JP2000281723A - Propylenic resin composition and film or sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a propylenic resin composition giving a propylenic film or sheet which is largely improved in heat seal strength. SOLUTION: Peak top temperature (Tc) in the maximum temperature of a crystallizing curve and a differential calorie (ΔHm) of a melting curved measured using a differential scanning calorimeter(DSC) satisfy Tc>=((1/4).ΔHm+90), and further, a frequency (ω) and ΔHm in which a storage elastic modulus (G') and loss elastic modulus (G") in frequency dispersion measurement of ΔHm and melt viscoleasticity satisfy G'=G" fulfill ω<=((1/10).ΔHm+15).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a propylene-based resin composition and a film and a sheet comprising the same, and more particularly to a novel film and a sheet which are excellent in flexibility and transparency and have greatly improved heat seal strength. And a film and sheet comprising the same. Further, the propylene-based resin composition of the present invention is also suitably used as at least one component of a laminated film or a coextruded laminated film or sheet.

[0002]

2. Description of the Related Art A crystalline propylene polymer film has been widely used as a packaging film, taking advantage of its excellent rigidity, transparency and moisture-proof properties. Packaging films are often processed into bags and used.However, a series of operations to close the bag mouth after processing the film into a bag and filling the contents are usually performed by pressing the film with a heated rod. Is performed by an operation called heat sealing for melting and bonding. In recent years, these series of bag making and packaging processes have been accelerated in order to improve productivity, and materials having a reduced heat seal temperature and improved heat seal strength, that is,
There is a strong demand for the development of materials having excellent low-temperature heat sealability. By the way, blends of ethylene-propylene copolymer rubber (EPR), ethylene-1-butene copolymer rubber (EBR) and the like have been widely used as a technique for improving the heat sealing property of a propylene-based polymer film. However, in such a conventional technique, although the heat sealing temperature is lowered, the heat sealing strength is disadvantageously reduced.

[0003] On the other hand, in the field of soft films and sheets, vinyl chloride resins have been frequently used in the past, but in recent years, problems such as the generation of chlorine gas in the combustion process and damage to incinerators have been raised. Thus, the emergence of alternative resins is desired. By the way, the propylene-based polymer has a feature that flexibility can be imparted by lowering its stereoregularity or by copolymerizing a comonomer such as ethylene and 1-butene. A number of techniques have been proposed as alternatives to soft vinyl chloride resins. However, these have the drawback of lowering the stereoregularity or copolymerizing comonomers such as ethylene and 1-butene, resulting in lower heat resistance and heat seal strength of the propylene-based polymer. Further, various propylene-based resin compositions in which a crystalline component such as propylene homopolymer and an elastomer component such as propylene and ethylene copolymer are blended to improve this drawback have been proposed. And the elastomer component formed a so-called sea-island structure, resulting in poor transparency. As described above, the prior art was not able to satisfy all of transparency, flexibility, heat sealing strength, and heat resistance.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel propylene-based resin composition which provides a propylene-based film or sheet whose heat-sealing temperature is appropriately lowered and whose heat-sealing strength is greatly improved, and It is to provide a film and a sheet comprising the same. Further, another object of the present invention is to provide a novel propylene-based resin composition which is rich in flexibility, excellent in transparency, excellent in heat resistance, and greatly improved in heat-sealing strength, and can be used as a substitute for a soft vinyl chloride-based resin. And a film and a sheet comprising the same.

[0005]

Means for Solving the Problems The present inventors have conducted intensive studies to achieve the above object, and as a result, have found that the peak top temperature on the highest temperature side of the crystallization curve measured by a differential scanning calorimeter is different from that of the present invention. The propylene-based resin composition satisfies the specific relationship where the differential calorific value of the melting curve satisfies the specific relationship, and the frequency and the differential calorific value at which the storage elastic modulus and the loss elastic modulus in the frequency dispersion measurement of the melt viscoelasticity are equal to each other satisfy the specific relationship. The inventors have found that a film or sheet having an excellent balance of transparency and having greatly improved heat seal strength is provided, and the present invention has been completed. That is, the present invention provides the following propylene-based resin composition, and films and sheets comprising the same. 1. Peak top temperature (Tc) on the highest temperature side in the crystallization curve measured by a differential scanning calorimeter (DSC)
(° C.)) and the differential calorific value (ΔHm (J /
g)) satisfies the following relational expression (1-1), Tc ≧ (１ ／) · ΔHm + 90 (1-1) and the storage elastic modulus (G ′ ( Pa)) and a frequency (ω (rad / sec)) at which the loss elastic modulus (G ″ (Pa)) becomes equal to ΔHm satisfying the following relational expression (2-1).

Ω ≦ (1/10) · ΔHm + 15 (2-1) The propylene-based resin composition according to the above item 1, comprising 1 to 99% by weight of a propylene-based polymer [I] satisfying the following (1) to (3) and 99 to 1% by weight of a crystalline propylene-based polymer [II]. (1) The component amount (W25) eluting at 25 ° C. or lower in the temperature raising chromatography is 20 to 100% by weight. (2) The component amount (H25) eluting in hexane at 25 ° C. is 0 to 80% by weight. (3) In the DSC measurement, the melting point (Tm (° C.)) is not shown, or when it shows Tm, Tm and the melting endotherm ΔH
(J / g) satisfies the following relationship: ΔH ≧ 6 × (Tm-140) 2. The propylene resin composition according to the above item 1, comprising 1 to 99% by weight of a propylene homopolymer [a] satisfying the following (1) to (3) and 99 to 1% by weight of a crystalline propylene polymer [II]. (1) The mesopentad fraction (mmmm) is 20 to 60 mol%. (2) The racemic pentad fraction (rrrr) and (1-mm)
mmr) satisfies the following relationship: [rrrr / (1-mmmm)] ≦ 0.1 (3) The component amount (W25) that elutes at 25 ° C. or lower in the temperature rising chromatography is 20 to 100% by weight. The propylene-based polymer [I] in the above item 2 or the propylene homopolymer [a] in the above item 3 is the following (1)
4. The propylene-based resin composition according to the above item 2 or 3, which satisfies (2). (1) Gel permeation chromatograph (GPC)
Molecular weight distribution (Mw / Mn) measured by the method is 4 or less (2) intrinsic viscosity measured at 135 ° C. in tetralin solvent
[η] is 0.5 to 15.0 deciliter / g. The propylene-based resin composition according to any one of the above items 2 to 4, wherein the propylene-based polymer [I] in the above item 2 or the propylene homopolymer [a] in the above item 3 does not show a melting point (Tm (° C)) in DSC measurement. object. 6. A film or sheet having a layer comprising the propylene-based resin composition according to any one of the above 1 to 5. 7. 7. The film or sheet according to the above item 6, wherein the haze of the film or sheet measured according to JIS K7105 is 10% or less.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, a propylene-based resin composition [1] of the present invention and a film or sheet [2] comprising the same will be described.
Will be described in detail. [1] Propylene-based resin composition The propylene-based resin composition [1] of the present invention is substantially composed of a propylene homopolymer and / or a propylene-based copolymer, and is a scanning calorimeter (DSC). The peak top temperature (Tc (° C.)) on the highest temperature side in the crystallization curve and the differential calorie (ΔHm) in the melting curve
(J / g)) satisfies the following relational expression Tc ≧ (（) · ΔHm + 90 (1-1), and the storage elastic modulus (G ′ (Pa)) in the melt viscoelasticity frequency dispersion measurement. And the loss modulus (G "(P
a)) is a resin composition in which the frequency (ω (rad / sec)) and ΔHm satisfy the following relational expression: ω ≦ (1/10) · ΔHm + 15 (2-1). By satisfying the above requirements, the propylene-based resin composition of the present invention provides a film or sheet having excellent flexibility and transparency and having greatly improved heat seal strength. For example, if the tensile modulus is 10
A film having a pressure of 00 MPa or less, a haze of 5% or less, and a heat seal strength of 1000 gf / 15 mm or more is obtained. In particular, regarding the heat seal strength, when the sealing temperature is high, for example, 160 ° C. or higher, there is an advantage that a film having significantly excellent heat seal strength can be obtained. Further, as compared with other propylene resin compositions having the same flexibility, there is an advantage that the heat sealing temperature is high and the heat resistance is high.

The propylene-based resin composition of the present invention is suitably used not only as a film or sheet, but also as a component of at least one layer of a laminated or coextruded laminated film or sheet. If the requirement of (1-1) is not satisfied, the flexibility of the obtained film or sheet is reduced, and the transparency is also reduced. In addition, although the obtained film or sheet has flexibility if the requirement (2-1) is not satisfied, the heat seal strength does not improve or the transparency does not become excellent. The propylene-based resin composition of the present invention satisfies Tc ≧ (）) · ΔHm + 92 (1-2) and ω ≦ (1/10) · ΔHm + 13 (2-2). A resin or resin composition to be filled is excellent in flexibility and transparency, and a film or sheet with improved seal strength is obtained, which is more preferable.

The exploratory calorimeter (DS) in the present invention
The peak top temperature (Tc (° C.)) on the highest temperature side in the crystallization curve measured by C) and the differential calorific value (ΔHm (J / g)) in the melting curve are determined by the following measurement methods. That is, using a DSC7 differential scanning calorimeter manufactured by Perkin Elmer, 10 mg of a sample was previously melted at 230 ° C. in a nitrogen atmosphere for 3 minutes, and then 10 ° C./m 2.
The temperature was lowered to 0 ° C. in. The peak top temperature on the highest temperature side of the obtained crystallization curve was Tc (° C.). After holding at this temperature for 3 minutes, the differential calorie of the melting curve obtained by increasing the temperature at 10 ° C./min is ΔHm (J /
g).

In addition, the storage elastic modulus (G ′ (Pa) and the loss elastic modulus (G ″ (P
a)) frequency (ω (rad / sec))
Is determined by the following measurement method. That is, using a cone-type plate (diameter 25.0 mm, cone angle 0.10 radian) in a rotational type rheometer manufactured by Rheometrics, frequency dispersion measurement of melt viscoelasticity was performed at a temperature of 175 ° C and an initial strain of 20%. The storage modulus (G ′ (Pa) and the loss modulus (G ″ (Pa)) and G ′
= G ". The complex elastic modulus G * (iω) at the frequency (ω (rad / sec)) is determined by the stress σ * and the strain γ *. In other words, G * (iω) = σ * / γ * = G ′ (ω) + iG ″ (ω). Here, i is an imaginary unit.

The propylene resin composition of the present invention is not particularly limited as long as it is a propylene resin composition satisfying at least the above requirements. For example, the following (1)-
A propylene-based resin composition comprising 1 to 99% by weight of the propylene-based polymer [I] satisfying (3) and 99 to 1% by weight of the crystalline propylene-based polymer [II] is exemplified. (1) The component amount (W25) eluting at 25 ° C. or lower in the temperature raising chromatography is 20 to 100% by weight. (2) The component amount (H25) eluting in hexane at 25 ° C. is 0 to 80% by weight. (3) In the DSC measurement, the melting point (Tm (° C.)) is not shown, or when it shows Tm, Tm and the melting endotherm ΔH
Satisfies the following relationship: ΔH ≧ 6 × (Tm-140) The propylene-based polymer [I] of the present invention satisfies the above-mentioned relationship, thereby reducing the amount of the sticky component and the low elastic modulus of the obtained film or sheet. And the balance of transparency is excellent. That is, the elasticity is low, the softness (also referred to as flexibility) is excellent, the sticky component is small, and the surface characteristics (for example,
(E.g., less migration of sticky components to bleed and other products), and excellent transparency. Next, the requirement of the propylene-based polymer [I] in the present invention will be described.

The propylene polymer [I] in the present invention
Means that the component amount (W25) of the propylene-based polymer eluted at 25 ° C. or lower in the temperature raising chromatography is 20 to 1
00% by weight. Preferably, 30 to 100% by weight,
Particularly preferably, it is 50 to 100% by weight. W25
Is an index indicating whether or not the propylene-based polymer [I] is soft. When this value is increased, it means that the component having a high elastic modulus is increased and / or the non-uniformity of the stereoregularity distribution is widened. In the present invention, W
If 25 is less than 20%, flexibility may be lost, which is not preferable. In addition, W25 is the following operation method,
It is the amount (% by weight) of the component that is eluted without being adsorbed by the packing material at a TREF column temperature of 25 ° C. in the elution curve obtained by measuring the temperature by the temperature rising chromatography of the apparatus configuration and the 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. Let it. Thereafter, the column was heated at a heating rate of 40 ° C./hour for 1 column.
The temperature is raised to 35 ° C. to obtain an elution curve. (B) Apparatus configuration TREF column: Silica gel column (4.6φ x 150mm) manufactured by GL Sciences Flow cell: 1mm optical path length KBr cell manufactured by GL Sciences Pump: SSC-3100 pump manufactured by Senshu Kagaku Valve oven: GL Sciences Model 554 oven (high temperature type) TREF oven: GL Science's two-line temperature controller: Rigaku Corporation REX-C100 temperature controller Detector: Infrared detector for liquid chromatography FOXBORO's MIRAN 1A CVF 10-way valve : Barco electric valve loop: Barco 500 microliter loop (c) Measurement conditions Solvent: o-dichlorobenzene Sample concentration: 7.5 g / liter Injection volume: 500 microliter Pump flow rate: 2.0 ml / min Detection Wave number: 3. 1 μm Column packing material: Chromosolve P (30 to 60 mesh) Column temperature distribution: within ± 0.2 ° C. The propylene polymer [I] in the present invention has a component amount (H25) eluted in hexane at 25 ° C. of 0 to 0. 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
When it exceeds, the amount of the sticky component is large, and the blocking and the transparency are reduced, so that it may not be used for food or medical use.

H25 is the weight (W ₀ ) of the propylene-based polymer [I] 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 dried. ₁ ) is a weight loss rate obtained by measuring and calculating by the following formula. H25 = [(W ₀ −W ₁ ) / W ₀ ] × 100 (%) The propylene-based polymer [I] in the present invention does not show a melting point (Tm (° C.)) or a Tm in DSC measurement. In the case shown, Tm and the melting endotherm ΔH (J / g) satisfy the following relationship.

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

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

The propylene polymer [I] in the present invention
Is not particularly limited as long as the above requirements are satisfied,
A propylene homopolymer and a propylene-based copolymer are exemplified. Among them, the propylene-based polymer [I] in the present invention described above is more preferably realized by the following propylene homopolymer [a] or propylene-based copolymer [a ']. [A] Propylene homopolymer The propylene homopolymer [a] in the present invention is a polymer that requires the following (1) to (3). (1) The mesopentad fraction (mmmm) is 20 to 60 mol%, and (2) the racemic pentad fraction (rrrr)
And (1-mmmm) satisfy the following relationship, and [rrrr / (1-mmmm)] ≦ 0.1 (3) The amount (W25) of the component eluted at 25 ° C. or lower in the temperature rising chromatography is 20 to When the propylene homopolymer [a] of the present invention satisfies the above relationship, the resulting film or sheet has an excellent balance between the amount of sticky components, low elastic modulus, and transparency.
That is, the elastic modulus is low, the softness (also referred to as 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 the present invention, the mesopendad fraction (mm)
mm fraction) means A. Zambell (A. Zambell)
i) et al., "Macromolecules, 6 , 9
25 (1973) "and ¹³ C-
It is a meso fraction in a pentad unit in a polypropylene molecular chain measured by a signal of a methyl group in an NMR spectrum. When this is increased, it means that stereoregularity is increased. The propylene homopolymer [a] in the present invention has a mesopentad fraction (mmmm) of 20 mol%.
If it is less than 5, it may cause stickiness. If it exceeds 60 mol%, the elastic modulus may increase, which is not preferable. 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 of the pentad unit and showing the uniformity of the regular distribution of the propylene homopolymer. When this value is increased, the regularity distribution is widened, and high regularity PP and AP like the conventional polypropylene produced using the existing catalyst system.
It becomes a mixture of P, which means that stickiness increases and transparency decreases. If the [rrrr / (1-mmmm)] of the propylene homopolymer [a] in the present invention exceeds 0.1, it may cause stickiness. In addition, ¹³ C-
The measurement of the NMR spectrum was carried out by A. Zambelli (A. Za).
"Macromolecule"
s, 8 , 687 (1975) ", with 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 <Calculation formula> M = m / S × 100 R = γ / S × 100 S = Pββ + Pαβ + Pαγ S: Signal intensity of side chain methyl carbon atom of all propylene units Pββ: 19.8 to 22.5 ppm P αβ: 18.0 to 17.5 ppm P αγ: 17.5 to 17.1 ppm γ: Racemic pentad chain: 20.7 to 20.3 ppm m: Mesopentad chain: 21.7 to 22.5 ppm Next, the meaning and measurement method of W25 for the propylene homopolymer [a] in the present invention will be described with reference to the propylene-based polymerization described above. Is the same as in [I]. W25 of the propylene homopolymer [a] in the present invention is 20
%, The flexibility may be lost.

Further, in the present invention, the propylene homopolymer [a] has the following (4) mesopentad fraction (mmmm) of 30 to 50% among the above requirements.
(5) racemic pentad fraction (rrrr) and (1-mmmm) satisfy the following relationship, [rrrr / (1-mmmm)] ≦ 0.08 and (6) It is more preferable that the amount of the component (W25) eluted at 25 ° C. or lower is 30 to 100% by weight, (7) the mesopentad fraction (mmmm) is 30 to 50%, and (8) the racemic pentad component. The ratio (rrrr) and (1-mmmm) satisfy the following relationship: [rrrr / (1-mmmm)] ≦ 0.06 and (9) the amount of the component eluted at 25 ° C. or lower (W25) ) Is preferably from 50 to 100% by weight.

The propylene homopolymer [a] in the present invention has a gel permeation (G
PC) method, the molecular weight distribution (Mw / Mn) is 4
The intrinsic viscosity [η] measured at 135 ° C. or lower and / or in a tetralin solvent is preferably 0.5 to 15.0 deciliter / g, the Mw / Mn is 3.5 or less, and / or the [η] is 1.0 or less. ~ 5.0 deciliter / g is more preferable.
It is particularly preferable that w / Mn is 3 or less and / or [η] is 1.0 to 3.0 deciliter / g. Molecular weight distribution (Mw / M
If n) exceeds 4, the film or sheet may be sticky. If the intrinsic viscosity [η] is less than 0.5 deciliter / g, stickiness may occur or 15.0.
If the content exceeds deciliter / g, gels or fish eyes may be generated on the film or sheet.

The above Mw / Mn is a value calculated from a weight average molecular weight Mw and a number average molecular weight Mn in terms of polyethylene measured by gel permeation chromatography (GPC) using the following apparatus and conditions. GPC measuring device Column: TOSO GMHHR-H (S) HT Detector: RI detector for liquid chromatogram WATERS 150C Measurement conditions Solvent: 1,2,4-trichlorobenzene Measurement temperature: 145 ° C Flow rate: 1.0 ml / min Sample concentration: 2.2 mg / milliliter Injection amount: 160 microliter Calibration curve: Universal Calibration Analysis program: HT-GPC (Ver. 1.0) Further, propylene homopolymer [a] in the present invention
Is the melting endotherm Δ by DSC measurement in addition to the above requirements.
When H is 20 J / mol or less, flexibility is excellent and preferable. 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 is obtained by the above method.

Further, as the propylene homopolymer [a] in the present invention, particularly, a differential scanning calorimeter (DSC)
Preferably, no crystallization peak is observed in the crystallization curve of the measurement. Here, a differential scanning calorimeter (DSC)
The fact that no crystallization peak is observed in the crystallization curve of the measurement means that a differential scanning calorimeter (manufactured by Perkin Elmer, D
Using SC-7), 10 mg of a sample was placed in a nitrogen atmosphere at 230
After melting at 0 ° C for 3 minutes, the temperature is lowered to 0 ° C at 10 ° C / minute. At this time, it means that no exothermic crystallization curve is observed, and further, no heat endothermic curve is observed when the temperature is raised at 10 ° C./min after holding at 0 ° C. for 3 minutes. When a propylene homopolymer has a crystallization peak observed in a crystallization curve measured by a differential scanning calorimeter (DSC), a film or sheet having excellent flexibility may not be obtained.

In general, during the polymerization of propylene, the carbon atom on the methylene side of the propylene monomer is bonded to the active site of the catalyst, and the propylene monomer is coordinated and polymerized in the same manner in the order of 1,2. Polymerization of insertion is usually performed, but rarely, 2,1 insertion or 1,3 insertion (also referred to as abnormal insertion) may occur. The homopolymer [a] in the present invention preferably has a small amount of the 2,1 or 1,3 insertion. Further, the ratio of these insertions is expressed by the following relational expression (1) [(m−2,1) 10 (r−2,1) 10 (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) 10 (r−2,1) 10 (1,3)] ≦ 1.0 (%) (2) Satisfaction is more preferable. In particular, the one that satisfies the relational expression (3) [(m−2,1) 10 (r−2,1) 10 (1,3)] ≦ 0.1 (%) (3) is most preferable. This relational expression (1)
If not, the crystallinity may be reduced more than expected, which may cause stickiness.

(M-2,1), (r-2,1) and (1,3) are reported by Grassi et al. (Macromolucule).
s, 21 , p. 617 (1988)) and a report by Busico et al. (Macromolucules, 27 , p. 7538 (1994)).
It is each insertion content determined from the integral intensity of each peak after the assignment of the peak of the ¹³ C-NMR spectrum was determined. That is, (m−2,1) is Pα, γthreth that appears around 17.2 ppm with respect to the integrated intensity in the entire methyl carbon region.
It is the meso-2,1 insertion content (%) calculated from the ratio of the integrated intensity of the peak attributed to o. (R-2,1) is
15.0p for integrated intensity in all methyl carbon region
It is the racemic-2,1 insertion content (%) calculated from the ratio of the integrated intensities of the peaks belonging to Pα and γthreo appearing near pm. (1, 3) is Tβ, which appears near 31.0 ppm relative to the integrated intensity in the entire methine carbon region.
1,3 insertion content (%) calculated from the ratio of the integrated intensity of the peaks belonging to γ10.

Further, the propylene homopolymer [a] in the present invention was measured by ¹³ C-NMR spectrum
It is more preferable that the peak attributable to the end of the molecular chain (n-butyl group) derived from the 2,1 insertion is not substantially observed. Regarding the molecular chain terminal derived from this 2,1 insertion,
Jungling et al. (J. Polym. Sci .: Part
A: Po1ym. Chem., 33 , p1305 (1995))
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, the peak appearing at around 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.

In addition to the above requirements, the propylene homopolymer [a] of the present invention preferably further has an extraction amount of boiling diethyl ether, which is an index of the elastic modulus, of 5% by weight or more. The boiling diethyl ether extraction amount is measured using a Soxhlet extractor under the following conditions. Extracted sample: 1-2 g Sample shape: powder-like (pelletized, crushed,
Extraction solvent: diethyl ether Extraction time: 10 hours Number of extractions: 180 times or more Calculation method of extraction amount: Calculated by the following formula. [Extraction amount to diethyl ether (g) / charged powder weight (g)] × 100 Further, the propylene homopolymer [a] in the present invention is:
In addition to the above, the tensile modulus is preferably 100 MPa or less, more preferably 70 MPa or less. [A '] Propylene-based copolymer The propylene-based copolymer [a'] in the present invention is propylene and ethylene and / or α- having 4 to 20 carbon atoms, which require the following (1) to (2). It is an olefin copolymer. (1) The stereoregularity index (P) by ¹³ C-NMR measurement is 55 to 90 mol%, and (2) the component amount (W25) eluted at 25 ° C. or lower in the temperature rising chromatography is 20 to 100% by weight. When the propylene-based copolymer [a '] of the present invention satisfies the above relationship, the resulting film or sheet has an excellent balance between the amount of sticky components, low elastic modulus, and transparency. That is, low elasticity and softness (also called flexibility)
It is advantageous in that it has excellent non-sticky components, excellent surface properties (e.g., little transfer of sticky components to bleed and other products), and excellent transparency. The stereoregularity index (P) in the present invention was determined by measuring a ¹³ C-NMR spectrum using the above-mentioned JNM-EX400 type NMR apparatus manufactured by JEOL Ltd. under the same conditions as above, and measuring the propylene chain mesotriad (mm). ) The value obtained by measuring the fraction. The larger this value is, the higher the stereoregularity is. The propylene copolymer [a '] in the present invention more preferably has a stereoregularity index (P) of 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. 90 mol%
If it exceeds, it may be 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.

Further, in addition to the above requirements, the propylene-based copolymer [a '] of the present invention has a molecular weight distribution (Mw / Mw) measured by a gel permeation (GPC) method.
n) is 4 or less and / or the intrinsic viscosity [η] measured at 135 ° C. in a tetralin solvent is preferably 0.5 to 15.0 deciliter / g, and Mw / Mn is 3.5 or less and / or
[η] is more preferably 1.0 to 5.0 deciliter / g, Mw / Mn is 3 or less, and / or [η] is 1.0 to 5.0 deciliter / g.
3.0 deciliter / g is particularly preferred. If the molecular weight distribution (Mw / Mn) exceeds 4, stickiness may occur on the film or sheet. Intrinsic viscosity [η] is 0.5
If it is less than deciliter / g, stickiness may occur, and if it exceeds 15.0 deciliter / g, gel or fisheye may be generated on the film or sheet.

The method of measuring Mw / Mn is the same as described above. Further, in addition to the above-mentioned requirements, the propylene-based copolymer [a '] according to the present invention is preferably excellent in flexibility when the melting endotherm ΔH measured by DSC is 20 J / mol or less. Further, as the propylene-based copolymer [a '] in the present invention, particularly, a differential scanning calorimeter (DS
C) It is preferable that no crystallization peak is observed in the crystallization curve measured. If a crystallization peak is observed in a crystallization curve measured by a differential scanning calorimeter (DSC), a film or sheet having excellent flexibility may not be obtained. The measuring methods of ΔH, Tm and Tc are the same as described above.

The propylene-based copolymer [a '] in the present invention preferably has an extraction amount of boiling diethyl ether, which is an index of the elastic modulus, of 5% by weight or more in addition to the above requirements. The measurement of the amount of boiling diethyl ether extracted is the same as described above. In addition, the tensile modulus is 10
0 MPa or less, more preferably 7 MPa or less.
0 MPa or less.

With respect to the propylene copolymer [a '] in the present invention, the α-olefin having 4 to 20 carbon atoms includes ethylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene , 1-octene, 1-
Examples thereof include 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 [a '] 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%. [Method for producing propylene homopolymer [a] and propylene-based copolymer [a ']] The method for producing propylene homopolymer [a] and propylene-based copolymer [a'] in the present invention includes a metallocene catalyst. And a method of copolymerizing propylene with ethylene and / or an α-olefin having 4 to 20 carbon atoms. As the metallocene catalyst,
JP-A-58-19309, JP-A-61-1303
No. 14, JP-A-3-1630088, JP-A-4
Cyclopentadienyl group, substituted cyclopentadienyl group, indenyl group, substituted indenyl group and the like described in Alternatively, a transition metal compound having two ligands, and a catalyst obtained by combining a transition metal compound in which the ligands are geometrically controlled and a promoter are exemplified.

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

[0033]

Embedded image

[Wherein, M is a member of Groups 3 to 10 of the periodic table or La
E represents a tanthanoid metal element ¹And E^TwoIs it
Substituted cyclopentadienyl group, indenyl group, substituted
Indenyl group, heterocyclopentadienyl group,
Telocyclopentadienyl group, amide group, phosphide
Ligand selected from the group consisting of a group, a hydrocarbon group and a silicon-containing group
And A¹And A^TwoTo form a crosslinked structure via
And they may be the same or different
X represents a σ-binding ligand, and when there are a plurality of Xs,
A plurality of X may be the same or different, and other X,
E¹, E^TwoAlternatively, it may be crosslinked with Y. Y is Lewis salt
A plurality of Y are the same or different
Other Y, E¹, E^TwoOr cross-linked with X
May be, A¹And A^TwoIs the two that binds the two ligands
A divalent crosslinking group, a hydrocarbon group having 1 to 20 carbon atoms,
A halogen-containing hydrocarbon group having a prime number of 1 to 20, a silicon-containing group,
Germanium-containing groups, tin-containing groups, -O-, -CO-,
-S-, -SO_Two-, -Se-, -NR¹-, -PR¹
-, -P (O) R¹-, -BR¹-Or-AlR¹-
And R¹Is a hydrogen atom, a halogen atom, a carbon number of 1 to 20
Hydrocarbon groups, halogen-containing hydrocarbons having 1 to 20 carbon atoms
Denote groups, which 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. Transition metallization represented by
And (B) Transition metallization of the component (B-1) (A)
Reacts with the compound or its derivative to form an ionic complex
And (2) aluminoxane
Propylene alone in the presence of a polymerization catalyst containing
Or propylene and ethylene and / or
A method of copolymerizing an α-olefin having 4 to 20 carbon atoms is
No.

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

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

Next, A ¹ and A ² are divalent bridging groups for bonding the two ligands, and are a hydrocarbon group having 1 to 20 carbon atoms and a halogen-containing hydrocarbon group having 1 to 20 carbon atoms. , Silicon-containing group, germanium-containing group, tin-containing group, -O-, -C
O -, - S -, - SO 2 -, - Se -, - NR 1 -, -
PR ^1- , -P (O) R ^1- , -BR ¹ -or -AlR
¹ - are shown, R ¹ represents a hydrogen atom, a halogen atom, a carbon number 1
A hydrocarbon group having 1 to 20 carbon atoms; and a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, which may be the same or different. At least one of such crosslinking groups is preferably a crosslinking group comprising a hydrocarbon group having 1 or more carbon atoms. As such a crosslinking group, for example, a general formula

[0038]

Embedded image

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

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

[0041]

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, A ¹ , A ² , q and r are the same as above. X ¹ represents a σ-bonding ligand, and when plural X ^1, a plurality of X ¹ may be the same or different, may be crosslinked with other X ¹ or Y ^1. Specific examples of X ¹ include the same as those exemplified in the description of X in the general formula (I). Y
¹ represents a Lewis base, and when there are a plurality of Y ¹ ,
¹ may be the same or different, and may be crosslinked with another Y ¹ or X ¹ . Specific examples of Y ¹ include the same as those exemplified in the description of Y in the general formula (I). R ^{4 to} R ⁹ each represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms,
The halogen-containing hydrocarbon group, the silicon-containing group or the hetero atom-containing group, at least one of which must not be a hydrogen atom. Further, R ^{4 to} R ⁹ may be the same or different, and adjacent groups may be bonded to each other to form a ring.

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

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

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

[Z ¹ ] ⁻ , that is, [M ¹ G ¹ G
² ... G ^f ], B and A are specific examples of M ^1.
l, Si, P, As, Sb, etc., preferably B and Al
Is mentioned. Specific examples of G ¹ , G ^{2 to} G ^f include dimethylamino and diethylamino as dialkylamino groups, and methoxy, ethoxy, n-butoxy groups as alkoxy or aryloxy groups.
Methyl, ethyl, n-propyl, isopropyl, n-butyl, hydrocarbon groups such as phenoxy
Fluorine, chlorine, bromine, halogen atoms such as isobutyl group, n-octyl group, n-eicosyl group, phenyl group, p-tolyl group, benzyl group, 4-t-butylphenyl group and 3,5-dimethylphenyl group; Iodine, p-fluorophenyl group as a hetero atom-containing hydrocarbon group, 3,5
-Difluorophenyl group, pentachlorophenyl group,
Organic metalloid groups such as 3,4,5-trifluorophenyl group, pentafluorophenyl group, 3,5-bis (trifluoromethyl) phenyl group and bis (trimethylsilyl) methyl group, as pentamethylantimony group, trimethylsilyl group, trimethyl Examples include a germyl group, a diphenylarsine group, 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 -10 or less are trifluoromethanesulfonic acid anion (CF ₃ SO ₃ ) ⁻ , bis (trifluoromethanesulfonyl) ) Methyl anion, bis (trifluoromethanesulfonyl) benzyl anion, bis (trifluoromethanesulfonyl) amide, perchlorate anion (Cl
O ₄ ) ^- , trifluoroacetic acid anion (CF ₃ CO ₂ )
^- , Hexafluoroantimony anion (Sb
F ₆ ) ^- , a fluorosulfonic acid anion (FS
O ₃ ) ^- , chlorosulfonic acid anion (ClS
O ₃ ) ^- , fluorosulfonate anion / 5-antimony fluoride (FSO ₃ / SbF ₅ ) ^- , fluorosulfonate anion / 5-arsenic fluoride (FSO ₃ / As)
F ₅₎ ^-, trifluoromethanesulfonic acid / antimony pentafluoride _{(CF 3 SO 3 / SbF 5} ) - and the like.

Specific examples of such an ionic compound which reacts with the transition metal compound of the component (A) to form an ionic complex, ie, 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) Butyl) ammonium, dimethyldiphenylammonium tetraphenylborate, triphenyl (methyl) ammonium tetraphenylborate, trimethylanilinium tetraphenylborate, methylpyridinium tetraphenylborate, benzylpyridinium tetraphenylborate, methyltetraphenylborate (2-cyanopyridinium) , 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, porphyrin manganese porphyrin, silver tetrafluoroborate, silver hexafluorophosphate, silver hexafluoroarsenate,
Examples thereof include silver perchlorate, silver trifluoroacetate, and silver trifluoromethanesulfonate.

The component (B-1), which is capable of forming an ionic complex by reacting with the transition metal compound of the component (A), may be used alone or in combination of two or more. You may. On the other hand, as the aluminoxane of the component (B-2), the general formula (V)

[0051]

Embedded image

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

[0053]

Embedded image

(Wherein, 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 method is not particularly limited, and the reaction may be performed according to a known method. For example, a method in which an organoaluminum compound is dissolved in an organic solvent and then brought into contact with water, a method in which an organoaluminum compound is initially added during polymerization and then water is added, and a crystal water contained in a metal salt or the like is used. A method of reacting water adsorbed on an inorganic or organic substance with an organoaluminum compound, a method of reacting a trialkylaluminoxane with a trialkylaluminum, and further reacting water. The aluminoxane may be insoluble in toluene.

These aluminoxanes may be used alone or in 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.

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

Specific examples of the compound represented by the general formula (VII) include trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, dimethylaluminum chloride, diethylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, 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 production method of the present invention, preliminary contact can also be performed using the components (A), (B) and (C) described above. The preliminary contact can be performed by bringing the component (A) into contact with the component (B), for example, but the method is not particularly limited, and a known method can be used. These preliminary contacts are effective in reducing the catalyst cost, such as improving the catalyst activity and reducing the proportion of the cocatalyst (B) used. Further, by bringing the component (A) and the component (B-2) into contact with each other, an effect of improving the molecular weight can be seen together with the above-mentioned effect. The preliminary contact temperature is usually -20 ° C to 2 ° C.
00 ° C, preferably -10 ° C to 150 ° C, more preferably 0 ° C to 80 ° C. In the preliminary contact, an inert hydrocarbon, an aliphatic hydrocarbon, an aromatic hydrocarbon, or the like can be used as a solvent. Particularly preferred among these are aliphatic hydrocarbons.

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

In the present invention, at least one of the catalyst components can be used by being supported on a suitable carrier. There is no particular limitation on the type of the carrier, an inorganic oxide carrier,
Any of other inorganic carriers and organic carriers can be used, but inorganic oxide carriers and other inorganic carriers are particularly preferred. As the inorganic oxide carrier, specifically, SiO 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, glass fiber and the like can be mentioned. Among them, SiO ₂ and Al ₂ O ₃ are particularly preferable. In addition, the inorganic oxide carrier contains a small amount of carbonate,
It may contain nitrates, sulfates and the like.

On the other hand, as a carrier other than the above, MgC
l_Two, Mg (OC_TwoH_Five)_TwoSuch as magnesium compounds
General formula MgR represented by¹⁷ _XX¹ _yMagne represented by
Examples of the compound include a calcium compound and a complex salt thereof. This
Where R¹⁷Is an alkyl group having 1 to 20 carbon atoms,
20 alkoxy groups or aryl groups having 6 to 20 carbon atoms,
X ¹Represents a halogen atom or an alkyl group having 1 to 20 carbon atoms.
Where x is 0-2, y is 0-2, and x + y = 2
is there. Each R¹⁷And each X¹May be the same, and
They may be 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 is MgC
l ₂ , MgCl (OC ₂ H ₅ ), Mg (OC ₂ H ₅ ) ₂ ,
SiO ₂ and Al ₂ O ₃ are preferred. The shape of the carrier varies depending on the type and the production method, but the average particle size is usually 1 to 300 µm, preferably 10 to 200 µm, more preferably 20 to 100 µm.

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

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

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

The method of 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 component (A) and the component (B), a carrier and, if necessary, the organoaluminum compound of the component (C) are added, and an olefin such as ethylene is added at normal pressure to 20 kg / cm ² to obtain -20 to 200 A method in which preliminary polymerization is performed at a temperature of 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 use 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. Further, the use ratio of the component (A) to the carrier is preferably 1: 5 to 1: 10000, more preferably 1:10 to 1: 500 by weight.

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

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 used in the present invention is produced by homopolymerizing propylene or copolymerizing propylene with ethylene and / or an α-olefin having 4 to 20 carbon atoms using the polymerization catalyst described above. .

In this case, the polymerization method is not particularly limited.
Rally polymerization, gas phase polymerization, bulk polymerization, solution polymerization,
Any method such as suspension polymerization may be used.
Lie polymerization and gas phase polymerization are particularly preferred. About polymerization conditions
The polymerization temperature is usually -100 ~ 250 ℃, preferably
Is -50 to 200C, more preferably 0 to 130C.
You. In addition, the ratio of catalyst used to
Nomer / the component (A) (molar ratio) is preferably 1 to 1.
0 ⁸, Especially 100 to 10^FivePreferably, Further
The polymerization time is usually 5 minutes to 10 hours, and the reaction pressure is preferably
Normal pressure ~ 200kg / cm^TwoG, particularly preferably normal pressure
~ 100kg / cm^TwoG.

Methods for controlling the molecular weight of the polymer include selection of the type and amount of each catalyst component, the amount used, and the polymerization temperature, as well as 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.

At the time of polymerization, preliminary polymerization can be carried out using the polymerization catalyst. The prepolymerization can be carried out by 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. Particularly preferred among these are aliphatic hydrocarbons. Further, the prepolymerization may be performed without a solvent.

In the prepolymerization, the intrinsic viscosity [η] (measured in decalin at 135 ° C.) of the prepolymerized product is 0.2 deciliter / g or more, especially 0.5 deciliter / g or more, and the transition metal component in the catalyst is used. The amount of the prepolymerized product per 1 mmol is from 1 to 10,000 g, especially from 10 to 10 g.
It is desirable to adjust the conditions so as to be 00 g. Next, the crystalline propylene polymer [II] in the present invention will be described below.

The crystalline propylene according to the present invention
As the polymer [II], a propylene-based polymer exhibiting crystallinity is used.
There is no particular limitation as long as they are united. For example, propyle
Homopolymer, propylene-ethylene random copolymer
Copolymer, propylene-ethylene-1-butene random copolymer
And propylene-ethylene block copolymers
Can be Further, the content of the crystalline propylene polymer [II]
In each case, select the size from the viewpoint of moldability.
Melt indexing for T die cast film molding
It is preferable that the weight is about 2 to 20 g / 10 min,
For sheet molding, a material of about 1 to 10 g / 10 min is preferable.
Good. Of these, the purpose of the film or sheet
It can be arbitrarily selected and used depending on the intended use. Concrete
For example, heat resistance and heat sealing strength are important.
Propylene-based material with high melting point and high crystallinity
Polymers are preferred and described in JP-A-8-85711.
What was done can be illustrated. That is, (1) isotactic venta, which is a stereoregularity index
Is 85.0 to 92.0 mol% and n-heptane
Tan insoluble part amount (H) is 98.0 to 97.0% by weight.
And the relationship between P and H satisfies the equation 0.750P + 27.125 <H, and (2) the melt index (MI)
Is 1 to 20 g / 10 min and the temperature is 175 ° C.
The frequency ω obtained by the frequency dispersion measurement ₀= 1
0⁰rad / sec relaxation time τ (sec) and M
A polypropylene polymer having a relationship with I satisfying the following formula: τ ≦ 0.65-0.025MI.

More preferably, (1 ′) the isotactic bentad fraction (P), which is an index of stereoregularity, is 85.0 to 92.0 mol%, and the n-heptane insoluble part amount (H) is 86. 0 to 97.0% by weight, and the relationship between P and H satisfies the following equation: 0.750P1026.000 <H, and (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 MI, a polypropylene polymer satisfying the formula: τ ≦ 0.63-0.025MI.

The meanings of P, H, MI, ω ₀ and τ, the measuring method, and the method for producing the propylene polymer are as described in JP-A-8-85711. When improving the low-temperature heat-sealing property of a film or sheet, a crystalline propylene polymer [I
I] is also preferably propylene, ethylene random copolymer, propylene, ethylene, 1-butene random copolymer, etc. excellent in low-temperature heat sealability.
629, JP-A-9-272718, JP-A-10-130336, and the like. That is, a propylene copolymer which is a copolymer of propylene and ethylene and satisfies the following conditions may be used. (JP-A-9-208629) The combined amount of ethylene units in the copolymer (χ (wt
%)) Is 3 to 10% by weight. 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%) (I) E ≦ 2.6 (χ = 6 to 10 wt%) · (II) The melting point (Tm (° C.)) measured by a differential scanning calorimeter and χ satisfy the relationship of the formula (III) or (IV). Tm ≦ 140 (χ = 3 to 5 wt%) III) Tm ≦ 165-5χ (χ = 5 to 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 the formula (1) E ≦ 0.25χ1.1 (1) The melting point (Tm (° C.)) measured by the differential scanning calorimeter and χ satisfy the relationship of the formula (2) Tm ≦ 165-5} (2) The isotactic triad fraction (mm (mol%)) of the PPP chain portion measured by ¹³ C-NMR is 9
Next, as the ethylene / 1-butene / propylene copolymer, those described in JP-A-11-60639 can be mentioned. That is, a propylene-based random copolymer which is a copolymer of propylene, ethylene and 1-butene, and satisfies the following conditions. Total amount of ethylene units in the copolymer (α mol%)
And the combined amount of 1-butene units (β mol%) satisfies the expression (1). 4 ≦ α + β ≦ 15 (1) Melt index of copolymer (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 by (α +
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.

When the crystalline propylene polymer [II] in the present invention does not show crystallinity, the heat resistance of the film or sheet may be reduced. In the present invention, the propylene polymer [I] and the crystalline propylene polymer [II] may be dry-blended using a Henschel mixer or the like, or may be uniaxial or biaxial. It may be melt-kneaded using an extruder, a Banbury mixer or the like. The proportion of [I] is usually 1 to 99% by weight, preferably 10 to 90% by weight, particularly preferably 20 to 80% by weight.
If [I] is less than 1% by weight, the flexibility may be reduced.

Various additives may be added to the propylene-based resin composition of the present invention, if desired. 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 61
8 (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 (Sand (manufactured)), phosphite 168 (Ciba-Geigy (manufactured)) and the like.

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-Geigy (manufactured)), Irganox 1010 (Ciba-Geigy (manufactured)), ADK STAB AO-60 (Asahi Denka (manufactured)), Sumilizer BP-
101 (Sumitomo Chemical Co., Ltd.), Tominox TT (Yoshitomi Pharmaceutical Co., Ltd.), TTHP (Toray Co., Ltd.), Irganox 3114 (Ciba Geigy Co., Ltd.), 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 (manufactured)), Irganox 245 (Ciba-Geigy (manufactured)), Adekastab AO-
70 (Asahi Denka Co., Ltd.), Tominox 917 (Yoshitomi Pharmaceutical Co., Ltd.), ADK STAB AO-80 (Asahi Denka Co., Ltd.),
SUMILIZER GA-80 (Sumitomo Chemical Co., Ltd.) and the like.

Specific examples of the sulfur-based antioxidants 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.) ,
Antix 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.

Examples of antioxidants for use in films and sheets include Irganox 1010: Substance name: pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] Irgafos 168: Substance name: Tris (2,4-di-t
-Butylphenyl) phosphite Irganox 1076: Substance: Octadecyl-3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate Irganox 1330: Substance: 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-
4-Hydroxybenzyl) benzene Irganox 3114: Substance: Tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate P-EPQ: Substance: Tetrakis (2,4-di-t-) Butylphenyl) 4,4′-biphenylene-diphosphite is particularly preferred.

When an antioxidant is used in the present invention, the antioxidant may be added in an amount of about 0.001 to 1 part by weight based on 100 parts by weight of the propylene resin composition.
This is preferable because yellowing and the like can be prevented. Specific examples of use of the above antioxidants include: Example 1 Irganox 1010 1000 ppm PEP-Q 1000 ppm Example 2 Irganox 1076 1200 ppm PEP-Q 600 ppm Irgafos 168 800 ppm Example 3 Irganox 1010 400 to 1000 ppm Irgafos 168 750 to 750 1500 ppm.

As a neutralizing agent for film and sheet applications,
Calcium stearate, zinc stearate, magnesium stearate, hydrotalcite (DHT-4
A): Composition formula: Mg _4.5 Al ₂ (OH) ₁₃ CO ₃ · 3.
5H ₂ O and the like are particularly preferred. As an antiblocking agent for use in films and sheets, “Sylysia”: synthetic silica based on Fuji Silysia (manufactured), “Mizukasil”: synthetic silica based on Mizusawa Chemical Industries, Ltd., and the like are particularly preferable.

Examples of slip agents for use in films and sheets include erucamide, oleic amide, stearamide, behenic amide, ethylene bisstearic amide, ethylene bisoleic amide, stearyl erucamide, and oleyl palmitamide. Particularly preferred.
When using a nucleating agent in the present invention, the amount of the nucleating agent is usually 10 ppm based on the propylene-based resin composition.
And more preferably in the range of 10 to 10000 ppm, more preferably in the range of 10 to 5000 ppm, and still more preferably in the range of 10 to 2500 ppm.
If it is less than 10 ppm, no improvement in low-temperature heat-sealing properties is observed, while if it exceeds 10,000 ppm, not only does the preferred effect not increase, but it also causes poor appearance.

[0089]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the present invention. First, a method for evaluating resin characteristics and film quality in the present invention will be described. "Evaluation Method of Resin Properties" (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 and Abnormal Insertion Fraction It was measured by the method described in the text of the specification. That is, the mesopendad fraction (mmmm fraction) and the racemic pentad fraction (rrrr fraction) were determined by A. Zambelli and others using "Macromol".
ecules, 6 , 925 (1973) ", the methyl group signal in the ¹³ C nuclear magnetic resonance spectrum was measured, and the isotactic fraction and atactic fraction in pentad units in the polypropylene molecular chain were measured. The rate was determined by the following formula. <Calculation formula> M = m / S × 100 R = γ / S × 100 S = Pββ + Pαβ + Pαγ S: Signal intensity of side chain methyl carbon atom of all propylene units Pββ: 19.8 to 22.5 ppm Pαβ: 18 0.0 to 17.5 ppm P αγ: 17.5 to 17.1 ppm γ: Racemic pentad chain: 20.7 to 20.3 ppm m: Mesopentad chain: 21.7 to 22.5 ppm Also, (m−2,1 ), (R-2,1) and (1,3)
Are reported by Grassi et al. (Macromolucules, 21 , p. 61).
7 (1988)) and a report by Busico et al. (Macromolucul).
es, 27 , p. 7538 (1994)), the assignment of peaks in the ¹³ C-NMR spectrum was determined, and each insertion content was calculated from the integrated intensity of each peak. (M-2, 1) is 17.2 ppm with respect to the integrated intensity in the entire methyl carbon region.
The ratio of the integrated intensity of peaks belonging to Pα and γthreo appearing in the vicinity was calculated as the meso-2,1 insertion content (%). (R-2,1) is Pα, γthreth which appears around 15.0 ppm with respect to the integrated intensity in the entire methyl carbon region.
The ratio of the integrated intensity of the peak attributed to o was calculated as racemic-2,1 insertion content (%). (1,3) was calculated as the 1,3 insertion content (%), which is the ratio of the integrated intensity of the peak belonging to Tβ, γ10 appearing around 31.0 ppm to the integrated intensity in the entire methine carbon region. When peaks to be attributed to meso-2,1 insertion, racemic-2,1 insertion or 1,3 insertion may not be identifiable due to hiding in noise, etc., the content of each heterogeneous bond (m −2,
1), (r-2,1) or (1,3) was regarded as 0.

The measurement of the ¹³ C nuclear magnetic resonance spectrum was performed using the following apparatus and conditions. Apparatus: JNM-EX400 type ¹³ CN manufactured by JEOL Ltd.
MR apparatus Method: Proton complete decoupling method Concentration: 220 mg / ml Solvent: 90:10 (volume ratio) mixed solvent of 1,2,4-trichlorobenzene and heavy benzene Temperature: 130 ° C. Pulse width: 45 ° Pulse repetition time: 4 seconds integration: 10000 times (3) Measurement of molecular weight distribution (Mw / Mn) Mw / Mn was measured by the method described in the specification text. That is, 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 the GPC method 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) (4) DSC measurement It was measured by the method described in the text of the specification. That is, a differential scanning calorimeter (manufactured by Perkin-Elmer, DS
Using C-7), a sample of 10 mg was placed in a nitrogen atmosphere at 230 ° C.
, And then the temperature was lowered to 0 ° C at 10 ° C / minute, and further held at 0 ° C for 3 minutes, and then the temperature was raised at 10 ° C / minute, and the melting endothermic amount obtained was ΔHm or ΔH. . The peak top of the maximum peak of the melting endothermic curve obtained at this time was defined as a melting point: Tm. In addition, 2
After holding at 30 ° C. for 3 minutes, the temperature is lowered to 0 ° C. at 10 ° C./min. The peak top of the maximum peak of the crystallization exothermic curve obtained at this time was defined as crystallization temperature: Tc. (5) Temperature rising fractionation chromatograph The amount W25 (% by weight) of the component eluted without being adsorbed by the filler at the TREF column temperature of 25 ° C. in the elution curve was determined as follows. (A) Operation method The sample solution is introduced into a TREF column adjusted to a temperature of 135 ° C., and then gradually cooled to 0 ° C. at a temperature decreasing rate of 5 ° C./hour to crystallize the sample on the surface of the filler. Thereafter, the column was heated to 135 ° C. at a rate of 40 ° C./hour to obtain an elution curve. (B) Apparatus configuration TREF column: Silica gel column (4.6φ x 150mm) manufactured by GL Sciences Flow cell: 1mm optical path length KBr cell manufactured by GL Sciences Pump: SSC-3100 pump manufactured by Senshu Kagaku Valve oven: GL Sciences Model 554 oven (high temperature type) TREF oven: GL Science's two-line temperature controller: Rigaku Corporation REX-C100 temperature controller Detector: Infrared detector for liquid chromatography FOXBORO's MIRAN 1A CVF 10-way valve : Barco electric valve loop: Barco 500 microliter loop (c) Measurement conditions Solvent: o-dichlorobenzene Sample concentration: 7.5 g / liter Injection volume: 500 microliter Pump flow rate: 2.0 ml / min Detection Wave number: 3. 1μm column filler: Chromosorb P (30 to 60 mesh) Column temperature distribution: a within ± 0.2 ° C. (6) Tensile modulus propylene polymer to create a press-molded into test pieces,
It measured by the tensile test based on JISK-7113.

Crosshead speed: 50 mm / min Load cell: 100 kg (7) Heated fractionation chromatograph The amount of components eluted without being adsorbed by the packing material at a TREF column temperature of 25 ° C. in the elution curve as follows: W25 (% by weight) was determined. (A) Operation method The sample solution is introduced into a TREF column adjusted to a temperature of 135 ° C., and then gradually cooled to 0 ° C. at a rate of 5 ° C./hour, held for 30 minutes, and the sample is adsorbed on the filler. Thereafter, the column was heated to 135 ° C at a heating rate of 40 ° C / hour.
The temperature was raised to ℃ to obtain an elution curve. (B) Apparatus configuration TREF column: Silica gel column (4.6φ x 150mm) manufactured by GL Sciences Flow cell: 1mm optical path length KBr cell manufactured by GL Sciences Pump: SSC-3100 pump manufactured by Senshu Kagaku Valve oven: GL Sciences Model 554 oven (high temperature type) TREF oven: GL Science's two-line temperature controller: Rigaku Corporation REX-C100 temperature controller Detector: Infrared detector for liquid chromatography FOXBORO's MIRAN 1A CVF 10-way valve : Barco electric valve loop: Barco 500 microliter loop (c) Measurement conditions Solvent: o-dichlorobenzene Sample concentration: 7.5 g / liter Injection volume: 500 microliter Pump flow rate: 2.0 ml / min Detection Wave number: 3. 1μm column filler: Chromosorb P (30 to 60 mesh) Column temperature distribution: Ingredient Amount (H25) H25 eluting within ± 0.2 ° C. (8) hexane was determined by measuring by the measuring conditions below.

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

H25 = [(W ₀ −W ₁ ) / W ₀ ] × 100 (%) “Evaluation method of film quality” All the films formed were annealed at a temperature of 40 ° C. for 24 hours. 2
After conditioning for 16 hours or more at 3 ± 2 ° C. and 50 ± 10% humidity, measurement was performed under the same temperature and humidity conditions. (1) Heat seal temperature and heat seal strength Measured according to JIS Z-1707. . Specifically, after sealing with a heat seal bar calibrated by a surface thermometer under the following conditions, leaving it at room temperature for 24 hours, peeling strength (heat sealing) by a T-type peeling method at room temperature and a peeling rate of 200 mm / min. Strength) was measured. The heat sealing temperature was defined as a temperature at which the peel strength was 300 g / 15 mm, and was calculated from a seal temperature-peel strength curve. Sealing conditions Sealing surface: metal roll surface / metal roll surface Sealing area: 15 × 10 mm Sealing pressure: 2.0 kg / cm2 Sealing time: 1 second Sealing temperature: several points so that heat sealing temperature can be interpolated (2) Transparency (Haze) Measured according to JIS K7105 (3) Tensile modulus Measured by a tensile test according to JIS K7127 under the following conditions Crosshead speed: 500 mm / min Load cell: 10 kg Measurement direction: Machine direction (MD) (4) Frequency Dispersion Measurement of Melt Viscoelasticity A cone plate (diameter 25.0 mm, cone angle 0.1
0 radian), temperature 175 ° C, initial strain 20%
The frequency dispersion of the melt viscoelasticity was measured under the following conditions. Complex modulus G * (iω) at frequency (ω (rad / sec))
Is described by stress σ * and strain γ *, G * (iω)
= Σ * / γ * = G ′ (ω) + iG ″ (ω), where i is an imaginary unit. Example 1 (1) Preparation of catalyst (dimethylsilylene) ₂ (3-n- Butylindenyl)
₂ Synthesis of zirconium dichloride (1,2′-dimethylsilylene) (2,
0.83 g of 1′-dimethylsilylene) (indene) ₂
(2.4 mmol) and 50 mL of ether. -7
After cooling to 8 ° C. and adding 3.1 mL (5.0 mmol) of n-BuLi (hexane solution 1.6 M), the mixture is stirred at room temperature for 12 hours. The solvent was distilled off, and the solid obtained was distilled off with hexane 20.
By washing with mL, 1.1 g (2.3 mmol) of a lithium salt is obtained as an ether adduct. This lithium salt is dissolved in 50 mL of THF and cooled to -78 ° C. 0.57 mL (5.3 mmol) of n-butyl bromide is slowly added dropwise and stirred at room temperature for 12 hours. After distilling off the solvent and extracting with 50 mL of hexane, the solvent was removed and (1,2′-
Dimethylsilylene) (2,1'-dimethylsilylene)
0.81 g of (3-n-butylindene) ₂ (1.77
mmol). (Yield: 74%) Next, the (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) (3-n-butylindene) ₂ obtained above was placed in a Schlenk bottle under a nitrogen gas stream. .81
g (1.77 mmol) and 100 mL of ether. After cooling to −78 ° C., n-BuLi (hexane solution 1.
After adding 2.7 mL (4.15 mmol) of 54M),
Stir at room temperature for 12 hours. The solvent was distilled off, and the obtained solid was washed with hexane to obtain 0.28 g (1.43 mmol) of a lithium salt as an ether adduct.

Under a nitrogen stream, the lithium salt obtained above is dissolved in 50 mL of toluene. Cooled to −78 ° C., and zirconium tetrachloride 0.33 previously cooled to −78 ° C.
g (1.42 mmol) in toluene (50 mL) is added dropwise. After the addition, the mixture is stirred at room temperature for 6 hours. Thereafter, the mixture is filtered, and the solvent of the filtrate is distilled off. By recrystallization from dichloromethane (1,2'-dimethylsilylene)
0.2 g of (2,1′-dimethylsilylene) (3-n-butylindenyl) ₂ zirconium dichloride (0.
32 mmol) were obtained. (Yield 22%) The result of measurement by ¹ H-NMR (90 MHz, CDCl ₃ ) was: δ 0.88, 0.99 (12H, dimethylsilylene), 0.7-1.0, 1.1-. 1.5 (18
H, n-Bu), 7.0-7.6 (8H, benzene ring proton). (2) Polymerization of propylene In a stainless steel autoclave having an internal volume of 10 liters, 6 liters of heptane, 6 mmoles of triisobutylaluminum, and 5 mmoles of methylaluminoxane (manufactured by Albemarle Co., Ltd.) were combined with (1,2′-dimethylsilylene) obtained above. ) (2,1′-Dimethylsilylene) (3-n-butylindenyl) ₂ Zirconium dichloride 5 μmol was preliminarily contacted in toluene for 5 minutes, and the catalyst component was charged. Here, after the introduction of hydrogen ^{0.5kg / cm 2 G, 8.0kg /} cm 2 during the polymerization pressure by introducing propylene gas to G was fed propylene by pressure controller so as to be constant at a total pressure. After conducting polymerization at a polymerization temperature of 50 ° C. for 30 minutes, the content was taken out and dried under reduced pressure to obtain a propylene homopolymer (B-1). (3) Mixing and kneading The following additives were formulated into the polypropylene homopolymer (B-1) obtained above, and extruded and granulated by a single screw extruder (Model TLC35-20 manufactured by Tsukada Juki Seisakusho). Then, a pellet was obtained. (Additive formulation) Phenolic antioxidant: Irganox 1010 1000 ppm manufactured by Ciba Specialty Chemicals Phosphorous antioxidant: P-EPQ 500 ppm manufactured by Ciba Specialty Chemicals Neutralizer: calcium stearate: 500 ppm Neutralizer: DHT -4A: 500 ppm (4) Production of resin composition As propylene polymer [I], 15 parts by weight of propylene polymer [a-1] produced by the above method and as crystalline propylene polymer [II] Idemitsu Polypro F
-704NP is charged into a blender of 85 parts by weight and mixed well, and then a single screw extruder (TLC3 manufactured by Tsukada Juki Seisakusho)
5-20). (5) Film formation From the pellets of the propylene-based resin composition thus obtained, using a 20 mmφ extruder manufactured by Tsukada Juki Seisakusho, the resin temperature at the T-die outlet was 190 ° C. and the chill roll temperature was 30.
A film having a thickness of 50 μm was formed under the conditions of a temperature of 6 ° C. and a take-up speed of 6 m / min. Table 1 shows the obtained results.
And Table 2. Example 2 The same procedure as in Example 1 was carried out except that the blend ratio was changed to 30 parts by weight of the propylene-based polymer [a-1] and 70 parts by weight of Idemitsu Polypro-F-704NP. Table 2 shows the obtained results. Example 3 The same procedure as in Example 1 was carried out except that the blend ratio was changed to 60 parts by weight of the propylene-based polymer [a-1] and 40 parts by weight of Idemitsu Polypro-F-704NP. Table 2 shows the obtained results. [Comparative Example 1] The same procedure was performed as in Example 1 except that an ethylene-propylene copolymer rubber (grade name: EP913Y) manufactured by Nippon Synthetic Rubber Co., Ltd. was used instead of the propylene-based polymer [a-1]. . Table 2 shows the obtained results. [Comparative Example 2] The same procedure was performed as in Example 2 except that an ethylene-propylene copolymer rubber (grade name: EP913Y) manufactured by Nippon Synthetic Rubber Co., Ltd. was used instead of the propylene-based polymer [a-1]. . Table 2 shows the obtained results. [Comparative Example 3] The same operation as in Example 3 was performed except that ethylene-propylene copolymer rubber (grade name: EP913Y) of Nippon Synthetic Rubber Co., Ltd. was used instead of the propylene-based polymer [a-1]. . Table 2 shows the obtained results. Comparative Example 4 The same procedure was performed as in Example 1 except that propylene-based polymer [I] was not blended and Idemitsu Polypro F-704NP was used alone. Table 2 shows the obtained results. Comparative Example 5 The same procedure as in Example 1 was carried out except that propylene-based polymer [I] was not blended and Idemitsu Polypro F-454NP was used alone. Table 2 shows the obtained results. Comparative Example 6 The same procedure as in Example 1 was carried out except that propylene-based polymer [I] was not blended and Idemitsu TPO E2900 was used alone. Table 2 shows the obtained results.

[0095]

[Table 1]

[0096]

[Table 2]

[0097]

The propylene-based resin composition of the present invention provides a propylene-based film or sheet whose heat-sealing temperature is appropriately lowered and the heat-sealing strength is greatly improved. In addition, the propylene-based resin composition of the present invention provides films and sheets that are rich in flexibility, excellent in transparency, excellent in heat resistance, and have greatly improved heat seal strength, and can be used as a substitute for soft vinyl chloride-based resin. It is preferably used.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4F071 AA20 AA81 AA84 AA88 AA89 AF20 AF20Y AF30 AF59 BA01 BB06 BC01 BC12 BC17 4J002 BB12W BB12X BB14W BB14X BB15W BB15X BP02W FD030 FD070 A04 AQA AQA A04 AQA AQA AQ CA01 CA04 DA00 DA04 DA09 DA22 DA40 DA41 DA62 FA10

Claims (7)

[Claims] 1. A peak top temperature (Tc (° C.)) on the highest temperature side in a crystallization curve measured by a differential scanning calorimeter (DSC) and a differential calorie (ΔHm) in a melting curve.
(J / g)) satisfies the following relational expression (1-1): Tc ≧ (１ ／) · ΔHm + 90 (1-1) and storage elastic modulus in melt viscoelasticity frequency dispersion measurement ( G ′ (Pa)) and a frequency (ω (rad / sec)) at which the loss modulus (G ″ (Pa)) becomes equal to ΔHm satisfying the following relational expression (2-1): a propylene-based resin composition. ≦ (1/10) · ΔHm + 15 (2-1) 2. The composition according to claim 1, comprising 1 to 99% by weight of a propylene-based polymer [I] satisfying the following (1) to (3) and 99 to 1% by weight of a crystalline propylene-based polymer [II]. Propylene resin composition. (1) The component amount (W25) eluting at 25 ° C. or lower in the temperature raising chromatography is 20 to 100% by weight. (2) The component amount (H25) eluting in hexane at 25 ° C. is 0 to 80% by weight. (3) In the DSC measurement, the melting point (Tm (° C.)) is not shown, or when it shows Tm, Tm and the melting endotherm ΔH
(J / g) satisfies the following relationship: ΔH ≧ 6 × (Tm−140) 3. The method according to claim 1, comprising 1 to 99% by weight of a propylene homopolymer [a] satisfying the following (1) to (3) and 99 to 1% by weight of a crystalline propylene polymer [II]. Propylene resin composition. (1) The mesopentad fraction (mmmm) is 20 to 60 mol%. (2) The racemic pentad fraction (rrrr) and (1-mm)
mm) satisfies the following relationship: [rrrr / (1-mmmm)] ≦ 0.1 (3) The component amount (W25) eluted at 25 ° C. or lower in the temperature rising chromatography is 20 to 100% by weight. 4. The propylene polymer [I] according to claim 2 or the propylene homopolymer [a] according to claim 3 satisfies the following (1) and / or (2).
Or the propylene-based resin composition according to 3. (1) Gel permeation chromatograph (GPC)
Molecular weight distribution (Mw / Mn) measured by the method is 4 or less (2) intrinsic viscosity measured at 135 ° C. in tetralin solvent
[η] is 0.5 to 15.0 deciliter / g 5. The propylene polymer [I] according to claim 2 or the propylene homopolymer [a] according to claim 3 does not show a melting point (Tm (° C.)) in DSC measurement. A propylene-based resin composition according to any one of the above. 6. A film or sheet having a layer comprising the propylene-based resin composition according to claim 1. 7. The haze of a film or sheet measured according to JIS K7105 is 10% or less.
A film or sheet as described.