyl (fluorenyl) silanezirconium dimethyl, (t-butylamido) dimethyl (fluorenyl)
Silane zirconium dichloride, dimethyl (t-butylamido) (tetramethyl-eta ⁵ - cyclopentadienyl) silylene) titanium dichloride, {(t-butylamido) (tetramethyl-eta ⁵ - cyclopentadienyl) -1,2 ethanediyl} titanium dichloride, {dimethyl (phenylamide) (tetramethyl- eta ⁵ - cyclopentadienyl) silylene} titanium dichloride, {dimethyl (t-butylamido) (tetramethyl -
η ⁵ -cyclopentadienyl) silylene｝ titanium dimethyl, ｛dimethyl (4-methylphenylamide) (tetramethyl-η ⁵ -cyclopentadienyl) silylene｝ titanium dichloride, ｛dimethyl (t-butylamide) (η ^5- include cyclopentadienyl) Jishiriren} titanium dichloride, and (t-butylamido) dimethyl (fluorenyl) silane titanium dimethyl - cyclopentadienyl) silylene} titanium dichloride, {tetramethyl (t-butylamido) (tetramethyl-eta ⁵ Can be

The above transition metal complexes can be used alone or in combination of two or more. Support The transition metal compound as described above can be used by being supported on a particulate carrier.

Examples of such a particulate carrier include Si
O ₂ , Al ₂ O ₃ , B ₂ O ₃ , MgO, ZrO ₂ , CaO, T
inorganic carriers such as iO ₂ , ZnO, SnO ₂ , BaO, and ThO, polyethylene, polypropylene, poly-1-butene,
Organic carriers such as poly-4-methyl-1-pentene and styrene-divinylbenzene copolymer can be used. These particulate carriers can be used alone or in combination of two or more.

Next, the component (b) forming the metallocene catalyst, that is, the ionized ionic compound (b-1), the organic aluminum oxy compound (b-2) and the organic aluminum compound (b-3) will be described.

(B-1) Ionized Ionic Compound The ionized ionic compound (b-1) is a compound which reacts with the transition metal M in the transition metal compound (a) to form an ionic complex. Examples of such an ionized ionic compound include JP-A-1-501950 and JP-A-1-501950.
No. 502036, JP-A-3-179005,
JP-A-3-179006, JP-A-3-20770
No. 3, JP-A-3-207704, USP-5
Examples thereof include Lewis acids, ionic compounds, borane compounds and carborane compounds described in No. 321106.

As the Lewis acid, a compound represented by BR ₃ (where R is a fluorine atom, a phenyl group which may have a substituent such as a methyl group or a trifluoromethyl group or a fluorine atom). For example, trifluoroboron, triphenylboron, tris (4-fluorophenyl) boron, tris (3,5-difluorophenyl)
Boron, tris (4-fluoromethylphenyl) boron,
Tris (pentafluorophenyl) boron, tris (p-
Tolyl) boron, tris (o-tolyl) boron, tris (3,5-dimethylphenyl) boron, MgCl ₂ , Al ₂ O
₃ , SiO ₂ —Al ₂ O _{3 and the} like.

Examples of the ionic compound include trialkyl-substituted ammonium salts, N, N-dialkylanilinium salts, dialkylammonium salts, and triarylphosphonium salts. Specifically, the trialkyl-substituted ammonium salts include, for example, triethylammonium tetra (phenyl) boron, tripropylammonium tetra (phenyl) boron, tri (n-butyl) boron.
And ammonium tetra (phenyl) boron. Examples of the dialkyl ammonium salt include di (1-propyl) ammonium tetra (pentafluorophenyl) boron and dicyclohexylammonium tetra (phenyl) boron. Further, as ionic compounds, triphenylcarbenium tetrakis (pentafluorophenyl) borate, tri-n-butylammonium tetrakis (pentafluorophenyl) borate, N, N-dimethylaniliniumtetrakis (pentafluorophenyl) borate, ferrocenium tetraborate (Pentafluorophenyl) borate and the like can also be mentioned.

As the borane compound, decaborane (1
4), bis [tri (n-butyl) ammonium] nonaborate, bis [tri (n-butyl) ammonium] decaborate, bis [tri (n-butyl) ammonium] bis (dodecahydride dodecaborate) nickelate (II
And salts of metal borane anions such as I).

Examples of the carborane compound include 4-carbanonaborane (14), 1,3-dicarbanonaborane (13), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carboundecaborate) Nickelates (I
V), dodecaborane, 1-carboundecaborane, bis-n-
Butyl ammonium (1-carbedodeca) borate, tri
n-butylammonium (7,8-dicarbaundeca) borate, tri-n-butylammonium (trideca hydride)
-7-carboundeca) borate and the like, and salts of metal carborane anions.

The ionized ionic compound (b-
1) can be used alone or in combination of two or more. The ionized ionic compound (b-1) can be used by being supported on the above-mentioned particulate carrier.

(B-2) Organoaluminum oxy compound (b-2) The organoaluminum oxy compound may be a conventionally known aluminoxane.
A benzene-insoluble organic aluminum oxy compound as exemplified in JP-A-87-87 may be used.

The conventionally known aluminoxane (alumoxane) is specifically represented by the following general formula.

[0077]

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In the formula, R is a hydrocarbon group such as a methyl group, an ethyl group, a propyl group and a butyl group, preferably a methyl group and an ethyl group, particularly preferably a methyl group. m is an integer of 2 or more, preferably 5 or more, more preferably 5 to 40, particularly preferably 10 to 40.

Here, the aluminoxane has the formula (OAl (R
¹⁾ represented alkyloxy aluminum units and formula (OAl (R ²⁾ represented alkyloxy aluminum units (where they are in) is in), R ¹ and R ² are the same hydrocarbon group as R, R ¹ And R ² represent different groups.).

A conventionally known aluminoxane can be produced, for example, by the following method. (1) Compounds containing water of adsorption or salts containing water of crystallization, such as hydrated magnesium chloride, hydrated copper sulfate, hydrated aluminum sulfate, hydrated nickel sulfate, hydrated cerous chloride A method of adding an organoaluminum compound such as trialkylaluminum to a hydrocarbon medium suspension of the above to react. (2) A method in which water, ice or steam is allowed to directly act on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran. (3) A method of reacting an organoaluminum compound such as trialkylaluminum with an organotin oxide such as dimethyltin oxide or dibutyltin oxide in a medium such as decane, benzene or toluene.

The aluminoxane may contain a small amount of an organic metal component. Alternatively, the solvent or unreacted organoaluminum compound may be removed from the recovered solution of aluminoxane by distillation, and then redissolved in a solvent or suspended in a poor solvent of aluminoxane.

As the organoaluminum compound used for preparing the aluminoxane, the same compounds as the below-mentioned organoaluminum compound (b-3) can be mentioned. The above-mentioned organoaluminum compounds can be used alone or in combination.

Solvents used for the preparation of aluminoxanes include aromatic hydrocarbons such as benzene, toluene, xylene, cumene and cymene; and aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane and octadecane. Alicyclic hydrocarbons such as cyclopentane, cyclohexane, cyclooctane and methylcyclopentane; petroleum fractions such as gasoline, kerosene and light oil or halides of the above aromatic hydrocarbons, aliphatic hydrocarbons and alicyclic hydrocarbons (E.g., chlorinated products, brominated products, etc.). Others
Ethers such as ethyl ether and tetrahydrofuran can also be used. Among these solvents, aromatic hydrocarbons and aliphatic hydrocarbons are particularly preferred.

Such an organoaluminum oxy compound (b-2) can be used by being supported on the above-mentioned particulate carrier. Organoaluminum Compound (b-3) As the organoaluminum compound, a compound having at least one Al-carbon bond in a molecule can be used. As such a compound, for example, the following general formula (III)
The organic aluminum compound represented by these is mentioned.

R ⁹ _n AlX _3-n (III) (wherein, R ⁹ is a hydrocarbon group having 1 to 12 carbon atoms, X is a halogen atom or a hydrogen atom, and n is 1 to 3)
3. In the above general formula (III), R ⁹ has 1 to 1 carbon atoms.
2 hydrocarbon groups such as an alkyl group, a cycloalkyl group or an aryl group, specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an isobutyl group,
Examples include a pentyl group, a hexyl group, an octyl group, a cyclopentyl group, a cyclohexyl group, a phenyl group and a tolyl group.

Such an organoaluminum compound (II)
Specific examples of I) include the following compounds. Trialkylaluminum such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, tri (2-ethylhexyl) aluminum, tridecylaluminum; alkenylaluminum such as isoprenylaluminum; dimethylaluminumchloride, diethylaluminumchloride Dialkylaluminum halides such as diisopropylaluminum chloride, diisobutylaluminum chloride and dimethylaluminum bromide; alkylaluminum halides such as methylaluminum sesquichloride, ethylaluminum sesquichloride, isopropylaluminum sesquichloride, butylaluminum sesquichloride and ethylaluminum sesquibromide Alkyl aluminum dihalides such as methylaluminum dichloride, ethylaluminum dichloride, isopropylaluminum dichloride and ethylaluminum dibromide; alkylaluminum hydrides such as diethylaluminum hydride and diisobutylaluminum hydride.

Further, the organic aluminum compound (b-3)
Use a compound represented by the following general formula (IV)
You can also. R⁹ _nAll_3-n ... (IV) (wherein, R⁹ Is the same as above, and L is -OR^TenGroup,-
OSiR¹¹ _Three Group, -OAlR¹² _Two Group, -NR¹³ _Two Group,-
SiR¹⁴ _Three Group or -N (R¹⁵) AlR¹⁶ _Two And n
Is 1-2, and R^Ten, R¹¹, R¹² And R¹⁶ Is meth
Group, ethyl group, isopropyl group, isobutyl group, cycle
Rhexyl group, phenyl group, etc. ¹³Is hydrogen field
Child, methyl group, ethyl group, isopropyl group, phenyl
Group, trimethylsilyl group, etc.¹⁴And R¹⁵ 
Represents a methyl group, an ethyl group or the like. ) Among such organoaluminum compounds, R⁹ _n 
Al (OALR)^Ten _Two )_3-nA compound represented by, for example,
Et_Two AlOAlEt_Two , (Iso-Bu)_Two AlOAl (iso
-Bu)_Two Are preferred.

[0088] Among the above general formula (III) and an organic aluminum compound represented by (IV), the general formula R ⁹ ₃ Al
The compound represented by is preferable, and a compound in which R ⁹ is an isoalkyl group is particularly preferable.

In the present invention, as the catalyst for producing the α-olefin polymer (B), the above-mentioned metallocene catalyst is preferably used. It is also possible to use a titanium-based catalyst comprising a solid titanium catalyst component and an organoaluminum compound, and a vanadium-based catalyst comprising a soluble vanadium compound and an organoaluminum compound.

In the present invention, at least one or more α-olefins selected from α-olefins having 2 to 20 carbon atoms are usually copolymerized in the liquid phase in the presence of the above-mentioned metallocene catalyst. In this case, a hydrocarbon solvent is generally used, but propylene may be used as the solvent.
The copolymerization can be carried out by either a batch method or a continuous method.

When the copolymerization is carried out by a batch method using a metallocene catalyst, the transition metal compound (a) in the polymerization system usually has a concentration of 0.0000 per liter of polymerization volume.
It is used in an amount of 5 to 1 mmol, preferably 0.0001 to 0.5 mmol.

The ionized ionic compound (b-1) has a molar ratio ((b-1) / (a)) of the ionized ionic compound to the transition metal compound (a) of 0.5 to 20, preferably 1 It is used in such an amount as to be.

Organic aluminum oxy compound (b-2)
Is the molar ratio (Al / M) of the aluminum atom (Al) to the transition metal atom (M) in the transition metal compound (a).
And it is used in an amount such that it becomes 1 to 10,000, preferably 10 to 5,000.

The organoaluminum compound (b-3) is
The amount is usually about 0 to 5 mmol, preferably about 0 to 2 mmol, per liter of polymerization volume.
The copolymerization reaction is usually carried out at a temperature of -20 to 150 ° C, preferably 0 to 120 ° C, more preferably 0 to 100 ° C, and a pressure exceeding 0 to 80 kg / cm ² , preferably exceeding 0. This is carried out under the condition of て 50 kg / cm ² .

The reaction time (average residence time when the polymerization is carried out by a continuous method) varies depending on conditions such as the catalyst concentration and the polymerization temperature, but is usually 5 minutes to 3 hours, preferably 10 minutes to 1 hour. .5 hours.

At least one α-olefin selected from α-olefins having 2 to 20 carbon atoms is used in an amount such that the α-olefin polymer (B) having the specific composition as described above is obtained. It is supplied to the polymerization system. At the time of copolymerization, a molecular weight regulator such as hydrogen can be used.

As described above, at least one kind of α-olefin selected from α-olefins having 2 to 20 carbon atoms.
When an olefin is polymerized, the α-olefin polymer (B) is usually obtained as a polymerization solution containing the same. This polymerization liquid is treated by a conventional method to obtain an α-olefin-based copolymer (B).

[0098] As the crystal nucleating agent used in the crystal nucleating agent present invention, used without various crystalline nucleating agents conventionally known it is particularly limited. Among them, the following nucleating agents can be exemplified as preferred crystal nucleating agents.

[0099]

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(Wherein, R ¹ represents an oxygen atom, a sulfur atom or a hydrocarbon group having 1 to 10 carbon atoms, and R ² and R ^{3 each} represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. , R ² and R ³ may be the same or different from each other, may be R ² , R ³ or R ² and R ³ may be bonded to form a ring, and M is a metal having 1 to 3 valences. Represents an atom, and n is an integer of 1 to 3.) Specifically, 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′-methylene-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) phosphate] , 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] and aluminum-tris [2,2′-ethylidene-bis (4,6-di-t-butylphenyl) phosphate] and mixtures of two or more thereof. be able to.

[0101]

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(Wherein, R ⁴ represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, M represents a metal atom having 1 to 3 valences, and n represents an integer of 1 to 3). Typically, 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-butylphenyl) phosphate and mixtures of two or more thereof can do.

[0103]

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(In the formula, R ⁵ is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.) Specifically, 1,3,2,4-
Dibenzylidene sorbitol, 1,3-benzylidene-2,4-p
-Methylbenzylidene sorbitol, 1,3-benzylidene-
2,4-p-ethylbenzylidene sorbitol, 1,3-p-methylbenzylidene-2,4-benzylidene sorbitol, 1,3-p-
Ethylbenzylidene-2,4-benzylidene sorbitol,
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) sorbitol, 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 1,4-di (p-ethoxybenzylidene) sorbitol, 1,3-benzylidene-2
-4-p-chlorobenzylidene sorbitol, 1,3-p-chlorobenzylidene-2,4-benzylidene sorbitol, 1,3-p-
Chlorbenzylidene-2,4-p-methylbenzylidenesorbitol, 1,3-p-chlorobenzylidene-2,4-p-ethylbenzylidenesorbitol, 1,3-p-methylbenzylidene-2,4
-P-chlorobenzylidene sorbitol, 1,3-p-ethylbenzylidene-2,4-p-chlorobenzylidene sorbitol and 1,3,2,4-di (p-chlorobenzylidene) sorbitol and mixtures of two or more thereof Can be illustrated, especially 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 mixtures of two or more thereof are preferred.

Examples of other crystal nucleating agents include metal salts of aromatic carboxylic acids and aliphatic carboxylic acids, and specific examples thereof include aluminum benzoate, aluminum pt-butylbenzoate, sodium adipate, and thiophene. Examples include sodium phenecarboxylate and sodium pyrrolecarboxylate. Further, as a crystal nucleating agent, a polymer nucleating agent such as polyethylene and Teflon (registered trademark) can also be mentioned. Among these nucleating agents, sorbitol compounds are preferred.

Composition The soft syndiotactic polypropylene-based composition according to the present invention comprises the above-mentioned syndiotactic propylene polymer (A), the above α-olefin polymer (B) and the above crystal nucleating agent (C). , The weight ratio {(A) / (B)} of the syndiotactic propylene polymer (A) and the α-olefin polymer (B) is 90/10 to 10/90, preferably 80/20 to 20 / 80, more preferably 7
5/25 to 40/60, and the nucleating agent (C) is added in an amount of 0.01 to 100 parts by weight of the total amount of the syndiotactic propylene polymer (A) and the α-olefin polymer (B). To 1 part by weight, preferably 0.1 to 0.8 part by weight.

When the composition is contained in the proportions (A) and (B) as described above, and a nucleating agent is further added thereto, the resulting soft syndiotactic polypropylene-based composition has transparency, flexibility, It tends to have excellent heat sealability and impact resistance.

The melt tension (M) of the soft syndiotactic polypropylene composition according to the present invention is also described.
T) is usually 0.5 to 10 g, preferably 1 to 10 g, and is excellent in moldability such as film moldability. In addition,
The melt tension (MT) was measured at a measurement temperature of 2 with a melt tension tester (manufactured by Toyo Seiki Seisaku-sho, Ltd.).
It is determined as the tension applied to the filament when the strand extruded under the condition of 00 ° C. and the extrusion speed of 15 mm / min is taken out at a constant speed (10 m / min).

Soft syndiotactic polypropylene
Production of a system composition The above-mentioned soft syndiotactic polypropylene-based composition is prepared by mixing the respective components in the above-described quantitative ratios by various known methods, for example, a Henschel mixer, a V-blender, a ribbon blender, a tumbler blender, and the like. how to,
Or after mixing, single screw extruder, twin screw extruder, kneader,
After melt-kneading with a Banbury mixer or the like, it can be produced by a method of granulating or pulverizing.

The soft syndiotactic polypropylene composition includes heat stabilizers, weather stabilizers, antistatic agents, pigments, dyes, rust inhibitors, and other copolymers (elastomer) described in detail below. , An elastomer resin) and the like can be blended within a range that does not impair the object of the present invention.

Other Copolymers The soft syndiotactic polypropylene-based composition according to the present invention may contain "other copolymers" if necessary.

Examples of such “other copolymers” include an aromatic hydrocarbon block copolymer (D) which may be hydrogenated and an ethylene / α-olefin block copolymer (described later). E), an ethylene / triene copolymer (F), an ethylene / styrene-based copolymer, an ethylene / diene copolymer, and the like. These copolymers are used alone or in combination of two or more.

These “other copolymers” can be used as the soft syndiotactic polypropylene composition 10 of the present invention.
0 to 40 parts by weight, preferably 0 to 100 parts by weight,
It is used in a proportion of up to 30 parts by weight.

When the “other copolymer” is used in the above ratio, a composition capable of producing a molded article having an excellent balance of rigidity, hardness, transparency and impact resistance is obtained. Aromatic hydrocarbon block copolymers which may be hydrogenated
Body (D) The aromatic hydrocarbon-based block copolymer (D) optionally used in the present invention which is optionally hydrogenated is an elastomer, and has a block polymer unit (X) derived from aromatic vinyl. And a block polymerized unit (Y) derived from a conjugated diene, and an aromatic vinyl / conjugated diene block copolymer (D1) or a hydrogenated product thereof (D2).

The form of the aromatic vinyl / conjugated diene block copolymer (D1) having such a structure is, for example, X (Y
X) n or (XY) n (n is an integer of 1 or more). Among these, a block copolymer in the form of X (YX) n, particularly XYX is preferred, and specifically, in the form of polystyrene-polybutadiene (or polyisoprene or polyisoprene-butadiene) -polystyrene. Styrene block copolymers are preferred.

In such an aromatic hydrocarbon block copolymer, the aromatic vinyl block polymerization unit (X), which is a hard segment, exists as a cross-linking point of the conjugated diene block polymerization unit (Y) and is physically crosslinked ( Domain). Conjugated diene block polymer units (Y) existing between the aromatic vinyl block polymer units (X)
Is a soft segment and has rubber elasticity.

Specific examples of the aromatic vinyl forming the aromatic vinyl block polymerized unit (X) include styrene, α-methylstyrene, 3-methylstyrene, p-methylstyrene, and 4-propyl. Styrene, 4-dodecylstyrene, 4-cyclohexylstyrene, 2-ethyl-4-
Styrene derivatives such as benzylstyrene and 4- (phenylbutyl) styrene are exemplified. Of these, styrene is preferred.

Further, the conjugated diene block polymerization unit (Y)
Examples of the conjugated diene that forms are butadiene, isoprene, pentadiene, 2,3-dimethylbutadiene, and combinations thereof. Of these, butadiene or isoprene or a combination of butadiene and isoprene is preferred.

When the conjugated diene block polymerized unit (Y) is derived from butadiene and isoprene, it is preferable to contain the unit derived from isoprene in a proportion of 40 mol% or more.

The conjugated diene block polymerization unit (Y) comprising butadiene / isoprene copolymerization unit
Is a random copolymerized unit of butadiene and isoprene,
It may be either a block copolymer unit or a tapered copolymer unit.

The aromatic vinyl / conjugated diene block copolymer (D1) has an aromatic vinyl block polymerization unit (X) content of 22% by weight or less, preferably 5 to 22% by weight. . The content of the aromatic vinyl polymerized unit can be measured by a conventional method such as infrared spectroscopy and NMR spectroscopy.

The aromatic vinyl / conjugated diene block copolymer (D1) has a melt flow rate (MFR; AS).
TM D 1238, 200 ° C, load 2.16 kg)
Usually 5 g / 10 min or more, preferably 5 to 100 g /
10 minutes.

Various methods can be used to produce the above-mentioned aromatic vinyl / conjugated diene block copolymer (D1). For example, (1) an alkyllithium compound such as n-butyllithium is used as an initiator. A method of sequentially polymerizing an aromatic vinyl compound and then a conjugated diene,
(2) a method of polymerizing an aromatic vinyl compound and then a conjugated diene and coupling them with a coupling agent; and (3) a method of sequentially polymerizing a conjugated diene and then an aromatic vinyl compound using a lithium compound as an initiator. Can be mentioned.

The hydrogenated aromatic vinyl-conjugated diene block copolymer (D2) is obtained by hydrogenating the above-mentioned aromatic vinyl-conjugated diene block copolymer (D1) by a known method. Can be obtained by Hydrogenated aromatic vinyl / conjugated diene block copolymer (D2)
Usually has a hydrogenation rate of 90% or more.

This hydrogenation ratio is a value when the total amount of carbon-carbon double bonds in the conjugated diene block polymerization unit (Y) is 100%. Specific examples of the hydrogenated product (D2) of the aromatic vinyl / conjugated diene block copolymer include a hydrogenated product of a styrene / isoprene block copolymer (SEP) and a styrene / isoprene / styrene block copolymer. Hydrogenated polymer (SEPS; polystyrene / polyethylene / propylene / polystyrene block copolymer),
Hydrogenated styrene-butadiene block copolymer (SE
BS; polystyrene / polyethylene / butylene / polystyrene block copolymer), and more specifically, HYBRAR (manufactured by Kuraray Co., Ltd.), Clayton (manufactured by Shell Chemical Co., Ltd.), and Carrieflex TR (shell chemical) Co., Ltd.), Solprene (manufactured by Philips Petro Rifum), Europrene SOLT (manufactured by Anich), Tufprene (manufactured by Asahi Kasei Corporation), Solprene-T (manufactured by Nippon Elastomer), JSR-TR (manufactured by Nippon Gosei) Rubber Co., Ltd.), Electrified STR (Denki Kagaku Kogyo Co., Ltd.)
), Quintac (manufactured by Nippon Zeon Co., Ltd.), Clayton G (manufactured by Shell Chemical Co., Ltd.), Tuftec (manufactured by Asahi Chemical Industry Co., Ltd.) (all trade names), and the like.

The hydrogenated product (D2) of the aromatic vinyl / conjugated diene block copolymer includes, among these, SEB
S and SEPS are preferably used. The aromatic hydrocarbon-based block copolymer (D) which may be hydrogenated is usually 0 to 30% by weight, preferably 0 to 2% by weight, based on 100 parts by weight of the soft syndiotactic polypropylene composition.
It is desirable to use 5% by weight. When the aromatic hydrocarbon-based block copolymer (D) which may be hydrogenated is used at the above ratio, rigidity and hardness, transparency,
A composition that can prepare a molded article having an excellent balance of impact resistance is obtained.

Ethylene / α-olefin block copolymer
The ethylene / α-olefin block copolymer (E) optionally used in the present invention is an elastomer,
A crystalline polyethylene portion comprising 0 to 20 mol% of a repeating unit derived from an α-olefin having 3 to 10 carbon atoms and 100 to 80 mol% of a repeating unit derived from ethylene; It is composed of a low crystalline copolymer part or an amorphous copolymer part containing two or more kinds of repeating units derived from α-olefin.

In the present invention, a repeating unit derived from ethylene is contained in a proportion of 30 to 95 mol% and has 3 carbon atoms.
70 to 5 repeating units derived from olefins of
An ethylene / α-olefin block copolymer containing at a mole percentage is preferred. In particular, a repeating unit derived from ethylene is contained in a proportion of 60 to 90 mol%, and a repeating unit derived from an olefin having 3 to 20 carbon atoms is 40%.
An ethylene / α-olefin block copolymer containing 10 to 10 mol% is preferred.

Here, as the α-olefin having 3 to 20 carbon atoms, specifically, propylene, 1-butene, 1-butene
Pentene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 3-methyl-1-butene, 1-decene, 1-dodecene, 1-tetradodecene, 1-hexadecene, 1-octadecene, 1-eicosene, cyclopentene,
Cycloheptene, norbornene, 5-ethyl-2-norbornene, tetracyclododecene, 2-ethyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene And the like.

In the crystalline polyethylene part, two or more kinds of the repeating units derived from the above α-olefin having 3 to 20 carbon atoms may be contained. Further, the ethylene / α-olefin block copolymer (E) used in the present invention may contain a repeating unit derived from a diene compound having 4 to 20 carbon atoms at a ratio of 5 mol% or less. .

Specific examples of such a diene compound include 1,3-butadiene, 1,3-pentadiene, 1,4-pentadiene, 1,3-hexadiene, 1,4-hexadiene, 1,5- Hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,
4-hexadiene, 6-methyl-1,6-octadiene, 7-methyl-1,6-octadiene, 6-ethyl-1,6-octadiene, 6-
Propyl-1,6-octadiene, 6-butyl-1,6-octadiene, 6-methyl-1,6-nonadiene, 7-methyl-1,6-nonadiene, 6-ethyl-1,6-nonadiene, 7- Ethyl-1,6-nonadiene, 6-methyl-1,6-decadiene, 7-methyl-1,6-decadiene, 6-methyl-1,6-undecadiene, 1,7-octadiene, 1,9-decadiene, Examples include isoprene, butadiene, ethylidene norbornene, vinyl norbornene, dicyclopentadiene, and the like.

Such an ethylene / α-olefin block copolymer (E) has a melt flow rate (MFR;
(ASTM D 1238, 190 ° C, load 2.16 kg)
Is usually 0.0001 to 500 g / 10 min, preferably 0.1 g.
0001-300 g / 10 min, more preferably 0.00
01 to 200 g / 10 min, and the density (ASTMD
1505) is 0.85 to 0.90 g / cm ³ , preferably 0.85 to 0.89 g / cm ³ , and more preferably 0.86 to 0.89 g / cm ³ .

The degree of crystallinity of the boiling heptane-insoluble component in the ethylene / α-olefin block copolymer (E) measured by an X-ray diffraction method is usually 0 to 30%, preferably 0 to 28%, more preferably. 0 to 25%.

The boiling heptane-insoluble component of the ethylene / α-olefin block copolymer (E) is prepared as follows. That is, 3 g of a polymer sample, 20 mg of 2,6-di-tert-butyl-4-methylphenol and 500 ml of n-decane were placed in a 1-liter flask equipped with a stirrer,
Heat and dissolve on a 5 ° C. oil bath. After the polymer sample is dissolved, it is cooled to room temperature over about 8 hours, and then kept on a 23 ° C. water bath for 8 hours. An n-decane suspension containing the precipitated polymer (23 ° C. decane-insoluble component) was added to G-4 (or G-
After filtration and separation through a glass filter of 2) and drying under reduced pressure, 1.5 g of the polymer is subjected to Soxhlet extraction using heptane for 6 hours or more to obtain a boiling heptane-insoluble component.

The degree of crystallinity is measured as follows using the boiling heptane-insoluble component obtained as described above as a sample. That is, a sample was formed into a square plate having a thickness of 1 mm by a pressure molding machine at 180 ° C., and immediately thereafter, measured using a press sheet obtained by cooling with water using a Rotaflex RU300 measuring device manufactured by Rigaku Corporation. (Output 50 kV, 250 mA). As a measuring method at this time, a transmission method is used, and the measurement is performed while rotating the sample.

The density of the boiling heptane-insoluble component of the ethylene / α-olefin block copolymer (E) used in the present invention is usually 0.86 g / cm ³ or more, preferably 0.1 g / cm ³ or more.
It is 87 g / cm ³ or more.

The ethylene / α-olefin block copolymer (E) had an n-decane soluble component at 23 ° C. of 0.1%.
It is in the range of 1-99%, preferably 0.5-99%, more preferably 1-99%.

In the present invention, the amount of n-decane-soluble components at 23 ° C. of the ethylene / α-olefin block copolymer (E) is measured as follows. That is, 3 g of the polymer sample, 2,6-di-ter
t-butyl-4-methylphenol 20 mg, n-decane 50
Add 0 ml and heat and dissolve on an oil bath at 145 ° C. After the polymer sample is dissolved, it is cooled to room temperature over about 8 hours, and then kept on a 23 ° C. water bath for 8 hours. The precipitated polymer and an n-decane solution containing the dissolved polymer were subjected to G-4
(Or G-2) through a glass filter.
The solution obtained in this way is 10 mmHg, 150 ° C.
The polymer dissolved in the n-decane solution was dried by heating under the conditions described above until the amount was determined. The weight of the polymer was determined as the decane-soluble component at 23 ° C. C. The amount of n-decane-soluble component is calculated as a percentage based on the weight of the polymer sample.

The ethylene used in the present invention is
The α-olefin block copolymer (E) can be prepared by a conventionally known method. The ethylene / α-olefin block copolymer (E) is based on 100 parts by weight of the soft syndiotactic polypropylene composition.
Usually, it is desirable to use 0 to 40% by weight, preferably 0 to 35% by weight. When the ethylene / α-olefin block copolymer (E) is used at the above ratio,
As a result, a composition that can prepare a molded article having an excellent balance between rigidity, hardness, transparency, and impact resistance is obtained.

Ethylene / triene copolymer (F) The ethylene / triene copolymer (F) used as required in the present invention is an elastomer, and is a random copolymer of ethylene and triene.

Specific examples of the triene to be copolymerized with ethylene include 6,10-dimethyl-1,5,9-undecatriene,
8-dimethyl-1,4,8-decatriene, 5,9-dimethyl-1,4,8-
Decatriene, 6,9-dimethyl-1,5,8-decatriene, 6,
8,9-trimethyl-1,5,8-decatriene, 6-ethyl-10-methyl-1,5,9-undecatriene, 4-ethylidene-1,6-octadiene, 7-methyl-4-ethylidene- 1,6-octadiene,
4-ethylidene-8-methyl-1,7-nonadiene (EMND),
7-methyl-4-ethylidene-1,6-nonadiene, 7-ethyl-4-
Ethylidene-1,6-nonadiene, 6,7-dimethyl-4-ethylidene-1,6-octadiene, 6,7-dimethyl-4-ethylidene-1,6
-Nonadiene, 4-ethylidene-1,6-decadiene, 7-methyl
-4-ethylidene-1,6-decadiene, 7-methyl-6-propyl-
4-ethylidene-1,6-octadiene, 4-ethylidene-1,7-nonadiene, 8-methyl-4-ethylidene-1,7-nonadiene, 4-
Non-conjugated trienes such as ethylidene-1,7-undecadiene;
Conjugated trienes such as 1,3,5-hexatriene; and the like. These trienes can be used alone or in combination of two or more.

The above-mentioned triene is, for example, EP0
It can be prepared by a conventionally known method as described in JP 691354A1 and WO96 / 20150.

In the ethylene / triene copolymer (F) used in the present invention, the content of the repeating unit derived from triene is usually 0.1 to 30 mol%, preferably 0.1 to 20 mol%, more preferably 0.1 to 20 mol%. Preferably, it is in the range of 0.5 to 15 mol%. It is desirable that the iodine value is usually 1 to 200, preferably 1 to 100, and more preferably 1 to 50.

Further, ethylene / triene copolymer (F)
Has an intrinsic viscosity [η] measured in decahydronaphthalene at 135 ° C. of 0.01 to 10 dl / g, preferably 0.1 to 10 dl / g.
05 to 10 dl / g, more preferably 0.1 to 10 d / g
It is desirably within the range of 1 / g.

The ethylene / triene copolymer (F) as described above can be prepared by a conventionally known method. The ethylene / triene copolymer (F) is preferably used in an amount of usually 0 to 40% by weight, preferably 0 to 35% by weight, based on 100 parts by weight of the soft syndiotactic polypropylene composition. When the ethylene / triene copolymer (F) is used in the above ratio, a composition that can prepare a molded article having an excellent balance between rigidity, hardness, transparency, and impact resistance is obtained.

Molded Articles The soft syndiotactic polypropylene-based composition according to the present invention as described above can be widely used for conventionally known polyolefin applications. For example, various compositions including sheets, unstretched or stretched films, filaments and the like can be used. It can be used by shaping into a shaped body.

Specific examples of the molded article include known thermoforming methods such as extrusion molding, injection molding, inflation molding, blow molding, extrusion blow molding, injection blow molding, press molding, vacuum molding, calendar molding, and foam molding. The obtained molded article is exemplified. The molded product will be described below with reference to several examples.

When the molded article according to the present invention is, for example, an extruded molded article, its shape and product type are not particularly limited, but for example, sheets, films (unstretched), pipes,
Examples include hoses, wire coatings, and filaments, and particularly preferred are sheets, films, and filaments.

When extruding the soft syndiotactic polypropylene-based composition, conventionally known extruders and molding conditions can be employed, such as a single screw extruder, a kneading extruder, a ram extruder, and a gear extruder. The molten syndiotactic polypropylene composition can be extruded from a T-die or the like using an extruder or the like to form a sheet or film (unstretched).

The stretched film can be obtained by subjecting the extruded sheet or extruded film (unstretched) as described above to a known stretching method such as a tenter method (longitudinal and transverse stretching, transverse and longitudinal stretching), a simultaneous biaxial stretching method and a uniaxial stretching method. It can be obtained by stretching.

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

Further, an inflation film can be produced as a film-shaped molded product. When the soft syndiotactic polypropylene composition according to the present invention is subjected to inflation molding, drawdown hardly occurs.

The sheet and film formed from the soft syndiotactic polypropylene composition according to the present invention as described above are hardly charged, have flexibility such as tensile elasticity, heat resistance, heat sealability, and impact resistance. It is excellent in aging resistance, transparency, transparency, gloss, rigidity, moisture resistance and gas barrier properties, and can be widely used as a packaging film. Particularly, since it has excellent moisture-proof properties, it is suitably used for press-through packs used for packaging tablets, capsules and the like of chemicals.

The filament can be produced, for example, by extruding a molten soft syndiotactic polypropylene-based composition through a spinneret. The filament thus obtained may be further drawn. This stretching may be carried out so that at least the uniaxial direction of the filament is molecularly oriented, and is usually desirably performed at a magnification of about 5 to 10 times. The filament comprising the soft syndiotactic polypropylene-based composition according to the present invention is hardly charged, and is excellent in transparency, rigidity, heat resistance and impact resistance.

An injection molded article can be produced by injection molding a soft syndiotactic polypropylene composition into various shapes using a conventionally known injection molding apparatus under known conditions. The injection molded article comprising the soft syndiotactic polypropylene-based composition according to the present invention is hardly charged, and is excellent in rigidity, heat resistance, impact resistance, surface gloss, chemical resistance, abrasion resistance, etc. It can be widely used for trim materials for automobiles, exterior materials for automobiles, housings and containers for home electric appliances.

The blow molded article can be produced by blow molding a soft syndiotactic polypropylene composition using a conventionally known blow molding apparatus under known conditions.

For example, in extrusion blow molding, the above soft syndiotactic polypropylene-based composition is extruded from a die in a molten state at a resin temperature of 100 ° C. to 300 ° C. to form a tubular parison, and then the parison is placed in a mold having a desired shape. After the air was blown, the resin temperature was 130 ° C.
A hollow molded article can be manufactured by mounting the mold at a temperature of 300 ° C. The stretching (blow) magnification is desirably about 1.5 to 5 times in the lateral direction.

In the injection blow molding, the soft syndiotactic polypropylene-based composition was used at a resin temperature of 1%.
By injecting into a parison mold at 00 ° C. to 300 ° C. to form a parison, then holding the parison in a mold having a desired shape, then blowing air, and mounting the parison in a mold at a resin temperature of 120 ° C. to 300 ° C. A hollow molded body can be manufactured.

The stretching (blow) magnification is 1.1 to 1.1 in the longitudinal direction.
It is preferably 1.8 times and 1.3 to 2.5 times in the horizontal direction. The blow molded article comprising the soft syndiotactic polypropylene composition according to the present invention is excellent in transparency, rigidity, heat resistance and impact resistance, and also excellent in moisture resistance.

Examples of the press-formed body include a mold stamping-formed body. For example, the base material and the skin material are simultaneously press-formed and the base material according to the present invention is subjected to composite integral forming (mold stamping forming). It can be formed of a soft syndiotactic polypropylene-based composition.

Specific examples of such a molded stamping molded body include automotive interior materials such as door trim, rear package trim, seat back garnish, and instrument panel.

The flexible syndiotactic polypropylene-based composition according to the present invention exhibits transparency and high rigidity. For example, it exhibits sufficiently high rigidity even if it contains an elastomer component. Can be.
For example, it can be suitably used particularly for applications such as interior and exterior materials of automobiles, housings of home appliances, and various containers.

The press-formed product comprising the soft syndiotactic polypropylene composition according to the present invention is hardly charged, and has rigidity, heat resistance, transparency, impact resistance, aging resistance, surface gloss, chemical resistance, and abrasion resistance. Excellent wear properties.

The flexible syndiotactic polypropylene composition of the present invention can be molded by the above-mentioned various molding methods and can be suitably used, for example, in the following applications.

Film: multilayer stretched film, multilayer unstretched film, laminate film, shrink film,
Stretch film, wrap film, protect film, retort film, porous film, barrier film, metallized film, agricultural film Sheet and sheet molded products: wallpaper, foam sheet, electric wire coating, prester packaging, tray, stationery, food containers, toy,
Cosmetic containers, medical equipment, detergent containers, flooring materials, cushion floors, decorative sheets, shoe soles Blow products: bottles Extruded products: tubes, wire coating, cable coating, pipes,
Gasket Fiber: Fiber, flat yarn Non-woven and non-woven products: Non-woven fabric, filter Injection: Automotive interior skin material, automotive exterior material, daily necessities, home appliances, caps, containers, pallets Modifier: adhesive, lubrication Oil additives, hot melt adhesives, toner release agents, pigment dispersants, asphalt modifiers Others: sealants, vacuum molded products, powder slush products

[0166]

According to the present invention, it is possible to obtain a molded article having an excellent balance among transparency, impact resistance, flexibility, heat resistance, scratch resistance and the like.

[0167]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.

Hereinafter, physical test conditions and the like will be described. 1. Tensile modulus (Young modulus); JIS K
Measured at 23 ° C. using a JIS No. 3 dumbbell at a span distance of 30 mm and a pulling speed of 30 mm / min in accordance with 6301. 2. Martens hardness (1 / mm): Using a Martens hardness scratch hardness tester manufactured by Tokyo Ikki, a groove width generated when a sample having a thickness of 3 mm was scratched by applying a load of 20 g of a scratch indenter to the test piece, The reciprocal was calculated. 3. Needle penetration temperature (° C); in accordance with JIS K7196,
Using a test piece having a thickness of 2 mm, a pressure of ² kg / cm ² was applied to a 1.8 mmφ plane indenter at a heating rate of 5 ° C./min, and the needle entry temperature (° C.) was determined from a TMA curve. 4. Haze (%): Digital turbidimeter (NDH-20D) manufactured by Nippon Denshoku Industries Co., Ltd., using a test piece having a thickness of 1 mm.
Was measured. 5. Melting point (Tm) and glass transition temperature (Tg); DS
An endothermic curve of C is obtained, and the temperature at the maximum peak position is defined as Tm.

For the measurement, the sample was packed in an aluminum pan,
The temperature was raised to 200 ° C. at a rate of 200 ° C./min.
It was determined from an endothermic curve when the temperature was raised at 0 ° C./min.

6. Intrinsic viscosity [η]: measured at 135 ° C. in decalin. 7. Molecular weight distribution (Mw / Mn): measured at 140 ° C. in an orthodichlorobenzene solvent using GPC (gel permeation chromatography).

[0171]

[Synthesis Example 1] Syndiotactic polypropylene
According to the method described in adult Hei 2-274763 discloses, using diphenylmethylene (cyclopentadienyl) catalysts consisting of fluorenyl zirconium dichloride and methylaluminoxane, syndiotactic by bulk polymerization of propylene in the presence of hydrogen Tic polypropylene was obtained. The resulting syndiotactic polypropylene has a melt flow index of 4.4 g / 10 min.
The molecular weight distribution by PC was 2.3, and the syndiotactic triad fraction measured by ¹³ C-NMR was 0.1.
823, and the Tm measured by differential scanning calorimetry was 12
7 ° C. and Tc was 57 ° C.

[0172]

Synthesis Example 2 Synthesis of α-Olefin Polymer In a 1.5-liter autoclave dried under reduced pressure and purged with nitrogen, 750 ml of heptane was added at room temperature, followed by triisobutylaluminum (hereinafter abbreviated as “TIBA”). 0.3 ml of a 0 mmol / ml toluene solution was added so that the aluminum atom became 0.3 mmol,
Under agitation, 30 liters (propylene, 25 ° C., 1 atm) of propylene were charged, and the temperature was raised to reach 60 ° C. Thereafter, the inside of the system was pressurized with ethylene to 5.9 kg / cm ² G, and (dimethyl (t-butylamide) (tetramethyl-η ⁵ -cyclopentadienyl) silane) dichloride titanium was synthesized by a known method. Toluene solution (0.0001
mM / ml) and 2.0 ml of a toluene solution of (triphenylcarbenium tetra (pentafluorophenyl) borate (0.001 mM / ml) were added.
Copolymerization of propylene and ethylene was started. The catalyst concentration at this time was 0.0005 mmol / liter of (dimethyl (t-butylamide) (tetramethyl-η ⁵ -cyclopentadienyl) silane) dichloride titanium and triphenylcarbenium tetra (penta (Fluorophenyl) borate was 0.002 mmol / l. During the polymerization, the internal pressure was maintained at 5.9 kg / cm ² G by continuously supplying ethylene. After 15 minutes, the polymerization reaction was stopped by adding methyl alcohol. After depressurization, the polymer solution was taken out and washed with an aqueous solution obtained by adding 5 ml of concentrated hydrochloric acid to 1 liter of water at a ratio of 1: 1 to transfer the catalyst residue to the aqueous phase. After the contact mixed solution was allowed to stand, the aqueous phase was separated and removed, and further washed twice with distilled water to separate the polymerization liquid phase from oil and water. Next, the polymer liquid phase separated from the oil and water was brought into contact with a three-fold amount of acetone under vigorous stirring to precipitate a polymer, and then thoroughly washed with acetone, and a solid part (copolymer) was collected by filtration. It dried at 130 degreeC and 350 mmHg for 12 hours under nitrogen flow.

The yield of the atactic propylene / ethylene copolymer obtained as described above was 29 g,
The intrinsic viscosity [η] measured in decalin at 135 ° C. is 3.2.
dl / g, a glass transition temperature (Tg) of −22 ° C., an ethylene content of 16.0 mol%, and an activity of 3
It was 10 kg / mmol Zr · hr, and the molecular weight distribution by GPC was 2.6. The Young's modulus was 3 MPa.

[0174]

Synthesis Example 3 Synthesis of α-Olefin Polymer To a 1.5 liter autoclave dried under reduced pressure and purged with nitrogen, 750 ml of heptane was added at room temperature, and then a 1.0 mmol / ml toluene solution of TIBA was added to an aluminum atom. 0.3 ml so that becomes 0.3 mmol
In addition, 28 liters of propylene (25
(1 ° C., 1 atm), and the temperature was raised to reach 60 ° C. Thereafter, the system was pressurized with ethylene to 5.9 kg / cm ² G, and toluene of rac-dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl) zirconium dichloride synthesized by a known method was used. Solution (0.0001
(mM / ml) and 9.38 ml of a toluene solution of methylaluminoxane (0.01 mM / ml) were added to initiate copolymerization of propylene and ethylene. The catalyst concentration at this time was rac-dimethylsilylene-
Bis ｛1- (2-methyl-4-phenylindenyl) zirconium dichloride was 0.0005 mmol / liter and methylaluminoxane was 0.125 mmol / liter. During the polymerization, the internal pressure was maintained at 5.9 kg / cm ² G by continuously supplying ethylene. After 15 minutes, the polymerization reaction was stopped by adding methyl alcohol. After depressurization, the polymer solution was taken out and washed with an aqueous solution obtained by adding 5 ml of concentrated hydrochloric acid to 1 liter of water at a ratio of 1: 1 to transfer the catalyst residue to the aqueous phase. After the contact mixed solution was allowed to stand, the aqueous phase was separated and removed, and further washed twice with distilled water to separate the polymerization liquid phase from oil and water. Next, the polymer liquid phase separated from the oil and water was brought into contact with a three-fold amount of acetone under vigorous stirring to precipitate a polymer, and then thoroughly washed with acetone, and a solid part (copolymer) was collected by filtration. It dried at 130 degreeC and 350 mmHg for 12 hours under nitrogen flow.

The yield of the isotactic propylene / ethylene copolymer obtained as described above was 26 g, the intrinsic viscosity [η] measured in decalin at 135 ° C. was 2.8 dl / g, and the glass transition Temperature Tg is -47 ° C
The ethylene content was 30.0 mol%, the activity was 276 kg / mmol Zr · hr, and the molecular weight distribution by GPC was 2.7.

Although the melting peak measured by DSC was observed, it was broad, but could not be quantified. The Young's modulus was 3 MPa.

[0177]

Synthesis Example 4 Synthesis of α-Olefin Polymer In a 1.5-liter autoclave dried under reduced pressure and purged with nitrogen, 750 ml of heptane was added at room temperature, and then a 1.0 mmol / ml toluene solution of TIBA was added to an aluminum atom. Then, 0.3 ml was added so that the amount became 0.3 mmol, and propylene was added to 50.7 with stirring.
Liter (25 ° C, 1 atm)
° C was reached. Then 5.5 kg of ethylene in the system
/ Cm ² G, and a solution of diphenylmethylene (cyclopentadienyl) fluorenylzirconium dichloride in heptane (0.00%) synthesized by a known method.
3.75 ml of (02 mM / ml), (triphenylcarbenium tetra (pentafluorophenyl) borate)
2.0 ml of toluene solution (0.002 mM / ml)
In addition, copolymerization of propylene and ethylene was started. The catalyst concentration at this time was 0.001 mmol / liter of diphenylmethylene (cyclopentadienyl) fluorenyl zirconium dichloride and 0.004 mmol / liter of triphenylcarbenium tetra (pentafluorophenyl) borate with respect to the whole system. Liters.

During the polymerization, the internal pressure was maintained at 5.5 kg / cm ² G by continuously supplying ethylene. Thirty minutes after the start of the polymerization, the polymerization reaction was stopped by adding methyl alcohol. After depressurization, the polymer solution was taken out, and the polymer solution was washed with an aqueous solution obtained by adding 5 ml of concentrated hydrochloric acid to 1 liter of water at a ratio of 1: 1. Transferred to the aqueous phase. After the catalyst mixed solution was allowed to stand, the aqueous phase was separated and removed, and further washed twice with distilled water, and the polymerization liquid phase was separated into oil and water. Next, the polymer liquid phase separated from the oil and water was brought into contact with a three-fold amount of acetone under vigorous stirring to precipitate a polymer, which was thoroughly washed with acetone, and a solid part (copolymer) was collected by filtration. 130 ° C, 350mmH under nitrogen flow
g for 12 hours.

The yield of the syndiotactic propylene / ethylene copolymer obtained as described above was 50 g, the intrinsic viscosity [η] measured in decalin at 135 ° C. was 2.4 dl / g, and the glass transition Temperature Tg is -28 ° C
And an ethylene content of 24.0 mol%, GPC
The molecular weight distribution (Mw / Mn) measured by was 2.9. Young's modulus was 2 MPa. Also,
Under the above-mentioned DSC measurement conditions, a melting peak was not substantially observed.

[0180]

Synthesis Example 5 Synthesis of α-Olefin Polymer In a 1.5-liter autoclave dried under reduced pressure and purged with nitrogen, 710 ml of heptane was added at room temperature, and then a 1.0 mmol / ml toluene solution of TIBA was added to aluminum atom. Then, 1.0 ml was added so that the amount became 1.0 mmol, and 25 g of 1-butene was inserted with stirring, and the temperature was raised to 30 ° C. Thereafter, the system was pressurized with propylene to a pressure of 6.0 kg / cm ² G, and (dimethyl (t-butylamide) (tetramethyl-η ⁵ -cyclopentadienyl) silane) dichloride titanium was synthesized by a known method. Solution in toluene (0.01 mM
/ Ml) and 4.5 ml of a toluene solution of methylaluminoxane (1 mM / ml) were added to initiate copolymerization of propylene and 1-butene. At this time, the catalyst concentration was (dimethyl (t-butylamide)
(Tetramethyl-η ⁵ -cyclo-pentadienyl) silane
The amount of titanium dichloride was 0.01 mmol / l, and that of methylaluminoxane was 6.0 mmol / l.

During the polymerization, propylene is continuously supplied.
And the internal pressure is 6.0 kg / cm. ^TwoG. Heavy
15 minutes after the start of the polymerization, the polymerization reaction
The addition was stopped. After depressurizing, remove the polymer solution
Take out the polymer solution and add 1 liter of water
Aqueous solution to which 5 ml of concentrated hydrochloric acid was added)
Wash the polymer solution using the
Was moved to. After allowing this catalyst mixed solution to stand, the aqueous phase
, And washed twice with distilled water.
Water separated. Next, the polymerization liquid phase separated from the oil-water is 3 times
With strong agitation to precipitate the polymer
After that, the solid part (copolymer) is sufficiently washed with acetone and filtered.
Collected by excess. 130 ° C, 350mm under nitrogen flow
Dried at Hg for 12 hours.

The yield of the atactic propylene / butene copolymer obtained as described above was 130 g,
The intrinsic viscosity [η] measured in decalin at 135 ° C. is 1.1.
dl / g, glass transition temperature (Tg) was -8 ° C, butene content was 6.2 mol%, and molecular weight distribution (Mw / Mn) measured by GPC was 2.8. The Young's modulus was 5 MPa. In addition, the aforementioned D
Under the SC measurement conditions, substantially no melting peak was observed.

[0183]

Synthesis Example 6 Synthesis of α-Olefin Polymer In a 1.5 liter autoclave dried under reduced pressure and purged with nitrogen, 675 ml of heptane was added at room temperature, and then a 1.0 mmol / ml toluene solution of TIBA was added to an aluminum atom. Then, 1.0 ml was added so that the amount became 1.0 mmol, and 30 g of 1-butene was added with stirring.
It was inserted and the temperature was raised to reach 30 ° C. Thereafter, the system was pressurized with propylene to 6.0 kg / cm ² G, and a toluene solution of diphenylmethylene (cyclopentadienyl) fluorenylzirconium dichloride (0.01 mM / ml) synthesized by a known method. 0.75m
l, methylaluminoxane in toluene solution (1.0 mM
/ Ml) was added to initiate copolymerization of propylene and 1-butene. At this time, the catalyst concentration was 0.01 mmol / L for diphenylmethylene (cyclopentadienyl) fluorenylzirconium dichloride and 6.0 mmol / L for methylaluminoxane with respect to the whole system.

During the polymerization, propylene is continuously supplied.
And the internal pressure is 6.0 kg / cm. ^TwoG. Heavy
15 minutes after the start of the polymerization, the polymerization reaction
The addition was stopped. After depressurizing, remove the polymer solution
Take out the polymer solution and add 1 liter of water
Aqueous solution to which 5 ml of concentrated hydrochloric acid was added)
Wash the polymer solution using the
Was moved to. After allowing this catalyst mixed solution to stand, the aqueous phase
, And washed twice with distilled water.
Water separated. Next, the polymerization liquid phase separated from the oil-water is 3 times
With strong agitation to precipitate the polymer
After that, the solid part (copolymer) is sufficiently washed with acetone and filtered.
Collected by excess. 130 ° C, 350mm under nitrogen flow
Dried at Hg for 12 hours.

The yield of the syndiotactic propylene / butene copolymer thus obtained was 75 g, the intrinsic viscosity [η] measured at 135 ° C. in decalin was 2.7 dl / g, and the glass transition Temperature Tg is -5.3
° C, the heat of fusion is 20 J / g, the butene content is 11 mol, and the molecular weight distribution (M
w / Mn) was 2.4. Young's modulus is 1
It was 45 MPa.

[0186]

Synthesis Example 7 Synthesis of α-Olefin Polymer To a 1.5-liter autoclave dried under reduced pressure and purged with nitrogen, 535 ml of heptane was added at room temperature, and then a 1.0 mmol / ml toluene solution of TIBA was added to an aluminum atom. 0.23 ml was added so that the amount became 0.3 mmol in terms of, and 1-octene was added to 15
After inserting 0 g, the temperature was raised and reached 30 ° C. Thereafter, the system was pressurized with propylene to 6.0 kg / cm ² G, and a toluene solution of diphenylmethylene (cyclopentadienyl) fluorenylzirconium dichloride synthesized by a known method synthesized by a known method ( 0.0
0.75 ml of (1 mM / ml) and 1.5 ml of a toluene solution of (triphenylcarbenium tetra (pentafluorophenyl) borate) (0.02 mM / ml) were added to initiate copolymerization of propylene and 1-octene. At this time, the concentration of the catalyst was 0.01 mmol / liter of diphenylmethylene (cyclopentadienyl) fluorenylzirconium dichloride and (triphenylcarbenium tetra (pentafluorophenyl) borate) with respect to the whole system.
Was 0.04 mmol / l.

During the polymerization, propylene is continuously supplied.
And the internal pressure is 6.0 kg / cm. ^TwoG. Heavy
15 minutes after the start of the polymerization, the polymerization reaction
The addition was stopped. After depressurizing, remove the polymer solution
Take out the polymer solution and add 1 liter of water
Aqueous solution to which 5 ml of concentrated hydrochloric acid was added)
Wash the polymer solution using the
Was moved to. After allowing this catalyst mixed solution to stand, the aqueous phase
, And washed twice with distilled water.
Water separated. Next, the polymerization liquid phase separated from the oil-water is 3 times
With strong agitation to precipitate the polymer
After that, the solid part (copolymer) is sufficiently washed with acetone and filtered.
Collected by excess. 130 ° C, 350mm under nitrogen flow
Dried at Hg for 12 hours.

The yield of the syndiotactic propylene / octene copolymer thus obtained was 53 g, the intrinsic viscosity [η] measured in decalin at 135 ° C. was 2.7 dl / g, and the glass transition Temperature Tg is -18 ° C
The octene content was 18 mol, and the molecular weight distribution (Mw / Mn) measured by GPC was 2.4.
Young's modulus was 2 MPa. Further, under the above-mentioned DSC measurement conditions, a melting peak was not substantially observed.

[0189]

Example 1 70 parts by weight of the syndiotactic polypropylene obtained in Synthesis Example 1 and the atactic propylene / ethylene copolymer 30 obtained in Synthesis Example 2
Parts by weight and 0.02 parts by weight of a sorbitol-based crystal nucleating agent (trade name: Gelol MD, manufactured by Shin Nippon Riken)
The mixture was melt-kneaded to obtain a soft syndiotactic polypropylene composition.

[0190]

Example 2 In Example 1, the atactic propylene / ethylene copolymer obtained in Synthesis Example 2 was replaced with
Using the isotactic propylene / ethylene copolymer obtained in Synthesis Example 3, except that the amount of syndiotactic polypropylene was 50 parts by weight and the amount of the isotactic propylene / ethylene copolymer was 50 parts by weight. In the same manner as in Example 1, a soft syndiotactic polypropylene-based composition was obtained.

[0191]

Example 3 In Example 1, instead of the atactic propylene / ethylene copolymer obtained in Synthesis Example 2,
Syndiotactic propylene obtained in Synthesis Example 4
A soft syndiotactic polymer was prepared in the same manner as in Example 1 except that the amount of syndiotactic polypropylene was 60 parts by weight and the amount of syndiotactic propylene / ethylene copolymer was 40 parts by weight using an ethylene copolymer. A tick polypropylene composition was obtained.

[0192]

Example 4 In Example 1, instead of the atactic propylene / ethylene copolymer obtained in Synthesis Example 2,
A soft syndiotactic polypropylene-based composition was obtained in the same manner as in Example 1, except that the atactic propylene / ethylene copolymer obtained in Synthesis Example 5 was used.

[0193]

Example 5 In Example 1, instead of the atactic propylene / ethylene copolymer obtained in Synthesis Example 2,
Syndiotactic propylene obtained in Synthesis Example 6
A soft syndiotactic polymer was prepared in the same manner as in Example 1 except that the amount of syndiotactic polypropylene was 10 parts by weight and the amount of syndiotactic propylene / ethylene copolymer was 90 parts by weight using a butene copolymer. A tick polypropylene composition was obtained.

[0194]

Example 6 In Example 1, instead of the atactic propylene / ethylene copolymer obtained in Synthesis Example 2,
Syndiotactic propylene obtained in Synthesis Example 7
A soft syndiotactic polypropylene composition was obtained in the same manner as in Example 1 except that the octene copolymer was used.

[0195]

Comparative Example 1 A polypropylene composition was obtained in the same manner as in Example 1, except that the sorbitol crystal nucleating agent was not used.

[0196]

Comparative Example 2 A polypropylene composition was obtained in the same manner as in Example 2 except that the sorbitol crystal nucleating agent was not used.

[0197]

Comparative Example 3 A polypropylene composition was obtained in the same manner as in Example 3, except that the sorbitol crystal nucleating agent was not used.

[0198]

Comparative Example 4 A polypropylene composition was obtained in the same manner as in Example 4, except that the sorbitol crystal nucleating agent was not used.

[0199]

Comparative Example 5 A polypropylene composition was obtained in the same manner as in Example 5, except that the sorbitol crystal nucleating agent was not used.

[0200]

Comparative Example 6 A soft syndiotactic polypropylene composition was obtained in the same manner as in Example 6, except that the sorbitol crystal nucleating agent was not used.

The physical properties of the polypropylene compositions obtained in the above Examples and Comparative Examples were measured. Table 2 shows the results.

[0202]

[Table 2]

Continued on the front page (72) Inventor Kazuyoshi Kaneko 1-2-1, Waki, Waki-cho, Kuga-gun, Yamaguchi Prefecture F-term in Mitsui Chemicals, Inc. (reference) 4J002 BB02X BB11X BB12W BB14W BB16X EL106 EW046 FD206 GG02 4J028 AA01A AB00A AB01A AC01A AC08A AC09A AC26A AC27A AC45A AC49A BA00A BA01B BA02B BA03B BB00A BB01B BB02B BC12B BC15B BC16B BC17B BC19B BC25B BC27B EB02 EB04 EB05 EB07 EB08 EB09 EB10 EC18 EB13 EB14

Claims (5)

[Claims] (A) a repeating unit (a) derived from propylene having a substantially syndiotactic structure and, if necessary, a repeating unit (b) derived from ethylene and / or 4 to 20 carbon atoms. Wherein the repeating unit (a) is contained in a proportion of 90 to 100 mol%, and the repeating unit (b) is contained in a proportion of 0 to 10 mol%. Unit (c) is contained at a ratio of 0 to 9.5 mol%, and the intrinsic viscosity [η] measured in decalin at 135 ° C. is 0.5 to 10 d.
1 / g; and (B) at least one kind of a repeating unit derived from an α-olefin selected from α-olefins having 2 to 20 carbon atoms; An α-olefin polymer containing one or more kinds of repeating units at a ratio of 50 to 100 mol% and a Young's modulus of 150 MPa or less, and (C) a crystal nucleating agent, Weight ratio of syndiotactic propylene polymer (A) to the α-olefin polymer (B)） (A) /
(B)｝ is in the range of 90/10 to 10/90, and the crystal nucleating agent (100 parts by weight of the total amount of the syndiotactic propylene polymer (A) and the α-olefin polymer (B) ( A soft syndiotactic polypropylene composition containing C) in an amount of 0.01 to 1 part by weight. 2. The (A) syndiotactic propylene polymer has a syndiotacticity of 0.6 or more as viewed from the triad chain of propylene, and the α-olefin polymer (B) has a decalinicity of 135 ° C. Intrinsic viscosity [η] measured in solution is 0.01 to 10 dl /
g, the molecular weight distribution (Mw / Mn) determined by gel permeation chromatography is 4 or less, the glass transition temperature is -5 ° C or less, and the (C) crystal nucleating agent is a sorbitol-based crystal. The soft syndiotactic polypropylene-based composition according to claim 1, which is a nucleating agent. 3. The (B) α-olefin polymer has at least one kind selected from α-olefins having 3 to 20 carbon atoms in a proportion of 50 to 99 mol% of repeating units derived from ethylene. The flexible syndiotactic polypropylene-based composition according to claim 1 or 2, which is a copolymer containing a repeating unit derived from an α-olefin of 1 to 50 mol%. 4. The (B) α-olefin polymer comprises at least one repeating unit derived from propylene in an amount of 50 to 99 mol% and selected from ethylene and α-olefins having 4 to 20 carbon atoms. 3. A copolymer containing a repeating unit derived from the above α-olefin in a proportion of 1 to 50 mol%.
2. The soft syndiotactic polypropylene-based composition according to item 1. 5. The (B) α-olefin polymer is
(A) a transition metal compound represented by the following general formula (I) or (II), and (b) (b-1) the transition metal compound (a)
A metallocene catalyst comprising at least one compound selected from the group consisting of a compound which reacts with a transition metal M in the compound to form an ionic complex, (b-2) an organic aluminum oxy compound, and (b-3) an organic aluminum compound 5. The composition obtained in the presence of
A soft syndiotactic polypropylene composition according to any of the above, (In the formulas (I) and (II), M is Ti, Zr, Hf, R
n, Nd, Sm or Ru, Cp ¹ and Cp ²
Is a cyclopentadienyl group, an indenyl group, a fluorenyl group or a derivative thereof bonded to M by π, and X ¹ and X ² are an anionic ligand or a neutral Lewis base ligand. , Y is a ligand containing a nitrogen atom, an oxygen atom, a phosphorus atom or a sulfur atom, and Z is a C, O, B, S, Ge, Si or Sn atom or a group containing these atoms . )