JP2001191463A - Polyolefin resin multilayered laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyolefin resin multilayered laminate excellent in low temperature heat sealability and having sufficient interlaminar strength. SOLUTION: The polyolefin resin multilayered laminate is constituted so that at least one of the outermost layers thereof comprises a propylene polymer [A] satisfying that (1) the amount of a component eluted into hexane at 25 deg.C (H25) is 0-80 weight % and (2) a melting point [Tm( deg.C)] is not shown in DSC measurement and, when Tm is shown, Tm and melting endotherm ΔH (J/g) satisfy relation: 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 polyolefin resin multilayer laminate, and more particularly, to a polyolefin resin multilayer laminate having excellent low-temperature heat sealability and sufficient interlayer strength without using an adhesive or the like.

[0002]

2. Description of the Related Art A crystalline propylene polymer film has been widely used as a packaging film because of its excellent rigidity, transparency and moisture-proof property. The crystalline propylene polymer film may be used alone, or may be used as a multilayer laminated with a film made of an ethylene-vinyl acetate copolymer or a linear polyethylene. Regardless of the single-layer or multi-layer form, packaging films are often processed into bags, and the process of processing the film into bags, filling the contents, and closing the bag mouth usually involves heating. This is performed by an operation called heat sealing in which the films are pressed together with a stick and melt-bonded to each other. In recent years, these series of bag making and packaging processes have been accelerated to improve productivity, and there has been a strong demand for the development of materials having excellent heat sealability. In order to smoothly perform these secondary processing steps, the film is required to have slip properties and anti-blocking properties as essential properties.

However, heat sealing of a propylene homopolymer film requires high-temperature, long-time pressing, and ethylene or 1-ethylene is used to improve this drawback.
Copolymerization of propylene with butene and other α-olefins has been widely practiced. However, in the prior art, it was necessary to copolymerize a large amount of a comonomer such as ethylene, 1-butene, and other α-olefins in order to obtain a sufficient heat sealing property improving effect. Further, these comonomers are often concentrated in low molecular weight components and have become sticky components having poor crystallinity (hereinafter referred to as sticky components). For this reason, rigidity, which is an inherent feature of the polypropylene film, is greatly reduced, the films are blocked from each other, hindering the secondary processing, and the appearance is deteriorated due to whitening of the bleeding, so that they cannot be put to practical use. Conventionally, attempts have been made to dissolve and remove the sticky components in an inert solvent.However, it is necessary to efficiently wash off the sticky components and suppress the low-temperature melting components that contribute to heat sealing properties from being reduced by washing. Was very difficult and not industrially satisfactory.

[0004] In recent years, high-speed film forming by large-scale film forming machines has been promoted in order to increase the productivity of film forming, and as a result, film forming conditions have changed from those in the past. It is also required that the film quality does not deteriorate. On the other hand, when the multilayer laminate is molded without using an adhesive, there is a problem that a sufficient interlaminar strength cannot be obtained. At present, they are bonded using an agent.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a polyolefin resin multilayer laminate having excellent low-temperature heat sealability and sufficient interlayer strength without using an adhesive or the like. is there.

[0006]

Means for Solving the Problems The inventors of the present invention have made intensive studies to achieve the above-mentioned object, and as a result, have found that at least one of the outermost layers is composed of a layer made of a specific propylene-based polymer. It has been found that this object can be achieved by the body, and based on this finding, the present invention has been completed. That is, the present invention provides the following polyolefin resin multilayer laminate. 1. A polyolefin resin multilayer structure in which at least one of the outermost layers is composed of a layer composed of a propylene-based polymer [A] satisfying the following (1) and (2). (1) The component amount (H25) eluted in hexane at 25 ° C. is 0 to 80% by weight. (2) In the DSC measurement, the melting point (Tm (° C.)) is not shown, or if Tm is shown, Tm and the melting endotherm ΔH
(J / g) satisfies the following relationship. ΔH ≧ 6 × (Tm-140) 2. The polyolefin resin multilayer laminate according to the above 1, wherein the component amount (W25) of the propylene-based polymer [A], which elutes at 25 ° C. or lower in a temperature rising chromatography, is 20 to 100% by weight. 3. 3. The polyolefin resin multilayer laminate according to the above 1 or 2, wherein the propylene-based polymer [A] is a propylene homopolymer [A-1] satisfying the following (1) and (2). (1) Mesopentad fraction [mmmm] is 20 to 60 mol% (2) Racemic pentad fraction [rrrr] and 1- [mm]
mm] satisfies the following relationship. [Rrrr] / (1- [mmmm]) ≦ 0.1 The polyolefin resin multilayer laminate according to the above 1 or 2, wherein the propylene-based polymer [A] is a propylene-based copolymer [A-2] satisfying the following (1). (1) The stereoregularity index (P) by ¹³ C-NMR measurement is 55 to 90 mol%. 5. The molecular weight distribution (Mw / Mn) of the propylene-based polymer [A], propylene homopolymer [A-1] or propylene-based copolymer [A-2] measured by gel permeation chromatography (GPC) is as follows. The polyolefin resin multilayer laminate according to any one of the above items 1 to 4, which has an intrinsic viscosity [η] of 0.5 to 15.0 deciliter / g as measured at 135 ° C in a tetralin solvent or less. 6. Propylene polymer [A], propylene homopolymer [A-1] or propylene copolymer [A-2],
(A) a compound capable of forming an ionic complex by reacting with a transition metal compound represented by the following general formula (I) and (B) a transition metal compound of the component (A) or a derivative thereof (B-
1) and in the presence of a polymerization catalyst containing at least one component selected from the group consisting of aluminoxanes (B-2),
6. The polyolefin resin multilayer laminate according to any one of the above 1 to 5, obtained by polymerizing propylene or propylene with ethylene and / or an α-olefin having 4 to 20 carbon atoms.

[0007]

Embedded image中 In the formula, M is a group 3 to 10 of the periodic table or a lanthanoid
Indicates the metal element of the column, E ¹And E^TwoAre placed independently
Substituted cyclopentadienyl group, indenyl group, substituted inde
Nyl group, heterocyclopentadienyl group, substituted heterocy
Clopentadienyl group, amide group, phosphide group, carbonized
A ligand selected from a hydrogen group and a silicon-containing group.
A¹And A^TwoTo form a crosslinked structure via
They may be the same or different, and X is σ
Represents a binding ligand, and when there are a plurality of Xs, a plurality of Xs
It may be the same or different, other X, E¹, E^TwoOr Y
And may be crosslinked. Y represents a Lewis base;
When there is a number, a plurality of Y may be the same or different,
Other Y, E¹, E^TwoOr X may be cross-linked,¹Passing
And A^TwoIs a divalent bridging group that connects two ligands
Wherein each independently represents a hydrocarbon having 1 to 20 carbon atoms
Groups, halogen-containing hydrocarbon groups having 1 to 20 carbon atoms, silicon-containing
Organic group, germanium-containing group, tin-containing group, -O-, -C
O-, -S-, -SO_Two-, -Se-, -NR-, -P
R-, -P (O) R-, -BR- or -AlR-
R represents a hydrogen atom, a halogen atom, a carbon atom having 1 to 20 carbon atoms.
Hydrogen groups or halogen-containing hydrocarbon groups having 1 to 20 carbon atoms
And they may be the same or different
No. q is an integer of 1 to 5 and represents ((valence of M) -2).
And r represents an integer of 0 to 3. ｝ 7. The other layer is composed of propylene polymer [A] and propylene.
Propylene-based polymerization other than propylene homopolymer [A-1]
7. The composition according to claim 1, which comprises at least one layer composed of a body.
The propylene-based resin multilayer laminate according to any one of the above. 8. Polyolefin polyolefin according to any one of the above 1 to 7
A layer laminate, obtained by a T-die casting method
Polyolefin resin multilayer laminate. 9. Tensile modulus TM (MPa) and heat sealing temperature H
Any one of the above 1 to 8, wherein ST (° C.) satisfies the following relationship:
3. The polyolefin resin multilayer laminate according to item 1.

[0008] TM ≧ 12.5 × HST-700

[0009]

DETAILED DESCRIPTION OF THE INVENTION The present invention is a multilayer laminate of a polyolefin resin as described above. Hereinafter, the present invention will be described in detail.

In the polyolefin resin multilayer laminate of the present invention, at least one of the outermost layers has the following (1) and (2):
Is a multilayer laminate composed of a layer made of a propylene-based polymer [A] satisfying the following. (1) The amount of the component (H25) eluted in hexane at 25 ° C. is 0 to 80% by weight. (2) In the DSC measurement, if the melting point (Tm (° C.)) is not shown or Tm is shown, Tm Endotherm of melting ΔH
(J / g) satisfies the following relationship: ΔH ≧ 6 × (Tm-140) As described above, the polyolefin resin multilayer laminate of the present invention has a specific property in which at least one of the outermost layers has little stickiness and is excellent in transparency. Since it is made of a propylene-based polymer [A], it has excellent low-temperature heat sealability and has sufficient interlayer strength without using an adhesive or the like. Propylene-based polymer [A] The propylene-based polymer [A] in the present invention has a component amount (H25) eluted in hexane at 25 ° C of 0 to 80% by weight.
It is. It is preferably from 0 to 50% by weight, particularly preferably from 0 to 25% by weight. 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. H25 is 80% by weight
If it exceeds, the amount of the sticky component is large, and the blocking resistance and the transparency are lowered, so that it cannot be used for food or medical products. H25 refers to the weight (W ₀ ) of the propylene-based polymer and the weight (W ₀ ) of the polymer after being allowed to stand in 200 mL of hexane at 25 ° C. for 3 days or more and then dried.
₁ ) is a weight loss rate obtained by measuring and calculating by the following formula. H25 = [(W ₀ −W ₁ ) / W ₀ ] × 100 (%) Further, the propylene polymer in the present invention does not show a melting point (Tm (° C.)) or shows Tm in DSC measurement. In this case, Tm and the melting endotherm ΔH (J /
g) satisfies the following relationship.

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

Incidentally, Tm and ΔH were determined 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.

When the propylene polymer in the present invention satisfies the above relationship, the resulting polyolefin resin multilayer laminate has an excellent balance between the amount of sticky component, low elastic modulus and 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.

In addition to the above requirements, the propylene-based polymer of the present invention has a component amount of the propylene-based polymer (W
25) is preferably 20 to 100% by weight. More preferably, it is 30 to 100% by weight, particularly preferably 50 to 100% by weight. 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 the unevenness of the stereoregularity distribution is widened.
In the present invention, if W25 is less than 20%, flexibility may be lost, which is not preferable. In addition, W25 is
It is the amount (% by weight) of a component which is not adsorbed to the filler and eluted at a TREF column temperature of 25 ° C. in an elution curve measured and measured by temperature raising chromatography under the following operation method, apparatus configuration and measurement conditions. . (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. I let it. Thereafter, the column was heated at a heating rate of 40 ° C./hour for 1 column.
The temperature was 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 to 60 mesh) Column temperature distribution: Within ± 0.2 ° C. As the propylene-based polymer [A] in the present invention, if it satisfies the above-mentioned requirements, in particular There is no limitation, but more specifically, a propylene homopolymer [A-
1] or a propylene-based copolymer [A-2]. Propylene homopolymer [A-1] Propylene homopolymer [A-1] is a polymer having properties shown in the following (1) and (2). (1) The mesopentad fraction [mmmm] is 20 to 60 mol%, and (2) the racemic pentad fraction [rrrr].
[Rrrr] / (1- [mmmm]) ≦ 0.1 When the propylene homopolymer [A-1] of the present invention satisfies the above relationship, a sticky component is obtained. And the balance between transparency and low elastic modulus 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. As a result, a polyolefin resin multilayer laminate having excellent low-temperature heat sealability and having sufficient interlayer strength without using an adhesive or the like can be obtained.

The mesopendad fraction ([mmmm] fraction) used in the present invention refers to A. Zambelli (A. Za).
"Macromolecule"
s, 6 , 925 (1973) ", and 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. When the mesopentad fraction [mmmm] of the propylene homopolymer is less than 20 mol%,
May cause stickiness. If it exceeds 60 mol%, the elastic modulus is undesirably high. Similarly, the racemic pendad 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 the pentad unit 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 high stereoregularity PP and APP is obtained as in the case of conventional polypropylene manufactured using an existing catalyst system, which means that stickiness increases and transparency decreases. . [Rrrr] / (1) of propylene homopolymer
-[Mmmm]) exceeds 0.1, causing stickiness. The measurement of the ¹³ C-NMR spectrum was performed by A.
"Macr" by A. Zambelli and others.
omolecules, 8 , 687 (1975) ", according to the following apparatus and conditions according to the assignment of peaks.

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 As the propylene homopolymer in the present invention, (3) the mesopentad fraction [mmmm] is 30 to 50%.
(4) racemic pentad fraction [rrrr] and 1- [mm
mm] more preferably satisfies the relationship of [rrrr] / (1- [mmmm]) ≦ 0.08, and particularly preferably satisfies the relationship of [rrrr] / (1- [mmmm]) ≦ 0.06. It is most preferable to satisfy the following relationship: rrrr] / (1− [mmmm]) ≦ 0.05.

Further, in addition to the above-mentioned requirements, the propylene homopolymer of the present invention is preferably excellent in flexibility because it has a melting endotherm ΔH of 20 J / g or less as measured by DSC. 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 ΔH was determined by the above method.

Furthermore, the propylene homopolymer in 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. Is preferably 100 ° C. or less. Note that Tm and Tc were determined 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.
The temperature dropped until. 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.

Furthermore, the amount (W25) of the component eluted at 25 ° C. or lower in the temperature raising chromatography is 30 to 100.
% By weight, and particularly preferably 50 to 100% by weight. If W25 is less than 20%, flexibility may be lost. The meaning and measurement method of W25 are the same as described above.

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). 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 determined 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 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. (Macromo).
lucules, 21 , p. 617 (1988)) and a report by Busico et al. (Macromolecule).
s, 27 , p. ¹³ C based on the 7538 (1994))
-It is each insertion content obtained by determining the assignment of the peak of the NMR spectrum and calculating from the integrated intensity of each peak. That is,
(M−2,1) is Pα, γthre 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 a racemic-2,1 insertion content (%) calculated from a ratio of integrated intensities of peaks belonging to Pα and γthreo appearing near pm. (1,3) is the value of T which appears around 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 the peaks belonging to β, 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. Chem. , 33 , p1305 (19
95)), the assignment of peaks in the ¹³ C-NMR 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. The ¹³ C-NMR measurement for abnormal insertion or molecular chain terminal measurement may be performed using 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 weight or more. The boiling diethyl ether extraction amount was measured using a Soxhlet extractor under the following conditions.

Extracted sample: 1 to 2 g Sample shape: powder-like (pelletized, 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 to diethyl ether (g) / charged powder weight (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. Propylene-based copolymer [A-2] Propylene-based copolymer [A-2] is a copolymer satisfying the following (1). (1) When the propylene-based copolymer of the present invention having a stereoregularity index (P) of 55 to 90 mol% as determined by ¹³ C-NMR measurement satisfies the above-mentioned relationship, the sticky component of the obtained multilayer laminate is obtained. Excellent balance between low amount, low elastic modulus and 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. Stereoregularity index (P) in the present invention
Is JNM-EX400 type NMR manufactured by JEOL Ltd.
Using a device, a ¹³ C-NMR spectrum was measured in the same manner as described above, and a mesotriad (m
m) Value obtained by measuring the fraction. The larger this value is, the higher the stereoregularity is. As the propylene copolymer in the present invention, a stereoregularity index (P)
Is more preferably 65 to 80 mol%. If the stereoregularity index (P) is less than 55 mol%, the elasticity is too low, and the moldability may be poor. On the other hand, if it exceeds 90 mol%, it may become hard and not soft. Further, W25 is more preferably 30 to 100% by weight, and particularly preferably 50 to 100% by weight. W25
If less than 20%, flexibility may be lost. The meaning of W25 and the measuring method are the same as described above.

Furthermore, in addition to the above requirements, the propylene-based copolymer of the present invention is preferably excellent in flexibility because it has a melting endotherm ΔH of 20 J / g or less as measured by DSC. Furthermore, melting point (Tm) and crystallization temperature (Tc)
It may or may not be present, but it is preferable that it does not have a softness point 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.

The propylene copolymer in the present invention is:
In addition to the above requirements, it is preferable that the extraction amount of boiling diethyl ether, which is an index of the elastic modulus, is 5% by weight 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. Specific examples of the propylene-based copolymer in the present invention include propylene and ethylene and / or 4-2 carbon atoms.
0 α-olefin copolymer. Carbon number 4
And α-olefins of 1 to 20 as 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene,
Examples include -octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene. In the present invention, one or more of these can be used.

Further, the propylene-based copolymer in 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%.

The propylene-based polymer [A], propylene homopolymer [A-1] and propylene-based copolymer [A-2] include, in addition to the above requirements, gel permeation (GPC). Molecular weight distribution (Mw
/ Mn) is 1.5 to 4 and / or 13 in tetralin solvent.
The intrinsic viscosity [η] measured at 5 ° C. is preferably 0.5 to 15.0 deciliter / g, and the Mw / Mn is 1.5 to 3.0.
5 and / or [η] is 1.0 to 5.0 deciliter / g
Is more preferable, and Mw / Mn is particularly preferably 1.5 to 3 and / or [η] is particularly preferably 1.0 to 3.0 deciliter / g. If the molecular weight distribution (Mw / Mn) exceeds 4, stickiness may occur, and if the intrinsic viscosity [η] is less than 0.5 deciliter / g, stickiness may occur. Also one
If it exceeds 5.0 deciliters / g, the flowability may be reduced and the moldability may be poor. In addition, Mw / Mn
Is a value calculated from the weight average molecular weight Mw and the 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) Further, the propylene-based polymer [A] and propylene homopolymer [A- 1] and a propylene-based copolymer [A-2]
(A) a transition metal compound represented by the following general formula (I), and (B) a compound capable of forming an ionic complex by reacting with the transition metal compound of the component (A) or a derivative thereof. In the presence of a polymerization catalyst containing at least one component selected from the group consisting of (B-1) and aluminoxane (B-2), propylene or propylene and ethylene and / or an α-olefin having 4 to 20 carbon atoms are polymerized. The polymer obtained by this is preferable.

[0030]

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 replaced independently
Cyclopentadienyl group, indenyl group, substituted indenyl
Group, heterocyclopentadienyl group, substituted heterocyclyl
Lopentadienyl group, amide group, phosphide group, hydrocarbon
A ligand selected from an elementary group and a silicon-containing group,
A¹And 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 Y and frame
You may have a bridge. Y represents a Lewis base;
A plurality of Y may be the same or different,
Y, E¹, E^TwoOr X may be cross-linked,¹And A^Two
Is a divalent bridging group connecting the two ligands,
Each independently a hydrocarbon group having 1 to 20 carbon atoms, 1 to 2 carbon atoms
0 halogen-containing hydrocarbon group, silicon-containing group, germanium
Group, tin-containing group, -O-, -CO-, -S-,-
SO_Two-, -Se-, -NR-, -PR-, -P (O)
R-, -BR- or -AlR-, wherein R is a hydrogen atom,
Halogen atom, hydrocarbon group having 1 to 20 carbon atoms, 1 carbon atom
Represent up to 20 halogen-containing hydrocarbon groups,
They may be the same or different. q is an integer of 1 to 5
[(Valence of M) -2], and r represents an integer of 0 to 3
You. In the general formula (I), M is a group 3 to 10 of the periodic table.
Or a metal element of the lanthanoid series, as a specific example
Is titanium, zirconium, hafnium, yttrium,
Vanadium, chromium, manganese, nickel, cobalt,
Palladium and lanthanoid metals
However, among these, olefin polymerization activity
Tan, zirconium and hafnium are preferred. E¹
And E^TwoAre each independently a substituted cyclopentadienyl
Group, indenyl group, substituted indenyl group, heterocyclo
Pentadienyl group, substituted heterocyclopentadienyl
Group, amide group (-N <), phosphide group (-P <), π
Bonding hydrocarbon group (> CR¹²-,> C <) and silicon
Organic group (> SiR)¹²−,> Si <) (where R¹²Is hydrogen
Or a hydrocarbon group having 1 to 20 carbon atoms or a hetero atom.
A ligand selected from the group consisting of¹as well as
A^TwoTo form a crosslinked structure. π-bonded carbonization
Hydrogen group [> CR¹²-,> C <] is pentadienyl
And a boratabenzene group. Silicon-containing groups
[> SiR¹²-,> Si <] represents -CH_Two-Si
(CH_Three) <, -Si (CH_Three) <And the like. Ma
E¹And E^TwoMay be the same or different
No. This E¹And E^TwoAs a substituted cyclopentadienyl
Preferred are a benzyl group, an indenyl group and a substituted indenyl group.

X represents a σ-binding ligand, and when there are a plurality of Xs, the plurality of Xs may be the same or different, and may be cross-linked to another X, E ¹ , E ² or Y. Good. Specific examples of X include a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an amide group having 1 to 20 carbon atoms, and a carbon atom. Examples thereof include a silicon-containing group having 1 to 20 carbon atoms, a phosphide group having 1 to 20 carbon atoms, a sulfide group having 1 to 20 carbon atoms, and an acyl group having 1 to 20 carbon atoms. Examples of the halogen atom include a chlorine atom, a sulfoxide group having 1 to 20 carbon atoms, a fluorine atom, a bromine atom and an iodine atom. Carbon number 1-2
Specific examples of the hydrocarbon group 0 include alkyl groups such as methyl group, ethyl group, propyl group, butyl group, hexyl group, cyclohexyl group and octyl group; alkenyl groups such as vinyl group, propenyl group and cyclohexenyl group. Groups; arylalkyl groups such as benzyl, phenylethyl, phenylpropyl; phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenyl, naphthyl,
And aryl groups such as a methylnaphthyl group, an anthracenyl group and a phenanthonyl group. Among them, methyl group,
An alkyl group such as an ethyl group and a propyl group and an aryl group such as a phenyl group are preferred. Examples of the alkoxy group having 1 to 20 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a phenylmethoxy group, a phenylethoxy group, and the like. Examples of the aryloxy group having 6 to 20 carbon atoms include a phenoxy group, a methylphenoxy group, and a dimethylphenoxy group. Examples of the amide group having 1 to 20 carbon atoms include a dimethylamide group, a diethylamide group, a dipropylamide group, a dibutylamide group, a dicyclohexylamide group, an alkylamide group such as a methylethylamide group; a divinylamide group, a dipropenylamide group,
An alkenylamide group such as a dicyclohexenylamide group; an arylalkylamide group such as a dibenzylamide group, a phenylethylamide group and a phenylpropylamide group; and an arylamide group such as a diphenylamide group and a dinaphthylamide group. Examples of the silicon-containing group having 1 to 20 carbon atoms include monohydrocarbon-substituted silyl groups such as methylsilyl group and phenylsilyl group; dihydrocarbon-substituted silyl groups such as dimethylsilyl group and diphenylsilyl group; trimethylsilyl group, triethylsilyl group; Trihydrocarbon-substituted silyl groups such as tripropylsilyl group, tricyclohexylsilyl group, triphenylsilyl group, dimethylphenylsilyl group, methyldiphenylsilyl group, tritolylsilyl group and trinaphthylsilyl group; hydrocarbons such as trimethylsilyl ether group A substituted silyl ether group; a silicon-substituted alkyl group such as a trimethylsilylmethyl group; and a silicon-substituted aryl group such as a trimethylsilylphenyl group. Examples of the phosphide group having 1 to 20 carbon atoms include an alkyl phosphide group such as a methyl phosphide group, an ethyl phosphide group, a propyl phosphide group, a butyl phosphide group, a cyclohexyl phosphide group, a hexyl phosphide group, and an octyl phosphide group; An alkenyl phosphide group such as a phosphide group and a propenyl phosphide group; and an aryl phosphide group such as a phenyl phosphide group. Carbon number 1
As the sulfide group of -20, a methyl sulfide group,
Alkyl sulfide groups such as ethyl sulfide group, propyl sulfide group, butyl sulfide group, hexyl sulfide group, cyclohexyl sulfide group and octyl sulfide group; alkenyl sulfide groups such as vinyl sulfide group, propenyl sulfide group and cyclohexenyl sulfide group; benzyl sulfide group , An arylalkyl sulfide group such as phenylethyl sulfide group, phenylpropyl sulfide group; phenyl sulfide group, tolyl sulfide group, dimethyl phenyl sulfide group, trimethyl phenyl sulfide group, ethyl phenyl sulfide group, propyl phenyl sulfide group, biphenyl sulfide group, naphthyl Sulfide group, methylnaphthyl sulfide group, anthracenyl sulfide group, phenanthyl sulfide group What aryl sulfide groups. Examples of the sulfoxide group having 1 to 20 carbon atoms include alkyl sulfoxide groups such as methyl sulfoxide group, methyl sulfoxide group, propyl sulfoxide group, butyl sulfoxide group, hexyl sulfoxide group, cyclohexyl sulfoxide group and octyl sulfoxide group; vinyl sulfoxide group and propenyl sulfoxide. An alkenyl sulfoxide group such as a cyclohexenyl sulfoxide group; an arylalkyl sulfoxide group such as a benzyl sulfoxide group, a phenylethyl sulfoxide group or a phenylpropyl sulfoxide group; a phenyl sulfoxide group;
Tolylsulfoxide group, dimethylphenylsulfoxide group, trimethylphenylsulfoxide group, ethylphenylsulfoxide group, propylphenylsulfoxide group,
Biphenylsulfoxide group, naphthylsulfoxide group,
And arylsulfoxide groups such as methylnaphthylsulfoxide group, anthracenylsulfoxide group, and phenanthonylsulfoxide group. Examples of the acyl group having 1 to 20 carbon atoms include formyl group, acetyl group, propionyl group, butyryl group, valeryl group, palmitoyl group, tearoyl group, alkylacyl group such as oleoyl group, benzoyl group, toluoyl group, salicyloyl group, Arylacyl groups such as a cinnamoyl group, a naphthoyl group, and a phthaloyl group; oxalyl groups, malonyl groups, and succinyl groups each derived from a dicarboxylic acid such as oxalic acid, malonic acid, and succinic acid; 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 another Y, E ¹ , E ² or X. Specific examples of the Lewis base of Y include amines, ethers, phosphines, thioethers and the like. Examples of the amines include amines having 1 to 20 carbon atoms, and specifically, methylamine, ethylamine,
Alkylamines such as propylamine, butylamine, cyclohexylamine, methylethylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, dicyclohexylamine and methylethylamine; vinylamine, propenylamine, cyclohexenylamine, divinylamine, dipropenylamine, diamine Alkenylamines such as cyclohexenylamine; arylalkylamines such as phenylmethylamine, phenylethylamine and phenylpropylamine; and arylamines such as diphenylamine and dinaphthylamine. As ethers, methyl ether, ethyl ether, propyl ether, isopropyl ether,
Aliphatic single ether compounds such as butyl ether, isobutyl ether, n-amyl ether, isoamyl ether; methyl ethyl ether, methyl propyl ether;
Aliphatic mixed ether compounds such as methyl isopropyl ether, methyl-n-amyl ether, methyl isoamyl ether, ethyl propyl ether, ethyl isopropyl ether, ethyl butyl ether, ethyl isobutyl ether, ethyl n-amyl ether, ethyl isoamyl ether; vinyl ether; Aliphatic unsaturated ether compounds such as allyl ether, methyl vinyl ether, methyl allyl ether, ethyl vinyl ether and ethyl allyl ether; such as anisole, phenetole, phenyl ether, benzyl ether, phenylbenzyl ether, α-naphthyl ether and β-naphthyl ether; Aromatic ether compound, ethylene oxide, propylene oxide, trimethylene oxide, tetrahydrofuran, tetrahydropyran, dioxane And the like. Examples of the phosphines include phosphines having 1 to 20 carbon atoms. Specifically, methyl phosphine,
Mono (cyclo) alkyl phosphines such as ethyl phosphine, propyl phosphine, butyl phosphine, hexyl phosphine, cyclohexyl phosphine, and octyl phosphine; (Cyclo) alkyl phosphines; tri (cyclo) alkyl phosphines such as trimethyl phosphine, triethyl phosphine, tripropyl phosphine, tributyl phosphine, trihexyl phosphine, tricyclohexyl phosphine, and trioctyl phosphine; vinyl phosphine, propenyl phosphine,
Monoalkenyl phosphine such as cyclohexenyl phosphine; dialkenyl phosphine in which two alkenyl hydrogen atoms of phosphine are substituted; trialkenyl phosphine in which three alkenyl hydrogen atoms of phosphine are substituted;
Arylalkylphosphines such as benzylphosphine, phenylethylphosphine and phenylpropylphosphine; diarylalkylphosphines or aryldialkylphosphines in which three hydrogen atoms of phosphine are substituted with three aryl or alkenyl; phenylphosphine;
Tolylphosphine, dimethylphenylphosphine, trimethylphenylphosphine, ethylphenylphosphine, propylphenylphosphine, biphenylphosphine, naphthylphosphine, methylnaphthylphosphine,
Aryl phosphines such as anthracenyl phosphine and phenanthyl phosphine; di (alkyl aryl) in which two hydrogen atoms of phosphine are substituted by alkyl aryl
Phosphine; tri (alkylaryl) phosphine in which three alkylaryls have been substituted for phosphine hydrogen atoms; Examples of the thioethers include a sulfide representing X.

A¹And A^TwoIs a divalent linking two ligands
A hydrocarbon group having 1 to 20 carbon atoms,
A halogen-containing hydrocarbon group of 1 to 20; a silicon-containing group;
Rumanium-containing group, tin-containing group, -O-, -CO-,-
S-, -SO_Two-, -Se-, -NR-, -PR-,-
P (O) R-, -BR- or -AlR-, wherein R is water
An element atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms,
A halogen-containing hydrocarbon group having 1 to 20 carbon atoms;
They may be the same or different. A ¹And A^Two
At least one of them is a hydrocarbon group having 1 or more carbon atoms
It is preferably a cross-linking group consisting of Such a crosslinking group
Is, for example, an ethylene group, 1,2-cyclohexyl
Group, dimethylsilylene group, diphenylsilylene group,
Tylphenylsilylene group, dimethylgermylene group,
Tilstannylene group, tetramethyldisilylene group, dife
Nyldisilylene group and the following general formula:

[0033]

Embedded image (R ² and R ³ each independently represent a hydrogen atom or a carbon atom
In the 20 hydrocarbon groups, they may be the same or different, and may combine with each other to form a ring structure. e shows the integer of 1-4. ). Specific examples of the crosslinking group represented by the above general formula include a methylene group, an ethylidene group, a propylidene group, an isopropylidene group, a cyclohexylidene group, and a vinylidene group (CH ₂ ＣC ＝).
Among them, an ethylene group, an isopropylidene group and a dimethylsilylene group are preferred. q represents an integer of 1 to 5 and represents ((valence of M) -2), and r represents an integer of 0 to 3.

In the transition metal compound represented by the general 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 is preferred. Among the transition metal compounds represented by the general formula (I), the general formula (II)

[0035]

Embedded image 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, A¹,
A^Two, Q and r are the same as above. X ¹Is the distribution of σ connectivity
Indicates a ligand, X¹If there are multiple Xs¹Is the same
May be different, other X¹Or Y¹Even if cross-linked
Good. This X¹As a specific example of the general formula (I),
The same ones as exemplified in the description can be given.
Y¹Represents a Lewis base;¹If there is more than one,
¹May be the same or different, and the other Y¹Or X¹And frame
You may have a bridge. This Y¹As a specific example of the general formula
The same ones as those exemplified in the description of Y in (I) may be cited.
Can be. R^Four~ R⁹Are hydrogen atom and halogen atom, respectively
, A hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms.
Hydrogen-containing hydrocarbon groups, silicon-containing groups or heteroatoms
Represents a group, at least one of which is not a hydrogen atom
is necessary. Also, R^Four~ R⁹Same but different
Adjacent groups may be bonded to each other to form a ring
May be formed. Above all, R⁶And R⁷Forms a ring
And R⁸And R⁹Preferably form a ring
Good. R^FourAnd R^FiveAs oxygen, halogen, silicon, etc.
Groups containing a hetero atom of
No.

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) [(III), (IV) wherein L ¹ is a Lewis base, [Z]
^- is a non-coordinating anion [Z ^{1] -} and [Z ^{2] -,} wherein [Z ^{1] -} anion in which [M ¹ more groups are bonded to the element G ¹ G ² ··· G ^{f -} (Where M ¹ is the fifth in the periodic table)
It represents a Group 15 element, preferably a Group 13-15 element of the periodic table. G ^{1 to} G ^f are a hydrogen atom, a halogen atom,
An alkyl group having 1 to 20 carbon atoms, a dialkylamino group having 2 to 40 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, and 7 carbon atoms Alkyl aryl group of ~ 40, carbon number 7
Arylalkyl group having 1 to 20 carbon atoms, halogen-substituted hydrocarbon group having 1 to 20 carbon atoms, acyloxy group having 1 to 20 carbon atoms,
It represents an organic metalloid group or a heteroatom-containing hydrocarbon group having 2 to 20 carbon atoms. Two or more of G ^{1 to} G ^f may form a ring. f is [(valence of the center metal M ¹⁾ +
1]. ), [Z ^{2] -} is the logarithm of the reciprocal of the acid dissociation constant (pKa) -10 below Bronsted acid alone or Bronsted acid and Lewis acid combination of conjugate base, or a general superacid defined The conjugate base of the acid used. Further, a Lewis base may be coordinated. 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. L ² is M ² , R ¹¹ R ¹² M ³ , R
¹³ ₃ C or R ¹⁴ M ^3, respectively R ¹¹ and R ¹² are a cyclopentadienyl group, substituted cyclopentadienyl group, an indenyl group or a fluorenyl group, R ¹³ having 1 to 20 carbon atoms
Represents an alkyl group, 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 ], and is 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 ], specific examples of M ¹ include B, Al, S
i, P, As, Sb and the like, preferably B and Al. Specific examples of G ¹ , G ^{2 to} G ^f include dimethylamino and diethylamino as dialkylamino groups, methoxy, ethoxy, n-butoxy, phenoxy and the like as alkoxy or aryloxy groups. Methyl group, ethyl group, n-
Propyl, isopropyl, n-butyl, isobutyl, n-octyl, n-eicosyl, phenyl, p-tolyl, benzyl, 4-t-butylphenyl, 3,5-dimethylphenyl For example, fluorine, chlorine, bromine, iodine as a halogen atom, p-fluorophenyl group, 3,5-difluorophenyl group, pentachlorophenyl group, 3,4,
5-trifluorophenyl group, pentafluorophenyl group, 3,5-bis (trifluoromethyl) phenyl group,
Pentamethylantimony, trimethylsilyl, trimethylgermyl, diphenylarsine, organic metalloid groups such as bis (trimethylsilyl) methyl group,
Examples include a dicyclohexylantimony group and diphenylboron.

Further, 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 trifluoromethanesulfonic acid anion (C
F ₃ SO ₃ ) ^- , bis (trifluoromethanesulfonyl)
Methyl anion, bis (trifluoromethanesulfonyl) benzyl anion, bis (trifluoromethanesulfonyl) amide, perchlorate anion (ClO ₄ ) ⁻ , trifluoroacetic acid anion (CF ₃ CO ₂ ) ⁻ , hexafluoroantimony anion (SbF ₆ ) ^-, fluorosulfonic acid anion (FSO ₃₎ ^-, chlorosulfonic acid anion (ClSO ₃₎ ^-, fluorosulfonic acid anion / antimony pentafluoride ^{_{(FSO 3 / SbF 5) -}} , fluorosulfonic acid anion / 5- fluoride Arsenic (FSO ₃ / AsF ₅ )
^-, trifluoromethanesulfonic acid / antimony pentafluoride _{(CF 3 SO 3 / SbF 5} ) - and the like.

Specific examples of the 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)

[0045]

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

[0046]

Embedded image (In the formula, R ¹⁵ and w are the same as those in the general 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 means is not particularly limited, and the reaction may be carried out 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 water is added later, water of crystallization contained in a metal salt, etc., inorganic substances Reacting water adsorbed on organic substances with organic aluminum compounds,
There is a method of reacting a tetraalkyldialuminoxane with a trialkylaluminum and then reacting with water. The aluminoxane may be insoluble in toluene.

These aluminoxanes may be used alone or in a combination of two or more. When the (B-1) compound is used as the (B) catalyst component, the molar ratio of the (A) catalyst component to the (B) catalyst component is preferably from 10: 1 to 1: 100, Preferably 2: 1
If the ratio deviates from the above range, the catalyst cost per unit weight polymer increases,
Not practical. When the compound (B-2) is used, the molar ratio is preferably 1: 1 to 1: 1,000,000,
More preferably, the range is from 1:10 to 1: 10000. If the ratio is outside this range, the cost of the catalyst per unit weight of polymer increases, which is not practical. As the catalyst component (B), (B-1) and (B-2) can be used alone or in combination of two or more.

As the polymerization catalyst in the present invention, 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 general formula
(VII) R ¹⁶ _v AlJ _3-v (VII) wherein R ¹⁶ is an alkyl group having 1 to 10 carbon atoms, J is a hydrogen atom, an alkoxy group having 1 to 20 carbon atoms, and 6 to 6 carbon atoms. 20
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 and 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 present invention, preliminary contact can also be performed using the above-mentioned components (A), (B) and (C). 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. In addition, the preliminary contact temperature is usually −20 ° C. to 200 ° C.,
Preferably −10 ° C. to 150 ° C., more preferably 0 ° C.
８０80 ° 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 of these are:
It is an aliphatic hydrocarbon.

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, Fe 2 O
_{3, B 2 O 3, CaO} , ZnO, BaO, ThO 2 and mixtures thereof, for example, silica alumina, zeolite, ferrite, and glass fiber. 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 MgR represented by l ₂ , Mg (OC ₂ H ₅ ) _2, etc.
Magnesium compounds and their complex salts represented by the ¹⁷ _X X ¹ _y can be exemplified. Here, R ¹⁷ has 1 to 20 carbon atoms.
An alkyl group, an alkoxy group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, X ¹ represents a halogen atom or an alkyl group having 1 to 20 carbon atoms, x is 0 to 2, y is 0 to
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,
More preferably, it is 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, causing a decrease in bulk density and clogging of a hopper. The specific surface area of the carrier is usually 1 to 1000 m ² / g, preferably 50 to 1000 m ² / g.
500 m ² / g, pore volume is usually 0.1-5 cm ³ / g,
Preferably it is 0.3-3 cm < ³ > / 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 from the volume of nitrogen gas adsorbed according to, for example, the BET method.

Further, when the carrier is an inorganic oxide, it is usually at 150 to 1000 ° C., preferably at 200 to 80 ° C.
It is desirable to use it after firing at 0 ° 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 component (A) and the component (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 components (A) and (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 weight ratio of the component (B-1) to the carrier is preferably 1: 5 to 1:10.
000, more preferably 1:10 to 1: 500, and the ratio of the component (B-2) to the carrier is preferably 1: 0.5 to 1: 1000 by weight, more preferably It is desirable to set it as 1: 1 to 1:50. When two or more components (B) are used as a mixture, it is desirable that the use ratio of each component (B) to the carrier be within the above range in terms of weight ratio. The proportion of the component (A) and the carrier is as follows:
It is desirable that the weight ratio is preferably 1: 5 to 1: 10000, more preferably 1:10 to 1: 500.

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 average particle size of the polymerization catalyst thus prepared is usually 2 to 200 μm, preferably 10 to 15 μm.
0 μm, particularly preferably 20 to 100 μm, and the specific surface area is usually 20 to 1000 m ² / g, preferably 50
５００500 m ² / g. If the average particle size is less than 2 μm, fine powder in the polymer may increase, and if it exceeds 200 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. Further, in the polymerization catalyst,
The amount of transition metal in 100 g of the support is usually 0.05 to 10
g, particularly preferably 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 in this way, a polymer having a high bulk density and excellent particle size distribution, which are industrially advantageous, can be obtained. The propylene-based polymer [A], propylene homopolymer [A-1] and propylene-based copolymer [A-2] are propylene homopolymerized using the above-mentioned polymerization catalyst, or propylene and ethylene and And / or copolymerized with an α-olefin having 4 to 20 carbon atoms. In this case, the polymerization method is not particularly limited, and any method such as a slurry polymerization method, a gas phase polymerization method, a bulk polymerization method, a solution polymerization method, and a suspension polymerization method may be used. The polymerization method is 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^FiveTona
Preferably. Further, the polymerization time is usually from 5 minutes to 10 minutes.
Time and reaction pressure are preferably normal pressure to 20 MPa (Gau
ge), particularly 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, the amount of polymerization 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 above-mentioned 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, particularly 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.

The propylene polymer [A], the propylene homopolymer [A-1] and the propylene copolymer [A-2] are those in which various additives are formulated as necessary. You may. Various additives used as desired include antioxidants, neutralizing agents, slip agents, antiblocking agents, antifogging agents, and antistatic agents. These additives may be used alone or in a combination of two or more. For example, examples of the antioxidant include a phosphorus-based antioxidant, a phenol-based antioxidant, and a sulfur-based antioxidant.

Specific examples of the phosphorus-based antioxidant include trisnonylphenyl phosphite, tris (2,4-di-
t-butylphenyl) phosphite, distearylpentaerythritol diphosphite, bis (2,4-di-
t-butylphenyl) pentaerythritol phosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl Phosphite, tetrakis (2,4-di-t-butylphenyl) -4,4-biphenylene-di-phosphonite,
ADK STAB 1178 (Asahi Denka Co., Ltd.), SUMILIZER TNP (Sumitomo Chemical Co., Ltd.), JP-135 (Johoku Chemical Co., Ltd.), ADK STAB 2112 (Asahi Denka Co., Ltd.), J
PP-2000 (Johoku Chemical Co., Ltd.), Weston 6
18 (GE (product)), ADK STAB PEP-24G (Asahi Denka (product)), ADK STAB PEP-36 (Asahi Denka (product)), ADK STAB HP-10 (Asahi Denka (product)),
Sandstab P-EPQ (Clariant (product)),
And phosphite 168 (manufactured by Ciba Specialty Chemicals).

Specific examples of the phenolic antioxidant include 2,6-di-t-butyl-4-methylphenol,
n-octadecyl-3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate, tetrakis [methylene-3- (3,5-di-t-butyl-4-
Hydroxyphenyl) propionate] methane, tris (3,5-di-t-butyl-4-hydroxybenzyl)
Isocyanurate, 4,4'-butylidenebis- (3-
Methyl-6-t-butylphenol), triethylene glycol-bis [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionate], 3,9-
Bis {2- [3- (3-t-butyl-4-hydroxy-
5-methylphenyl) propionyloxy] -1,1-
Dimethylethyl {-2,4,8,10-tetraoxaspiro [5,5] undecane, Sumilizer BHT (Sumitomo Chemical Co., Ltd.), Yoshinox BHT (Yoshitomi Pharmaceutical Co., Ltd.), Antage BHT (Kawaguchi Chemical Co., Ltd.) ), Irganox 1076 (Ciba Specialty Chemicals Co., Ltd.), Irganox 1010 (Ciba Specialty Chemicals Co., Ltd.), ADK STAB AO-60 (Asahi Denka Co., Ltd.), Sumilizer BP-101 (Sumitomo Chemical Co., Ltd.) ), Tominox TT (Yoshitomi Pharmaceutical Co., Ltd.), TT
HP (Toray (product)), Irganox 3114 (Ciba Specialty Chemicals (product)), ADK STAB AO
-20 (Asahi Denka Co., Ltd.), ADK STAB AO-40 (Asahi Denka Co., Ltd.), Sumilizer BBM-S (Sumitomo Chemical Co., Ltd.), Yoshinox BB (Yoshitomi Pharmaceutical Co., Ltd.), Antage W-300 (Kawaguchi Chemical (product)), Irganox 245 (Ciba Specialty Chemicals (product)), ADK STAB AO-70 (Asahi Denka (product)), Tominox 917 (Yoshitomi Pharmaceutical (product)), ADK STAB AO-80
(Asahi Denka Co., Ltd.), Sumilizer GA-80 (Sumitomo Chemical Co., Ltd.) and the like.

Specific examples of the sulfur-based antioxidant include dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate. Pentaerythritol tetrakis (3-laurylthiopropionate),
Sumilizer TPL (Sumitomo Chemical Co., Ltd.), Yoshinox DLTP (Yoshitomi Pharmaceutical Co., Ltd.), Antiox L (Nippon Oil & Fats Co., Ltd.), Sumilizer TPM (Sumitomo Chemical Co., Ltd.), Yoshinox DMTP (Yoshitomi Pharmaceutical Co., Ltd.) ,
Antiox M (Nippon Oil & Fats), Sumilizer T
PS (Sumitomo Chemical Co., Ltd.), Yoshinox DSTP (Yoshitomi Pharmaceutical Co., Ltd.), Antiox S (Nippon Oil & Fats Co., Ltd.),
ADK STAB AO-412S (Asahi Denka Co., Ltd.), SEE
NOX 412S (Cipro Kasei Co., Ltd.), Sumilizer TDP (Sumitomo Chemical Co., Ltd.) and the like.

Among these, preferred phenolic antioxidants include Ciba Specialty Chemicals (Irganox 1010): Substance: pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4) -Hydroxyphenyl) propionate] Irganox 1076 (manufactured by Ciba Specialty Chemicals): Substance: Octadecyl-3- (3,5-di-
t-butyl-4-hydroxyphenyl) propionate Ciba Specialty Chemicals (Irganox 1330): Substance: 1,3,5-trimethyl-2,4
6-Tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene Ciba Specialty Chemicals Co., Ltd. Irganox 3114: Substance: Tris (3,5-di-t-butyl-benzene)
4-hydroxybenzyl) isocyanurate and the like. Preferred examples of the phosphorus-based antioxidant include: Ciba Specialty Chemicals (Irgafos 1)
68: substance name: tris (2,4-di-t-butylphenyl) phosphite P-EPQ (manufactured by Clariant): substance name: tetrakis (2,4-di-t-butylphenyl) 4,4′- Biphenylene-di-phosphite and the like.

When an antioxidant is used in the present invention, the polymer [A], [A-1] or [A-2]
About 0.001 to 1 part by weight may be added to 0 part by weight. This is preferable because yellowing and the like can be prevented.

Examples of the neutralizing agent include calcium stearate, zinc stearate, magnesium stearate, hydrotalcites (for example, D
HT-4A: Composition formula: Mg _4.5 Al ₂ (OH) ₁₃ CO _3.
3.5H ₂ O), lithium-aluminum composite hydroxide (for example, Mizukarak of Mizusawa Chemical Industries, Ltd .: composition formula: [Li ₂ Al ₄ (OH) ₁₂ ] CO ₃ .mH ₂ O, where m ≒ 3) And the like are particularly preferred.

As the anti-blocking agent, a synthetic silica-based anti-blocking agent “Sylysia” manufactured by Fuji Silysia (manufactured by) and a synthetic silica-based anti-blocking agent “Mizukasil” manufactured by Mizusawa Chemical Industries (manufactured by) are particularly preferable.

As the slip agent, erucamide, oleamide, stearamide, behenic amide, ethylenebisstearic amide, ethylenebisoleic amide, stearyl erucamide, and oleyl palmitamide are particularly preferred.

In the present invention, various additives may be added in an amount of about 0.001 to 1 part by weight based on 100 parts by weight of the polymer [A], [A-1] or [A-2]. The following examples can be given as specific examples of the additive formulation. Example of additive formulation (A) Antioxidant Irganox 10 from Ciba Specialty Chemicals
10: 1000 ppm Irgafos 168 from Ciba Specialty Chemicals: 1000 ppm Neutralizer Calcium stearate: 1000 ppm Antiblocking agent Silica-based antiblocking agent from Fuji Silysia: 23
00 ppm slip agent erucamide: 500 ppm In the polyolefin resin multilayer laminate of the present invention, at least one surface of the outermost layer (also referred to as a heat seal layer) has at least one surface of the above-mentioned propylene polymer [A] and propylene homopolymer [A-
1] and the propylene-based copolymer [A-2], there is no particular limitation on the structure of the other layers (also referred to as an intermediate layer or a laminate layer). As other layers, the propylene-based polymer [A], propylene homopolymer [A-1] and propylene-based copolymer [A
-2]. Among them, a propylene-based polymer is preferably mentioned. The propylene-based polymer is not particularly limited as long as it is a propylene-based polymer exhibiting crystallinity (hereinafter also referred to as a crystalline propylene-based polymer). For example, the crystalline propylene-based polymer includes a propylene homopolymer, a propylene-ethylene random copolymer, a propylene-ethylene-1-butene random copolymer, a propylene-ethylene block copolymer, and the like. In addition, the molecular weight of the crystalline propylene-based polymer is selected from the viewpoint of moldability in each case, and a melt index (230 ° C., 2160 gf) of 2 to 20 g is used for T-die cast film molding.
/ 10 min is preferable.
It is preferably about 10 to 10 g / 10 min. From these, it can be arbitrarily selected and used depending on the intended use of the film or sheet. For example, a propylene homopolymer having a high melting point and high crystallinity is preferred for applications where heat resistance and heat seal strength are important.
No. 85711 can be exemplified. That is, (1) the isotactic Ventad fraction P, which is a stereoregularity index, is 85.0 to 92.0 mol%, and the n-heptane insoluble portion amount H is 98.0 to 97.0 wt%, And P
And H satisfy the formula 0.750P + 27.125 <H, and (2) the melt index (MI)
(230 ° C., 2160 gf, hereinafter the same) is 1 to 20 g /
10 min and at a temperature of 175 ° C., a frequency ω ₀ = 10 ⁰ rad / se obtained by frequency dispersion measurement
A polypropylene-based polymer in which the relationship between the relaxation time τ (sec) and MI in c satisfies the formula τ ≦ 0.65-0.025MI is exemplified.

More preferably, (1 ′) isotactic bentad fraction P which is an index of stereoregularity is 85.0 to 92.0 mol%, and n-heptane insoluble part amount H is 86.0 to 97.%. 0% by weight and the relationship between P and H satisfies the equation 0.750P1026.000 <H, and the (2 ′) melt index (M
I) is 1 to 25 g / 10 min and the temperature is 175
In ° C., the frequency ω ₀ obtained by the frequency dispersion measurement
= 10 ⁰ rad / sec relaxation time in τ (sec)
And a MI is such that a polypropylene-based polymer satisfies the formula τ ≦ 0.63-0.025MI.

The meanings of P, H, MI, ω ₀ and τ, the measuring method, the method for producing the propylene polymer and the like are as described in JP-A-8-85711.

When improving the low-temperature heat-sealing property of a film or sheet, the crystalline propylene-based polymer may be a propylene / ethylene random copolymer or propylene / ethylene / 1-butene random copolymer having excellent low-temperature heat sealability. Polymers (hereinafter also referred to as propylene-based random copolymers) and the like are preferable.
9, JP-A-9-272718, JP-A-10-272718
And those described in JP-A-130336 can be exemplified. That is, a propylene-based random copolymer which is a copolymer of propylene and ethylene and satisfies the following conditions can be given. (JP-A-9-208629)
Publication) The combined amount of ethylene units in the copolymer (χ (wt
%)) Is 3 to 10 wt%. Melt index of copolymer (MI (g / 10m
in)) is 4 to 12 g / 10 min. The boiling diethyl ether extraction amount (E (wt%))
Satisfies the relationship of the formula (I) or (II). E ≦ 0.25χ1.1 (χ = 3 to 6 wt%) (E) E ≦ 2.6 (χ = 6 to 10 wt%) ·・ ・ (II) Tm ≦ 140 (χ = 3 to 5 wt%) where melting point (Tm (° C.)) measured by a differential scanning calorimeter and χ satisfy the relationship of formula (III) or (IV). III) Tm ≦ 165-5χ (χ = 5-10 wt%) (IV) The isotactic triad fraction (mm (mol%)) of the PPP chain portion measured by ¹³ C-NMR is 9
8.0 mol% or more Alternatively, a random copolymer of propylene and ethylene, which satisfies the following conditions, may be mentioned. (JP-A-9-272718) The combined amount of ethylene units in the copolymer (χ (wt
%)) Is from 0.2 to 4 wt%. The melt index (MI (g / 10 m
in)) is 4 to 12 g / 10 min. The boiling diethyl ether extraction amount (E (wt%))
Satisfies the relationship of equation (1) E ≦ 0.25χ1.1 (1) Melting point (Tm (° C.)) measured by a differential scanning calorimeter and χ satisfy the relationship of equation (2) Tm ≦ 165-5} (2) The isotactic triad fraction (mm (mol%)) of the PPP chain portion measured by ¹³ C-NMR is 9
Next, the ethylene / 1-butene / propylene copolymer is described in JP-A-11-6063.
No. 9 publication. That is,
A copolymer of propylene, ethylene and 1-butene, which is a propylene-based random copolymer satisfying the following conditions: The content of ethylene units (α mol%) and the content of 1-butene units (β mol%) in the copolymer satisfy the formula (1). 4 ≦ α + β ≦ 15 (1) Melt index (MI (g / 10 mi
n)) is 1 to 12 g / 10 min. When the relationship between the boiling diethyl ether extraction amount (E) and (α + β) is (α + β) ≦ 12, the equation (2) is expressed as
When β)> 12, the relation of the expression (3) is satisfied. E ≦ 0.2 (α + β) 10 0.6 (2) E ≦ 3.0 (3) Differential scanning calorimeter The melting point (Tm (° C.)) and (α + β) satisfy the formula (4): Tm ≦ 164-3.6 (α + β) (4) Stereoregularity index measured by ¹³ C-NMR P (mol
%) Is 98 mol% or more gel permeation chromatography (GPC)
The ratio (Mw / Mn) between the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by the method described above is 6 or less (Japanese Unexamined Patent Publication No.
The meaning of each parameter, the measuring method, and the method for producing each polymer are as described in the respective publications. If the propylene-based polymer (crystalline propylene-based polymer and propylene-based random copolymer) does not exhibit crystallinity, the rigidity and heat resistance of the film or sheet may be reduced.

In the polyolefin resin multilayer laminate of the present invention, the other layers (intermediate layers or laminate layers) are made of a crystalline propylene-based polymer other than the polymers [A], [A-1] and [A-2]. Particularly preferred is a propylene-based resin multilayer laminate containing at least one layer composed of the united layers.

The intermediate layer or laminate layer in the present invention is a resin layer formed by dry-blending the above-mentioned crystalline propylene polymer and propylene random copolymer using a Henschel mixer or the like. Or a resin layer formed by melt-kneading using a single-screw or twin-screw extruder, a Banbury mixer, or the like. The proportion of the propylene random copolymer is usually 1 to 99% by weight, preferably 10 to 90% by weight.
% By weight, particularly preferably 20 to 80% by weight.
If the propylene-based random copolymer is less than 1% by weight, transparency and impact resistance may be reduced.

The method for producing the multi-layered polyolefin resin laminate of the present invention is not particularly limited, and examples thereof include a method for producing by a melt co-extrusion molding method. Above all,
The T-die cast molding method, in which high-speed molding can be performed by a large molding machine, is particularly preferable. Pickup speed is usually 50m / min
Alternatively, the film forming conditions may be higher than this. The thickness of the layer made of the propylene-based polymer [A] forming at least one of the outermost layers of the multilayer laminate of the present invention and the thickness of the multilayer laminate are not particularly limited.
About 000 μm, and about 10 to 5000 μm.

The polyolefin resin multilayer laminate of the present invention is not particularly limited as long as it is obtained as described above. Those that satisfy the relationship are more preferable.

TM ≧ 12.5 × HST-700 The method of measuring the tensile modulus TM and the heat sealing temperature HST will be described in detail in Examples.

[0090]

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

First, the “resin property evaluation method” and the “layered body evaluation method” in 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 Rigo Co., Ltd. (2) Measurement of Pentad Fraction, Triad Fraction, and Abnormal Insertion Fraction The measurement of ¹³ C nuclear magnetic resonance spectrum was carried out by A. Zambelli et al.
ecules, 8 , 687 (1975) ", according to 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 (3) Measurement of molecular weight distribution (Mw / Mn) Mw / Mn is a weight average molecular weight Mw and number average in terms of polystyrene measured by a GPC method using the following apparatus and conditions. This is a value calculated from the molecular weight Mn. 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) (4) DSC measurement Differential scanning calorimeter (Perkin-Elmer, DSC) −
7) Using a 10 mg sample at 230 ° C. in a nitrogen atmosphere for 3
After melting for 1 minute, 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 increased at 10 ° C./min. The peak top of the maximum peak of the melting endothermic curve obtained at this time was defined as melting point: Tm (° C.). "Evaluation method of laminate" All of the molded laminates were annealed at a temperature of 40 ° C for 24 hours, and further subjected to a temperature of 23
After conditioning for 16 hours or more at 50 ° C. and a humidity of 50 ± 10%, the measurement was performed under the same temperature and humidity conditions. (1) Interlayer strength The seal layer (side A) and other layers could be separated by tweezers x (weak = bad), and those that could not be separated were marked o (strong = good). (2) Tensile modulus Measured by a tensile test under the following conditions in accordance with JIS K-7127.

Cross head speed: 500 mm / min Load cell: 15 kg Measurement direction: machine direction (MD direction) (3) Heat seal strength and heat seal temperature Measured according to JIS Z-1707. The two laminates were overlapped so that the outermost layer made of the propylene-based polymer [A] or its comparative polymer was opposed to each other, and this was heat-sealed with a heat seal bar. The fusion conditions are described below. The temperature of the heat seal bar is calibrated by a surface thermometer. After sealing, it was allowed to stand at room temperature for 24 hours, and then at room temperature, the peeling rate was 200 mm / min, and the peeling strength was measured by a T-type peeling method. The heat seal temperature was determined by calculating a temperature at which the peel strength (heat seal strength) becomes 2.94 N / 15 mm from a seal temperature-peel strength curve.

Sealing time: 2 seconds Sealing area: 15 × 10 mm Sealing pressure: 0.5 MPa (Gauge) Sealing temperature: Several points were measured so that the heat sealing temperature could be interpolated [Production Example 1] Preparation of catalyst component [( Synthesis of 1,2′-dimethylsilylene) (2,1′-dimethylsilylene) (3-n-butylindenyl) ₂ zirconium dichloride] (1,2′-dimethylsilylene) (2,1′- Dimethylsilylene) (indene) ₂
Was added thereto, cooled to -78 ° C, and n-butyllithium (hexane solution: 1.6 mol) was added in 3.1 ml (5.0 mmol). Thereafter, the mixture was 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. The obtained lithium salt was dissolved in 50 ml of tetrahydrofuran (THF) and cooled to -78 ° C. 0.57 ml of n-butyl bromide (5.3 mmol)
Was slowly added dropwise, followed by stirring at room temperature for 12 hours.
After distilling off the solvent and extracting with 50 ml of hexane, the hexane was distilled off to remove (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) (3-n-butylindene) ₂ . 0.81 g (1.77 mmol) were obtained (74% yield).

Next, the (1,2′-dimethylsilylene) obtained above was placed in a Schlenk bottle under a nitrogen stream.
0.81 g (1.77 mmol) of (2,1′-dimethylsilylene) (3-n-butylindene) ₂ was added.
The mixture was cooled to -78 ° C, and 2.7 ml of n-butyllithium (hexane solution: 1.54 mol) (4.1 ml) was added.
(5 mmol) and stirred at room temperature for 12 hours. The solvent was distilled off, and the obtained solid was washed with hexane to give a lithium salt as an ether adduct in 0.2%.
8 g (1.43 mmol) were obtained.

The obtained lithium salt was dissolved in 50 ml of toluene under a stream of nitrogen, cooled to -78 ° C, and 0.33 of zirconium tetrachloride previously cooled to -78 ° C was added thereto.
g (1.42 mol) of toluene (50 ml) were added dropwise. After completion of the dropwise addition, the mixture was left at room temperature for 6 hours.
The solution was filtered and the solvent of the filtrate was distilled off. By recrystallizing the obtained solid with dichloromethane, (1,
0.2 g (0.32 mol) of 2'-dimethylsilylene) (2,1'-dimethylsilylene) (3-n-butylindenyl) ₂ zirconium dichloride was obtained (yield: 22).
%).

The ¹ H-NMR of this product was determined,
The following results were obtained. ¹ H-NMR (90 MHz, CD
Cl ₃ ) (δ, ppm): 0.88, 0.99 (12
H, dimethylsilylene), 0.7-1.0, 1.1-
1.5 (18H, n-butyl), 7.0-7.6 (8
(H, benzene ring proton) [Example 1] In a stainless steel autoclave having an internal volume of 10 liters, 5 liters of heptane, 5 mmoles of triisobutylaluminum, and 19 mmoles of methylaluminoxane (manufactured by Albemarle Co.) were converted to aluminum in terms of aluminum. [(1,2′-dimethylsilylene) (2,1′-dimethylsilylene) (3-n-butylindenyl) ₂ ) A catalyst component obtained by pre-contacting 19 μmol of zirconium dichloride in toluene for 30 minutes was added. Then, the temperature was raised to 40 ° C., and the total pressure was 0.8 MPa (Gaug).
Propylene gas was introduced until e). During polymerization, propylene gas is supplied by a pressure regulator so that the pressure becomes constant,
One hour later, the content was taken out and dried under reduced pressure to obtain polypropylene [A-1]. The obtained polypropylene [A-1] was evaluated for the “resin properties” described above, and the results are shown in Table 1. Further, the obtained polypropylene [A-1] was subjected to the following additive formulation, and pelletized by a Model 35B extruder manufactured by Toshiba Machine Co., Ltd. Antioxidant Ciba Specialty Chemicals Irganox 10
10: 1000 ppm Irgafos 16 from Ciba Specialty Chemicals
8: 1000 ppm Neutralizing agent Calcium stearate: 1000 ppm Antiblocking agent Silica-based antiblocking agent of Fuji Silysia Ltd .: 23
00 ppm slip agent erucamide: 500 ppm (molding of laminate) T-die of Eshin Engineering Co., Ltd., feed block of Tawaraya Iron Works, EX of Placo
40 type extruder (NO.1), VS30-26 type extruder (NO.2) manufactured by Tanabe Plastic Machinery Co., Ltd., R manufactured by Rikua Corporation
A feed-block type T-die multilayer laminate molding machine composed of a T-3-30 type extruder (No. 3) was used. The layer configuration is such that the resin extruded by the N0.2 extruder is divided into two layers, and NO. 1 / N
O. 2 / NO. 3 / NO. 2 and 3 types and 4 layers. In Example 1 of the present invention, NO. No. 1 extruder was used to prepare the above polypropylene [A-1] pellets. 2 and N
O. 3 Extrude Idemitsu polypropylene E-105GM from the extruder to obtain polypropylene [A-1] layer / E-105
A laminate having a total thickness of 30 μm was formed at a GM layer = 1/2 layer thickness ratio. At this time, the resin temperature at the feed block portion and the outlet of the T-die were set at 230 ° C., the chill roll temperature was set at 30 ° C., and the take-off speed was set at 25 m / min. Table 2 shows the results of the evaluation of the obtained laminate according to the above-described “Lamination Evaluation Method”. [Example 2] In a polymerization tank having an internal volume of 200 liters, the catalyst component obtained in Production Example 1 was added at 46.7 μmol / hour and triisobutylaluminum (TIBA) was added at 11: 1.
At 7 mmol / h, methylaluminoxane (MAO)
At 46.7 mmol / h, heptane at 46.7 l / h, propylene at 3.4 kg / h and hydrogen (H ₂ / C ₃ = 0.20) at 60 ° C., 0. 8
Polymerization was performed at MPa. Next, the polymer solution was sent to a degassing tank, and propylene and hydrogen were degassed by charging methanol at 10 ml / hour. The content was taken out and dried under reduced pressure to obtain polypropylene [A-1]. The obtained polypropylene [A-1]
Was evaluated for the “resin properties” described above, and the results are shown in Table 1. In addition, the obtained polypropylene [A-
1], the following additives were formulated, extruded and granulated with a single screw extruder (Model TLC35-20, manufactured by Tsukada Juki Seisakusho) to obtain pellets. Antioxidant: Irganox 1010 manufactured by Ciba Specialty Chemicals: 500 ppm and Irgafos 168 manufactured by Ciba Specialty Chemicals: 1000 ppm Neutralizing agent: calcium stearate: 1000 ppm Antiblocking agent: ······ Silica: 3000 ppm Slip agent ··· Erucamide: 1000 ppm A laminate was produced in the same manner as in Example 1 except that the above pellets were used. Table 2 shows the obtained results. [Comparative Example 1] An ethylene-vinyl acetate copolymer (Mitsui DuPont Polychemical P250JC) was used instead of polypropylene [A-1], and Idemitsu Polypropylene E-30 was used instead of Idemitsu Polypropylene E-105GM.
The procedure was performed in the same manner as in Example 1 except that 4GP was used.
Table 2 shows the obtained results.

Table 1 Resin Properties Example 1 Example 2 H25 (wt%) 1720 Tm (° C) Not shown Not shown 6 × (Tm-140)--ΔH (J / g) Not shown Not shown [η] (Dl / g) 2.5 1.78 [mmmm] (mol%) 41 39.5 [rrrr] / (1- [mmmm]) 0.049 0.045 2,1 insertion (mol%) 0 1 , 3 insertion (mol%) 00 Mw / Mn 2.4 1.99

Table 2 Physical properties of laminate Example 1 Example 2 Comparative example 1 layer simple strength ○ ○ × Tensile modulus TM (MPa) 550 570 570 540 Heat seal temperature (HST) (° C) 80 80 76 Heat seal strength ( 1) (N / 15m) 1.17 1.10 0.71 Heat seal strength (2) (N / 15m) 1.85 1.75 1.06 Heat seal strength (3) (N / 15m) 2.42 2.50 2.68 Heat seal strength (4) (N / 15m) 2.92 3.50 3.91 Heat seal strength (5) (N / 15m) 7.08 6.50- However, the heat seal strength is the value of the sample laminated under the following conditions. (1) Sealed temperature = 65 ° C (2) Sealed temperature = 70 ° C (3) Sealed temperature = 75 ° C (4) Sealed temperature = 80 ° C (5) Sealed temperature = 85 ° C

[0100]

Industrial Applicability The polyolefin resin multilayer laminate of the present invention is excellent in low-temperature heat sealability, has sufficient interlayer strength without using an adhesive or the like, and is suitable for packaging films and sheets.

Claims (9)

[Claims] At least one of the outermost layers has the following (1)
And a polyolefin resin multilayer structure composed of a layer composed of a propylene-based polymer [A] satisfying (2). (1) The amount of the component (H25) eluted in hexane at 25 ° C. is 0 to 80% by weight. (2) In the DSC measurement, if the melting point (Tm (° C.)) is not shown or Tm is shown, Tm Endotherm of melting ΔH
(J / g) satisfies the following relationship: ΔH ≧ 6 × (Tm−140) 2. The amount of a component (W
The polyolefin resin multilayer laminate according to claim 1, wherein 25) is 20 to 100% by weight. 3. A propylene homopolymer [A-] wherein the propylene-based polymer [A] satisfies the following (1) and (2):
3] The polyolefin resin multilayer laminate according to claim 1 or 2]. (1) Mesopentad fraction [mmmm] is 20 to 60 mol% (2) Racemic pentad fraction [rrrr] and 1- [mm]
[rrrr] / (1- [mmmm]) ≦ 0.1 4. The polyolefin resin multilayer laminate according to claim 1, wherein the propylene-based polymer [A] is a propylene-based copolymer [A-2] satisfying the following (1). (1) The stereoregularity index (P) by ¹³ C-NMR measurement is 55 to 90 mol%. 5. A propylene polymer [A], a propylene homopolymer [A-1] or a propylene copolymer [A-
2] Gel permeation chromatograph (GPC)
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 0.5 to 15.0 deciliter / g. The polyolefin resin multilayer laminate according to any one of the above. 6. A propylene-based polymer [A], propylene
Homopolymer [A-1] or propylene-based copolymer [A-
2] is (A) a transition metallization represented by the following general formula (I)
And (B) the transition metal compound or the component (A).
Capable of forming an ionic complex by reacting with derivatives of
Group consisting of (B-1) and aluminoxane (B-2)
Of a polymerization catalyst containing at least one component selected from the group consisting of:
In the presence, propylene or propylene and ethylene and / or
By polymerizing an α-olefin having 4 to 20 carbon atoms
The polyolefin according to any one of claims 1 to 5, which is obtained.
Resin multilayer laminate. Embedded image中 In the formula, M is a group 3 to 10 of the periodic table or a lanthanoid
Indicates the metal element of the column, E ¹And E^TwoAre placed independently
Substituted cyclopentadienyl group, indenyl group, substituted inde
Nyl group, heterocyclopentadienyl group, substituted heterocy
Clopentadienyl group, amide group, phosphide group, carbonized
A ligand selected from a hydrogen group and a silicon-containing group.
A¹And A^TwoTo form a crosslinked structure via
They may be the same or different, and X is σ
Represents a binding ligand, and when there are a plurality of Xs, a plurality of Xs
It may be the same or different, other X, E¹, E^TwoOr Y
And may be crosslinked. Y represents a Lewis base;
When there is a number, a plurality of Y may be the same or different,
Other Y, E¹, E^TwoOr X may be cross-linked,¹Passing
And A^TwoIs a divalent bridging group that connects two ligands
Wherein each independently represents a hydrocarbon having 1 to 20 carbon atoms
Groups, halogen-containing hydrocarbon groups having 1 to 20 carbon atoms, silicon-containing
Organic group, germanium-containing group, tin-containing group, -O-, -C
O-, -S-, -SO_Two-, -Se-, -NR-, -P
R-, -P (O) R-, -BR- or -AlR-
R represents a hydrogen atom, a halogen atom, a carbon atom having 1 to 20 carbon atoms.
Hydrogen groups or halogen-containing hydrocarbon groups having 1 to 20 carbon atoms
And they may be the same or different
No. q is an integer of 1 to 5 and represents ((valence of M) -2).
And r represents an integer of 0 to 3. ｝ 7. The method according to claim 1, wherein the other layer contains at least one layer composed of a crystalline propylene polymer other than the propylene polymer [A] and the propylene homopolymer [A-1]. 3. The propylene-based resin multilayer laminate according to item 1. 8. The polyolefin multilayer laminate according to claim 1, which is obtained by a T-die casting method. 9. The tensile modulus TM (MPa) and the heat sealing temperature HST (° C.) satisfy the following relationship.
The polyolefin resin multilayer laminate according to any one of the above. TM ≧ 12.5 × HST-700