JP2001172325A - Propylene-based polymer and resin composition and molded article comprising the polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a propylene-based polymer which yields a molded article which is not too sticky and which has excellent softness and transparency. SOLUTION: The propylene-based polymer satisfies the following conditions (1) and (2): (1) the polymer has 0-80 mass % of a component soluble in hexane at 25 deg.C; (2) the polymer shows no melting point (Tm( deg.C)) or has a Tm and an endothermic heat of fusion, ΔH, which satisfy ΔH>=6×(Tm-140).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a propylene polymer, a resin composition comprising the polymer, a molded product and a resin modifier, and more particularly, to a resin composition having less stickiness and excellent softness and transparency. The present invention relates to a propylene-based polymer giving a molded article, a resin composition comprising the polymer, a molded article and a resin modifier.

[0002]

2. Description of the Related Art Conventionally, vinyl chloride resin has been widely used as a soft resin, but it is known that vinyl chloride resin generates harmful substances in the burning process, and it is strongly desired to develop a substitute. It is rare. As a substitute for the soft vinyl chloride resin, there is a propylene-based polymer. Propylene-based polymers are produced in the presence of various catalysts. However, propylene-based polymers produced using conventional catalyst systems have many sticky components when trying to be soft (that is, those with low elastic modulus). There was a drawback that it would be. The APP component, which is a cause of the sticky component, increases, and the surface characteristics of the obtained molded article deteriorate. In addition, when developing a molded article in the form of a sheet or film into food, medical use, etc.,
Various problems may occur. Therefore, a propylene-based polymer in which the balance between the low elastic modulus and the amount of the sticky component is improved is desired.

[0003]

DISCLOSURE OF THE INVENTION The present invention relates to a propylene-based polymer which gives a molded article having low stickiness and excellent softness and transparency, a resin composition comprising the polymer, a molded article and a resin modification. It is intended to provide an agent.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies in order to achieve the above object, and as a result, (1) 25 ° C.
The amount of the component eluted in hexane is in a specific range, and (2) a propylene-based polymer that does not show a melting point or shows a melting point in a DSC measurement and the melting point and the melting endotherm satisfy a specific relationship. The present inventors have found that the amount of the sticky component, the low elastic modulus and the balance of transparency are excellent, and the present invention has been completed. That is, the present invention provides the following propylene-based polymer, a resin composition comprising the polymer, a molded product, and a resin modifier. 1. A propylene-based polymer satisfying the following (1) and (2). (1) The amount of the component (H25) eluted in hexane at 25 ° C. is 0 to 80% by mass. (2) In the DSC measurement, if the melting point (Tm (° C.)) is not shown or Tm is shown, Tm is used. Endotherm of melting ΔH
(J / g) satisfies the following relationship: ΔH ≧ 6 × (Tm-140) 2. The propylene-based polymer according to the above 1, wherein the amount of the component (W25) eluted at 25 ° C. or lower in the temperature rising chromatography is 20 to 100% by mass. 3. A propylene homopolymer satisfying the following (1) to (3). (1) The mesopentad fraction (mmmm) is 20 to 60 mol%. (2) The racemic pentad fraction (rrrr) and (1-mm)
mmr) satisfies the following relationship: [rrrr / (1-mmmm)] ≦ 0.1 (3) The component amount (W25) eluted at 25 ° C. or lower in the temperature rising chromatography is 20 to 100% by mass. 4. The propylene homopolymer according to the above 3, wherein the pentad fraction (rmrm) exceeds 2.5 mol%. 5. The propylene homopolymer according to the above 3 or 4, wherein the mesotriad fraction (mm), the racemic triad fraction (rr), and the triad fraction (mr) satisfy the following relationship.

(Mm) × (rr) / (mr) ² ≦ 2.0 A propylene copolymer satisfying the following (1) and (2). (1) The stereoregularity index (P) determined by ¹³ C-NMR measurement is 55 to 90 mol%. (2) The component amount (W25) eluted at 25 ° C. or lower in the temperature rising chromatography is 20 to 100 mass%. Yes 7. Gel permeation chromatograph (GPC)
Any of the above 3 to 5, wherein the molecular weight distribution (Mw / Mn) measured by the method is 4 or less and / or the intrinsic viscosity [η] measured in a tetralin solvent at 135 ° C. is 0.5 to 15.0 deciliter / g. 7. A propylene homopolymer or a propylene-based copolymer according to 6 above. 8. (A) reacts with a transition metal compound represented by the following general formula (I) and (B) (B-1) the transition metal compound of the component (A) or a derivative thereof to form an ionic complex. The propylene homopolymer according to any one of the above 3 to 5 or 7, which is obtained by polymerizing propylene in the presence of a polymerization catalyst containing a compound selected from (B-2) an aluminoxane and a compound to be obtained.

[0006]

Embedded image

[Wherein, M is a member of Groups 3 to 10 of the periodic table or La
E represents a tanthanoid metal element ¹And E^TwoIs it
Substituted cyclopentadienyl group, indenyl group, substituted
Indenyl group, heterocyclopentadienyl group,
Telocyclopentadienyl group, amide group, phosphide
Ligand selected from the group consisting of a group, a hydrocarbon group and a silicon-containing group
And A¹And A^TwoTo form a crosslinked structure via
And they may be the same or different
X represents a σ-binding ligand, and when there are a plurality of Xs,
A plurality of X may be the same or different, and other X,
E¹, E^TwoAlternatively, it may be crosslinked with Y. Y is Lewis salt
A plurality of Y are the same or different
Other Y, E¹, E^TwoOr cross-linked with X
May be, A¹And A^TwoIs the two that binds the two ligands
A divalent crosslinking group, a hydrocarbon group having 1 to 20 carbon atoms,
A halogen-containing hydrocarbon group having a prime number of 1 to 20, a silicon-containing group,
Germanium-containing groups, tin-containing groups, -O-, -CO-,
-S-, -SO_Two-, -Se-, -NR¹-, -PR¹
-, -P (O) R¹-, -BR¹-Or-AlR¹-
And R¹Is a hydrogen atom, a halogen atom, a carbon number of 1 to 20
A hydrocarbon group or a halogen-containing hydrocarbon having 1 to 20 carbon atoms
Denote radicals, which may be the same or different
Good. q is an integer of 1 to 5 and represents ((valence of M) -2).
And r represents an integer of 0 to 3. 9. (A) a transition metal compound represented by the following general formula (I)
And (B) (B-1) a transition metal compound of the component (A)
Reacts with substances or their derivatives to form ionic complexes
Compounds selected from the group consisting of
And ethylene in the presence of a polymerization catalyst containing
And / or α-olefin having 4 to 20 carbon atoms
9. The propion according to 6 or 7 above,
Len copolymer.

[0008]

Embedded image

[Wherein, M is group 3 to 10 of the periodic table or La
E represents a tanthanoid metal element ¹And E^TwoIs it
Substituted cyclopentadienyl group, indenyl group, substituted
Indenyl group, heterocyclopentadienyl group,
Telocyclopentadienyl group, amide group, phosphide
Ligand selected from the group consisting of a group, a hydrocarbon group and a silicon-containing group
And A¹And A^TwoTo form a crosslinked structure via
And they may be the same or different
X represents a σ-binding ligand, and when there are a plurality of Xs,
A plurality of X may be the same or different, and other X,
E¹, E^TwoAlternatively, it may be crosslinked with Y. Y is Lewis salt
A plurality of Y are the same or different
Other Y, E¹, E^TwoOr cross-linked with X
May be, A¹And A^TwoIs the two that binds the two ligands
A divalent crosslinking group, a hydrocarbon group having 1 to 20 carbon atoms,
A halogen-containing hydrocarbon group having a prime number of 1 to 20, a silicon-containing group,
Germanium-containing groups, tin-containing groups, -O-, -CO-,
-S-, -SO_Two-, -Se-, -NR¹-, -PR¹
-, -P (O) R¹-, -BR¹-Or-AlR¹-
And R¹Is a hydrogen atom, a halogen atom, a carbon number of 1 to 20
A hydrocarbon group or a halogen-containing hydrocarbon having 1 to 20 carbon atoms
Denote radicals, which may be the same or different
Good. q is an integer of 1 to 5 and represents ((valence of M) -2).
And r represents an integer of 0 to 3. 10. The propylene-based weight according to any one of 1 to 9 above.
Coalesce, propylene homopolymer or propylene copolymer
A propylene-based resin composition obtained by adding a nucleating agent to a body. 11. The propylene system according to any one of the above 1 to 10
Polymer, propylene homopolymer, propylene copolymer
Or a molded product obtained by molding a propylene-based resin composition. 12. The propylene-based polymerization according to any one of the above 1 to 9
, Propylene homopolymer or propylene copolymer
A propylene-based resin modifier comprising

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The propylene-based polymer [1] of the present invention, its production method [2], the propylene-based resin composition [3] and the molded article [4] and the propylene-based resin modifier [5] ] Will be described in detail. [1] Propylene-based polymer The propylene-based polymer of the present invention is a polymer that requires the following (1) and (2). (1) The amount of the component (H25) eluted in hexane at 25 ° C. is 0 to 80% by mass. (2) In the DSC measurement, if the melting point (Tm (° C.)) is not shown or Tm is shown, Tm is used. Endotherm of melting ΔH
(J / g) satisfies the following relationship: ΔH ≧ 6 × (Tm-140) The propylene-based polymer of the present invention has a component amount (H25) eluted in hexane at 25 ° C. of 0 to 80% by mass. It is preferably from 0 to 50% by mass, particularly preferably from 0 to 25% by mass. H25 is an index indicating whether the amount of a so-called sticky component that causes stickiness and a decrease in transparency is large or small, and a higher value indicates a larger amount of the sticky component. When H25 exceeds 80% by mass, the amount of the sticky component is large, and the blocking resistance and the transparency are lowered, so that it cannot be used for foods and medical products.

Incidentally, H25 means the mass (W ₀ ) of the propylene polymer and the polymer in 200 mL of hexane.
After drying at 25 ° C for 3 days or more, mass after drying (W ₁ )
Is measured and calculated by the following equation. H25 = [(W ₀ −W ₁ ) / W ₀ ] × 100 (%) Further, the propylene polymer of the present invention does not show a melting point (Tm (° C.)) or shows Tm in DSC measurement. In this case, Tm and the melting endothermic amount ΔH satisfy the following relationship.

ΔH ≧ 6 × (Tm−140) More preferably, ΔH ≧ 3 × (Tm−120), and particularly preferably ΔH ≧ 2 × (Tm−100).

Note that Tm and ΔH are obtained by DSC measurement. That is, using a differential scanning calorimeter (manufactured by Perkin-Elmer, DSC-7), 10 mg of a sample was melted at 230 ° C. for 3 minutes in a nitrogen atmosphere, and then 0 ° C. at 10 ° C./min.
Cool down to Furthermore, after holding at 0 ° C. for 3 minutes, 10
The peak top of the maximum peak of the melting endothermic curve obtained by increasing the temperature at a rate of ° C./min is the melting point: Tm, and the melting endotherm in this case is ΔH.

By satisfying the above relationship, the propylene-based polymer of the present invention has an excellent balance between the amount of the sticky component of the obtained molded article, the low elastic modulus and the transparency. That is, the elastic modulus is low, the softness (also called flexibility) is excellent, the sticky component is small, and the surface characteristics (for example, the transfer of the sticky component to bleed and other products are small) are excellent, and There is an advantage that transparency is also excellent.

[0015] The propylene polymer of the present invention has the above-mentioned requirements and 25 ° C.
Component amount of propylene polymer eluted below (W25)
Is preferably 20 to 100% by mass. More preferably, 30 to 100% by mass, particularly preferably 50% by mass.
１００100% by mass. W25 is an index indicating whether or not the propylene-based polymer is soft. When this value is increased, it means that the component having a high elastic modulus is increased and / or the non-uniformity of the stereoregularity distribution is widened. In the present invention, if W25 is less than 20%, flexibility may be lost, which is not preferable. W25 refers to the amount of the component eluted without being adsorbed by the packing material at a TREF column temperature of 25 ° C. in an elution curve obtained by measuring with a temperature rising chromatography using the following operation method, apparatus configuration, and measurement conditions. (% By mass). (A) Operation method The sample solution was introduced into a TREF column adjusted to a temperature of 135 ° C., and then gradually cooled to 0 ° C. at a rate of 5 ° C./hour, and held for 30 minutes to crystallize the sample on the surface of the filler. Let it. Thereafter, the column was heated at a heating rate of 40 ° C./hour for 1 column.
The temperature is raised to 35 ° C. to obtain an elution curve. (B) Apparatus configuration TREF column: Silica gel column (4.6 mm x 150 mm) manufactured by GL Sciences Flow cell: 1 mm optical path length KBr cell manufactured by GL Sciences Pump: SSC-3100 pump manufactured by Senshu Kagaku Valve oven: GL Sciences Model 554 oven (high temperature type) TREF oven: GL Science's two-line temperature controller: Rigaku Corporation REX-C100 temperature controller Detector: Infrared detector for liquid chromatography FOXBORO's MIRAN 1A CVF 10-way valve : Barco electric valve loop: Barco 500 microliter loop (c) Measurement conditions Solvent: o-dichlorobenzene Sample concentration: 7.5 g / liter Injection volume: 500 microliter Pump flow rate: 2.0 ml / min Detection Number: 3.41 μm Column filler: Chromosolve P (30-60 mesh) Column temperature distribution: Within ± 0.2 ° C. The propylene polymer of the present invention is not particularly limited as long as it satisfies the above requirements. And a propylene homopolymer and a propylene-based copolymer. In particular, the propylene-based polymer of the present invention described above is more preferably realized by the following [a] propylene homopolymer or [a '] propylene copolymer.

[A] Propylene homopolymer The propylene homopolymer of the present invention has the following (1) to
It is a polymer that requires (3). (1) The mesopentad fraction (mmmm) is 20 to 60 mol%, and (2) the racemic pentad fraction (rrrr) and (1-mm)
mm) satisfies the following relationship, and [rrrr / (1-mmmm)] ≦ 0.1 (3) The amount of the component (W25) eluted at 25 ° C. or lower in the temperature rising chromatography is 20 to 100% by mass. When the propylene homopolymer of the present invention satisfies the above-mentioned relationship, the balance between the amount of the sticky component, the low elastic modulus, and the transparency of the obtained molded article is excellent. That is, the elastic modulus is low, the softness (also called flexibility) is excellent, the sticky component is small, and the surface characteristics (for example, the transfer of the sticky component to bleed and other products are small) are excellent, and There is an advantage that transparency is also excellent.

The mesopendad fraction (mmmm fraction) used in the present invention is defined by A. Zambb (A. Zamb).
elli) et al., "Macromolecules,
6 , 925 (1973) ",
It is a meso fraction in pentad units in a polypropylene molecular chain measured by a signal of a methyl group in a ¹³ C-NMR spectrum. When this is increased, it means that stereoregularity is increased. If the propylene homopolymer of the present invention has a mesopentad fraction (mmmm) of less than 20 mol%, it causes stickiness. If it exceeds 60 mol%, the elastic modulus is undesirably high. Similarly, the racemic pentad fraction (rrrr fraction) is a racemic fraction in pentad units in a polypropylene molecular chain. [Rrrr / (1
−mmmm)] is an index obtained from the above-mentioned fraction in pentad units and representing the uniformity of the regularity distribution of the propylene homopolymer. When this value is increased, the regularity distribution is widened, and a mixture of highly ordered PP and APP is obtained as in the case of conventional polypropylene produced using an existing catalyst system, which means that stickiness increases and transparency decreases. The propylene homopolymer of the present invention [rrrr / (1
-Mmmm)] exceeds 0.1, causing stickiness. The measurement of the ¹³ C-NMR spectrum was performed by A. Zambelli et al.
moleculars, 8 , 687 (1975) "according to the assignment of peaks, using the following apparatus and conditions.

Apparatus: JNM-EX40 manufactured by JEOL Ltd.
Type 0 ¹³ C-NMR apparatus Method: Proton complete decoupling method Concentration: 220 mg / mL Solvent: 90:10 (volume ratio) mixed solvent of 1,2,4-trichlorobenzene and heavy benzene Temperature: 130 ° C. Pulse width: 45 ° Pulse repetition time: 4 seconds Integration: 10000 times Next, W for the propylene homopolymer in the present invention
The meaning and measurement method of 25 are the same as those in the above-mentioned propylene-based polymer [1]. When W25 of the propylene homopolymer in the present invention is less than 20%,
Lack of flexibility.

The propylene homopolymer of the present invention has the following (4) mesopentad fraction (mmm
m) is 30 to 50%, and (5) the racemic pentad fraction (rrrr) and (1-mmmm) satisfy the following relationship, [rrrr / (1-mmmm)] ≦ 0.08 and ( 6) It is more preferable that the amount (W25) of the component eluted at 25 ° C. or lower in the temperature raising chromatography be 30 to 100% by mass, and (7) the racemic pentad fraction (rrrr) and (1-mmmm) Satisfies the following relationship: [rrrr / (1-mmmm)] ≦ 0.06 and (8) the component amount (W25) eluted at 25 ° C. or lower in the temperature rising chromatography is 50 to 100% by mass. It is particularly preferable to satisfy the following. (9) The racemic pentad fraction (rrrr) and (1-mmmm) satisfy the following relationship, [rrrr / (1-mmmm)] ≦ 0.05, and (10) 25 ° C. in temperature rising chromatography
Component amount (W25) eluted below is 60 to 100% by mass
It is most preferable to satisfy the following.

The propylene homopolymer of the present invention preferably has a pentad fraction (rmrm) of more than 2.5 mol%. When the pentad fraction (rmrm) exceeds 2.5 mol%, the randomness increases and the transparency further improves. Furthermore, mesotriad fraction (mm), racemic triad fraction (rr), triad fraction (mr)
That satisfy the following relationship is preferable.

(Mm) × (rr) / (mr) ² ≦ 2.0 This relationship indicates an index of the randomness of the polymer. Excellent balance of recovery rate. In the propylene homopolymer of the present invention, the value on the left side of the above formula is usually 2 or less, preferably 1.8 to 0.5, and more preferably 1.5 to 0.5. The triad fraction is determined in the same manner as the pentad fraction.

In addition to the above requirements, the propylene homopolymer of the present invention has a molecular weight distribution (Mw / Mn) of 4 or less as measured by a gel permeation (GPC) method and / or is measured at 135 ° C. in a tetralin solvent. The intrinsic viscosity [η] is preferably 0.5 to 15.0 deciliter / g.
Mn is 3.5 or less and / or [η] is more preferably 1.0 to 5.0 deciliter / g, and Mw / Mn is 3 or less and / or [η] is 1.0 to 3.0 deciliter / g. Is particularly preferred. More preferably, [η] is 1.5.
~ 3.0 deciliter / g, particularly preferably 2.0 ~
2.5 deciliters / g. Molecular weight distribution (Mw / M
If n) exceeds 4, stickiness may occur, and if the intrinsic viscosity [η] is less than 0.5 deciliter / g, stickiness may occur. On the other hand, if it exceeds 15.0 deciliters / g, the fluidity is reduced and the moldability may be poor.

The above Mw / Mn is a value calculated from a mass average molecular weight Mw and a number average molecular weight Mn in terms of polyethylene measured by gel permeation chromatography (GPC) using the following apparatus and conditions. GPC measuring device Column: TOSO GMHHR-H (S) HT Detector: RI detector for liquid chromatogram WATERS 150C Measurement conditions Solvent: 1,2,4-trichlorobenzene Measurement temperature: 145 ° C. Flow rate: 1.0 ml / min Sample concentration: 2.2 mg / milliliter Injection amount: 160 microliter Calibration curve: Universal Calibration Analysis program: HT-GPC (Ver. 1.0) Furthermore, the propylene homopolymer of the present invention has, in addition to the above requirements, Melting endotherm ΔH by DSC measurement is 20 J / g
The following is preferred because of excellent flexibility. ΔH is an index indicating whether the material is soft or not, and when this value is increased, it means that the elastic modulus is high and the softness is low. Note that Δ
H is determined by the above method.

Furthermore, the propylene homopolymer of the present invention may or may not have a melting point (Tm) and a crystallization temperature (Tc), but it has no softness or has a low value, especially about Tm. The temperature is preferably 100 ° C. or lower. Note that Tm and Tc are determined by DSC measurement. That is, using a differential scanning calorimeter (DSC-7, manufactured by Perkin-Elmer Co., Ltd.), 10 mg of a sample is melted at 230 ° C. for 3 minutes in a nitrogen atmosphere, and then the temperature is lowered to 0 ° C. at 10 ° C./min. The peak top of the maximum peak of the crystallization exothermic curve obtained at this time is the crystallization temperature: Tc. Further, after holding at 0 ° C. for 3 minutes, the temperature is raised at a rate of 10 ° C./min, and the melting peak: Tm is the peak top of the maximum peak of the melting endothermic curve.

In general, during the polymerization of propylene, the carbon atom on the methylene side of the propylene monomer is bonded to the active site of the catalyst, and the propylene monomer is coordinated and polymerized in the same manner in the order of 1,2. Polymerization of insertion is usually performed, but rarely, 2,1 insertion or 1,3 insertion (also referred to as abnormal insertion) may occur. The homopolymer of the present invention preferably has a small amount of the 2,1 or 1,3 insertion. The ratio of these insertions is expressed by the following relational expression (1) [(m−2,1) + (r−2,1) + (1,3)] ≦ 5.0 (%) (1) [Wherein (m-2,1) is the meso-2,1 insertion content (%) measured by ¹³ C-NMR, and (r-2,1) is the ¹³ C-N
Racemic-2,1 insertion content (%) measured by MR,
(1,3) indicates the 1,3 insertion content (%) measured by ¹³ C-NMR. Is preferable, and the relational expression (2) [(m−2,1) + (r−2,1) + (1,3)] ≦ 1.0 (%) (2) Satisfaction is more preferable. In particular, those satisfying the relational expression (3) [(m−2, 1) + (r−2, 1) + (1, 3)] ≦ 0.1 (%) (3) are most preferable. This relational expression (1)
If not, the crystallinity may be reduced more than expected, which may cause stickiness.

(M-2,1), (r-2,1) and (1,3) are reported by Grassi et al. (Macromolucule).
s, 21 , p. 617 (1988)) and a report by Busico et al. (Macromolucules, 27 , p. 7538 (1994)).
It is each insertion content determined from the integral intensity of each peak after the assignment of the peak of the ¹³ C-NMR spectrum was determined. That is, (m−2,1) is Pα, γthreth that appears around 17.2 ppm with respect to the integrated intensity in the entire methyl carbon region.
It is the meso-2,1 insertion content (%) calculated from the ratio of the integrated intensity of the peak attributed to o. (R-2,1) is
15.0p for integrated intensity in all methyl carbon region
It is the racemic-2,1 insertion content (%) calculated from the ratio of the integrated intensities of the peaks belonging to Pα and γthreo appearing near pm. (1, 3) is Tβ, which appears near 31.0 ppm relative to the integrated intensity in the entire methine carbon region.
1,3 insertion content (%) calculated from the ratio of the integrated intensity of peaks belonging to γ +.

Furthermore, the propylene homopolymer of the present invention
More preferably, in the measurement of the ¹³ C-NMR spectrum, a peak substantially not observed at the molecular chain end (n-butyl group) derived from the 2,1 insertion is observed. This two
For the molecular chain ends from one insertion, see Jungli
ng et al. (J. Polym. Sci .: Part A: Po1ym. C
^{hem., 33, 13 C-} NMR based on p1305 (1995))
The assignment of peaks in the spectrum is determined, and each insertion content is calculated from the integrated intensity of each peak. In the case of isotactic polypropylene, a peak appearing at about 18.9 ppm is assigned to the unsubstituted methyl group carbon of the n-butyl group.
In addition, ¹³ C-NM for abnormal insertion or molecular chain end measurement
The measurement of R may be performed with the above-described apparatus and conditions.

Further, in addition to the above requirements, the propylene homopolymer of the present invention preferably further has a boiling diethyl ether extraction amount, which is an index of the elastic modulus, of 5% by mass or more. The boiling diethyl ether extraction amount is measured using a Soxhlet extractor under the following conditions.

Extracted sample: 1 to 2 g Sample shape: powder (Pellets are crushed,
Extraction solvent: diethyl ether Extraction time: 10 hours Number of extractions: 180 or more Extraction amount calculation method: Calculated by the following formula. [Extraction amount to diethyl ether (g) / prepared powder mass (g)] × 100 In addition to the above, the propylene homopolymer of the present invention preferably further has a tensile modulus of 100 MPa or less. Preferably it is 70 MPa or less.

[A '] Propylene copolymer The propylene copolymer of the present invention has the following (1) to
It is a copolymer of propylene and ethylene and / or an α-olefin having 4 to 20 carbon atoms, which requires (2). (1) The stereoregularity index (P) determined by ¹³ C-NMR measurement is 55 to 90 mol%, and (2) the amount of the component eluted at 25 ° C. or lower in temperature rising chromatography (W25)
When the propylene-based copolymer of the present invention satisfies the above relationship, the obtained molded product has an excellent balance between the amount of the sticky component, the low elastic modulus, and the transparency. In other words, it has a low elastic modulus, is excellent in softness (also called flexibility), has few sticky components, and has excellent surface characteristics (e.g., represented by little transfer of sticky components to bleed and other products), and It has the feature of being excellent in transparency. The stereoregularity index (P) in the present invention is the same as JNM-E manufactured by JEOL Ltd.
This is a value obtained by measuring a ¹³ C-NMR spectrum using an X400 type NMR apparatus under the same conditions as above and measuring a mesotriad (mm) fraction of a propylene chain. The larger this value is, the higher the stereoregularity is. The propylene copolymer of the present invention more preferably has a stereoregularity index (P) of 65 to 80 mol%. When the stereoregularity index (P) is less than 55 mol%, the elasticity is too low, resulting in poor moldability. On the other hand, if it exceeds 90 mol%, it becomes hard and not soft. W25 is 3
The content is more preferably 0 to 100% by mass, and 50 to 10% by mass.
It is particularly preferred that the content be 0% by mass. When W25 is less than 20%, flexibility is lost. The meaning of W25 and the measuring method are the same as described above.

Further, the propylene copolymer of the present invention has a gel permeation (GPC) in addition to the above requirements.
The molecular weight distribution (Mw / Mn) measured by the method is 4 or less and / or the intrinsic viscosity [η] measured at 135 ° C. in a tetralin solvent is preferably 0.5 to 15.0 deciliter / g, and the Mw / Mn is 3 .5 or less and / or [η] is 1.0
~ 5.0 deciliter / g is more preferable, and Mw / M
It is particularly preferable that n is 3 or less and / or [η] is 1.0 to 3.0 deciliter / g. If the molecular weight distribution (Mw / Mn) exceeds 4, stickiness may occur. If the intrinsic viscosity [η] is less than 0.5 deciliters / g, stickiness may occur, and if it exceeds 15.0 deciliters / g, the fluidity may be reduced, resulting in poor moldability. The method of measuring Mw / Mn is the same as described above.

Further, in addition to the above requirements, the propylene-based copolymer of the present invention has a melting endothermic amount Δ
When H is 20 J / g or less, flexibility is excellent and preferable. Further, a melting point (Tm) and a crystallization temperature (Tc) may or may not be present, but it is preferable that the resin does not have softness or has a low value, particularly, Tm is 100 ° C. or less. The measuring methods of ΔH, Tm and Tc are the same as described above.

In addition to the above requirements, the propylene copolymer of the present invention preferably further has a boiling diethyl ether extraction amount, which is an index of the elastic modulus, of 5% by mass or more.
The measurement of the amount of boiling diethyl ether extracted was the same as described above.

The tensile modulus is preferably 100 MPa or less, more preferably 70 MPa or less. Regarding the propylene-based copolymer in the present invention, the α-olefin having 4 to 20 carbon atoms is ethylene, 1-
Butene, 1-pentene, 4-methyl-1-pentene, 1
-Hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and the like. In the present invention, one or more of these are used be able to.

Further, the propylene-based copolymer of the present invention is preferably a random copolymer. Further, the structural unit obtained from propylene is preferably at least 90 mol%, more preferably at least 95 mol%.

[Method for producing propylene homopolymer (a) and propylene copolymer (a ')] The method for producing the propylene homopolymer (a) and the propylene copolymer (a') in the present invention is as follows. And a method of homopolymerizing propylene using a catalyst system called a metallocene catalyst or a method of copolymerizing propylene with ethylene and / or an α-olefin having 4 to 20 carbon atoms. Examples of metallocene-based catalysts include JP-A-58-19309, JP-A-61-130314, JP-A-3-1630088, JP-A-4-300877, and JP-A-4-21.
Transition having one or two ligands such as a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, and a substituted indenyl group as described in JP-A No. 1694, JP-A No. 1-50203, and the like. Examples include a metal compound and a catalyst obtained by combining a promoter with a transition metal compound in which the ligand is geometrically controlled.

In the present invention, among the metallocene catalysts, it is preferable that the ligand is composed of a transition metal compound forming a crosslinked structure via a crosslinking group.
A method of homopolymerizing propylene using a metallocene catalyst obtained by combining a transition metal compound forming a crosslinked structure via two crosslinking groups with a cocatalyst, or propylene and ethylene and / or α having 4 to 20 carbon atoms -A method of copolymerizing an olefin is more preferred. To give a concrete example, (A) general formula (I)

[0038]

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[Wherein M is a group 3 to 10 of the periodic table or La
E represents a tanthanoid metal element ¹And E^TwoIs it
Substituted cyclopentadienyl group, indenyl group, substituted
Indenyl group, heterocyclopentadienyl group,
Telocyclopentadienyl group, amide group, phosphide
Ligand selected from the group consisting of a group, a hydrocarbon group and a silicon-containing group
And A¹And A^TwoTo form a crosslinked structure via
And they may be the same or different
X represents a σ-binding ligand, and when there are a plurality of Xs,
A plurality of X may be the same or different, and other X,
E¹, E^TwoAlternatively, it may be crosslinked with Y. Y is Lewis salt
A plurality of Y are the same or different
Other Y, E¹, E^TwoOr cross-linked with X
May be, A¹And A^TwoIs the two that binds the two ligands
A divalent crosslinking group, a hydrocarbon group having 1 to 20 carbon atoms,
A halogen-containing hydrocarbon group having a prime number of 1 to 20, a silicon-containing group,
Germanium-containing groups, tin-containing groups, -O-, -CO-,
-S-, -SO_Two-, -Se-, -NR¹-, -PR¹
-, -P (O) R¹-, -BR¹-Or-AlR¹-
And R¹Is a hydrogen atom, a halogen atom, a carbon number of 1 to 20
A hydrocarbon group or a halogen-containing hydrocarbon having 1 to 20 carbon atoms
Denote radicals, which may be the same or different
Good. q is an integer of 1 to 5 and represents ((valence of M) -2).
And r represents an integer of 0 to 3. Transition metallization represented by
And (B) Transition metallization of the component (B-1) (A)
Reacts with the compound or its derivative to form an ionic complex
And (B-2) aluminoxane
Propylene alone in the presence of a polymerization catalyst containing
Polymerization method, or propylene and ethylene and / or
Is a method of copolymerizing an α-olefin having 4 to 20 carbon atoms
Is mentioned.

In the general formula (I), M represents a metal element belonging to Groups 3 to 10 of the periodic table or a lanthanoid series;
Specific examples include titanium, zirconium, hafnium, yttrium, vanadium, chromium, manganese, nickel, cobalt, palladium, and lanthanoid-based metals. Of these, titanium, zirconium, and hafnium are preferable in terms of olefin polymerization activity. It is suitable. E ¹ and E ² represent a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a heterocyclopentadienyl group, a substituted heterocyclopentadienyl group, an amide group (-N <), and a phosphine group (-P <),
Hydrocarbon group [>CR-,> C <] and silicon-containing group [> S
iR-,> Si <] (where R is hydrogen or carbon number 1 to
20 hydrocarbon groups or hetero atom-containing groups), and forms a crosslinked structure via A ¹ and A ² . E ¹ and E ² may be the same or different. As E ¹ and E ² , a substituted cyclopentadienyl group, an indenyl group and a substituted indenyl group are preferred.

X represents a σ-binding ligand, and when there are a plurality of Xs, a plurality of Xs may be the same or different and are cross-linked to other X, E ¹ , E ² or Y. You may.
Specific examples of X include a halogen atom, a carbon number of 1 to 20.
Hydrocarbon group, C1-C20 alkoxy group, C6-C20 aryloxy group, C1-C20 amide group, C1-C20 silicon-containing group, C1-C20 phosphide Group, sulfide group having 1 to 20 carbon atoms, 1 carbon atom
And 20 acyl groups. On the other hand, Y represents a Lewis base, and when there are a plurality of Ys, the plurality of Ys may be the same or different, and may be crosslinked with other Y, E ¹ , E ² or X. Specific examples of the Lewis base of Y include amines, ethers, phosphines, thioethers and the like.

Next, A ¹ and A ² are divalent bridging groups for bonding two ligands, and are a hydrocarbon group having 1 to 20 carbon atoms and a halogen-containing hydrocarbon group having 1 to 20 carbon atoms. , Silicon-containing group, germanium-containing group, tin-containing group, -O-, -C
O -, - S -, - SO 2 -, - Se -, - NR 1 -, -
PR ^1- , -P (O) R ^1- , -BR ¹ -or -AlR
¹ - shows a, R ¹ represents a hydrogen atom, a hydrocarbon group having a halogen atom or having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, they may be the same with or different from each other. As such a crosslinking group, for example, a general formula

[0043]

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(R ² and R ³ are each a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, which may be the same or different, and are bonded to each other to form a ring structure. And e represents an integer of 1 to 4. Specific examples thereof include methylene, ethylene, ethylidene, propylidene, isopropylidene, cyclohexylidene, and the like. 1,2-cyclohexylene group, vinylidene group (CH ₂ ＣC =), dimethylsilylene group, diphenylsilylene group, methylphenylsilylene group, dimethylgermylene group, dimethylstannylene group, tetramethyldisilylene group, diphenyldisilylene And the like. Among them, an ethylene group, an isopropylidene group and a dimethylsilylene group are preferred. q is an integer of 1 to 5 [(valence of M)-
2], and r represents an integer of 0 to 3.

In the transition metal compound represented by the formula (I), when E ¹ and E ² are a substituted cyclopentadienyl group, an indenyl group or a substituted indenyl group,
The bond of the crosslinking group of ¹ and A ² is (1,2 ′) (2,
1 ') Double cross-linking type is preferred. Such a general formula (I)
Among the transition metal compounds represented by the general formula (II)

[0046]

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A transition metal compound having a double-bridged biscyclopentadienyl derivative represented by the following formula as a ligand is preferable. In the general formula (II), M, A ¹ , A ² , q and r are the same as above. X ¹ represents a σ-bonding ligand, and when plural X ^1, a plurality of X ¹ may be the same or different, may be crosslinked with other X ¹ or Y ^1. Specific examples of X ¹ are the same as those exemplified in the description of X in the general formula (I). Y
¹ represents a Lewis base, and when there are a plurality of Y ¹ ,
¹ may be the same or different, and may be crosslinked with another Y ¹ or X ¹ . Specific examples of Y ¹ include the same as those exemplified in the description of Y in the general formula (I). R ^{4 to} R ⁹ each represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms,
The halogen-containing hydrocarbon group, the silicon-containing group or the hetero atom-containing group, at least one of which must not be a hydrogen atom. R ^{4 to} R ⁹ may be the same or different, and adjacent groups may be bonded to each other to form a ring. In particular, it is preferable that R ⁶ and R ⁷ form a ring, and that R ⁸ and R ⁹ form a ring. As R ⁴ and R ⁵ , groups containing a heteroatom such as oxygen, halogen, silicon and the like are preferable because of their high polymerization activity.

The transition metal compound having the double-bridged biscyclopentadienyl derivative as a ligand preferably has a (1,2 ') (2,1') double-bridged ligand. Specific examples of the transition metal compound represented by the general formula (I) include:
(1,2′-ethylene) (2,1′-ethylene) -bis (indenyl) zirconium dichloride, (1,2′-ethylene)
Methylene) (2,1′-methylene) -bis (indenyl) zirconium dichloride, (1,2′-isopropylidene) (2,1′-isopropylidene) -bis (indenyl) zirconium dichloride, (1,2′- Ethylene) (2,1′-ethylene) -bis (3-methylindenyl) zirconium dichloride, (1,2′-ethylene) (2,1′-ethylene) -bis (4,5-benzoindenyl) zirconium Dichloride, (1,2′-ethylene) (2,1′-ethylene) -bis (4-isopropylindenyl) zirconium dichloride, (1,2′-
Ethylene) (2,1′-ethylene) -bis (5,6-dimethylindenyl) zirconium dichloride, (1,
2′-ethylene) (2,1′-ethylene) -bis (4
7-diisopropylindenyl) zirconium dichloride, (1,2′-ethylene) (2,1′-ethylene)-
Bis (4-phenylindenyl) zirconium dichloride, (1,2′-ethylene) (2,1′-ethylene)-
Bis (3-methyl-4-isopropylindenyl) zirconium dichloride, (1,2′-ethylene) (2
1'-ethylene) -bis (5,6-benzoindenyl)
Zirconium dichloride, (1,2'-ethylene)
(2,1′-isopropylidene) -bis (indenyl)
Zirconium dichloride, (1,2'-methylene)
(2,1′-ethylene) -bis (indenyl) zirconium dichloride, (1,2′-methylene) (2,1′-
(Isopropylidene) -bis (indenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2
1'-dimethylsilylene) bis (indenyl) zirconium dichloride, (1,2'-dimethylsilylene)
(2,1′-dimethylsilylene) bis (3-methylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (3
-N-butylindenyl) zirconium dichloride,
(1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (3-i-propylindenyl) zirconium dichloride, (1,2′-dimethylsilylene)
(2,1′-dimethylsilylene) bis (3-trimethylsilylmethylindenyl) zirconium dichloride,
(1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (3-phenylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2
1'-dimethylsilylene) bis (4,5-benzoindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) bis (4-
Isopropylindenyl) zirconium dichloride,
(1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (5,6-dimethylindenyl) zirconium dichloride, (1,2′-dimethylsilylene)
(2,1′-dimethylsilylene) bis (4,7-di-i
-Propylindenyl) zirconium dichloride,
(1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (4-phenylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2
1'-dimethylsilylene) bis (3-methyl-4-i-
Propylindenyl) zirconium dichloride, (1,
2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (5,6-benzoindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1 ′
-Isopropylidene) -bis (indenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2
1'-isopropylidene) -bis (3-methylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-isopropylidene) -bis (3-
i-propylindenyl) zirconium dichloride,
(1,2′-dimethylsilylene) (2,1′-isopropylidene) -bis (3-n-butylindenyl) zirconium dichloride, (1,2′-dimethylsilylene)
(2,1′-isopropylidene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride,
(1,2′-dimethylsilylene) (2,1′-isopropylidene) -bis (3-trimethylsilylindenyl)
Zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-isopropylidene) -bis (3-phenylindenyl) zirconium dichloride, (1,2 ′
-Dimethylsilylene) (2,1′-methylene) -bis (indenyl) zirconium dichloride, (1,2′-
Dimethylsilylene) (2,1′-methylene) -bis (3
-Methylindenyl) zirconium dichloride, (1,
2'-dimethylsilylene) (2,1'-methylene) -bis (3-i-propylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-methylene) -bis (3- (n-butylindenyl) zirconium dichloride, (1,2′-dimethylsilylene)
(2,1′-methylene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride, (1,
2′-dimethylsilylene) (2,1′-methylene) -bis (3-trimethylsilylindenyl) zirconium dichloride, (1,2′-diphenylsilylene) (2
1'-methylene) -bis (indenyl) zirconium dichloride, (1,2'-diphenylsilylene) (2
1′-methylene) -bis (3-methylindenyl) zirconium dichloride, (1,2′-diphenylsilylene) (2,1′-methylene) -bis (3-i-propylindenyl) zirconium dichloride, (1 , 2'-Diphenylsilylene) (2,1'-methylene) -bis (3
-N-butylindenyl) zirconium dichloride,
(1,2′-diphenylsilylene) (2,1′-methylene) -bis (3-trimethylsilylmethylindenyl)
Zirconium dichloride, (1,2′-diphenylsilylene) (2,1′-methylene) -bis (3-trimethylsilylindenyl) zirconium dichloride,
2′-dimethylsilylene) (2,1′-dimethylsilylene) (3-methylcyclopentadienyl) (3′-methylcyclopentadienyl) zirconium dichloride,
(1,2′-dimethylsilylene) (2,1′-isopropylidene) (3-methylcyclopentadienyl) (3 ′
-Methylcyclopentadienyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-ethylene) (3-methylcyclopentadienyl) (3′-methylcyclopentadienyl) zirconium dichloride,
(1,2′-ethylene) (2,1′-methylene) (3-
Methylcyclopentadienyl) (3′-methylcyclopentadienyl) zirconium dichloride, (1,2′-
Ethylene) (2,1′-isopropylidene) (3-methylcyclopentadienyl) (3′-methylcyclopentadienyl) zirconium dichloride, (1,2′-methylene) (2,1′-methylene) ( 3-methylcyclopentadienyl) (3′-methylcyclopentadienyl) zirconium dichloride, (1,2′-methylene) (2
1'-isopropylidene) (3-methylcyclopentadienyl) (3'-methylcyclopentadienyl) zirconium dichloride, (1,2'-isopropylidene)
(2,1′-isopropylidene) (3-methylcyclopentadienyl) (3′-methylcyclopentadienyl)
Zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) (3,4-dimethylcyclopentadienyl) (3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride, (1 ,
2'-dimethylsilylene) (2,1'-isopropylidene) (3,4-dimethylcyclopentadienyl)
(3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride, (1,2′-dimethylsilylene)
(2,1′-ethylene) (3,4-dimethylcyclopentadienyl) (3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride, (1,2′-ethylene) (2,1′-methylene ) (3,4-Dimethylcyclopentadienyl) (3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride, (1,2′-ethylene) (2,1′-isopropylidene) (3,4- Dimethylcyclopentadienyl) (3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride,
2′-methylene) (2,1′-methylene) (3,4-dimethylcyclopentadienyl) (3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride,
(1,2′-methylene) (2,1′-isopropylidene) (3,4-dimethylcyclopentadienyl)
(3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride, (1,2′-isopropylidene)
(2,1′-isopropylidene) (3,4-dimethylcyclopentadienyl) (3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride, (1,2′-
Dimethylsilylene) (2,1'-dimethylsilylene)
(3-methyl-5-ethylcyclopentadienyl)
(3′-methyl-5′-ethylcyclopentadienyl)
Zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) (3-methyl-5
-Ethylcyclopentadienyl) (3'-methyl-5 '
-Ethylcyclopentadienyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) (3-methyl-5-isopropylcyclopentadienyl) (3'-methyl-5'- Isopropylcyclopentadienyl) zirconium dichloride,
(1,2′-dimethylsilylene) (2,1′-dimethylsilylene) (3-methyl-5-n-butylcyclopentadienyl) (3′-methyl-5′-n-butylcyclopentadienyl) Zirconium dichloride, (1,2'-
Dimethylsilylene) (2,1'-dimethylsilylene)
(3-methyl-5-phenylcyclopendienyl)
(3′-methyl-5′-phenylcyclopentadienyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-isopropylidene) (3-methyl-5-ethylcyclopentadienyl) ( 3'-methyl-
5'-ethylcyclopentadienyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-
Isopropylidene) (3-methyl-5-i-propylcyclopentadienyl) (3′-methyl-5′-i-propylcyclopentadienyl) zirconium dichloride,
(1,2′-dimethylsilylene) (2,1′-isopropylidene) (3-methyl-5-n-butylcyclopentadienyl) (3′-methyl-5′-n-butylcyclopentadienyl) Zirconium dichloride, (1,2'-
Dimethylsilylene) (2,1'-isopropylidene)
(3-methyl-5-phenylcyclopentadienyl)
(3′-methyl-5′-phenylcyclopentienyl)
Zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-ethylene) (3-methyl-5-ethylcyclopentadienyl) (3′-methyl-5′-ethylcyclopentadienyl) zirconium dichloride ,
(1,2′-dimethylsilylene) (2,1′-ethylene) (3-methyl-5-i-propylcyclopentadienyl) (3′-methyl-5′-i-propylcyclopentadienyl) zirconium Dichloride, (1,2′-dimethylsilylene) (2,1′-ethylene) (3-methyl-5-n-butylcyclopentadienyl) (3′-methyl-5′-n-butylcyclopentadienyl) ) Zirconium dichloride, (1,2′-dimethylsilylene)
(2,1′-ethylene) (3-methyl-5-phenylcyclopentadienyl) (3′-methyl-5′-phenylcyclopentadienyl) zirconium dichloride,
(1,2′-dimethylsilylene) (2,1′-methylene) (3-methyl-5-ethylcyclopentadienyl)
(3′-methyl-5′-ethylcyclopentienyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-methylene) (3-methyl-5-i-propylcyclopentadienyl) ( 3'-methyl-5'-
i-propylcyclopentadienyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-
Methylene) (3-methyl-5-n-butylcyclopentadienyl) (3′-methyl-5′-n-butylcyclopentadienyl) zirconium dichloride, (1,2′-
Dimethylsilylene) (2,1′-methylene) (3-methyl-5-phenylcyclopentadienyl) (3′-methyl-5′-phenylcyclopentadienyl) zirconium dichloride, (1,2′-ethylene) (2,1′-methylene) (3-methyl-5-i-propylcyclopentadienyl) (3′-methyl-5′-i-propylcyclopentadienyl) zirconium dichloride, (1,2 ′
-Ethylene) (2,1′-isopropylidene) (3-methyl-5-i-propylcyclopentadienyl) (3 ′
-Methyl-5'-i-propylcyclopentadienyl)
Zirconium dichloride, (1,2'-methylene)
(2,1′-methylene) (3-methyl-5-i-propylcyclopentadienyl) (3′-methyl-5′-i-
Propylcyclopentadienyl) zirconium dichloride, (1,2′-methylene) (2,1′-isopropylidene) (3-methyl-5-i-propylcyclopentadienyl) (3′-methyl-5′- Examples thereof include (i-propylcyclopentadienyl) zirconium dichloride and those obtained by substituting zirconium in these compounds with titanium or hafnium. Of course, it is not limited to these. Further, a similar compound of a metal element of another group or a lanthanoid series may be used.

Next, as the component (B-1) of the component (B), any compound which can react with the transition metal compound of the above component (A) to form an ionic complex can be used. The following general formulas (III), (IV) ([L ¹ −R ¹⁰ ] ^{k +} ) _a ([Z] ⁻ ) _b ... (III) ([L ² ] ^{k +} ) _a ([Z] ^-) _b ··· (IV) (provided that, L ² is ^{M 2, R 11 R 12 M} 3, R 13 3 C or R
A ¹⁴ M ^3. In the formulas (III) and (IV), L ¹ is a Lewis base, and [Z] ⁻ is
Non-coordinating anion [Z ^{1] -} and [Z ^{2] -,} wherein [Z ^{1] -} anion in which a plurality of groups are bonded to the element ^{[M 1 G 1 G 2 ··· G} f ] ^- ( Here, M ¹ is an element belonging to Groups 5 to 15 of the periodic table, preferably ^{13 to 1} of the periodic table.
Shows Group 5 elements. G ^{1 to} G ^f each represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, and a carbon atom having 2 to 4 carbon atoms.
0 dialkylamino group, C1-C20 alkoxy group, C6-C20 aryl group, C6-C20 aryloxy group, C7-C40 alkylaryl group, C7-C40 Arylalkyl group, 1 to 1 carbon atoms
A halogen-substituted hydrocarbon group of 20; an acyloxy group of 1 to 20 carbon atoms; an organic metalloid group; or a heteroatom-containing hydrocarbon group of 2 to 20 carbon atoms. 2 out of G ^{1 to} G ^f
One or more may form a ring. f is [(center metal M
Represents an integer of ¹ valence) +1]. ), [Z ² ] ^-
A conjugate base of a Bronsted acid alone or a combination of a Bronsted acid and a Lewis acid having a logarithm (pKa) of the reciprocal of the acid dissociation constant of −10 or less, or a conjugate base of an acid generally defined as a super strong acid is shown. Further, a Lewis base may be coordinated. Also, R ¹⁰ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group or an arylalkyl group, R ¹¹ and R ¹²
Represents a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group or a fluorenyl group, and R ¹³ represents an alkyl group having 1 to 20 carbon atoms, an aryl group, an alkylaryl group or an arylalkyl group. R ¹⁴ represents a macrocyclic ligand such as tetraphenylporphyrin and phthalocyanine. k is an ionic valence of [L ¹ -R ¹⁰ ] and [L ² ], an integer of 1 to 3, a is an integer of 1 or more, and b = (k × a). M ² contains an element from Groups 1 to ³ , 11 to 13, and 17 of the periodic table, and M ³ represents an element from Groups 7 to 12 of the periodic table. ] Can be suitably used.

Here, specific examples of L ¹ include ammonia, methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine,
Amines such as N, N-dimethylaniline, trimethylamine, triethylamine, tri-n-butylamine, methyldiphenylamine, pyridine, p-bromo-N, N-dimethylaniline, p-nitro-N, N-dimethylaniline, and triethylphosphine Phosphines such as triphenylphosphine and diphenylphosphine; thioethers such as tetrahydrothiophene; esters such as ethyl benzoate; and nitriles such as acetonitrile and benzonitrile.

Specific examples of R ¹⁰ include hydrogen, methyl group, ethyl group, benzyl group, and trityl group. Specific examples of R ¹¹ and R ¹² include cyclopentadienyl group, methylcyclopentane Examples thereof include a dienyl group, an ethylcyclopentadienyl group, and a pentamethylcyclopentadienyl group. Specific examples of R ¹³ include a phenyl group, a p-tolyl group, a p-methoxyphenyl group and the like, and specific examples of R ¹⁴ include a tetraphenylporphine, phthalocyanine, allyl, methallyl and the like. . Specific examples of M ² include Li, Na, K, Ag, Cu, Br, I, and I _3. Specific examples of M ³ include Mn, F
e, Co, Ni, Zn and the like.

[Z ¹ ] ^- , that is, [M ¹ G ¹ G
² ... G ^f ], B and A are specific examples of M ^1.
l, Si, P, As, Sb, etc., preferably B and Al
Is mentioned. Specific examples of G ¹ , G ^{2 to} G ^f include dimethylamino and diethylamino as dialkylamino groups, and methoxy, ethoxy, n-butoxy groups as alkoxy or aryloxy groups.
Methyl, ethyl, n-propyl, isopropyl, n-butyl, etc.
Fluorine, chlorine, bromine, halogen atoms such as isobutyl group, n-octyl group, n-eicosyl group, phenyl group, p-tolyl group, benzyl group, 4-t-butylphenyl group and 3,5-dimethylphenyl group; Iodine, a p-fluorophenyl group as a hetero atom-containing hydrocarbon group, 3,5
-Difluorophenyl group, pentachlorophenyl group,
Organic metalloid groups such as 3,4,5-trifluorophenyl group, pentafluorophenyl group, 3,5-bis (trifluoromethyl) phenyl group, bis (trimethylsilyl) methyl group, etc. as pentamethylantimony group, trimethylsilyl group, trimethyl Examples include a germyl group, a diphenylarsine group, a dicyclohexylantimony group, and diphenylboron.

In addition, a non-coordinating anion, ie, pKa
Specific examples of the conjugated base [Z ² ] ⁻ of a Brönsted acid alone or a combination of a Brönsted acid and a Lewis acid having a -10 or less are trifluoromethanesulfonic acid anion (CF ₃ SO ₃ ) ⁻ , bis (trifluoromethanesulfonyl) ) Methyl anion, bis (trifluoromethanesulfonyl) benzyl anion, bis (trifluoromethanesulfonyl) amide, perchlorate anion (Cl
O ₄ ) ^- , trifluoroacetic acid anion (CF ₃ CO ₂ )
^- , Hexafluoroantimony anion (Sb
F ₆ ) ^- , fluorosulfonic acid anion (FS
O ₃ ) ^- , chlorosulfonic acid anion (ClS
O ₃ ) ^- , fluorosulfonate anion / 5-antimony fluoride (FSO ₃ / SbF ₅ ) ^- , fluorosulfonate anion / 5-arsenic fluoride (FSO ₃ / As)
F ₅₎ ^-, trifluoromethanesulfonic acid / antimony pentafluoride _{(CF 3 SO 3 / SbF 5} ) - and the like.

Specific examples of such an ionic compound which reacts with the transition metal compound of the component (A) to form an ionic complex, that is, the compound of the component (B-1) include:
Triethylammonium tetraphenylborate, tri-n-butylammonium tetraphenylborate, trimethylammonium tetraphenylborate, tetraethylammonium tetraphenylborate, methyl (tri-n-butyl) ammonium tetraphenylborate, benzyltetraphenylborate (tri-n- Butyl) ammonium, dimethyldiphenylammonium tetraphenylborate, triphenyl (methyl) ammonium tetraphenylborate, trimethylanilinium tetraphenylborate, methylpyridinium tetraphenylborate, benzylpyridinium tetraphenylborate, methyl 2-phenylopyridinium Triethylammonium, tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate ) Tri-n-butylammonium borate, triphenylammonium tetrakis (pentafluorophenyl) borate, tetra-n-butylammonium tetrakis (pentafluorophenyl) borate, tetraethylammonium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) Benzyl (tri-n-butyl) ammonium borate, methyldiphenylammonium tetrakis (pentafluorophenyl) borate, triphenyl (methyl) ammonium tetrakis (pentafluorophenyl) borate, methylanilinium tetrakis (pentafluorophenyl) borate, tetrakis (pentane) Dimethylanilinium fluorophenyl) borate, trimethylanilinium tetrakis (pentafluorophenyl) borate, tetrakis Methylpyridinium pentafluorophenyl) borate, benzylpyridinium tetrakis (pentafluorophenyl) borate, methyl (2-cyanopyridinium) tetrakis (pentafluorophenyl) borate, benzyl (2-cyanopyridinium) tetrakis (pentafluorophenyl) borate, tetrakis ( Methyl pentafluorophenyl) borate (4-cyanopyridinium), triphenylphosphonium tetrakis (pentafluorophenyl) borate, dimethylanilinium tetrakis [bis (3,5-ditrifluoromethyl) phenyl] borate, ferrocenium tetraphenylborate, tetraphenyl Silver borate, trityl tetraphenylborate, tetraphenylporphyrin manganese tetraphenylborate, tetrakis (pentafluorophenyl) borate Rosenium, tetrakis (pentafluorophenyl)
(1,1'-dimethylferrocenium borate), decamethylferrocenium tetrakis (pentafluorophenyl) borate, silver tetrakis (pentafluorophenyl) borate, trityl tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) Lithium borate, sodium tetrakis (pentafluorophenyl) borate, manganese tetrakis (pentafluorophenyl) borate, theolaphenylporphyrin, silver tetrafluoroborate, silver hexafluorophosphate, silver hexafluoroarsenate,
Silver perchlorate, silver trifluoroacetate, silver trifluoromethanesulfonate and the like can be mentioned.

(B-1) may be used alone or in a combination of two or more. On the other hand, as the aluminoxane of the component (B-2), the general formula (V)

[0056]

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(Wherein R ¹⁵ is an alkyl group, alkenyl group, aryl group having 1 to 20, preferably 1 to 12 carbon atoms,
It represents a hydrocarbon group such as an arylalkyl group or a halogen atom, w represents an average degree of polymerization, and is usually an integer of 2 to 50, preferably 2 to 40. In addition, each R ¹⁵ may be the same or different. Aluminoxane represented by the general formula (VI):

[0058]

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(Wherein, R ¹⁵ and w are the same as those in formula (V)). Examples of the method for producing the aluminoxane include a method in which an alkylaluminum is brought into contact with a condensing agent such as water. The method is not particularly limited, and the reaction may be performed according to a known method. For example, a method in which an organoaluminum compound is dissolved in an organic solvent and brought into contact with water, a method in which an organoaluminum compound is initially added during polymerization and then water is added, and a crystal water contained in a metal salt or the like is used. A method of reacting water adsorbed on an inorganic or organic substance with an organoaluminum compound, a method of reacting a trialkylaluminum with a tetraalkyldialuminoxane, and further reacting water. The aluminoxane may be insoluble in toluene.

These aluminoxanes may be used alone or in combination of two or more. The usage ratio of (A) the catalyst component and (B) the catalyst component is as follows:
When the compound (B-1) is used as the catalyst component (B), the molar ratio is preferably from 10: 1 to 1: 100, more preferably from 2: 1 to 1:10. If it deviates, the cost of the catalyst per unit mass polymer increases, which is not practical. When the compound (B-2) is used, the molar ratio is preferably from 1: 1 to 1:10.
00000, more preferably 1:10 to 1: 10000
Is desirable. If the ratio is out of this range, the cost of the catalyst per unit mass polymer increases, which is not practical. The catalyst component (B) includes (B-1) and (B-
2) can be used alone or in combination of two or more.

The polymerization catalyst used in the production method of the present invention comprises:
An organoaluminum compound can be used as the component (C) in addition to the components (A) and (B). Here, as the organoaluminum compound of the component (C), a compound represented by the general formula (VII) R ¹⁶ _v AlJ _3-v (VII) wherein R ¹⁶ is an alkyl group having 1 to 10 carbon atoms, and J is Hydrogen atom, alkoxy group having 1 to 20 carbon atoms, 6 to 20 carbon atoms
And v is an integer of 1 to 3].

Specific examples of the compound represented by the general formula (VII) include trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, dimethylaluminum chloride, diethylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, dimethylaluminum Aluminum fluoride, diisobutylaluminum hydride, diethylaluminum hydride, ethylaluminum sesquichloride and the like.

These organoaluminum compounds may be used alone or in combination of two or more. In the production method of the present invention, preliminary contact can also be performed using the components (A), (B) and (C) described above. The preliminary contact can be performed by bringing the component (A) into contact with the component (B), for example, but the method is not particularly limited, and a known method can be used. These preliminary contacts are effective in reducing the catalyst cost, such as improving the catalyst activity and reducing the proportion of the cocatalyst (B) used. Further, by bringing the component (A) and the component (B-2) into contact with each other, an effect of improving the molecular weight can be seen together with the above-mentioned effect. The pre-contact temperature is usually -20 ° C to 2 ° C.
00 ° C, preferably -10 ° C to 150 ° C, more preferably 0 ° C to 80 ° C. In the preliminary contact, an inert hydrocarbon, an aliphatic hydrocarbon, an aromatic hydrocarbon, or the like can be used as a solvent. Particularly preferred among these are aliphatic hydrocarbons.

The molar ratio of the catalyst component (A) to the catalyst component (C) is preferably 1: 1 to 1: 1000.
0, more preferably 1: 5 to 1: 2000, and still more preferably 1:10 to 1: 1000.
By using the catalyst component (C), the polymerization activity per transition metal can be improved. However, if it is too much, the organoaluminum compound is wasted and a large amount remains in the polymer, which is not preferable.

In the present invention, at least one of the catalyst components can be used by being supported on a suitable carrier. There is no particular limitation on the type of the carrier, an inorganic oxide carrier,
Any other inorganic and organic carriers can be used, but inorganic oxide carriers or other inorganic carriers are particularly preferred.

As the inorganic oxide carrier, specifically, S
_{iO 2, Al 2 O 3,} MgO, ZrO 2, TiO 2, F
e ₂ O ₃ , B ₂ O ₃ , CaO, ZnO, BaO, ThO
₂ and mixtures thereof, for example, silica alumina, zeolite, ferrite, glass fiber and the like.
Among them, SiO ₂ and Al ₂ O ₃ are particularly preferable. The inorganic oxide carrier may contain a small amount of carbonate, nitrate, sulfate, or the like.

On the other hand, as a carrier other than the above, MgC
general formula Mg represented by l ₂ , Mg (OC ₂ H ₅ ) _2, etc.
Magnesium compounds and their complex salts represented by R ¹⁷ _{X X} ¹ _y can be exemplified. Here, R ¹⁷ has 1 to 1 carbon atoms.
20 alkyl group, an aryl group, X ¹ having 6 to 20 alkoxy groups or carbon atoms having 1 to 20 carbon atoms is an alkyl group having a halogen atom or a C 1-20, x is 0 to 2, y is 0 2 and x + y = 2. Each R ¹⁷ and each X ¹
May be the same or different.

As the organic carrier, polystyrene,
Styrene-divinylbenzene copolymer, polyethylene,
Examples thereof include polymers such as polypropylene, substituted polystyrene, and polyarylate, starch, and carbon.

The carrier used in the present invention includes:
MgCl ₂ , MgCl (OC ₂ H ₅ ), Mg (OC
₂ H _{5) 2,} such as SiO _2, Al ₂ O ₃ is preferred. The properties of the carrier vary depending on the type and manufacturing method, but the average particle size is usually 1 to 300 μm, preferably 10 to 200 μm.
m, more preferably 20 to 100 μm.

When the particle size is small, fine powder in the polymer increases,
If the particle size is large, coarse particles in the polymer increase and the bulk density is low.
It may cause clogging of the bottom and hopper. Also, the carrier ratio table
Area is usually 1-1000m^Two/ G, preferably 50 to
500m^Two/ G, pore volume is usually 0.1-5 cm^Three/
g, preferably 0.3 to 3 cm ^Three/ G.

If either the specific surface area or the pore volume deviates from the above range, the catalytic activity may decrease. The specific surface area and the pore volume can be determined, for example, from the volume of nitrogen gas adsorbed according to the BET method (Journal of the American Chemical Society, Vol. 60, p. 309 (1983)). reference).

Further, the above-mentioned carrier is usually 150 to 100
It is desirable to use by firing at 0 ° C, preferably 200 to 800 ° C. When at least one of the catalyst components is supported on the carrier, it is desirable to support at least one of the catalyst components (A) and (B), preferably both the catalyst components (A) and (B). .

The method for supporting at least one of the component (A) and the component (B) on the carrier is not particularly limited. For example, at least one of the components (A) and (B) is mixed with the carrier. Method, a method of treating a carrier with an organoaluminum compound or a halogen-containing silicon compound, and then mixing the carrier with at least one of the component (A) and the component (B) in an inert solvent.
Or a method of reacting the component (B) with an organoaluminum compound or a halogen-containing silicon compound, a method of supporting the component (A) or the component (B) on a carrier, and then mixing the component (B) or the component (A). And a method of mixing the contact reactant of the components (A) and (B) with the carrier, and a method of coexisting the carrier during the contact reaction between the components (A) and (B).

In the above and the above reactions,
An organoaluminum compound as the component (C) can be added. In the present invention, the above (A), (B),
When contacting (C), an elastic wave may be irradiated to prepare a catalyst. Examples of the elastic wave include a sound wave, particularly preferably an ultrasonic wave. Specifically, the frequency is 1 to 1
000 kHz ultrasonic wave, preferably 10-500 kHz
Ultrasound.

The catalyst thus obtained may be subjected to solvent distillation once, taken out as a solid, and then used for polymerization, or may be used for polymerization as it is. Further, in the present invention, a catalyst can be generated by performing an operation of loading at least one of the component (A) and the component (B) on a carrier in a polymerization system. For example, at least one of the component (A) and the component (B), a carrier and, if necessary, the organoaluminum compound of the component (C) are added, and an olefin such as ethylene is subjected to normal pressure to 2 MPa (gauge).
In addition, a method in which prepolymerization is performed at −20 to 200 ° C. for about 1 minute to 2 hours to generate catalyst particles can be used.

In the present invention, the use ratio of the component (B-1) to the carrier is preferably 1: 5 to 1:10 by mass ratio.
000, more preferably 1:10 to 1: 500, and the use ratio of the component (B-2) to the carrier is preferably 1: 0.5 to 1: 1000, more preferably, by mass ratio. It is desirable to set it as 1: 1 to 1:50. When two or more of the components (B) are used as a mixture, it is desirable that the ratio of each component (B) to the carrier be within the above range in terms of mass ratio. Further, the use ratio of the component (A) to the carrier is preferably 1: 5 to 1: 10000, more preferably 1:10 to 1: 500 by mass ratio.

Component (B) [Component (B-1) or (B-
When the usage ratio of the (2) component] and the carrier or the usage ratio of the component (A) and the carrier deviates from the above range, the activity may be reduced. The polymerization catalyst of the present invention thus prepared has an average particle size of usually 2 to 200 μm, preferably 1 to 200 μm.
It is 0 to 150 μm, particularly preferably 20 to 100 μm, and the specific surface area is usually 20 to 1000 m ² / g, preferably 50 to 500 m ² / g. If the average particle size is less than 2 μm, the fine powder in the polymer may increase,
If it exceeds 0 μm, coarse particles in the polymer may increase. If the specific surface area is less than 20 m ² / g, the activity may decrease, and if it exceeds 1000 m ² / g, the bulk density of the polymer may decrease. In the catalyst of the present invention, the amount of the transition metal in 100 g of the carrier is usually 0.05 to 1%.
It is preferably 0 g, especially 0.1 to 2 g. If the amount of the transition metal is outside the above range, the activity may be reduced.

By supporting on a carrier as described above, a polymer having a high bulk density and excellent particle size distribution, which are industrially advantageous, can be obtained. The propylene-based polymer used in the present invention is produced by homopolymerizing propylene or copolymerizing propylene with ethylene and / or an α-olefin having 4 to 20 carbon atoms using the polymerization catalyst described above. .

In this case, the polymerization method is not particularly limited, and a slurry polymerization method, a gas phase polymerization method, a bulk polymerization method, a solution polymerization method,
Any method such as a suspension polymerization method may be used, but a slurry polymerization method and a gas phase polymerization method are particularly preferred.

Regarding the polymerization conditions, the polymerization temperature is usually -1.
00 to 250 ° C, preferably -50 to 200 ° C, more preferably
Preferably it is 0-130 degreeC. In addition,
The ratio of the catalyst used is determined by the ratio of the starting monomer / component (A)
Ratio is preferably 1 to 10. ⁸, Especially 100 to 10^FiveWhen
Preferably, Further, the polymerization time is usually from 5 minutes to 1 minute.
0 hours, the reaction pressure is preferably normal pressure to 20 MPa (ga).
more preferably normal pressure to 10 MPa (gaug)
e).

Methods for controlling the molecular weight of the polymer include selection of the type and amount of each catalyst component used, the polymerization temperature, and polymerization in the presence of hydrogen. When a polymerization solvent is used, for example, aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene, alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclohexane, and aliphatic hydrocarbons such as pentane, hexane, heptane and octane And halogenated hydrocarbons such as chloroform and dichloromethane. These solvents may be used alone or in a combination of two or more. Further, a monomer such as an α-olefin may be used as the solvent. In addition, depending on the polymerization method, it can be carried out without a solvent.

In the polymerization, preliminary polymerization can be carried out using the polymerization catalyst. The prepolymerization can be performed by, for example, bringing a small amount of olefin into contact with the solid catalyst component, but the method is not particularly limited, and a known method can be used. The olefin used for the prepolymerization is not particularly limited, and may be the same as those exemplified above, for example, ethylene, α-α having 3 to 20 carbon atoms.
An olefin or a mixture thereof can be used, but it is advantageous to use the same olefin as the olefin used in the polymerization.

The prepolymerization temperature is usually from -20 to 20.
0 ° C, preferably -10 to 130 ° C, more preferably 0 ° C.
８０80 ° C. In the prepolymerization, an inert hydrocarbon, an aliphatic hydrocarbon, an aromatic hydrocarbon, a monomer, or the like can be used as a solvent. Of these, aliphatic hydrocarbons are particularly preferred. Further, the prepolymerization may be performed without a solvent.

In the prepolymerization, the intrinsic viscosity [η] (measured in decalin at 135 ° C.) of the prepolymerized product is 0.2 deciliter / g or more, especially 0.5 deciliter / g or more, and the transition metal component in the catalyst is used. The amount of the prepolymerized product per 1 mmol is from 1 to 10,000 g, especially from 10 to 10 g.
It is desirable to adjust the conditions so that the weight becomes 00 g.

[3] Propylene-based resin composition The propylene-based resin composition of the present invention comprises the propylene-based polymer [1], the propylene-based homopolymer [a], or the propylene-based copolymer [a ']. It is a resin composition obtained by adding a nucleating agent. In general, crystallization of a propylene-based polymer consists of two processes, a crystal nucleation process and a crystal growth process. It is said to affect the production rate. In particular, it is known that the presence of a substance having an effect of promoting molecular chain orientation through molecular chain adsorption or the like significantly increases the crystal nucleation rate. The nucleating agent in the present invention may be any as long as it has the effect of improving the progress rate of the crystal nucleation process. Substances that have the effect of improving the progress rate of the crystal nucleation process include substances that have the effect of promoting molecular chain orientation through the process of adsorbing the molecular chains of the polymer.

Specific examples of the nucleating agent in the present invention include:
High melting point polymer, organic carboxylic acid or its metal salt,
Aromatic sulfonates or metal salts thereof, organophosphate compounds or metal salts thereof, dibenzylidene sorbitol or derivatives thereof, rosin acid partial metal salts, inorganic fine particles, imides, amides, quinacridones, quinones or mixtures thereof Is mentioned.

As the high melting point polymer, polyethylene,
Polyolefins such as polypropylene, polyvinylcyclohexane, polyvinylcycloalkanes such as polyvinylcyclopentane, syndiotactic polystyrene, poly3-methylpentene-1, poly3-methylbutene-1,
And polyalkenylsilane.

Examples of the metal salt include aluminum benzoate, aluminum pt-butyl benzoate, sodium adipate, sodium thiophenecarboxylate, sodium pyrrolecarboxylate and the like.

As dibenzylidene sorbitol or its derivative, dibenzylidene sorbitol, 1,3:
2,4-bis (o-3,4-dimethylbenzylidene) sorbitol, 1,3: 2,4-bis (o-2,4-dimethylbenzylidene) sorbitol, 1,3: 2,4-bis (o- 4-ethylbenzylidene) sorbitol, 1,
3: 2,4-bis (o-4-chlorobenzylidene) sorbitol, 1,3: 2,4-dibenzylidene sorbitol and the like. Further, specifically, Gelol MD and Gelol MD-R (trade name) manufactured by Shin Nippon Rika (manufactured by) are also included.

Examples of the rosin acid partial metal salt include Pine Crystal KM1600, Pine Crystal KM1500 and Pine Crystal KM1300 manufactured by Arakawa Chemical Industries, Ltd.
(Product name) and the like.

Examples of the inorganic fine particles include talc, clay, mica, asbestos, glass fiber, glass flake, glass beads, calcium silicate, montmorillonite, bentonite, graphite, aluminum powder, alumina, silica, diatomaceous earth, titanium oxide, oxide Examples include magnesium, pumice powder, pumice balloon, aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate, dolomite, calcium sulfate, potassium titanate, barium sulfate, calcium sulfite, and molybdenum sulfide.

Examples of the amide compound include dianilide adipate and dianilide sperate. One of these nucleating agents may be used, or two or more of them may be used in combination.

In the propylene-based resin composition of the present invention, it is preferable to use inorganic fine particles such as an organic metal phosphate and / or talc represented by the following general formula as a nucleating agent, since it does not generate odor. This propylene-based resin composition is suitable for use in food products.

[0094]

Embedded image

(Wherein, R ¹⁸ is a hydrogen atom or a carbon atom having 1 to 4 carbon atoms)
R ¹⁹ and R ²⁰ are each a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group,
It represents an aryl group or an aralkyl group. M represents any one of an alkali metal, an alkaline earth metal, aluminum and zinc. When M is an alkali metal, m is 0, n
Represents 1; n represents 1 or 2 when M is an alkaline earth metal or zinc; m represents 1 when n is 1; m represents 0 when n is 2; Represents 1 and n represents 2. ) Specific examples of metal organic phosphates include ADK STAB NA
-11 and ADK STAB NA-21 (manufactured by Asahi Denka Co., Ltd.).

Further, when the propylene-based resin composition of the present invention uses the above-mentioned inorganic fine particles such as talc as a nucleating agent, when formed into a film, it has excellent slip properties and improved properties such as printing properties. Is preferred. Further, it is preferable to use the above-mentioned dibenzylidene sorbitol or a derivative thereof as a nucleating agent since the transparency is excellent. Furthermore, it is preferable to use the above-mentioned amide compound as a nucleating agent because of its excellent rigidity.

The propylene resin composition of the present invention comprises a propylene polymer [1], the propylene homopolymer [a] or the propylene copolymer [a '] and a nucleating agent, and if desired, It may be one obtained by dry blending various additives to be used with a Henschel mixer or the like. Alternatively, it may be melt-kneaded using a single-screw or twin-screw extruder, a Banbury mixer, or the like.
Alternatively, when using a high melting point polymer as a nucleating agent,
The propylene-based polymer may be produced by simultaneously or sequentially adding a high melting point polymer in a reactor. Various additives used as desired include antioxidants, neutralizing agents, slip agents, antiblocking agents, antifogging agents, and antistatic agents.

The amount of the nucleating agent added in the present invention is usually 10 ppm or more based on the propylene polymer [1], the propylene homopolymer [a] or the propylene copolymer [a '], Preferably 10 to 10000p
pm, more preferably 10 to 5000 pp
m, more preferably 10 to 2500 pp
m. If the amount is less than 10 ppm, the moldability is not improved. On the other hand, even if the amount exceeds 10,000 ppm, the preferable effect may not be increased.

[4] Molded article The molded article of the present invention comprises the above-mentioned propylene polymer [1],
The propylene homopolymer [a], the propylene-based copolymer [a '], or the propylene-based resin composition [3]
Is a molded article obtained by molding The molded article of the present invention,
It has the characteristics of softness (also called flexibility), high elastic recovery (property to return to the original state even when pulled), and softness, that is, low stickiness but low transparency and excellent transparency. is there.

Examples of the molded article of the present invention include films, sheets, containers, automobile interior materials, and housing materials for call products. Examples of the film include a food packaging film and an agricultural film (an example of a greenhouse). Examples of the container include a transparent case, a transparent box, a decorative box, and the like because of excellent transparency.

The molding method of the molded article includes an injection molding method,
Examples include a compression molding method, an injection compression molding method, a gas assist injection molding method, an extrusion molding method, and a blow molding method. The molding conditions are not particularly limited as long as the resin is at a temperature at which the resin melts and flows. Usually, the resin temperature is 50 ° C to 300 ° C,
It can be performed at a mold temperature of 60 ° C. or less. When a film is formed as the molded article of the present invention, a general compression molding method, an extrusion molding method, a blow molding method, a cast molding method, or the like can be used. The film may or may not be stretched. When stretching, biaxial stretching is preferred. Conditions for biaxial stretching include the following conditions. Molding conditions during sheet molding Resin temperature 50 to 200 ° C, chill roll temperature 50 ° C or less Longitudinal stretching condition 3 to 7 times stretching temperature, 50 to 100 ° C stretching condition Horizontal stretching condition 6 to 12 times stretching temperature, 50 to 100 ° C stretching temperature The surface of the film may be treated as necessary to increase the surface energy or polarize the surface. For example, examples of the treatment method include a corona discharge treatment, a chromic acid treatment, a flame treatment, a hot air treatment, and an ozone or ultraviolet irradiation treatment. Examples of the method for making the surface uneven include a sand blast method and a solvent treatment method.

The film may contain, if necessary, an antioxidant, a neutralizing agent, a slip agent, an antiblocking agent, an antifogging agent, an antistatic agent and the like, which are commonly used.
Furthermore, films containing inorganic fine particles such as talc also have excellent slip properties, so that secondary processing properties such as bag making and printing are improved, and they can be used for all general-purpose packaging films in high-speed manufacturing equipment such as various automatic filling packaging laminations. It is suitable.

A film formed by molding the propylene-based resin composition containing the above-mentioned dibenzylidene sorbitol or a derivative thereof as a nucleating agent is particularly suitable for packaging of toys, stationery and the like because of its excellent transparency and large display effect. is there.

A film formed by molding the propylene-based resin composition containing the amide compound as a nucleating agent is particularly excellent in rigidity and hardly causes problems such as wrinkles in high-speed bag making. Is suitable as any general-purpose packaging film.

[5] Propylene-based resin modifier The propylene-based resin modifier of the present invention includes the propylene-based polymer [1], the propylene homopolymer [a], or the propylene-based copolymer [a]. ']. The propylene-based resin modifier of the present invention is characterized in that it has a soft property, has a low stickiness, and can provide a molded article having excellent compatibility with the polyrefin resin.
That is, the propylene-based resin modifier of the present invention is, as described above, a propylene homopolymer, a propylene-based polymer is a specific one, and in particular, since there is a slight crystalline portion in the polypropylene chain portion, Less sticky than soft polyolefin resin as a modifier. Further, the propylene-based resin modifier of the present invention has excellent compatibility with polyolefin-based resins, particularly with polypropylene-based resins. As a result, the surface characteristics (such as stickiness) are less reduced and the transparency is higher than when a conventional modifier such as ethylene rubber is used. Having the above characteristics, the propylene resin modifier of the present invention can be suitably used as an agent for improving physical properties of flexibility and transparency.

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the present invention.

First, a method for evaluating the resin properties and physical properties of the polymer of the present invention will be described. (1) Measurement of [η] It was measured at 135 ° C. in a tetralin solvent using a VMR-053 automatic viscometer manufactured by Rigosha Co., Ltd. (2) Measurement of Pentad Fraction, Triad Fraction, and Abnormal Insertion Fraction It was measured by the method described in the text of the specification. That is, the mesopendad fraction (mmmm fraction), the triad fraction, and the racemic pentad fraction (rrrr fraction) are determined by A. Zambelli and the like as "Ma".
cromolecules, 6 , 925 (1973) "
The signal of the methyl group in the ¹³ C nuclear magnetic resonance spectrum was measured in accordance with the method proposed in the above, and the meso fraction and the racemic fraction in the pentad unit in the polypropylene molecular chain, and the triad fraction (mm, rr, mr ). (M-
(2,1), (r-2,1) and (1,3) are Grass
i's report (Macromolucules, 21 , p. 617 (1988))
And Busico et al. (Macromolucules, 27 , p.
7538 (1994)), the assignment of peaks in the ¹³ C-NMR spectrum was determined, and each insertion content was calculated from the integrated intensity of each peak. (M-2,1) is calculated as the meso-2,1 insertion content (%) of the ratio of the integrated intensity of the peak belonging to Pα, γthreo appearing around 17.2 ppm to the integrated intensity in the entire methyl carbon region. . (R-2,
1) is 1 to the integrated intensity in the entire methyl carbon region.
The ratio of the integrated intensity of the peaks belonging to Pα and γthreo appearing at around 5.0 ppm is represented by the racemic-2,1 insertion content (%).
It was calculated as (1,3) is the value of T which appears around 31.0 ppm relative to the integrated intensity in the entire methine carbon region.
The ratio of the integrated intensities of the peaks belonging to β and γ + was calculated as the 1,3 insertion content (%). When peaks to be attributed to meso-2,1 insertion, racemic-2,1 insertion or 1,3 insertion may not be identifiable due to hiding in noise, etc., the content of each heterogeneous bond (m −2, 1), (r−
(2,1) or (1,3) was regarded as 0.

The measurement of the ¹³ C nuclear magnetic resonance spectrum was performed using the following apparatus and conditions. Apparatus: JNM-EX400 type ¹³ CN manufactured by JEOL Ltd.
MR apparatus Method: Proton complete decoupling method Concentration: 220 mg / ml Solvent: 90:10 (volume ratio) mixed solvent of 1,2,4-trichlorobenzene and heavy benzene Temperature: 130 ° C. Pulse width: 45 ° Pulse repetition time: 4 seconds integration: 10000 times (3) Content (mol%) of comonomer unit in the copolymer Using a JNM-EX400 type NMR apparatus manufactured by JEOL, ¹³ C-NMR spectrum was measured under the following conditions. It was calculated by the following method.

Sample concentration: 220 mg / NMR solvent 3 ml NMR solvent: 1,2,4-trichlorobenzene / benzene-d6
(90/10 vol%) Measurement temperature: 130 ° C Pulse width: 45 ° Pulse repetition time: 10 seconds Integration count: 4000 times (a) Ethylene unit ¹³ C for random copolymer of propylene and ethylene
Table 1 shows the chemical shifts and assignments of each signal in the spectrum measured by -NMR.

[0109]

[Table 1]

The content of the ethylene unit in the copolymer (α (
Mol%)) was determined from the spectrum measured by ¹³ C-NMR according to the following formula (1). α = E / S × 100 (1) where S and E are respectively S = I _EPE + I _PPE + I
_{EEE + I PPP + I PEE +} I PEP E = I EEE +2/3 (I PEE + I EPE) +1/3 (I PPE + I
_PEP ), and I _EPE = I (12) I _PPE = I (15) + I (11) + (I (14) -I (11)) / 2 + I (1
0) I _EEE = I (18) / 2 + I (17) / 4 I _PPP = I (19) + (I (6) + I (7)) / 2 + I (3) + I (13)
+ I (11) + (I (14) -I (11)) / 2 I _PEE = I (20) I _PEP = (I (8) + I (9) -2 × I (11)) / 4 + I (21 ).

The isotactic triad fraction of the PPP chain was determined as the stereoregularity index (P (mol%)) of the copolymer according to the following equation (2). P = Im / I × 100 (2) where Im and I are respectively Im = I (22) I = I (22) + I (23) + I (24) − ｛(I (8) + I (9)) / 2
+ I (10) + 3/2 × I (11) + I (12) + I (13) + I (15)}. Here, I (1), I (2)... Indicate the intensity of the signal,. (4) Measurement of molecular weight distribution (Mw / Mn) Mw / Mn was measured by the method described in the text of the specification. That is, Mw / Mn is a value calculated from the mass average molecular weight Mw and the number average molecular weight Mn in terms of polyethylene measured by the GPC method using the following apparatus and conditions. GPC measuring device Column: TOSO GMHHR-H (S) HT Detector: RI detector for liquid chromatogram W
ATERS 150C Measurement conditions Solvent: 1,2,4-trichlorobenzene Measurement temperature: 145 ° C Flow rate: 1.0 ml / min Sample concentration: 2.2 mg / ml Injection volume: 160 microliter Calibration curve: Universal Caliber
Tion analysis program: HT-GPC (Ver. 1.0) (5) DSC measurement It was measured by the method described in the text of the specification. That is, a differential scanning calorimeter (manufactured by Perkin-Elmer, DS
Using C-7), a sample of 10 mg was placed in a nitrogen atmosphere at 230 ° C.
, And then the temperature was lowered to 0 ° C at 10 ° C / min, and further held at 0 ° C for 3 minutes, and then the temperature was raised at 10 ° C / min. Also,
The peak top of the maximum peak of the melting endothermic curve obtained at this time was defined as melting point: Tm. Further, at 230 ° C., 3
After holding for 1 minute, the temperature is lowered to 0 ° C. at a rate of 10 ° C./minute.
The peak top of the maximum peak of the crystallization exothermic curve obtained at this time was defined as crystallization temperature: Tc. (6) Elevated Temperature Separation Chromatograph The amount W25 (% by mass) of the component eluted without being adsorbed by the filler at the TREF column temperature of 25 ° C. in the elution curve was determined as follows. (A) Operation method A sample solution is introduced into a TREF column adjusted to a temperature of 135 ° C., and then gradually cooled to 0 ° C. at a rate of 5 ° C./hour, held for 30 minutes, and the sample is adsorbed on a filler. Thereafter, the column was heated at a rate of 40 ° C./hour to 135 columns.
The temperature was raised to ℃ to obtain an elution curve. (B) Apparatus configuration TREF column: Silica gel column (4.6φ x 150mm) manufactured by GL Sciences Flow cell: 1mm optical path length KBr cell manufactured by GL Sciences Pump: SSC-3100 pump manufactured by Senshu Kagaku Valve oven: GL Sciences Model 554 oven (high temperature type) TREF oven: GL Science's two-line temperature controller: Rigaku Corporation REX-C100 temperature controller Detector: Infrared detector for liquid chromatography FOXBORO's MIRAN 1A CVF 10-way valve : Barco electric valve loop: Barco 500 microliter loop (c) Measurement conditions Solvent: o-dichlorobenzene Sample concentration: 7.5 g / liter Injection volume: 500 microliter Pump flow rate: 2.0 ml / min Detection Wave number: 3. 1μm column filler: Chromosorb P (30 to 60 mesh) Column temperature distribution: within ± 0.2 ° C. (7) Tensile modulus propylene polymer to create a press-molded into test pieces,
It measured by the tensile test based on JISK-7113.

Test piece (No. 2 dumbbell) Thickness: 1 mm Crosshead speed: 50 mm / min Load cell: 100 kg (8) Internal haze A propylene polymer is press-molded to prepare a test piece.
It was measured by a test based on JIS K-7105.
The smaller the value, the better the transparency.

Test piece: 15 cm × 15 cm × 1 mm
(Test piece thickness = 1 mm) (9) Elastic recovery rate This was performed in the same manner as in the method described in JP-A-5-132590. That is, a propylene polymer was press-molded to prepare a JIS-2 dumbbell as a test piece. Mark of 25mm intervals in the constant-width portion of the dumbbell, which was used as a L _0. This test piece was tested with a tensile tester for a distance between chucks of 80 m.
After stretching from m to 160 mm at a pulling rate of 50 mm / min, the gap between the chucks was returned to the initial distance at −50 mm / min, and after 1 minute, the interval between marks placed on the dumbbell was measured and defined as L ₁ . The elastic recovery was calculated by the following equation. When this value was 0 or less, it was determined that there was no recovery. - _{[(2L 0 -L 1) / L} 0 ] × 100 · L _0: the indicia attached to the dumbbell initial length-L _1: length after stretching of indicia attached to the dumbbell (10) anti-blocking propylenic Press molding the polymer to create test specimens,
After bonding under the following conditions, the peel strength was measured with a tensile tester. -Test piece: 15mm x 62.5mm x 2mm-Adhesion conditions: Adhesion temperature 40 ° C, adhesion area 15mm x 31
mm, crimping load 0.7 kg, 3 hours Shear peeling condition: crosshead speed 50 mm / min (11) Izod impact strength A propylene polymer is press-molded to prepare a test piece,
According to JIS K-7110, specimen thickness = 3mm,
The measurement was performed at an ambient temperature of -5 ° C. (12) Component amount eluted in hexane (H25) H25 was determined by measuring under the following measurement conditions.

Sample: 0.1 to 5 g Sample shape: powder (Pellets are crushed,
Solvent: Hexane Elution conditions: 25 ° C., standing for 3 days or more Method for calculating elution amount: Calculate by the following formula.

H25 = [(W ₀ −W ₁ ) / W ₀ ] × 100 (%) (13) Measurement of Boiling Diethyl Ether Extraction Measurement was performed using a Soxhlet extractor under the following conditions.

Sample: 1-2 g Sample shape: powder-like (pelletized product was pulverized,
Extraction solvent: diethyl ether Extraction time: 10 hours Number of extractions: 180 or more Extraction amount calculation method: Calculated by the following formula. [Extraction amount into diethyl ether (g) / mass of charged powder (g)] × 100 [Example 1] Propylene homopolymer (1) Preparation of catalyst (1,2′-dimethylsilylene) (2,1′-) Synthesis of dimethylsilylene) -bis (3-n-butylindenyl) zirconium dichloride (1,2′-dimethylsilylene) (2,
1′-dimethylsilylene) -bis (indene)
3 g (2.4 mmol) and 50 mL of ether are charged.
After cooling to −78 ° C., n-BuLi (hexane solution 1.6)
After adding 3.1 mL (5.0 mmol) of M), the mixture is stirred at room temperature for 12 hours. The solvent was distilled off, and the obtained solid was washed with 20 mL of hexane to obtain 1.1 g (2.3 mmol) of a lithium salt as an ether adduct. This lithium salt is dissolved in 50 mL of THF and cooled to -78 ° C. 0.57 mL (5.3 mmol) of n-butyl bromide is slowly added dropwise and stirred at room temperature for 12 hours. After distilling off the solvent and extracting with 50 mL of hexane, the solvent was removed, and (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-n-butylindene) was added in 0.8 ml.
1 g (1.77 mmol) was obtained. Next, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-n-butylindene) obtained above was placed in a Schlenk bottle under a nitrogen stream. 0.
81 g (1.77 mmol) and 100 mL of ether are charged. After cooling to −78 ° C. and adding 2.7 mL (4.15 mmol) of n-BuLi (hexane solution 1.54 M), the mixture is stirred at room temperature for 12 hours. The solvent was distilled off, and the obtained solid was washed with hexane to obtain 0.28 g (1.43 mmol) of a lithium salt as an ether adduct.

Under a stream of nitrogen, the lithium salt obtained above is dissolved in 50 mL of toluene. Cooled to −78 ° C., and zirconium tetrachloride 0.33 previously cooled to −78 ° C.
g (1.42 mmol) in toluene (50 mL) is added dropwise. After the addition, the mixture is stirred at room temperature for 6 hours. Thereafter, the mixture is filtered, and the solvent of the filtrate is distilled off. By recrystallization from dichloromethane (1,2'-dimethylsilylene)
0.2 g of (2,1′-dimethylsilylene) -bis (3-n-butylindenyl) zirconium dichloride
(0.32 mmol) was obtained. (Yield 22%) The result of measurement by ¹ H-NMR (90 MHz, CDCl ₃ ) is: δ 0.88, 0.99 (12H, dimethylsilylene), 0.7-1.0, 1.1- 1.5 (18
H, n-Bu), 7.0-7.6 (8H, benzene ring proton). (2) Polymerization of propylene In a stainless steel autoclave having an internal volume of 10 liters, 6 liters of heptane, 6 mmoles of triisobutylaluminum, and 5 mmoles of methylaluminoxane (manufactured by Albemarle Co., Ltd.) were combined with (1,2′-dimethylsilylene) obtained above. ) (2,1'-dimethylsilylene) -bis (3-
A catalyst component obtained by precontacting 5 μmol of (n-butylindenyl) zirconium dichloride in toluene for 5 minutes was added. Here, 0.05 MPa of hydrogen (gaug
After introducing e), at a total pressure of 0.8 MPa (gauge)
Propylene gas was introduced until the pressure became constant during the polymerization, and propylene was supplied by a pressure regulator. Polymerization temperature 50
After conducting polymerization at 30 ° C. for 30 minutes, the contents were taken out,
By drying under reduced pressure, a propylene homopolymer was obtained. The obtained polymer was evaluated for the resin properties described above, and the results are shown in Table 2. (3) Compounding and kneading The following additives were formulated into the polypropylene homopolymer obtained above, and a single screw extruder (manufactured by Tsukada Juki Seisakusho: TLC)
35-20) to obtain pellets. (Additive formulation)-Phenolic antioxidant: 1000 ppm of Irganox 1010 manufactured by Ciba Specialty Chemicals-Phosphorous antioxidant: 500 ppm of P-EPQ-Neutralizer: calcium stearate: 500 ppm-Neutralizer: DHT-4A : 500 ppm (4) Evaluation of physical properties The evaluation was made by the evaluation methods described above. The obtained result is the third
It is shown in the table. [Example 2] Propylene homopolymer The same procedure as in Example 1 was carried out except that a propylene homopolymer was produced without hydrogenation. The results obtained are shown in Tables 2 and 3. Example 3 (1) Synthesis of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-methylindenyl) zirconium dichloride In a Schlenk bottle, (1,1) 4,4 g (12.8 mmol) of 2'-dimethylsilylene) (2,1'-dimethylsilylene) -bis (indene) and ether 10
Add 0 mL. After cooling to −78 ° C., 16.1 mL (25.7 mmol) of n-BuLi (hexane solution 1.6 M) was added.
l) After addition, stir at room temperature for 12 hours. The solvent is distilled off, and the obtained solid is washed with 20 mL of hexane to quantitatively obtain a lithium salt. This lithium salt is added to THF1
Dissolve in 00 mL and cool to -78 ° C. 6. methyl iodide
4 g (52.0 mmol) was slowly added dropwise at room temperature.
Stir for 2 hours. After distilling off the solvent and extracting with 50 mL of hexane, the solvent was removed and 4.5 g (12 mmol) of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-methylindene) was added. Obtained. (Yield 94%) Next, the (1,1) obtained above was placed in a Schlenk bottle under a nitrogen stream.
2.0 g (5.4 g) of 2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-methylindene)
mmol) and 100 mL of ether. 12. Cool to -78 ° C and add n-BuLi (hexane solution 1.6M) to 13.
After adding 5 mL (21.6 mmol), the mixture is stirred at room temperature for 12 hours. The solvent was distilled off, and the obtained solid was washed with hexane to obtain 1.1 g (2.9 mmol) of a lithium salt.
1) was obtained. Under a nitrogen stream, the lithium salt obtained above is dissolved in 100 mL of toluene. Cool to -78 ° C,
Here, zirconium tetrachloride which has been cooled to −78 ° C. in advance.
A suspension of 7 g (3.0 mmol) of toluene (100 mL) is added dropwise. After the addition, the mixture is stirred at room temperature for 6 hours. Thereafter, the mixture was filtered, and the precipitate was extracted from dichloromethane. By recrystallization from dichloromethane / hexane (1,2 ′
-Dimethylsilylene) (2,1'-dimethylsilylene)
0.5 g (0.94 mmol) of -bis (3-methylindenyl) zirconium dichloride was obtained. (Yield 3
2%) ¹ H-NMR (CDCl ₃ ):
δ 0.95,1.05 (12H, _{dimethylsilylene), 2.50 (6H, CH 3} ), 7.2-7.7 (8
H, Ar-H). (2) Homopolymerization of propylene In a stainless steel autoclave having an internal volume of 1 liter, 400 mL of heptane, 0.5 mmol of triisobutylaluminum, and 0.5 mmol of methylaluminoxane (manufactured by Albemarle Co.) were obtained as described above. '-Dimethylsilylene) (2,1'-dimethylsilylene) -bis (3-methylindenyl) zirconium dichloride (0.5 μmol) was pre-contacted in toluene for 5 minutes to add a catalyst component. Here, 0.03 MPa (g) of hydrogen
aug) at a total pressure of 0.8 MPa (gau).
The propylene gas was introduced until ge, and propylene was supplied by a pressure regulator so that the pressure during polymerization was constant. After performing polymerization at a polymerization temperature of 70 ° C. for 1 hour, the content was taken out and dried under reduced pressure to obtain a propylene homopolymer. The obtained polymer was evaluated for the resin properties described above, and the results are shown in Table 2. (3) Blending and kneading The same procedure as in Example 1 was carried out except that the propylene homopolymer obtained above was blended with the following additive formulation.

(Additive Formulation) ・ Phenolic antioxidant: 1000 ppm of Irganox 1010 manufactured by Ciba Specialty Chemicals ・ Phosphorus antioxidant: 1000 ppm of Irgafos 168 manufactured by Ciba Specialty Chemicals (4) Evaluation of physical properties Example 1 Performed in the same manner as in (4). Table 3 shows the obtained results. [Example 4] Propylene copolymer (1) Preparation of catalyst (a) (1,2'-ethylene) (2,1'-ethylene)
Production of -bis (3-methylindene) 1.12 g (3.94 mmol) of (1,2′-ethylene) (2,1′-ethylene) -bis (indene) in 50 ml of dehydrated ether under a nitrogen stream. Melted. -7
After cooling to 8 ° C., 5.01 ml of a hexane solution having a concentration of 1.57 mol / l of n-butyllithium (n-butyllithium: 7.87 mmol) was added dropwise over 30 minutes, and then the temperature was raised to room temperature. Stir for 8 hours. The ether solvent was distilled off under reduced pressure, and the residue was washed with hexane to obtain 1.12 g of a dilithium salt as an ether adduct.
(3.02 mmol) was obtained. This dilithium salt was dissolved in 50 ml of dehydrated tetrahydrofuran, and
Cooled to ° C. To this solution was added dropwise 10 ml of a tetrahydrofuran solution containing 0.42 ml (6.74 mmol) of methyl iodide over 20 minutes, and the mixture was allowed to warm to room temperature and then stirred for 8 hours. After evaporating the solvent under reduced pressure, the residue was extracted with ethyl acetate. The extracted solution is washed with water, the organic layer is dried over anhydrous magnesium sulfate, filtered, and the filtrate is evaporated to dryness under reduced pressure to obtain the desired product (1,2′-ethylene) (2,1′-ethylene). )-
0.87 g (2.78 mmol) of bis (3-methylindene) was obtained with a yield of 70.5%. It was present as an isomer mixture of double bonds in the five-membered ring moiety. (B) (1,2′-ethylene) (2,1′-ethylene)
Production of dilithium salt of -bis (3-methylindene) 0.87 g of (1,2′-ethylene) (2,1′-ethylene) -bis (3-methylindene) (2.
(78 mmol) dissolved in 35 mmol of ether.
Cooled to ° C. To this solution is added n-butyllithium 1.5
3.7 ml of a 7 mol / liter hexane solution (n-butyllithium: 5.81 mmol) was added to 30
After dropwise addition over a period of minutes, the mixture was heated to room temperature and stirred for 8 hours.
After distilling off the solvent under reduced pressure, the residue was washed with hexane to convert the dilithium salt into an ether adduct.
03 g (2.58 mmol) were obtained with a yield of 92.8%.

When ¹ H-NMR of this product was determined,
The following results were obtained. ¹ H-NMR (THF-d ₈ )
(Δ, ppm): 2.20 (6H, s), 3.25 (8H,
s), 6.0 to 7.4 (8H, m) (c) (1,2'-ethylene) (2,1'-ethylene)
Production of -bis (3-methylindenyl) zirconium dichloride 1.03 g (2.58) of an ether adduct of (1,2′-ethylene) (2,1′-ethylene) -bis (3-methylindene) dilithium salt (Mmol) was suspended in 25 ml of toluene and cooled to -78 ° C. To this, a suspension of zirconium tetrachloride (0.60 g, 2.58 mmol) in toluene (20 ml) was added over 20 minutes, the mixture was heated to room temperature, stirred for 8 hours, and the toluene supernatant was filtered off. The residue was extracted twice with 50 ml of dichloromethane. After distilling off the solvent under reduced pressure, the residue was recrystallized from dichloromethane / hexane to give
0.21 g of (1,2′-ethylene) (2,1′-ethylene) -bis (3-methylindenyl) zirconium dichloride was obtained at a yield of 17.3%.

When ¹ H-NMR of this product was determined,
The following results were obtained. ¹ H-NMR (CDCl ₃ ): 2.4
8 (6H, s), 3.33 to 3.85 (8H, m),
6.9 to 7.6 (8H, m) (2) Copolymerization of propylene / ethylene 1.2 liters of toluene and triisobutylaluminum in a 2 liter stainless steel autoclave.
5 mmol, methylaluminoxane (manufactured by Albemarle) 10 (Al) mmol, (1,2′-ethylene)
20 micromoles of (2,1′-ethylene) -bis (3-methylindenyl) zirconium dichloride were charged, the temperature was raised to 30 ° C., and an ethylene / propylene mixed gas (ethylene / propylene molar ratio = 1/100) was added. Introduced. Excess gas is discharged so that the total pressure becomes 0.7 MPa (gauge). After polymerization for 60 minutes while keeping the gas composition ratio in the system uniform, the content is taken out and dried under reduced pressure to obtain a propylene-based product. A copolymer was obtained. The blending and kneading and the evaluation of the resin properties and physical properties were performed in the same manner as in Example 1. The results obtained are shown in Tables 2 and 3. [Comparative Example 1] Propylene homopolymer (1) Preparation of magnesium compound A glass reactor with an internal volume of about 6 liters equipped with a stirrer was sufficiently replaced with nitrogen gas, and then ethanol was added to the reactor.
30 g, 16 g of iodine and 160 g of metallic magnesium were charged, heated with stirring, and reacted under reflux conditions until hydrogen gas was not generated from the inside of the system to obtain a solid reaction product. The reaction solution containing the solid product was dried under reduced pressure to obtain a magnesium compound. (2) Preparation of solid catalyst component (A) 160 g of the magnesium compound (not pulverized) obtained in the above (1) and 80 ml of purified heptane were placed in a glass reactor having an inner volume of 5 liter which was sufficiently substituted with nitrogen gas. ,
After charging 24 ml of silicon tetrachloride and 23 ml of diethyl phthalate, keeping the inside of the system at 80 ° C., adding 770 ml of titanium tetrachloride with stirring and reacting at 110 ° C. for 2 hours, solid components were separated and purified heptane at 90 ° C. And washed. Furthermore, 1220 ml of titanium tetrachloride was added, and
After reacting for an hour, it was sufficiently washed with purified heptane to obtain a solid catalyst component (A). (3) Gas phase polymerization of propylene In a polymerization tank having an internal volume of 200 liters, 6.0 g / hour of the solid catalyst component obtained in (2) above, 0.2 mol / hour of triisobutylaluminum (TIBA), 1-allyl −
0.014 mol / h of 3,4-dimethoxybenzene (ADMB), cyclohexylmethyldimethoxysilane (C
HMDMS) 0.012 mol / h, propylene 37k
g / hour, 70 ° C., 2.8 MPa (gaug
Polymerization was performed in e). (4) Mixing and kneading 2,5-Dimethyl-2,5-di- (t-butylperoxy) -hexane was mixed with the obtained polypropylene powder, and the same additive formulation as in Example 1 was performed. 40
It was extruded with a mmΦ extruder to obtain pellets. (5) Evaluation of Resin Properties and Physical Properties The evaluation was performed in the same manner as in Example 1. The results obtained are shown in Tables 2 and 3. [Reference Example] Affinity PL1880 Affinity PL188 manufactured by Dow Chemical Japan Co., Ltd.
Physical properties of the pellet No. 0 (trade name) were evaluated in the same manner as in Example 1 (4). Table 3 shows the obtained results. [Comparative Example 2] A homopolymer of propylene In a stainless steel autoclave having an internal volume of 1 liter, 400 mL of heptane, 0.5 mmol of triisobutylaluminum, and 2 micromol of dimethylanilinium (pentafluorophenyl) borate were added. 1
(Tertiary butylamido) dimethyl (tetramethyl-η ⁵ −) prepared in the same manner as in Example 1 of JP-A-63088.
A catalyst component obtained by pre-contacting 1 micromol of (cyclopentadienyl) silane titanium dichloride in toluene for 5 minutes was added. Here, hydrogen 0.03 MPa (gaug)
After introducing e), at a total pressure of 0.8 MPa (gauge)
Propylene gas was introduced until the pressure became constant during the polymerization, and propylene was supplied by a pressure regulator. Polymerization temperature 70
After polymerization at 1 ° C. for 1 hour, the content was taken out and dried under reduced pressure to obtain a propylene homopolymer. Example 1 Evaluation of compounding and kneading, resin properties and physical properties
The same was done. The results obtained are shown in Tables 2 and 3. [Example 5] Addition of nucleating agent The same procedure as in Example 1 was carried out except that the following additive formulation was applied to the propylene homopolymer obtained in Example 1. Table 4 shows the obtained results. (Additive formulation)-Phenolic antioxidant: 1000 ppm of Irganox 1010 manufactured by Ciba Specialty Chemicals-Phosphorus antioxidant: 500 ppm of P-EPQ-Neutralizer: calcium stearate: 500 ppm-Neutralizer: DHT-4A Nucleating agent: Nippon Riken Co., Ltd .: Gerol MD: 1000 ppm [Example 6] Addition of nucleating agent Except that the addition amount of the nucleating agent, Shin Nippon Riken Co., Ltd .: Gerol MD was set to 2000 ppm. Performed as in Example 5. Table 4 shows the obtained results. [Example 7] Addition of nucleating agent The same procedure as in Example 1 was carried out except that the propylene homopolymer obtained in Example 1 was subjected to the following additive formulation. Table 4 shows the obtained results.

Phenol antioxidant: Irganox 1010 1000 ppm manufactured by Ciba Specialty Chemicals Co., Ltd. Phosphorus antioxidant: Irgafos 168 1000 ppm manufactured by Ciba Specialty Chemicals Co., Ltd. 5000 ppm [Example 8] Addition of nucleating agent The same operation as in Example 7 was performed, except that the addition amount of nucleating agent manufactured by Shin Nippon Rikagaku Co., Ltd .: Gelol MD was 10,000 ppm. Table 4 shows the obtained results. [Example 9] Addition of nucleating agent Nucleating agent of Example 7: manufactured by Shin Nippon Chemical Co., Ltd .: Gelol M
D: 5000 ppm from Asahi Denka: NA-11: 200
The same operation as in Example 7 was performed except that 0 ppm was changed.
Table 4 shows the obtained results. Example 10 Effect of Modifier 70% by mass of the pellets obtained in Example 1 was blended with polypropylene E105GM manufactured by Idemitsu Petrochemical Co., Ltd., and the mixture was applied to a single screw extruder (Model TLC35-20 manufactured by Tsukada Juki Seisakusho). And extruded to obtain pellets. Evaluation of physical properties Example 1
Performed in the same manner as in (4). Table 5 shows the obtained results. [Example 11] Effect of modifier The blending ratio of the pellets obtained in Example 1 was 60% by mass.
The procedure was performed in the same manner as in Example 10 except that the above was changed to. Table 5 shows the obtained results. Example 12 Effect of Modifier The blending ratio of the pellets obtained in Example 1 was 30% by mass.
The procedure was performed in the same manner as in Example 10 except that the above was changed to. Table 5 shows the obtained results. [Comparative Example 3] With respect to polypropylene E105GM manufactured by Idemitsu Petrochemical Co., physical properties were evaluated in the same manner as in Example 1 (4). Table 5 shows the obtained results. [Comparative Example 4] The same procedure as in Example 10 was carried out except that the polymer obtained in Comparative Example 2 was blended with 50% by mass of polypropylene E105GM manufactured by Idemitsu Petrochemical Co., Ltd. Table 5 shows the obtained results. [Example 13] Propylene homopolymer A 1 L pressure-resistant autoclave made of sterylene-less with a stirrer was heated to 80 ° C, sufficiently dried under reduced pressure, returned to atmospheric pressure with dry nitrogen, and cooled to room temperature. Under a stream of dry nitrogen, 400 mL of dry deoxygenated heptane and 0.5 mL of a heptane solution of triisobutylaluminum (2.0 M) (1.0 m
mol) and stirred at 350 rpm for a while. On the other hand, cyclohexane (10 mL) and triisobutylaluminum heptane solution (2 M, 0.5 mL,
1.0 mmol), and a cyclohexane solution of dimethylanilinium tetrakis (pentafluorophenyl) borate (4 M, 1.0 mL, 4.0 mmol) and (1,2′-dimethylsilylene) obtained in Example 1.
4 μmol of (2,1′-dimethylsilylene) -bis (3-n-butylindenyl) zirconium dichloride was added, and the mixture was stirred at room temperature for 60 minutes. Then, the catalyst slurry was quickly charged into the autoclave. Then, hydrogen was charged up to 0.03 MPa (gauge). Thereafter, stirring was started at 400 rpm, and the pressure of propylene was gradually increased to a total pressure of 0.8 MPa (gauge), and at the same time, the temperature was slowly increased to 50 ° C. The polymerization was carried out for 30 minutes.

After completion of the reaction, unreacted propylene was removed by depressurization. The reaction mixture was poured into 2 L of methanol to precipitate polypropylene, followed by filtration and drying to obtain polypropylene. The results obtained in the same manner as in Example 1 are shown in Tables 6 and 7. [Example 14] Propylene homopolymer A 1-liter pressure-resistant autoclave with a stirrer made of styrene was heated to 80 ° C, dried sufficiently under reduced pressure, returned to atmospheric pressure with dry nitrogen, and cooled to room temperature. Under a stream of dry nitrogen, 400 mL of dry deoxygenated heptane and 1.0 mL of a heptane solution of triisobutylaluminum (2.0 M) (2.0 mm
l) and dimethylanilinium tetrakis (pentafluorophenyl) borate in a heptane slurry (2.0
μmol, 0.8 mL, 1.6 μmol).
The mixture was stirred at 50 rpm at room temperature for 5 minutes. Thereafter, and (1,2′-dimethylsilylene) (2,1′-
After adding 4 μmol of dimethylsilylene) -bis (3-n-butylindenyl) zirconium dichloride, hydrogen was introduced until the pressure became 0.03 MPa (gauge). Thereafter, stirring was started at 400 rpm, and the pressure of propylene was gradually increased to a total pressure of 0.8 MPa (gauge), and at the same time, the temperature was slowly increased to 50 ° C. The polymerization was carried out for 30 minutes. After the reaction, unreacted propylene was removed by depressurization. 2 L of reaction mixture
Was poured into methanol to precipitate polypropylene, followed by filtration and drying to obtain polypropylene. Example 1
The results obtained in the same manner as in Table 6 are shown in Tables 6 and 7. Example 15 (1,2′-dimethylsilylene) (2,
Synthesis of 1′-dimethylsilylene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride (1,2′-dimethylsilylene) (2,2)
3.0 g (6.97 mmol) of lithium salt of 1′-dimethylsilylene) -bis (indene) was added to 50 mL of THF.
And cooled to -78 ° C. 2.1 mL (14.2 mmol) of iodomethyltrimethylsilane is slowly added dropwise and stirred at room temperature for 12 hours. The solvent is distilled off and ether 5
Add 0 mL and wash with saturated ammonium chloride solution.
After liquid separation, the organic phase was dried and the solvent was removed to give (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-trimethylsilylmethylindene) in 3.04.
g (5.88 mmol) were obtained. (Yield: 84%) Next, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-trimethylsilylmethylindene) obtained above was placed in a Schlenk bottle under a nitrogen stream. .04 g (5.88 mmol) and ether 5
Add 0 mL. After cooling to −78 ° C., 7.6 mL (11.7 mmol) of n-BuLi (hexane solution 1.54 M) was added.
l) After addition, stir at room temperature for 12 hours. The solvent was distilled off, and the obtained solid was washed with 40 mL of hexane to obtain 3.06 g of a lithium salt as an ether adduct.
(5.07 mmol) was obtained. (Yield 73%) The result of measurement by ¹ H-NMR (90 MHz, THF-d ₈ ) was: δ 0.04 (s, 18H, trimethylsilyl), 0.48 (s, 12H, dimethylsilylene), 1 .10 (t, 6H, methyl), 2.59 (s,
4H, methylene), 3.38 (q, 4H, methylene),
6.2-7.7 (m, 8H, Ar-H).

Under a nitrogen stream, the lithium salt obtained above is dissolved in 50 mL of toluene. 1.2 g of zirconium tetrachloride cooled to −78 ° C. and previously cooled to −78 ° C.
A suspension of (5.1 mmol) in toluene (20 mL) is added dropwise. After the addition, the mixture is stirred at room temperature for 6 hours. The solvent of the reaction solution is distilled off. The obtained residue was recrystallized from dichloromethane to give 0.9 g of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride (1. 33 mmol) were obtained. (Yield 2
6%) ¹ H-NMR (90 MHz, CDCl ₃ ) gives the following results: δ 0.0 (s, 18H, trimethylsilyl), 1.02, 1.12 (s, 12H, dimethylsilylene), 2. 51 (dd, 4H, methylene), 7.1-
7.6 (m, 8H, Ar-H). (2) Homopolymerization Instead of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-n-butylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2 , 1'-Dimethylsilylene) -bis (3-
Polymerization was carried out in the same manner as (2) of Example 1 except that (trimethylsilylmethylindenyl) zirconium dichloride was used. The results obtained in the same manner as in Example 1 are shown in Tables 6 and 7. Example 16 (1,2′-dimethylsilylene) (2,
Synthesis of 1′-dimethylsilylene) -bis (3-ethoxymethylindenyl) zirconium dichloride (1,2′-dimethylsilylene) (2,
4.1 g (9.50 mmol) of lithium salt of 1′-dimethylsilylene) -bis (indene) was added to 50 mL of THF.
And cooled to -78 ° C. 1.9 mL (20.5 mmol) of chloromethylethyl ether is slowly added dropwise, and the mixture is stirred at room temperature for 12 hours. The solvent is distilled off and ether 50
Add mL and hydrolyze with saturated ammonium chloride solution. After liquid separation, the organic phase was dried and the solvent was removed (1,2 ′
-Dimethylsilylene) (2,1'-dimethylsilylene)
3.43 g of -bis (3-ethoxymethylindene)
(7.40 mmol) was obtained. (Yield: 78%) Next, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-ethoxymethylindene) obtained above was placed in a Schlenk bottle under a nitrogen stream. 0.43 g (7.40 mmol) and 50 mL of ether are charged. After cooling to −78 ° C. and adding 9.4 mL (14.8 mmol) of n-BuLi (hexane solution 1.57 M), the mixture is stirred at room temperature for 12 hours. The solvent was distilled off, and the obtained solid was washed with 50 mL of hexane to give 1.07 g (1.96 mmol) of a lithium salt as an ether adduct.
l) obtained. (Yield 26%) The lithium salt obtained above was mixed with toluene 50 under a nitrogen stream.
Dissolve in mL. Cool to −78 ° C.
0.46 g (1.96 g) of zirconium tetrachloride cooled to
(mmol) in toluene (20 mL) is added dropwise.
After the addition, the mixture is stirred at room temperature for 6 hours. The solvent of the reaction solution is distilled off. The resulting residue was extracted with 40 mL of hexane to give (1,2′-dimethylsilylene) (2,1 ′).
-Dimethylsilylene) -bis (3-ethoxymethylindenyl) zirconium dichloride 0.24 g (0.
39 mmol). (Yield 20%) (2) Homopolymerization Instead of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-n-butylindenyl) zirconium dichloride, (1,2 ′ -Dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-
Polymerization was carried out in the same manner as in Example 1, (2) except that (ethoxymethylindenyl) zirconium dichloride was used. The results obtained in the same manner as in Example 1 are shown in Tables 6 and 7.

[0124]

[Table 2]

[0125]

[Table 3]

[0126]

[Table 4]

[0127]

[Table 5]

[0128]

[Table 6]

[0129]

[Table 7]

[0130]

The propylene-based polymer, propylene homopolymer, propylene-based copolymer and the resin composition and molded article comprising the polymer according to the present invention have low stickiness, excellent softness and transparency, and a film. It is suitable as a sheet, a container, a car interior material, a housing material for home electric appliances, and the like. Examples of the film include a food packaging film and an agricultural film, and examples of the container include a transparent case, a transparent box, and a decorative box. Further, it can be suitably used as a substitute resin for a soft vinyl chloride resin. The propylene-based resin modifier of the present invention has a soft property, gives a molded article having little tackiness and excellent compatibility with a polyrefin resin.

Continued on front page F-term (reference) 4F071 AA14 AA15 AA15X AA20 AA20X AA21 AA21X AA22 AB09 AB18 AB20 AB21 AB23 AB24 AB26 AB28 AB30 AC05 AC07 AC09 AC12 AC14 AC15 AC19 AC20 BB03 BB05 BB06 BC07 4J002 BB012 BB012 BB012 BB121 BB012 BB012 BB012 BB012 BQ002 DA026 DA096 DE076 DE136 DE146 DE186 DE236 DG026 DG046 DG056 DJ006 DJ016 DJ026 DJ036 DJ046 DJ056 DL006 EC056 EE056 EG026 EG076 EN076 EU006 EU026 EU056 EV256 EV306 EW046 FA046 FA086 FD202 FD206 AC01A01 AC01 AC01A01AC01A01AC01 AC47A AC48A AC49A BA01A BB00B BB01A BB01B BC15B BC16B BC17B BC25A DA01 DA02 DA03 DA04 DA06 DA08 DA09 EA01 EB02 EB04 EB05 EB07 EB08 EB09 EB10 EC01 EC02 FA01 FA02 FA03 FA04 FA06 FA07 A04AGAQ AGAA AGAA GAA CA10 DA04 DA09 DA22 DA24 FA09

Claims (12)

[Claims] 1. A propylene-based polymer satisfying the following (1) and (2). (1) The amount of the component (H25) eluted in hexane at 25 ° C. is 0 to 80% by mass. (2) In the DSC measurement, if the melting point (Tm (° C.)) is not shown or Tm is shown, Tm is used. Endotherm of melting ΔH
(J / g) satisfies the following relationship: ΔH ≧ 6 × (Tm−140) 2. A temperature of 25 ° C. in thermal chromatography.
Component amount (W25) eluted below is 20 to 100% by mass
The propylene-based polymer according to claim 1, which is: 3. A propylene homopolymer satisfying the following (1) to (3). (1) The mesopentad fraction (mmmm) is 20 to 60 mol%. (2) The racemic pentad fraction (rrrr) and (1-mm)
mm) satisfies the following relationship: [rrrr / (1-mmmm)] ≦ 0.1 (3) The component amount (W25) eluted at 25 ° C. or lower in the temperature rising chromatography is 20 to 100% by mass. 4. The propylene homopolymer according to claim 3, wherein the pentad fraction (rmrm) exceeds 2.5 mol%. 5. The propylene homopolymer according to claim 3, wherein a mesotriad fraction (mm), a racemic triad fraction (rr), and a triad fraction (mr) satisfy the following relationship. (Mm) × (rr) / (mr) ² ≦ 2.0 6. A propylene copolymer satisfying the following (1) and (2). (1) The stereoregularity index (P) by ¹³ C-NMR measurement is 55 to 90 mol%. (2) The component amount (W25) eluting at 25 ° C. or lower in the temperature rising chromatography is 20 to 100% by mass. is there 7. A molecular weight distribution (Mw / Mn) measured by a gel permeation chromatography (GPC) method.
Is 4 or less and / or intrinsic viscosity [η] measured in a tetralin solvent at 135 ° C. is 0.5 to 15.0 deciliter /
The propylene homopolymer according to any one of claims 3 to 5, or the propylene-based copolymer according to claim 6, which is g. 8. A transition represented by the following general formula (I):
Metal compound and (B) (B-1) Transition of component (A)
Reacts with metal compounds or their derivatives to form ionic complexes
Selected from compounds that can be formed and (B-2) aluminoxanes
Propylene in the presence of a polymerization catalyst containing
9. The method according to claim 3, which is obtained by polymerizing
The propylene homopolymer according to any one of the above. Embedded image[Wherein, M is a group 3 to 10 of the periodic table or a lanthanoid type
Indicates the metal element of the column, E ¹And E^TwoAre the replacement symbols
Lopentadienyl group, indenyl group, substituted indenyl
Group, heterocyclopentadienyl group, substituted heterocyclo
Pentadienyl group, amide group, phosphide group, hydrocarbon
A ligand selected from a group and a silicon-containing group,
¹And A^TwoTo form a cross-linked structure through
May be the same or different, and X is a σ bond
A plurality of X are the same when there are a plurality of Xs
But may be different, other X, E¹, E^TwoOr with Y
It may be crosslinked. Y represents a Lewis base;
In some cases, a plurality of Y may be the same or different,
Y, E¹, E^TwoOr X may be cross-linked,¹Passing
And A^TwoIs a divalent bridging group connecting the two ligands.
A hydrocarbon group having 1 to 20 carbon atoms;
Hydrogen-containing hydrocarbon group, silicon-containing group, germanium-containing
Group, tin-containing group, -O-, -CO-, -S-, -SO_Two
-, -Se-, -NR¹-, -PR¹-, -P (O) R
¹-, -BR¹-Or-AlR¹-Indicates R¹Is hydrogen
Atom, halogen atom, hydrocarbon group having 1 to 20 carbon atoms or
A halogen-containing hydrocarbon group having 1 to 20 carbon atoms;
They may be the same or different. q is 1 to 5
Represents [(valence of M) -2], and r represents 0 to 3
Indicates an integer. ] 9. A transition represented by the following general formula (I):
Metal compound and (B) (B-1) Transition of component (A)
Reacts with metal compounds or their derivatives to form ionic complexes
Selected from compounds that can be formed and (B-2) aluminoxanes
Propylene in the presence of a polymerization catalyst containing
And ethylene and / or an α-olefin having 4 to 20 carbon atoms
8. The compound according to claim 6, which is obtained by copolymerizing
The propylene-based copolymer described above. Embedded image[Wherein, M is a group 3 to 10 of the periodic table or a lanthanoid type
Indicates the metal element of the column, E ¹And E^TwoAre the replacement symbols
Lopentadienyl group, indenyl group, substituted indenyl
Group, heterocyclopentadienyl group, substituted heterocyclo
Pentadienyl group, amide group, phosphide group, hydrocarbon
A ligand selected from a group and a silicon-containing group,
¹And A^TwoTo form a cross-linked structure through
May be the same or different, and X is a σ bond
A plurality of X are the same when there are a plurality of Xs
But may be different, other X, E¹, E^TwoOr with Y
It may be crosslinked. Y represents a Lewis base;
In some cases, a plurality of Y may be the same or different,
Y, E¹, E^TwoOr X may be cross-linked,¹Passing
And A^TwoIs a divalent bridging group connecting the two ligands.
A hydrocarbon group having 1 to 20 carbon atoms;
Hydrogen-containing hydrocarbon group, silicon-containing group, germanium-containing
Group, tin-containing group, -O-, -CO-, -S-, -SO_Two
-, -Se-, -NR¹-, -PR¹-, -P (O) R
¹-, -BR¹-Or-AlR¹-Indicates R¹Is hydrogen
Atom, halogen atom, hydrocarbon group having 1 to 20 carbon atoms or
A halogen-containing hydrocarbon group having 1 to 20 carbon atoms;
They may be the same or different. q is 1 to 5
Represents [(valence of M) -2], and r represents 0 to 3
Indicates an integer. ] 10. A propylene resin composition obtained by adding a nucleating agent to the propylene polymer, propylene homopolymer or propylene copolymer according to any one of claims 1 to 9. 11. A molded product obtained by molding the propylene polymer, propylene homopolymer, propylene copolymer or propylene resin composition according to any one of claims 1 to 10. 12. A propylene resin modifier comprising the propylene polymer, propylene homopolymer or propylene copolymer according to any one of claims 1 to 9.