JP3415204B2 - Polypropylene multilayer film - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] TECHNICAL FIELD The present invention relates to a polypropylene multilayer film.
More about lumps, stiffness, transparency and
Possessing excellent locking and heat sealing properties
It relates to a propylene multilayer film. [0002] BACKGROUND OF THE INVENTION Polypropylene such as crystalline polypropylene
Olefins are compounds of transition metals from Groups IV to VI of the periodic table
And organometallic compounds of metals of Groups I to III of the periodic table
Using a so-called Ziegler-Natta catalyst
It is well known that they can be obtained by polymerizing
ing. And using such a catalyst, high stereoregularity
A method for obtaining a crystalline polyolefin of high polymerization activity
For example, JP-A-61-209207, JP-A-62-104810
Report, JP-A-62-104811, JP-A-62-104812,
JP-A-62-104813, JP-A-1-311106,
Japanese Unexamined Patent Publication No. Hei 1-318011, Japanese Unexamined Patent Publication No. Hei 2-166104, etc.
Have been. [0003] Such highly stereoregular crystalline polypropylene
Pyrene has high rigidity and generally high heat distortion temperature, melting point,
It has excellent heat resistance and crystallization due to its crystallization temperature.
It has excellent properties such as high speed and high transparency. So
Suitable for various uses such as containers and films
Have been. [0004] By the way, crystalline polypropylene is
Disadvantage of poor heat sealability due to high melting point
There is. For this reason, in fields such as packaging films,
A seal material layer made of a fin-based random copolymer
Used as a multilayer film with heat sealability
Have been. But with such a multilayer film,
Thicker sealing material layer to obtain good heat sealing properties
And the rigidity of the multilayer film is reduced, and sufficient rigidity is obtained.
Thinner sealing material layer for
There is a problem of going down. The present inventors have studied in view of such a situation.
As a result, a substrate layer made of a specific propylene polymer,
Seal material made of specific propylene-based random copolymer
A thickness of the sealing material layer and a total thickness of the film.
Polypropylene with a ratio of 0.03 to 0.4
Multilayer film has excellent rigidity and heat sealability,
Found that it has excellent transparency and blocking resistance
As a result, the present invention has been completed. [0006] OBJECTS OF THE INVENTION The present invention provides rigidity, transparency and block resistance.
Polyp with excellent king properties and excellent heat sealing properties
The purpose is to provide propylene multi-layer film
You. [0007] SUMMARY OF THE INVENTION A polypropylene multilayer fill according to the present invention.
The base material layer made of the propylene polymer [A]
A sealing material layer made of a pyrene-based random copolymer [B];
A multilayer film having the propylene polymer
[A] is the melt at 230 ° C and 2.16 kg load.
Flow rate (MFR) of 0.1 to 500 g / 10 min
Range of boiling heptane insoluble components¹³C-NMR spec
From the absorption strength of Pmmmm and Pw in
Stereoregularity index [M obtained by (1)_Five] Value
0.970-0.995, insoluble in boiling heptane
Ingredient¹³Pmmrm, Pmrm in C-NMR spectrum
Absorption intensity of r, Pmrrr, Prrmr, Prmmr, Prrrr, Pw
From the stereoregularity index [M
_ThreeIs in the range of 0.0002 to 0.0050,
The crystallinity of insoluble heptane is 60% or more.
A pyrene polymer, and the propylene-based random copolymer
Form [B] is derived from an α-olefin having 4 or more carbon atoms.
Containing 2 to 15 mol% of the structural unit
Containing 5 mol% or less of structural units derived from
Melting point is 145 ℃ or less, 23 ℃ n-decane soluble component
Is 10% by weight or less and α having 4 or more carbon atoms
-Random copolymer with olefin or propylene
Of ethylene, α-olefin having 4 or more carbon atoms and ethylene
Dam copolymer, and the thickness of the sealing material layer,
Ratio to total film thickness (thickness of sealing material layer / film)
Is in the range of 0.03 to 0.4.
are doing; [0008] (Equation 3) (Where: [Pmmmm]: Isopropylene with 5 propylene units in a row
Due to the methyl group of the third unit in the site where
Coming absorption intensity, [Pw]: absorption derived from the methyl group of the propylene unit
Strength. ) [0010] (Equation 4)[0011] The polypropylene multilayer film according to the present invention
In the above, the propylene polymer [A] has the following formula (i):
Or a structural unit derived from the compound represented by (ii)
Polymer in an amount in the range of 10 to 10000 ppm.
It is desirable to have. [0012] Embedded image[0013] DETAILED DESCRIPTION OF THE INVENTION Polypropylene according to the present invention
The multilayer film will be specifically described. According to the present invention
Polypropylene multilayer film is made of propylene polymer
Provided on the base layer composed of [A] and the outermost layer of the multilayer film
Consisting of the obtained propylene random copolymer [B]
And a metal material layer. First, the polypropylene according to the present invention is described.
Propylene polymers and plastics used in multi-layer films
The propylene-based random copolymer will be described. Book
In the invention, the term "polymerization" means that only
Not be used in the sense of including copolymerization,
The term "polymer" refers not only to homopolymers, but also to copolymers.
Sometimes used to include the body. [0015]Propylene polymer [A] The propylene polymer [A] used in the present invention is propylene polymer.
It is a homopolymer of len. In such a propylene polymer, 230
° C, melt flow rate at 2.16 kg load (M
FR) is 0.1 to 500 g / 10 min, preferably 0.2 to 500 g / 10 min.
It is desirable to be in the range of 300 g / 10 minutes. The melt flow rate (MFR) is expressed by A
230 ° C, 2.16kg load according to STM D1238-65T
It is measured under the following conditions. Propylene used in the present invention
The polymer is composed of boiling heptane-insoluble components.¹³C-NMR spec
From the absorption intensity of Pmmmm and Pw in torr, the following formula (1)
Stereoregularity index [M_FiveIs 0.97
0-0.995, preferably 0.980-0.995, and so on.
More preferably, it is in the range of 0.982 to 0.995. [0018] (Equation 5) (Where: [Pmmmm]: Isopropylene with 5 propylene units in a row
Due to the methyl group of the third unit in the site where
Coming absorption intensity, [Pw]: absorption derived from the methyl group of the propylene unit
Strength. ) Next, the stereoregularity of the propylene polymer used in the present invention
Stereoregularity index [M_Five]
Explain physically. The homopolymer of propylene is, for example,
It can be expressed as in equation (A). [0021] Embedded image 3 units in 5 chains of propylene units represented by
The methyl group at the position (eg, Me^Three, Me^FourDerived from)¹³C
-The absorption intensity in the NMR spectrum
All methyl groups in the propylene unit (Me¹, Me^Two, Me^Three…)
When the derived absorption intensity is Pw, it is expressed by the above formula (A).
The stereoregularity of the polymer to be used is determined by the ratio of Pmmmm to Pw,
That is, the value [M obtained from the above equation (1)_Five]
can do. Therefore, the propyle used in the present invention
The stereoregularity of the boiling ethane-insoluble component of the polymer
Of boiling heptane-insoluble components of pyrene polymer¹³C-NMR
From the absorption intensity of Pmmmm and Pw in the spectrum,
Stereoregularity index [M obtained by (1)_Five] Value
Can be evaluated more. The propylene polymer used in the present invention is:
The boiling heptane insoluble component is determined by the above equation (1).
Stereoregularity index [M_FiveIs 0.970 to 0.995.
Within the range, and of the boiling heptane-insoluble component¹³CN
Pmmrm, Pmrmr, Pmrrr, Prm in MR spectrum
From the absorption intensity of rr, Prmmr, Prrrr, Pw, the following formula (2)
Stereoregularity index [M_Three] Is 0.00
20-0.0050, preferably 0.0023-0.00
45, more preferably in the range of 0.0025 to 0.0040
It is in. [0025] (Equation 6)In the above equation (2), [Pmmrm], [Pmrm
r], [Pmrrr], [Prmrr], [Prmmr], [Prrr
r] is a sequence of five consecutive
Of the methyl groups in the propylene unit, three are in the same direction,
Structure in which the individual faces in the opposite direction (hereinafter “M_ThreeStructure "
The third unit in the five propylene units having
It shows the absorption intensity derived from the methyl group of the eye. Sand
The stereoregularity index [M_Three]
Is the value of M in the propylene unit chain._ThreeStructure percentage
Is shown. The propylene polymer used in the present invention is:
The boiling heptane insoluble component is determined by the above equation (1).
Stereoregularity index [M_FiveIs 0.970 to 0.995.
Within the range, the boiling heptane-insoluble component is determined by the above equation (2).
Stereoregularity index [M_Three] Is 0.0002
Extremely long meso-chains in the range of ~ 0.0050
(Propylene alone with α-methyl carbon oriented in the same direction
Position chain). In general, polypropylene has a stereoregularity index.
[M_Three] Is longer the longer the meso-chain. But three-dimensional
Regularity index [M_Five] Value is extremely large and stereoregularity finger
Mark [M_Three] Is very small, the stereoregularity
Mark [M_Five] Are almost the same, the stereoregularity index
[M_Three] May increase the length of the meso chain.
You. For example, the structure (a) shown below is provided.
And a polypropylene having the structure (b)
When compared with Len, M_ThreeTable with structure (a)
The polypropylene used is M_ThreeStructure without structure
(B) longer meso chains compared to polypropylene
Have. (However, the following structure (a) and structure (b)
Both consist of 1003 propylene units
Do) [0030] Embedded image The polypropylene represented by the above structure (a)
Stereoregularity index [M_Five] Is 0.986,
Stereoregularity index of polypropylene represented by structure (b)
[M _Five] Is 0.985, and is represented by the structure (a).
Polypropylene and polypropylene represented by the structure (b)
Len stereoregularity index [M_Five] Are approximately equal
is there. However, M_ThreeTable with structure (a)
Of polypropylene contained in meso chains
Len units average 497 units and M_ThreeContains structure
Polypropylene represented by the non-structure (b)
The average number of propylene units in the chain is 250 units.
You. That is, the stereoregularity index [M_FiveIs very large
In heavy polypropylene, it is included in the propylene unit chain.
The ratio of the structure indicated by r (racemo) is extremely small
The structure indicated by r (racemo) is concentrated
Polypropylene (M_ThreePolypropylene with structure
) Means that the structure represented by r (racemo)
Polypropylene (M_ThreePolypropylene without structure
G) have a longer meso-chain. The propylene polymer used in the present invention is:
M as shown in the above structure (a) _ThreeHigh knot with structure
It is crystalline polypropylene and contains no boiling heptane-insoluble components.
Body regularity index [M_FiveIs in the range of 0.970 to 0.995.
And the stereoregularity index of the boiling heptane-insoluble component [M
_Three] Is in the range of 0.0020 to 0.0050. This
The propylene polymer used in the present invention such as
It is not clear, but compared to conventional highly crystalline polypropylene
High rigidity, heat resistance and moisture resistance. In addition,
Stereoregularity index of boiling heptane-insoluble component [M_Three]The value of the
Deviates from the range of 0.0002 to 0.0050,
The above characteristics may deteriorate. In the present invention, the boiling heptane-insoluble component is as follows:
It is prepared as follows. That is, one liter with a stirrer
3 g of the polymer sample, 2,6-ditert-butyl
20 mg of 4-methylphenol, 500 ml of n-decane
And dissolve by heating on an oil bath at 145 ° C. Polymer trial
After the ingredients are dissolved, cool to room temperature over about 8 hours,
And hold on a water bath at 23 ° C. for 8 hours. Precipitated polymer
N-decane suspension containing (23 ° C decane-insoluble component) G-4
(Or G-2) by filtration with a glass filter
After drying, 1.5 g of the polymer was treated with heptane for 6 hours or more.
The boiling heptane insoluble component extracted by Soxhlet
Becomes Boiling of the propylene polymer used in the present invention;
The amount of the butane-insoluble component is usually at least 80% by weight, preferably
90% by weight or more, more preferably 94% by weight or more,
95% by weight or more, particularly preferably 96% by weight
% Or more. In addition, the above-mentioned boiling heptane insoluble component amount
Means that the 23 ° C decane-soluble component is also soluble in boiling heptane.
It is calculated assuming. In the present invention, the boiling heptane-insoluble component N
The MR measurement is performed, for example, as follows. Sand
In addition, 0.35 g of the insoluble component was added to hexachlorobutadiene 2.
Heat and dissolve to 0 ml. Put this solution in a glass filter
After filtration in (G2), 0.5 ml of deuterated benzene was added.
In addition, it is charged into an NMR tube having an inner diameter of 10 mm. Soshi
Using a JEOL GX-500 type NMR measuring apparatus
At 20 ° C¹³A C-NMR measurement is performed. The number of integration is 10,
000 times or more. Stereoregularity index [M_Five]and
[M_Three] Is the value of each structure obtained by the above measurement.
From the peak intensity or the sum of the peak intensities based on
Can be The boiling point of the propylene polymer used in the present invention
The crystallinity of the insoluble heptane insoluble component is preferably 60% or more.
At least 65%, more preferably at least 70%
Is desirable. The crystallinity is measured as follows.
That is, the sample was 1 mm thick with a 180 ° C. pressure molding machine.
Press sheet obtained by immediately cooling with water after forming into a square plate of
Rotorflex RU3 manufactured by Rigaku Denki Co., Ltd.
Determined by measuring using a 00 measuring device
(Output 50 kV, 250 mA). In this case,
Is measured using the transmission method and rotating the sample.
I do. The propylene polymer used in the present invention is:
Derived from a compound represented by the following formula (i) or (ii)
Polymer consisting of 10 to 10,000 pp
m, preferably in an amount ranging from 100 to 5000 ppm.
It is desirable to have. [0038] Embedded image In the above formula (i), a symbol represented by X
Cycloalkyl groups such as cyclopentyl and cyclohexyl;
And an aryl group.
Phenyl, tolyl, xylyl, naphthyl
And the like. In the above formula (i) or (ii),
R¹, R^TwoAnd R^ThreeAs the hydrocarbon group represented by
Alkyls such as methyl, ethyl, propyl, butyl, etc.
Aryl groups such as a kill group, a phenyl group, and a naphthyl group;
Or a norbornyl group. Further R¹,
R^TwoAnd R^ThreeThe hydrocarbon groups represented by
Logens may be included. In the above formula (i) or (ii),
Specifically, the compound to be used is 3-methyl-1-butene, 3
-Methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-
1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-he
Xen, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexe
, 3-ethyl-1-hexene, allylnaphthalene, allyl
Norbornane, styrene, dimethylstyrenes, vinyl
Naphthalenes, allyltoluenes, allylbenzene,
Nylcyclohexane, vinylcyclopentane, vinyl
Examples include cloheptane and allyltrialkylsilanes
it can. Among these, 3-methyl-1-butene, 3-methyl-
1-pentene, 3-ethyl-1-hexene, vinylcyclohexene
Sun, allyltrimethylsilane, dimethylstyrene, etc.
Preferably, 3-methyl-1-butene,
Contains vinylcyclohexane and allyltrimethylsilane
More preferably, it contains 3-methyl-1-butene.
It is particularly preferred to have. The propylene polymer used in the present invention
Is an olefin having 20 or less carbon atoms other than propylene,
Or derived from a diene compound having 4 to 20 carbon atoms
A small amount of a constituent unit may be contained. As described above, the propylene polymer is
Even if it contains a small amount of monomer components other than
Regularity index [M_Five] And the stereoregularity index [M_Three]The value of the
Does not substantially affect the The propylene polymer used in the present invention is:
Density 0.909-0.936 g / cm^Three,Preferably
0.910-0.936 g / cm^ThreeIn the range of
Good. The propylene polymer used in the present invention
It is preferable that the amount of soluble components at 23 ° C in decane is 3.0% or less.
2.5% or less, more preferably 2.0% or less, particularly preferably
More preferably, it is 1.5% or less. The propylene polymer can be decanted at 23 ° C.
The amount of the dissolved component is measured as follows. That is,
In a 1 liter flask equipped with a stirrer, 3 g of the polymer sample was added.
2,6-ditert-butyl-4-methylphenol 20 mg, n-
Add 500ml of decane, heat and melt on 145 ℃ oil bath
Let it. After the polymer sample is dissolved, allow about 8 hours for room temperature
And then kept on a 23 ° C. water bath for 8 hours.
N-decane suspension containing precipitated polymer and dissolved polymer
And filtered with G-4 (or G-2) glass filter
I do. The obtained solution was dried at 10 mmHg and 150 ° C.
Dry until the weight of the mixed solvent
The amount of the soluble component of the polymer in the
Calculated as a percentage. The boiling point of the propylene polymer used in the present invention
The half-crystallization time at 135 ° C. of
00 seconds or less, preferably 100 seconds or less, more preferably
80 seconds or less, particularly preferably 70 seconds or less.
Good. It should be noted that boiling heptanes of the propylene polymer are not used.
The half-crystallization time at 135 ° C of the dissolved component is as follows.
Measured. That is, a differential calorimeter manufactured by PerkinElmer
Of the above polymer at 135 ° C. using heptane
Measures the relationship between heating value and time due to crystallization of insoluble components
And when the calorific value needs to reach 50% of the total calorific value
The half crystallization time is defined as the interval. The propylene polymer used in the present invention
Is the difference between the melting point and the crystallization temperature of the boiling heptane-insoluble component.
Is 45 ° C. or less, preferably 43 ° C. or less, more preferably
Is desirably 40 ° C. or less. The propylene polymer used in the present invention 1
The intrinsic viscosity [η] measured in decalin at 35 ° C. is
Always 0.001 to 30 dl / g, preferably 0.01 to 10 dl
/ G, particularly preferably in the range of 0.05 to 8 dl / g.
It is desirable. The propylene used in the present invention as described above
Polymers include, for example, [Ia] magnesium, titanium,
Solid containing halogen and electron donor as essential components
Body-shaped titanium catalyst component (a) and [II] organometallic catalyst component
(B) and [III] a silicon compound represented by the following formula (iii):
Object (c) or two or more
A compound (d) having an ether bond and R^a _nSi (OR^b)_4-n      … (Iii) Wherein n is 1, 2 or 3, and when n is 1, R
^aIs a secondary or tertiary hydrocarbon group, and n is 2 or
When 3, R^aAt least one is a second or third grade charcoal
A hydrogen group;^aAre the same or different
Well, R^bIs a hydrocarbon group having 1 to 4 carbon atoms,
When n is 2 or 3, R^bAre the same but different
It may be. Olefin polymerization catalyst formed from)
Preferably in the presence of [Ib] magnesium, titanium
, Halogens and electron donors as essential components
Solid titanium catalyst component (a) and organometallic catalyst component
In the presence of (b), represented by the following formula (i) or (ii)
At least one olefin selected from olefins
A pre-polymerization catalyst component obtained by pre-polymerizing [0052] Embedded image [II] The organometallic catalyst component (b) and [II]
I] a silicon compound (c) represented by the above formula (iii) or
Two or more ether bonds that exist through multiple atoms
Polymerization catalyst formed from compound (d) having
Produced by polymerizing propylene in the presence of a medium
can do. The propylene polymerization used in the present invention is described below.
That form the olefin polymerization catalyst used in the production of
The components will be specifically described. Solid titanium catalyst component
(A) is a magnesium compound as shown below,
Prepared by contacting compound and electron donor
be able to. Used for the preparation of the solid titanium catalyst component (a)
Specifically, for example, the following formula:
And a tetravalent titanium compound represented by the following formula: Ti (OR)_gX_4-g (Wherein, R is a hydrocarbon group and X is a halogen atom.
G is 0 ≦ g ≦ 4. ) Such a titanium compound
Specifically, TiCl_Four, TiBr_Four, TiI_FourSuch
Of titanium tetrahalide; Ti (OCH_Three) Cl_Three, Ti (O
C_TwoH_Five) Cl_Three, Ti (On-C_FourH₉) Cl_Three, Ti (OC_TwoH_Five) Br
_Three, Ti (O-iso-C_FourH₉) Br_Three Trihalogenated al such as
Coxy titanium; Ti (OCH_Three)_TwoCl_Two, Ti (OC_TwoH_Five)_TwoCl
_Two, Ti (On-C_FourH₉)_TwoCl_Two, Ti (OC_TwoH_Five)_TwoBr_TwoSuch as
Dialkoxytitanium dihalide; Ti (OCH_Three)_ThreeCl,
Ti (OC_TwoH_Five)_ThreeCl, Ti (On-C_FourH₉)_ThreeCl, Ti (OC_Two
H_Five)_ThreeMonohalogenated trialkoxy titers such as Br
N; Ti (OCH_Three)_Four, Ti (OC_TwoH_Five)_Four, Ti (On-C_FourH₉)
_Four, Ti (O-iso-C_FourH₉)_Four, Ti (O-2-ethylhexyl)_Four
It is possible to exemplify tetraalkoxy titanium etc.
Wear. Among these, halogen-containing titanium compounds
Are preferable, and titanium tetrahalide is more preferable.
And titanium tetrachloride is particularly preferred. These titanium compounds
May be used alone or in combination of two or more
May be. Furthermore, these titanium compounds are hydrocarbon
Compounds or halogenated hydrocarbon compounds
It may be. Used for the preparation of the solid titanium catalyst component (a)
Magnesium compounds that can be reduced
Gnesium compounds and non-reducing magnesium
Compounds can be mentioned. Here, a magnesium compound having a reducing property
Examples include a magnesium-carbon bond or a
Magnesium compounds having a magnesium-hydrogen bond
I can do it. Magnesium with such reducing properties
Dimethylmagnesium
System, diethyl magnesium, dipropyl magnesium,
Dibutyl magnesium, diamyl magnesium, dihexene
Sylmagnesium, didecylmagnesium, ethyl chloride
Magnesium, propyl magnesium chloride, butyl chloride
Magnesium, hexyl magnesium chloride, amyl chloride
Magnesium, butyl ethoxy magnesium, ethyl butyl
Chill magnesium, butyl magnesium hydride
And so on. These magnesium compounds
Can be used alone or as described later
The compound may form a complex compound. In addition, these
Gnesium compounds may be liquid or solid
Or react metal magnesium with the corresponding compound
You may be guided by letting them do so. During the preparation of the catalyst
Can be derived from metallic magnesium using the method of
Wear. Magnesium compound having no reducing property
Typical examples are magnesium chloride, magnesium bromide.
Like magnesium, magnesium iodide, magnesium fluoride
Magnesium halide; methoxymagnesium chloride,
Ethoxy magnesium chloride, isopropoxy chloride magne
Cium, butoxymagnesium chloride, octoxychloride
Alkoxy magnesium halides such as gnesium;
Magnesium phenoxy chloride, methyl phenoxy chloride
Allyloxymagnesium halides, such as gnesium;
Ethoxymagnesium, isopropoxymagnesium,
Butoxymagnesium, n-octoxymagnesium, 2-
Alkoxymags such as ethylhexoxymagnesium
Nesium; phenoxymagnesium, dimethylphenoki
Allyloxymagnesium such as simmagnesium; lau
Like magnesium phosphate, magnesium stearate
Magnesium carboxylate etc.
Wear. These non-reducing magnesium compounds
The product is made from the above-mentioned magnesium compound having a reducing property.
Derivatization during preparation of derived compounds or catalyst components
It may be a compound. Magnesification without reduction
Compound is derived from a reducing magnesium compound.
For example, for example, a magnesium compound having a reducing property
With halogen, polysiloxane compound, halogen-containing silicone
Run compounds, halogen-containing aluminum compounds, alcohol
Activated carbons such as alcohols, esters, ketones and aldehydes
-It may be brought into contact with a compound having an oxygen bond. In the present invention, the magnesium compound
The product is a magnesium compound having the above reducing property and
In addition to the magnesium compound having no intrinsic properties,
Complex compounds and complex compounds of nesium compounds and other metals
Alternatively, it may be a mixture with another metal compound. Further
Alternatively, two or more of the above compounds may be used in combination.
No. Used for the preparation of the solid titanium catalyst component (a)
Examples of the magnesium compound include, in addition to the above,
Although many magnesium compounds can be used,
Halogenation in the solid titanium catalyst component (a)
Preferably in the form of a magnesium compound containing
Therefore, use a halogen-free magnesium compound
In some cases, during the preparation, contact reaction with halogen-containing compounds
Preferably. Among the above-mentioned magnesium compounds,
Magnesium compounds having no intrinsic properties are preferable,
Magnesium compounds are more preferred, and magnesium chloride
Nesium, alkoxymagnesium chloride, allyloxy salt
Magnesium chloride is particularly preferred. The solid titanium catalyst component used in the present invention
(A) is a magnesium compound as described above,
Contact with such a titanium compound and an electron donor.
And is formed by In the preparation of the solid titanium catalyst component (a)
Specific examples of the electron donor used include the following.
Compounds. Methylamine, ethylamine,
Dimethylamine, diethylamine, ethylenediamine,
Tetramethylenediamine, hexamethylenediamine,
Amines such as ributylamine and tribenzylamine;
Pyrrole, methylpyrrole, dimethylpyrrole, etc.
Rolls; pyrroline; pyrrolidine; indole; pyridi
, Methylpyridine, ethylpyridine, propylpyridyl
Dimethyl pyridine, ethyl methyl pyridine, trime
Tylpyridine, phenylpyridine, benzylpyridine,
Pyridines such as pyridine chloride; piperidines, quinori
And nitrogen-containing cyclic compounds such as isoquinolines; tetra
Hydrofuran, 1,4-cineole, 1,8-cineole, pino
Olefuran, methylfuran, dimethylfuran, diphenyi
Lefuran, benzofuran, coumaran, phthalane, tetra
Cyclic acids, such as hydropyran, pyran, and ditedropyran
Elemental compounds; methanol, ethanol, propanol, pe
Nthanol, hexanol, octanol, 2-ethyl
Xanol, dodecanol, octadecyl alcohol,
Oleyl alcohol, benzyl alcohol, phenyle
Chill alcohol, cumyl alcohol, isopropyl alcohol
Carbon number of coal, isopropylbenzyl alcohol, etc.
Alcohols 1 to 18; phenol, cresol,
Silenol, ethylphenol, propylphenol,
Nonylphenol, cumylphenol, naphthol, etc.
6 to 20 carbon atoms which may have a lower alkyl group
Nols: acetone, methyl ethyl ketone, methyl iso
Butyl ketone, acetophenone, benzophenone, ace
C 3-15 carbon atoms such as tilacetone and benzoquinone
Tons; acetaldehyde, propionaldehyde, e
Cutylaldehyde, benzaldehyde, tolualdehyde
Aldehydes having 2 to 15 carbon atoms such as naphthaldehyde
C: methyl formate, methyl acetate, ethyl acetate, vinyl acetate
Propyl acetate, octyl acetate, cyclohexyl acetate
, Ethyl propionate, methyl butyrate, ethyl valerate,
Methyl chloroacetate, ethyl dichloroacetate, methacrylic acid
Methyl, ethyl crotonic acid, cyclohexanecarboxylic acid
Ethyl, methyl benzoate, ethyl benzoate, benzoic acid
Ropyl, butyl benzoate, octyl benzoate, benzoic acid
Cyclohexyl, phenyl benzoate, benzyl benzoate
, Methyl toluate, ethyl toluate, toluic acid
Amyl, ethyl ethyl benzoate, methyl anisate, male
N-butyl inmate, diisobutyl methylmalonate, cyclo
Hexene carboxylate di-n-hexyl, nadic acid diethyl
Diisopropyl tetrahydrophthalate, diphthalic phthalate
Ethyl, diisobutyl phthalate, di-n-butyl phthalate,
Di-2-ethylhexyl phthalate, γ-butyrolactone, δ-
Valerolactone, coumarin, phthalide, ethyl carbonate, etc.
Organic acid esters having 2 to 30 carbon atoms; acetyl chloride
Benzoyl chloride, toluic acid chloride, anise
Acid halides having 2 to 15 carbon atoms such as acid chloride;
Ether, ethyl ether, isopropyl ether,
Butyl ether, amyl ether, anisole, diphe
C2-C2 such as nyl ether epoxy-p-menthane
Ethers of 0; 2-isopentyl-2-isopropyl-1,3-
Dimethoxypropane, 2,2-isobutyl-1,3-dimethoxy
Propane, 2,2-isopropyl-1,3-dimethoxypropa
2-cyclohexylmethyl-2-isopropyl-1,3-dim
Toxipropane, 2,2-isopentyl-1,3-dimethoxyprop
Lopan, 2-isobutyl-2-isopropyl-1,3-dimethoxy
Propane, 2-cyclohexyl-2-isopropyl-1,3-dimethyl
Toxipropane, 2-cyclopentyl-2-isopropyl-1,
3-dimethoxypropane, 2,2-dicyclopentyl-1,3-di
Methoxypropane, 1,2-bis-methoxymethyl-bicyclo
-[2,2,1] -heptane, diphenyldimethoxysilane,
Sopropyl-t-butyldimethoxysilane, 2,2-diisobu
Tyl-1,3-dimethoxycyclohexane, 2-isopentyl-
2-isopropyl-1,3-dimethoxycyclohexane
Diethers; acetic acid amide, benzoic acid amide, toluyl
Acid amides such as acid amides; acetonitrile, benzoni
Nitriles such as tolyl and tolunitrile; acetic anhydride, none
Acid anhydrides such as water phthalic acid and benzoic anhydride are used.
It is. As an electron donor, one of the following
It is also possible to use a silicon compound represented by the general formula (iii).
Wear. In addition, titanium compound as above, magnesium
When contacting the compound and the electron donor,
Using a carrier compound, a carrier-supported solid titanium catalyst component
(A) can also be prepared. Examples of such a carrier compound include Al
_TwoO_Three, SiO_Two, B_TwoO_Three, MgO, CaO, TiO_Two, Z
nO, ZnO_Two, SnO_Two, BaO, ThO and Stille
And resins such as divinylbenzene copolymer.
be able to. Among these carrier compounds, preferably
SiO_Two, Al_TwoO_Three, MgO, ZnO, ZnO_TwoEtc.
I can do it. The above components include, for example, silicon,
Contact in the presence of other reagents such as
You may let it. Method for producing solid titanium catalyst component (a)
Is a titanium compound or a magnesium compound as described above.
And by contacting with an electron donor
Can adopt any method, including known methods
be able to. Specific examples of the solid titanium catalyst component (a)
The following is a brief description of some typical production methods. (1) Magnesium compounds, electron donors and hydrocarbon solvents
The solution consisting of the medium is brought into contact with the organometallic compound and solidified.
Titanium compound after or while precipitating the body
And contact reaction. (2) From magnesium compound and electron donor
After contacting and reacting the complex
A contact reaction of the compound. (3) In the contact substance between the inorganic carrier and the organomagnesium compound,
The titanium compound and preferably the electron donor are catalytically reacted.
How to let. At this time, the contact material should be
Contact reaction with compound and / or organometallic compound
Is also good. (4) Magnesium compound, electron donor, field
In some cases, the solution containing a hydrocarbon solvent may be mixed with an inorganic or
From the mixture with the organic carrier, the supported magnesium compound
Inorganic or organic carrier, and then contact the titanium compound.
How to touch. (5) Magnesium compounds, titanium compounds,
Solution containing an electron donor, and possibly a hydrocarbon solvent
The contact between the liquid and the inorganic or organic carrier
For obtaining a solid titanium catalyst component carrying titanium and titanium
Law. (6) An organic magnesium compound in a liquid state is
A method of contacting with a halogen-containing titanium compound. this
Sometimes an electron donor is used at least once. (7) Halogen-containing organomagnesium compound in liquid state
A method of contacting a titanium compound after the contact reaction with the compound.
At this time, the electron donor is used at least once. (8) Magnesium compound containing alkoxy group
With a halogen-containing titanium compound. this
Sometimes an electron donor is used at least once. (9) Magnesium compound containing alkoxy group and electric child
A method comprising contacting a complex comprising a donor with a titanium compound. (10) Alkoxy group-containing magnesium compound
A complex consisting of a metal and an electron donor with an organometallic compound
After that, a contact reaction with a titanium compound. (11) A magnesium compound, an electron donor, and a titanium compound
A method of contacting and reacting with an object in an arbitrary order. This reaction
Means that each component is an electron donor and / or an organometallic compound.
Pretreatment with a reaction aid such as silicon and halogen-containing silicon compounds
May be. In this method, the above electron donating
Preferably, the body is used at least once. (12) Liquid magnesium having no reducing ability
Compound and a liquid titanium compound, preferably an electron donor
Reaction in the presence of solid magnesium-titanium complex
A method of precipitating coalescence. (13) Titanium was added to the reaction product obtained in (12).
A method of further reacting the compound. (14) The reaction product obtained in (11) or (12)
A method in which the donor and the titanium compound are further reacted. (15) Magnesium compound and preferably electron
A solid substance obtained by grinding a donor and a titanium compound
Of halogen, a halogen compound and an aromatic hydrocarbon
How to handle with one. In this method,
Use only magnesium compounds or magnesium compounds
Complex compound consisting of a substance and an electron donor
Including the step of pulverizing the titanium compound and the titanium compound
Good. After the pulverization, a pretreatment with a reaction aid is performed, and then
You may process with a logen etc. Organic as reaction aid
Metal compounds or halogen-containing silicon compounds
I can do it. (16) After grinding the magnesium compound,
A method of contacting and reacting with a tan compound. At this time, when grinding
And / or use an electron donor or reaction aid during contact / reaction.
Preferably, it is used. (17) The compounds obtained in the above (11) to (16)
Treatment with halogens or halogenated compounds or aromatic hydrocarbons.
How to manage. (18) Metal oxide, containing organic magnesium and halogen
The contact reactant with the compound is preferably treated with an electron donor and
A method of contacting with a titanium compound. (19) Magnesium salt of organic acid, alkoxy
Magnesium such as magnesium and aryloxy magnesium
A titanium compound and / or a halogen compound
Reacting with the contained hydrocarbon and preferably with the electron donor
Method. (20) Magnesium compound and alkoxy titer
A titanium compound and a hydrocarbon solution containing at least
And / or a method of contacting with an electron donor. At this time
Halogen-containing compounds such as halogen-containing silicon compounds
Preferably. (21) Magnesium in liquid state without reducing ability
Reaction between the metal compound and the organometallic compound.
Precipitating gnesium-metal (aluminum) composite,
Then, the reaction between the electron donor and the titanium compound
Law. When preparing the solid titanium catalyst component (a)
The amount of each of the above components used in the preparation depends on the preparation method.
Although it cannot be specified unconditionally, for example, magnesium
The amount of the electron donor is preferably from 0.01 to 10 mol per mol of the compound.
Preferably, it is used in an amount of 0.1 to 5 mol, and the titanium compound
Is from 0.01 to 1000 mol, preferably from 0.1 to 200 mol.
Used in the amount of oil. The solid titanium catalyst thus obtained
Component (a) comprises magnesium, titanium, halogen and
Contains an electron donor as an essential component. This solid state
In the titanium catalyst component (a), halogen / titanium (raw
Is in the range of about 2 to 200, preferably about 4 to 100.
And the electron donor / titanium (molar ratio) is about 0.0
1 to 100, preferably in the range of about 0.02 to 10
Magnesium / titanium (atomic ratio) is about 1-100,
Preferably, it is in the range of about 2 to 50. Such a solid titanium catalyst component (a)
(Catalyst component [Ia]) is the solid titanium catalyst component.
(A) in the presence of the following organometallic catalyst component (b)
[Ib] preliminary obtained by performing pre-polymerization of fins
It is desirable to use it as a pre-polymerization catalyst component for polymerization. [Ib] Used for preparing a prepolymerized catalyst component
Examples of the organometallic catalyst component (b) include Group I of the periodic table.
~ Organometallic compounds of Group III metals are used, specifically
The following compounds are used. (B-1) Formula R¹ _mAl (OR^Two)_nH_pX_q (Where R¹And R^TwoUsually has 1 to 15 carbon atoms, preferably
Preferably they are hydrocarbon groups containing from 1 to 4
May be the same or different. X represents a halogen atom,
0 <m ≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, q is 0
≦ q <3 and m + n + p + q = 3
You. The organoaluminum compound represented by). (B-2) General formula M¹AlR¹ _Four (Where M¹Is Li, Na, K, and R¹Is the same as above
The same. ) And aluminum.
Complex alkylated compounds. (B-3) Formula R¹R^TwoM^Two (Where R¹And R^TwoIs the same as above, and M^TwoIs M
g, Zn or Cd. Group II represented by) or
Group III dialkyl compounds. Organoalumination belonging to the above (b-1)
Examples of the compound include the following compounds. General formula R¹ _mAl (OR^Two)_3-m (Where R¹And R^TwoIs the same as above, and m is
Or 1.5 ≦ m ≦ 3. Compound represented by)
object, General formula R¹ _mAlX_3-m (Where R¹Is the same as above, and X is halogen
M is preferably 0 <m <3. )
Compound, General formula R¹ _mAlH_3-m (Where R¹Is the same as described above, and m is preferably 2 ≦
m <3. ), A compound represented by General formula R¹ _mAl (OR^Two)_nX_q (Where R¹And R^TwoIs the same as above, and X is halo
Gen, 0 <m ≦ 3, 0 ≦ n <3, 0 ≦ q <3,
M + n + q = 3. )
I can do it. As the aluminum compound belonging to (b-1)
More specifically, triethylaluminum, trib
Trialkylaluminums such as chilled aluminum;
Trialkenyl alkyl such as lysoprenyl aluminum
Minium; diethylaluminum ethoxide, dibutyl
Dialkyl aluminum such as aluminum butoxide
Alkoxide; ethyl aluminum sesquiethoxide;
Alkyls such as butyl aluminum sesquibutoxide
Luminium sesquialkoxide; R¹ _2.5Al (OR^Two)
_0.5Partially Alkoxy having an average composition represented by
Alkylaluminum silicide; diethylaluminum
Muchloride, dibutylaluminum chloride, diethyl
Dialkyl aluminum such as aluminum bromide
Ride; ethyl aluminum sesquichloride, butyria
Luminium sesquichloride, ethyl aluminum sesquichloride
Alkyl aluminum sesquihalides such as bromide;
Ethyl aluminum dichloride, propyl aluminum
Al chloride such as dichloride and butyl aluminum dibromide
Partially halogenated, such as kill aluminum dihalide
Alkylaluminum; diethylaluminum
Dialkis such as hydride and dibutylaluminum hydride
Aluminum hydride; ethyl aluminum dihydrido
And propyl aluminum dihydride
Other partially hydrogenated, such as Luminium dihydride
Alkyl aluminum; ethyl aluminum ethoxy
Chloride, butylaluminum butoxycyclolide, ethyl
Alcohol such as aluminum ethoxy bromide
Xylated and halogenated alkyl aluminum
Can be mentioned. Compounds similar to (b-1) include acids
Two or more aluminum atoms are bonded through an element atom or nitrogen atom
Organic aluminum compounds. This
Examples of the compound such as (C)_TwoH_Five)_TwoAl
OAl (C_TwoH_Five)_Two, (C_FourH₉)_TwoAlOAl (C
_FourH₉)_Two, (C_TwoH_Five)_TwoAlN (C_TwoH_Five) Al (C
_TwoH_Five)_TwoIn addition to other materials, such as methylaluminoxane
Luminoxanes can be mentioned. Compounds belonging to the above (b-2) include Li
Al (C_TwoH_Five)_Four, LiAl (C₇H_Fifteen)_FourEtc.
be able to. Among them, the organoaluminum compound is
It is preferably used. [Ib] Olefium used for preparation of prepolymerized catalyst component
Is a compound represented by the above formula (i) or (ii)
Are preferably used, specifically, 3-methyl-1-butene
3-Methyl-1-pentene, 3-ethyl-1-pentene, 4-
Tyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl
-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-
Hexene, 3-ethyl-1-hexene, allylnaphthalene,
Allyl norbornane, styrene, dimethyl styrenes,
Vinylnaphthalenes, allyltoluenes, allylbenze
, Vinylcyclohexane, vinylcyclopentane, vinyl
Nylcycloheptane, allyltrialkylsilanes, etc.
And an olefin having a branched structure of these
Among them, 3-methyl-1-butene, 3-methyl-1-pentene,
Tyl-1-hexene, vinylcyclohexane, allyltri
Methylsilane, dimethylstyrene, etc. are preferred,
Cyl-1-butene, vinylcyclohequine, allyltrimethyl
Silane is more preferred, and 3-methyl-1-butene is particularly preferred.
Good. Other than these, ethylene, propylene, 1-butyl
Ten, 1-octene, 1-hexadecene, 1-eicosene, etc.
Can be used in combination. Extra weight
In this case, the concentration of the catalyst in the system in the main polymerization of propylene
A much higher concentration of catalyst can be used. Solid titanium catalyst component in prepolymerization
The concentration of (a) is 1 liter of an inert hydrocarbon medium described later.
Approximately 0.01 to 200 mm
Lmol, preferably in the range of about 0.05 to 100 mmol
Is desirable. The amount of the organometallic catalyst component (b) is
0.1 to 1000 g per 1 g of the tan catalyst component (a), preferably
Or in an amount such that 0.3-500 g of polymer is produced.
The titanium source in the solid titanium catalyst component (a)
Usually about 0.1 to 100 mmol, preferably
In the range of about 0.5 to 50 mmol.
No. When performing the prepolymerization, solid titanium
In addition to the catalyst component (a) and the organometallic catalyst component (b),
Donor (e) may be used. This electron donor (e)
Specifically, the solid titanium catalyst component (a) is first prepared.
The electron donor used in the production is represented by the formula (iii) described below.
Through the silicon compound (c) and a plurality of atoms
A compound (d) having two or more ether bonds,
Further, an organosilicon compound represented by the following formula (c-i)
Can be mentioned. R_nSi (OR ')_4-n        … (C-i) (Wherein R and R ′ are hydrocarbon groups, and 0 <n <4
Note that the organosiliconization represented by the formula (c-i)
The compound is a siliconized compound represented by the formula (iii) described below.
Compound (c) is not included. The organic compound represented by the general formula (c-i)
As the silicon compound, specifically, trimethylmethoxy
Sisilane, trimethylethoxysilane, dimethyl dimethoate
Xysilane, dimethyldiethoxysilane, diisopropyl
Ludimethoxysilane, diphenyldimethoxysilane,
Phenylmethyldimethoxysilane, diphenyldiethoxy
Silane, bis-tolyldimethoxysilane, bis-m-tolyl
Dimethoxysilane, bis p-tolyldimethoxysilane,
P-tolyldiethoxysilane, bisethylphenyldimethyl
Toxisilane, ethyltrimethoxysilane, ethyltri
Ethoxysilane, vinyltrimethoxysilane, methyl
Limethoxysilane, n-propyltriethoxysilane, de
Siltrimethoxysilane, decyltriethoxysilane,
Phenyltrimethoxysilane, γ-chloropropyltri
Methoxysilane, methyltriethoxysilane, ethylto
Liethoxysilane, vinyltriethoxysilane, n-butyl
Rutriethoxysilane, phenyltriethoxysilane,
γ-aminopropyltriethoxysilane, chlorotrie
Toxysilane, ethyltriisopropoxysilane, vinyl
Tributoxy silane, ethyl silicate, butyl silicate,
Trimethylphenoxysilane, methyltriaryloxy (a
llyloxy) silane, vinyl tris (β-methoxyethoxy)
Silane), vinyl triacetoxy silane, dimethyl tet
Laethoxydisiloxane and the like. These electron donors (e) are solely
Or two or more kinds can be used in combination. This electric child
The donor (e) is titanium in the solid titanium catalyst component (a).
0.1 to 50 moles, preferably 0.5 to 3 moles per mole of atom
0 mol, more preferably 1 to 10 mol.
You. The prepolymerization is carried out by adding the above formula to an inert hydrocarbon medium.
The olefin represented by (i) or (ii) and the above-mentioned catalyst
It is preferable to perform the reaction under mild conditions by adding a medium component. This
As the inert hydrocarbon medium used at the time of
Is propane, butane, pentane, hexane, hepta
Aliphatic charcoal such as octane, octane, decane, dodecane, kerosene
Hydrogen; cyclopentane, cyclohexane, methylcycl
Alicyclic hydrocarbons such as lopentane; benzene, tolue
Aromatic hydrocarbons such as ethylene and xylene; ethylene chloride
Halogenated hydrocarbons such as
Can include these contact substances. these
Among the inert hydrocarbon media, especially aliphatic hydrocarbons
Preferably, it is used. The reaction temperature at the time of the pre-polymerization
The polymer is practically insoluble in inert hydrocarbon media
Any temperature may be used, and it is usually about -20 to + 100 ° C,
Preferably about -20 to + 80 ° C, more preferably 0 to +
It is desirable to be in the range of 40 ° C. For pre-polymerization,
It is also possible to use molecular weight regulators such as hydrogen.
Wear. The prepolymerization is carried out using the solid titanium catalyst as described above.
About 0.1 to 1000 g per 1 g of the medium component (a), preferably
Should be performed to produce about 0.3 to 500 g of polymer.
Is desirable. If the prepolymerization amount is too large,
May reduce the (co) polymer production efficiency.
Film was formed from the (co) polymer obtained.
In some cases, fish eyes are likely to occur. Such a prepolymerization is carried out by a batch system or a continuous system.
I can. Propylene polymer used in the present invention
The olefin polymerization catalyst used for the production of
a] solid titanium catalyst component or [Ib] prepolymerized catalyst
Component, [II] organometallic catalyst component, and [III] siliconization
Compound (c) or two or more present through a plurality of atoms
And a compound (d) having an ether bond of
I have. [II] The organometallic catalyst component is as described above.
(Ib) The organic (b) used for preparing the prepolymerized catalyst component
The same one as the metal catalyst component can be used. [III] The silicon compound (c) is represented by the following formula (iii)
Compound. [0108] R^a _n-Si- (OR^b)_4-n      … (Iii) Wherein n is 1, 2 or 3, and when n is 1, R
^aIs a secondary or tertiary hydrocarbon group, and n is 2 or
When 3, R^aAt least one is a second or third grade charcoal
A hydrogen group;^aAre the same or different
Well, R^bIs a hydrocarbon group having 1 to 4 carbon atoms,
When n is 2 or 3, R^bAre the same but different
It may be. ) The siliconization represented by the formula (iii)
In the compound (c), a secondary or tertiary hydrocarbon group
Are cyclopentyl, cyclopentenyl, cyclo
Pentadienyl group, these groups having a substituent or
Hydrocarbon group in which carbon adjacent to Si is secondary or tertiary
Is mentioned. More specifically, a substituted cyclopentyl group and
Is a 2-methylcyclopentyl group,
Ethyl group, 2-ethylcyclopentyl group, 2-n-butylcyclyl
Lopentyl group, 2,3-dimethylcyclopentyl group, 2,4-di
Methylcyclopentyl group, 2,5-dimethylcyclopentyl
Group, 2,3-diethylcyclopentyl group, 2,3,4-trimethyl
Cyclopentyl group, 2,3,5-trimethylcyclopentyl
Group, 2,3,4-triethylcyclopentyl group, tetramethyl
Cyclopentyl group, tetraethylcyclopentyl group, etc.
Examples of cyclopentyl groups having an alkyl group
Can be. The substituted cyclopentenyl group includes 2-methyl
Rucyclopentenyl group, 3-methylcyclopentenyl group,
2-ethylcyclopentenyl group, 2-n-butylcyclopente
Nyl group, 2,3-dimethylcyclopentenyl group, 2,4-dimethyl
Rucyclopentenyl group, 2,5-dimethylcyclopentenyl
Group, 2,3,4-trimethylcyclopentenyl group, 2,3,5-tri
Methylcyclopentenyl group, 2,3,4-triethylcyclope
Pentenyl group, tetramethylcyclopentenyl group, tetra
A group having an alkyl group such as an ethylcyclopentenyl group
A clopentenyl group can be exemplified. The substituted cyclopentadienyl group includes 2-
Methylcyclopentadienyl group, 3-methylcyclopenta
Dienyl group, 2-ethylcyclopentadienyl group, 2-n-butyl
Tylcyclopentenyl group, 2,3-dimethylcyclopentadi
Enyl group, 2,4-dimethylcyclopentadienyl group, 2,5-
Dimethylcyclopentadienyl group, 2,3-diethylcyclo
Pentadienyl group, 2,3,4-trimethylcyclopentadie
Nyl group, 2,3,5-trimethylcyclopentadienyl group, 2,
3,4-triethylcyclopentadienyl group, 2,3,4,5-tetra
Lamethylcyclopentadienyl group, 2,3,4,5-tetraethyl
Rucyclopentadienyl group, 1,2,3,4,5-pentamethylc
Clopentadienyl group, 1,2,3,4,5-pentaethylcyclo
Cyclopenes having an alkyl group such as a pentadienyl group
A tadienyl group can be exemplified. The carbon adjacent to Si is a secondary carbon
Hydrocarbon groups include i-propyl, s-butyl, s-butyl
Examples include a mill group and an α-methylbenzyl group.
And a hydrocarbon group in which the carbon adjacent to Si is tertiary carbon
For example, t-butyl group, t-amyl group, α, α'-dimethyl
And an adenyl group.
You. The siliconization represented by the formula (iii)
Compound (c) is, when n is 1, cyclopentene
Rutrimethoxysilane, 2-methylcyclopentyl trime
Toxisilane, 2,3-dimethylcyclopentyltrimethoxy
Sisilane, cyclopentyltriethoxysilane, iso-butyl
Tyltriethoxysilane, t-butyltriethoxysila
, Cyclohexyltrimethoxysilane, cyclohexyl
Lutriethoxysilane, 2-norbornane trimethoxy
Trianes such as orchids and 2-norbornanetriethoxysilane
Lucoxysilanes are exemplified. When n is 2, dicyclopentyl
Diethoxysilane, t-butylmethyldimethoxysilane,
t-butylmethyldiethoxysilane, t-amylmethyldie
Toxysilane, dicyclohexyldimethoxysilane, silicone
Clohexylmethyldimethoxysilane, cyclohexyl
Methyldiethoxysilane, 2-norbornanemethyldimeth
Examples are dialkoxysilanes such as xysilane. When n is 2, the formula (iii)
The silicon compound (c) is a diamine represented by the following formula (iv):
It is preferably a methoxy compound. [0115] Embedded image Where R^aAnd R^cAre independent
A cyclopentyl group, a substituted cyclopentyl group, cyclo
Pentenyl group, substituted cyclopentenyl group, cyclopentane
A dienyl group, a substituted cyclopentadienyl group, or
Charcoal whose carbon adjacent to Si is secondary or tertiary carbon
Shows a hydride group. The silicon compound represented by the formula (iv)
For example, dicyclopentyldimethoxy
Orchid, dicyclopentenyl dimethoxysilane, dicyclo
Pentadienyldimethoxysilane, di-t-butyldimethoxy
Sisilane, di (2-methylcyclopentyl) dimethoxy
Orchid, di (3-methylcyclopentyl) dimethoxysila
Di (2-ethylcyclopentyl) dimethoxysilane,
Di (2,3-dimethylcyclopentyl) dimethoxysilane,
Di (2,4-dimethylcyclopentyl) dimethoxysilane,
Di (2,5-dimethylcyclopentyl) dimethoxysilane,
Di (2,3-diethylcyclopentyl) dimethoxysilane,
Di (2,3,4-trimethylcyclopentyl) dimethoxysila
Di (2,3,5-trimethylcyclopentyl) dimethoxy
Silane, di (2,3,4-triethylcyclopentyl) dimeth
Xysilane, di (tetramethylcyclopentyl) dimeth
Xysilane, di (tetraethylcyclopentyl) dimeth
Xysilane, di (2-methylcyclopentenyl) dimethoxy
Sisilane, di (3-methylcyclopentenyl) dimethoxy
Silane, di (2-ethylcyclopentenyl) dimethoxy
Orchid, di (2-n-butylcyclopentenyl) dimethoxy
Orchid, di (2,3-dimethylcyclopentenyl) dimethoxy
Silane, di (2,4-dimethylcyclopentenyl) dimethoxy
Sisilane, di (2,5-dimethylcyclopentenyl) dimeth
Xysilane, di (2,3,4-trimethylcyclopentenyl)
Dimethoxysilane, di (2,3,5-trimethylcyclopente
Nil) dimethoxysilane, di (2,3,4-triethylcyclo
Pentenyl) dimethoxysilane, di (tetramethylcyclyl)
Lopenthenyl) dimethoxysilane, di (tetraethylsi
Clopentenyl) dimethoxysilane, di (2-methylcyclyl)
Lopentadienyl) dimethoxysilane, di (3-methylsi
Clopentadienyl) dimethoxysilane, di (2-ethyl)
Cyclopentadienyl) dimethoxysilane, di (2-n-butyl)
Tylcyclopentenyl) dimethoxysilane, di (2,3-di
Methylcyclopentadienyl) dimethoxysilane, di
(2,4-dimethylcyclopentadienyl) dimethoxysila
Di (2,5-dimethylcyclopentadienyl) dimethoxy
Sisilane, di (2,3-diethylcyclopentadienyl) di
Methoxysilane, di (2,3,4-trimethylcyclopentadi
Enyl) dimethoxysilane, di (2,3,5-trimethylcyclyl)
Lopentadienyl) dimethoxysilane, di (2,3,4-tri
Ethylcyclopentadienyl) dimethoxysilane, di
(2,3,4,5-tetramethylcyclopentadienyl) dimethoate
Xysilane, di (2,3,4,5-tetraethylcyclopentadi
Enyl) dimethoxysilane, di (1,2,3,4,5-pentamethyl)
Rucyclopentadienyl) dimethoxysilane, di (1,2,
3,4,5-pentaethylcyclopentadienyl) dimethoxy
Silane, di-t-amyl-dimethoxysilane, di (α, α'-di
Methylbenzyl) dimethoxysilane, di (admanche)
G) dimethoxysilane, admantyl-t-butyldimeth
Xysilane, cyclopentyl-t-butyldimethoxysila
Diisopropyldimethoxysilane, di-s-butyldimene
Toxysilane, di-s-amyldimethoxysilane, isopro
Pill-s-butyldimethoxysilane and the like. When n is 3, tricyclopentyl
Lumethoxysilane, tricyclopentylethoxysila
, Dicyclopentylmethylmethoxysilane, dicyclo
Pentylethylmethoxysilane, dicyclopentylmethyl
Luethoxysilane, cyclopentyl dimethyl methoxy
Orchid, cyclopentyldiethylmethoxysilane, cyclo
Monoalkoxy such as pentyldimethylethoxysilane
Examples include silanes. Of these, dimethoxysilanes, particularly those of the formula
Dimethoxysilanes represented by (iv) are preferred,
Dicyclopentyldimethoxysilane, di-t-butyl
Rudimethoxysilane, di (2-methylcyclopentyl) di
Methoxysilane, di (3-methylcyclopentyl) dimeth
Xysilane, di-t-amyldimethoxysilane is preferred
No. These silicon compounds (c) may be used in combination of two or more.
Can be used. The plurality used in the present invention
Having two or more ether bonds that exist through an atom
Compound (d) (hereinafter sometimes referred to as polyether compound)
The atoms between these ether bonds are
From the group consisting of silicon, oxygen, sulfur, phosphorus, and boron
One or more selected atoms, and the number of atoms is two or more. This
Relatively bulky substitution of the atoms between the ether bonds of them
Groups, specifically having 2 or more carbon atoms, preferably 3 or more
And a substituent having a linear, branched, or cyclic structure.
Or a substituent having a branched or cyclic structure
Is desirable. Between two or more ether bonds
More than one, preferably 3-20, more preferably
Preferably 3 to 10, particularly preferably 3 to 7, carbon atoms
Included compounds are preferred. As such a polyether compound,
For example, a compound represented by the following formula can be mentioned.
You. [0122] Embedded image In the formula, n is an integer of 2 ≦ n ≦ 10;
¹ ~ R²⁶Is carbon, hydrogen, oxygen, halogen, nitrogen, sulfur,
At least one selected from phosphorus, boron and silicon
A substituent having the same kind of element,¹ ~ R²⁶, Good
Preferably R¹ ~ R²ⁿJointly form a ring other than a benzene ring
May contain atoms other than carbon in the main chain.
May be. As the above polyether compound,
Specifically, 2- (2-ethylhexyl) -1,3-dimethoxy
Propane, 2-isopropyl-1,3-dimethoxypropane, 2
-Butyl-1,3-dimethoxypropane, 2-s-butyl-1,3-di
Methoxypropane, 2-cyclohexyl-1,3-dimethoxy
Propane, 2-phenyl-1,3-dimethoxypropane, 2-
Mil-1,3-dimethoxypropane, 2- (2-phenylethyl
Le) -1,3-dimethoxypropane, 2- (2-cyclohexyl)
Ethyl) -1,3-dimethoxypropane, 2- (p-chlorophene
Nyl) -1,3-dimethoxypropane, 2- (diphenylmethyl)
Le) -1,3-dimethoxypropane, 2- (1-naphthyl) -1,3-
Dimethoxypropane, 2- (2-fluorophenyl) -1,3-
Dimethoxypropane, 2- (1-decahydronaphthyl) -1,3
-Dimethoxypropane, 2- (p-t-butylphenyl) -1,3-
Dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethyl
Toxipropane, 2,2-dicyclopentyl-1,3-dimethoxy
Cypropane, 2,2-diethyl-1,3-dimethoxypropane,
2,2-dipropyl-1,3-dimethoxypropane, 2,2-diiso
Propyl-1,3-dimethoxypropane, 2,2-dibutyl-1,3-
Dimethoxypropane, 2-methyl-2-propyl-1,3-dimethoate
Xipropane, 2-methyl-2-benzyl-1,3-dimethoxyprop
Lopan, 2-methyl-2-ethyl-1,3-dimethoxypropane,
2-methyl-2-isopropyl-1,3-dimethoxypropane, 2-
Methyl-2-phenyl-1,3-dimethoxypropane, 2-methyl
2-cyclohexyl-1,3-dimethoxypropane, 2,2-bis
(P-chlorophenyl) -1,3-dimethoxypropane, 2,2-
Bis (2-cyclohexylethyl) -1,3-dimethoxypro
Bread, 2-methyl-2-isobutyl-1,3-dimethoxypropa
2-Methyl-2- (2-ethylhexyl) -1,3-dimethoxy
Propane, 2,2-diisobutyl-1,3-dimethoxypropa
2,2-diphenyl-1,3-dimethoxypropane, 2,2-di
Benzyl-1,3-dimethoxypropane, 2,2-bis (cyclo
Hexylmethyl) -1,3-dimethoxypropane, 2,2-dii
Sobutyl-1,3-diethoxypropane, 2,2-diisobutyl-
1,3-dibutoxypropane, 2-isobutyl-2-isopropyl
1,3-dimethoxypropane, 2- (1-methylbutyl) -2-
Isopropyl-1,3-dimethoxypropane, 2- (1-methyl
Butyl) -2-s-butyl-1,3-dimethoxypropane, 2,2-di
-s-butyl-1,3-dimethoxypropane, 2,2-di-t-butyl
1,3-dimethoxypropane, 2,2-dineopentyl-1,3-
Dimethoxypropane, 2-isopropyl-2-isopentyl-
1,3-dimethoxypropane, 2-phenyl-2-isopropyl-
1,3-dimethoxypropane, 2-phenyl-2-s-butyl-1,3-
Dimethoxypropane, 2-benzyl-2-isopropyl-1,3-
Dimethoxypropane, 2-benzyl-2-s-butyl-1,3-dimethyl
Toxipropane, 2-phenyl-2-benzyl-1,3-dimethoxy
Cipropane, 2-cyclopentyl-2-isopropyl-1,3-di
Methoxypropane, 2-cyclopentyl-2-s-butyl-1,3-
Dimethoxypropane, 2-cyclohexyl-2-isopropyl
1,3-dimethoxypropane, 2-cyclohexyl-2-s-butyl
Tyl-1,3-dimethoxypropane, 2-isopropyl-2-s-butyl
Tyl-1,3-dimethoxypropane, 2-cyclohexyl-2-si
Clohexylmethyl-1,3-dimethoxypropane, 2,3-di
Phenyl-1,4-diethoxybutane, 2,3-dicyclohexyl
1,4-diethoxybutane, 2,2-dibenzyl-1,4-diethoxy
Xibutane, 2,3-dicyclohexyl-1,4-diethoxyb
Tan, 2,3-diisopropyl-1,4-diethoxybutane, 2,2
-Bis (p-methylphenyl) -1,4-dimethoxybutane, 2,
3-bis (p-chlorophenyl) -1,4-dimethoxybutane,
2,3-bis (p-fluorophenyl) -1,4-dimethoxybuta
2,4-diphenyl-1,5-dimethoxypentane, 2,5-di
Phenyl-1,5-dimethoxyhexane, 2,4-diisopropyl
1,5-dimethoxypentane, 2,4-diisobutyl-1,5-di
Methoxypentane, 2,4-diisoamyl-1,5-dimethoxy
Pentane, 3-methoxymethyltetrahydrofuran, 3-meth
Toximethyldioxane, 1,3-diisobutoxypropa
1,2-diisobutoxypropane, 1,2-diisobutoxy
Ethane, 1,3-diisoamyloxypropane, 1,3-diisone
Opentyloxyethane, 1,3-dineopentyloxypropa
2,2-tetramethylene-1,3-dimethoxypropane, 2,2
-Pentamethylene-1,3-dimethoxypropane, 2,2-hexa
Methylene-1,3-dimethoxypropane, 1,2-bis (methoxy
Cimethyl) cyclohexane, 2,8-dioxaspiro [5,
5] Undecane, 3,7-dioxabicyclo [3,3,1] nona
3,7-dioxabicyclo [3,3,0] octane, 3,3-di
Isobutyl-1,5-oxononane, 6,6-diisobutyl dio
Xyheptane, 1,1-dimethoxymethylcyclopentane,
1,1-bis (dimethoxymethyl) cyclohexane, 1,1-bi
S (methoxymethyl) bicyclo [2,2,1] heptane, 1,1
-Dimethoxymethylcyclopentane, 2-methyl-2-methoxy
Cimethyl-1,3-dimethoxypropane, 2-cyclohexyl-
2-ethoxymethyl-1,3-diethoxypropane, 2-cyclo
Hexyl-2-methoxymethyl-1,3-dimethoxypropane,
2,2-diisobutyl-1,3-dimethoxycyclohexane, 2-
Isopropyl-2-isoamyl-1,3-dimethoxycyclohexyl
Sun, 2-cyclohexyl-2-methoxymethyl-1,3-dimeth
Xycyclohexane, 2-isopropyl-2-methoxymethyl
1,3-dimethoxycyclohexane, 2-isobutyl-2-me
Toximethyl-1,3-dimethoxycyclohexane, 2-sic
Rohexyl-2-ethoxymethyl-1,3-diethoxycyclohe
Xane, 2-cyclohexyl-2-ethoxymethyl-1,3-dim
Toxicyclohexane, 2-isopropyl-2-ethoxyme
Tyl-1,3-diethoxycyclohexane, 2-isopropyl-
2-ethoxymethyl-1,3-dimethoxycyclohexane, 2-
Isobutyl-2-ethoxymethyl-1,3-diethoxycyclo
Xane, 2-isobutyl-2-ethoxymethyl-1,3-dimethoxy
Cyclohexane, tris (p-methoxyphenyl) phos
Fin, methylphenylbis (methoxymethyl) sila
Diphenylbis (methoxymethyl) silane, methyl
Cyclohexylbis (methoxymethyl) silane, di-t-
Butyl bis (methoxymethyl) silane, cyclohexyl
-t-butylbis (methoxymethyl) silane, i-propyl-
t-butylbis (methoxymethyl) silane
You. Of these, 1,3-diethers are preferred.
Commonly used, especially 2,2-diisobutyl-1,3-dimethoxy
Propane, 2-isopropyl-2-isopentyl-1,3-dimethoate
Xypropane, 2,2-dicyclohexyl-1,3-dimethoxy
Propane, 2,2-bis (cyclohexylmethyl) -1,3-di
Methoxypropane is preferably used. These polyether compounds (d) are two kinds
These can be used in combination. Next, used in the present invention
The method for producing the propylene polymer will be described. Book
The propylene polymer used in the invention is, for example,
[Ia] a solid titanium catalyst component, and [II] an organometallic catalyst
Component and [III] a silicon compound represented by the above formula (iii)
(C) or a polyether compound (d)
In the presence of an olefin polymerization catalyst,
b) a pre-polymerization catalyst component, and [II] an organometallic catalyst component,
[III] The silicon compound (c) represented by the above formula (iii)
Or olefin formed from polyether compound (d)
Polymerization of propylene in the presence of a polymerization catalyst (main polymerization)
Can be obtained. It should be noted that, when propylene is polymerized,
In addition to pyrene, small amounts of other olefins other than propylene
A small amount of diene compound in the polymerization system
You can also. Other olefins other than such propylene
Ethylene, 1-butene, 1-pentene, 1-hexene
Sen, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-
Octene, 3-methyl-1-butene, etc., having 3 to 8 carbon atoms
Refining. As the diene compound, 1,3-butadiene,
1,3-pentadiene, 1,4-pentadiene, 1,3-hexadiene
1,4-hexadiene, 1,5-hexadiene, 4-methyl-
1,4-hexadiene, 5-methyl-1,4-hexadiene, 6-
Tyl-1,6-octadiene, 7-methyl-1,6-octadiene,
6-ethyl-1,6-octadiene, 6-propyl-1,6-octadi
Ene, 6-butyl-1,6-octadiene, 6-methyl-1,6-nona
Diene, 7-methyl-1,6-nonadiene, 6-ethyl-1,6-nona
Diene, 7-ethyl-1,6-nonadiene, 6-methyl-1,6-deca
Diene, 7-methyl-1,6-decadiene, 6-methyl-1,6-un
Decadiene, 1,7-octadiene, 1,9-decadiene, iso
Prene, butadiene, ethylidene norbornene, vinyl
Carbon number of norbornene and dicyclopentadiene
And 4 to 20 diene compounds. The polymerization of propylene is usually carried out in the gas phase or
Performed in the liquid phase. The polymerization is slurry polymerization or solution polymerization.
When the reaction mode is adopted, the above-mentioned [Ib] is used as a reaction solvent.
Inert hydrocarbons used in the preparation of the prepolymerization catalyst component
Similar inert hydrocarbons can be used. In the polymerization system, the above [Ia] solid
The titanium catalyst component or [Ib] prepolymerization catalyst component
[Ia] in solid titanium catalyst component per liter of combined volume
Atom in titanium or titanium in [Ib] prepolymerization catalyst component
Usually, about 0.0001 to 50 mm
, Preferably used in an amount of about 0.001 to 10 mmol
Can be [II] The organometallic catalyst component is used in the polymerization system.
Per mole of titanium atom, [II] organometallic catalyst component contains
Metal atom is usually about 1 to 2000 mol, preferably
Is used in an amount to be about 2 to 500 mol. Further
And [III] a silicon compound (c) or a polyether compound
The product (d) is composed of [II] one metal atom in the organometallic catalyst component.
Usually about 0.001 to 50 mol, preferably about 0.00
It is used in such an amount as to be from 01 to 20 mol. If hydrogen is used during polymerization, the melt flow
Propylene polymer with a large amount of
Therefore, the molecular weight of the obtained propylene polymer can be adjusted.
Can be. Even in this case, the present invention provides
Crystallinity and stereoregularity index of the propylene polymer
Or decrease in catalyst activity.
Not even. In the present invention, the polymerization temperature of propylene
Is usually about -50 to 200 ° C, preferably about 20 to 1
The temperature is usually from normal pressure to 100 kg / cm.
^Two, Preferably about 2 to 50 kg / cm^TwoIs set to Heavy
For batch, semi-continuous and continuous methods
It can be carried out. Thus, a propylene polymer is produced.
Then, per unit amount of the solid catalyst component, the propylene polymer
Because the yield can be increased,
Of catalyst residues, especially halogen content,
Can be. Therefore, the catalyst in the propylene polymer
The removal operation can be omitted, and the obtained
When molding a molded body using a polymer,
It becomes easier to prevent. [0135] Such a propylene polymer is a
Very low morphus content and therefore hydrocarbon
The propylene polymer molded from this propylene polymer has a low soluble component.
Films have low surface tack. Production of propylene polymer used in the present invention
Can be divided into two or more stages by changing the reaction conditions.
Wear. In this case, using 2 to 10 polymerization reactors,
Alternatively, it is performed in the liquid phase. Polymerization is a reaction of slurry polymerization or solution polymerization
In the case of taking the form, the above-mentioned [Ib]
Same as inert hydrocarbon used in the preparation of polymerization catalyst components
Of inert hydrocarbons can be used. In such a polymerization method, the two containers
Of at least one of the above polymerization vessels,
To polymerize propylene (in the polymerization, hereinafter referred to as “A
), The intrinsic viscosity [η] is 3 to 40.
dl / g, preferably 5 to 30 dl / g, particularly preferably 7
Produce a polymer of ~ 25 dl / g. The boiling hepta of the polymer obtained by this A polymerization
Determined by NMR measurement of insoluble components
Pentad value ([M_Five]) Is 0.960-0.995,
Preferably 0.990-0.995, more preferably 0.90.
980-0.995, more preferably 0.982-0.9.
995 is desirable. The amount of a heptane-insoluble component in the polymer
Is at least 80%, preferably at least 90%, more preferably
Is at least 94%, more preferably at least 95%, particularly preferably
Or more preferably 96% or more. The polymer obtained by the A polymerization is as follows:
0.1 to 55 in the propylene polymer finally obtained.
%, Preferably 2 to 35%, particularly preferably 5 to 30%
Is desirably manufactured so as to be present in a proportion of The propylene polymer is used in two or more polymerization vessels.
When manufacturing by polymerization, the remaining two or more polymerization reactors
The polymerization of propylene is also performed in the
), The final product is melt flow
-Propylene polymerization with a rate of 0.1 to 500 g / 10 min
Get the body. In the polymerization system of A polymerization and B polymerization
Is the [Ia] solid titanium catalyst component or [Ib]
The pre-polymerization catalyst component contained [Ia] per liter of polymerization volume.
The titanium atom or [Ib] reserve in the solid titanium catalyst component
Usually converted to titanium atoms in the polymerization catalyst component,
0.0001 to 50 mmol, preferably about 0.001 to
Used in an amount of 10 mmol. [II] Organic metal
The catalyst component is [I
I] The metal atom contained in the organometallic catalyst component is usually about 1
~ 2000 mol, preferably about 2-500 mol
Used in such amounts. [III] Silicon compound
(C) or the polyether compound (d) is [II] organic
Usually about 0.00 per mole of metal atom in the metal catalyst component.
1 to 50 mol, preferably about 0.01 to 20 mol
Used in such amounts. Further, if necessary, any polymerization reactor may be used.
[Ia] solid titanium catalyst component or [Ib]
Polymerization catalyst component, [II] organometallic catalyst component, [III]
Provide the iodine compound (c) or polyether compound (d)
May be paid. In addition, solid
Donation used in preparing the titanium-like catalyst component (a)
And / or organosilicon represented by the above formula (c-i)
A compound may be supplied. In addition, in both the A polymerization and the B polymerization,
Even obtained by supplying or excluding hydrogen
The molecular weight of the polymer can be easily adjusted. This place
In the present invention, in the present invention, the resulting propylene polymer
The crystallinity and stereoregularity index do not decrease.
And the catalyst activity does not decrease. Hydrogen supply
Depends on the conditions, but the final polymer
The melt flow rate is 0.1 to 500 g / 10 min
Any amount that falls within the range may be used. The boiling heptane insoluble component [M_Five]of
The value is 0.975-0.995, preferably 0.980-0.995.
0.995, more preferably 0.982 to 0.995.
In the box, [M_Three] Is 0.0002 to 0.005.
0, preferably 0.0023 to 0.0045, more preferred
Or in the range of 0.0025 to 0.0040
I just need. The propylene in the A polymerization and the B polymerization
Is usually about -50 to 200 ° C, preferably
20 to 100 ° C., and the pressure is usually normal pressure to 10
0kg / cm^Two, Preferably 2 to 50 kg / cm^TwoSet to
Is done. Polymerization can be batch, semi-continuous or continuous
It can also be done in law. The propylene polymer used in the present invention is
A nucleating agent as described below may be blended. Propyle
By blending the core material with the polymer,
Higher speed of crystallization as well as crystallization
Becomes possible. Examples of the nucleating agent include various nucleating agents known in the art.
The agent is used without any particular limitation. Among them, preferred
Examples of the new nucleating agent include the following nucleating agents.
it can. [0150] Embedded image (Wherein R¹Is oxygen, sulfur, or carbon
A hydrocarbon group of the formulas 1 to 10,^Two, R^ThreeIs hydrogen
Is a hydrocarbon group having 1 to 10 carbon atoms;^Two, R^ThreeIs the same kind
Or heterogeneous, R^TwoEach other, R^ThreeBetween each other
Is R^TwoAnd R^ThreeMay be bonded to form a ring, and M is
A monovalent to trivalent metal atom, and n is an integer of 1 to 3
You. ) Specifically, sodium-2,2'-methylene-bis
(4,6-di-t-butylphenyl) phosphate, sodium
Um-2,2'-Ethylidene-bis (4,6-di-t-butylphenyl
Le) phosphate, lithium-2,2'-methylene-bis-
(4,6-di-t-butylphenyl) phosphate, lithium
-2,2'-Ethylidene-bis (4,6-di-t-butylphenyl) phenyl
Phosphate, sodium-2,2'-ethylidene-bis (4-i
-Propyl-6-t-butylphenyl) phosphate, lithium
Um-2,2'-methylene-bis (4-methyl-6-t-butylphenyl
Le) phosphate, lithium-2,2'-methylene-bis (4
-Ethyl-6-t-butylphenyl) phosphate, calcium
Um-bis [2,2'-thiobis (4-methyl-6-t-butylphen
Nil) phosphate], calcium-bis [2,2'-thio
Bis (4-ethyl-6-t-butylphenyl) phosphate]
 , Calcium-bis [2,2'-thiobis- (4,6-di-t-butyl
Ruphenyl) phosphate], magnesium-bis
[2,2'-thiobis (4,6-di-t-butylphenyl) phosph
), Magnesium-bis [2,2'-thiobis- (4-t-
Octylphenyl) phosphate], sodium-2,
2'-butylidene-bis (4,6-di-methylphenyl) phosph
Fate, sodium-2,2'-butylidene-bis (4,6-di-
(t-butylphenyl) phosphate, sodium-2,2'-
t-octylmethylene-bis (4,6-di-methylphenyl)
Phosphate, sodium-2,2'-t-octylmethylene-
Bis (4,6-di-t-butylphenyl) phosphate,
Lucium-bis- (2,2'-methylene-bis (4,6-di-t-butyl
Ruphenyl) phosphate), magnesium-bis [2,
2'-methylene-bis (4,6-di-t-butylphenyl) phosph
Fate], barium-bis [2,2'-methylene-bis (4,6
-Di-t-butylphenyl) phosphate], sodium
-2,2'-methylene-bis (4-methyl-6-t-butylphenyl)
Phosphate, sodium-2,2'-methylene-bis (4-
Ethyl-6-t-butylphenyl) phosphate, sodium
(4,4'-dimethyl-5,6'-di-t-butyl-2,2'-biphenyl
Le) phosphate, calcium-bis [(4,4'-dimethyl
-6,6'-di-t-butyl-2,2'-biphenyl) phosphate
G], sodium-2,2'-ethylidene-bis (4-m-butyl-
6-t-butylphenyl) phosphate, sodium-2,
2'-methylene-bis (4,6-di-methylphenyl) phosph
, Sodium-2,2'-methylene-bis (4,6-di-ethyl
Ruphenyl) phosphate, potassium-2,2'-ethylide
N-bis (4,6-di-t-butylphenyl) phosphate,
Calcium-bis [2,2'-ethylidene-bis (4,6-di-t-butyl
Tylphenyl) phosphate], magnesium-bis
[2,2'-ethylidene-bis (4,6-di-t-butylphenyl)
Phosphate], barium-bis [2,2'-ethylidene-
Bis (4,6-di-t-butylphenyl) phosphate],
Aluminum-tris [2,2'-methylene-bis (4,6-di-t-
Butylfel) phosphate] and aluminum-
Tris [2,2'-ethylidene-bis (4,6-di-t-butyl
Nil) phosphate] and mixtures of two or more of these
Things can be exemplified. Especially sodium-2,2'-methyl
Len-bis (4,6-di-t-butylphenyl) phosphate
Is preferred. [0152] Embedded image (Wherein, R^FourIs hydrogen or C1-C1
0 is a hydrocarbon group, and M is a 1-3 valent metal atom.
And n is an integer of 1 to 3. ) Specifically, Natori
Mu-bis (4-t-butylphenyl) phosphate, nato
Lithium-bis (4-methylphenyl) phosphate, na
Thorium-bis (4-ethylphenyl) phosphate,
Sodium-bis (4-i-propylphenyl) phosphe
Sodium-bis (4-t-octylphenyl) form
Sulfate, potassium-bis (4-t-butylphenyl) phenyl
Phosphate, calcium-bis (4-t-butylphenyl)
Le) phosphate, magnesium-bis (4-t-butyl)
Phenyl) phosphate, lithium-bis (4-t-butyl)
Ruphenyl) phosphate, aluminum-bis (4-t
-Butylphenyl) phosphate and their two
The above mixture can be exemplified. Especially sodium
-Bis (4-t-butylphenyl) phosphate is preferred
No. [0154] Embedded image (Wherein R^FiveIs hydrogen or C1-C1
0 hydrocarbon group. ) Specifically, 1,3,2,4-diben
Dilidene sorbitol, 1,3-benzylidene-2,4-p-methyl
Rubenzylidene sorbitol, 1,3-benzylidene-2,4-p
-Ethylbenzylidene sorbitol, 1,3-p-methylbenzene
Zylidene-2,4-benzylidene sorbitol, 1,3-p-ethyl
Rubenzylidene-2,4-benzylidene sorbitol, 1,3-p
-Methylbenzylidene-2,4-p-ethylbenzylidenesorby
Thor, 1,3-p-ethylbenzylidene-2,4-p-methylben
Dilidenesorbitol, 1,3,2,4-di (p-methylbenzyl
Den) sorbitol, 1,3,2,4-di (p-ethylbenzylide)
Sorbitol, 1,3,2,4-di (p-n-propylbenzylidene)
Den) sorbitol, 1,3,2,4-di (p-i-propylbenzyl)
Riden) sorbitol, 1,3,2,4-di (p-n-butylbenzyl)
Riden) sorbitol, 1,3,2,4-di (p-s-butylbenzyl)
Riden) sorbitol, 1,3,2,4-di (p-t-butylbenzyl)
Riden) sorbitol, 1,3,2,4-di (2 ', 4'-dimethyl
Benzylidene) sorbitol, 1,3,2,4-di (p-methoxy
Benzylidene) sorbitol, 1,3,2,4-di (p-ethoxybe
Benzylidene) sorbitol, 1,3-benzylidene-2-4-p-
Chlorbenzylidene sorbitol, 1,3-p-chlorobenzyl
Riden-2,4-benzylidene sorbitol, 1,3-p-chloro
Benzylidene-2,4-p-methylbenzylidene sorbitol
1,3-p-chlorobenzylidene-2,4-p-ethylbenzyl
Densorbitol, 1,3-p-methylbenzylidene-2,4-p-
Chlorbenzylidene sorbitol, 1,3-p-ethyl benzyl
Riden-2,4-p-chlorobenzylidene sorbitol and
1,3,2,4-di (p-chlorobenzylidene) sorbitol and
And mixtures of two or more of these, especially 1,3,2,4-
Dibenzylidene sorbitol, 1,3,2,4-di (p-methyl
Benzylidene) sorbitol, 1,3,2,4-di (p-ethylben
Zylidene) sorbitol, 1,3-p-chlorobenzylidene-
2,4-p-methylbenzylidene sorbitol, 1,3,2,4-di
(P-Chlorbenzylidene) sorbitol and their
Mixtures of two or more are preferred. Other nucleating agents include aromatic carboxylic acids
And metal salts of aliphatic carboxylic acids, and specifically,
Aluminum benzoate, p-t-butyl aluminum benzoate
Salt, sodium adipate, thiophenecarboxylic acid
Sodium, sodium pyrrolecarboxylate, etc.
Can be In addition, an inorganic compound such as talc described later
Can also be exemplified. Propile used in the present invention
In the propylene polymer, the nucleating agent is a propylene polymer 100
0.001 to 10 parts by weight with respect to parts by weight, preferably
0.01 to 5 parts by weight, particularly preferably 0.1 to 3 parts by weight
It is desirable to be blended in a ratio. The nucleating agent is added to the propylene polymer in the above amount.
By doing, the excellent propylene polymer originally has
Fine crystal grains and crystallinity without loss of properties
Is obtained. [0159]Propylene random copolymer [B] Propylene random copolymer used in the present invention
[B] is propylene and an α-olefin having 4 or more carbon atoms
Or a random copolymer of propylene or propylene with 4 carbon atoms
Random copolymer of the above α-olefin and ethylene
It is. Such a propylene random copolymer
In the structure, a structure derived from an α-olefin having 4 or more carbon atoms
2 to 15 mol%, preferably 3 to 10 mol%
5 moles of structural units derived from ethylene
%, Preferably 3 mol% or less.
Is desirable. Content of Structural Unit Derived from Ethylene
Increases the transparency when formed into a film
Or the transparency of the film may deteriorate over time.
There is. This deterioration of transparency with time is caused by the soft resin component.
Bleed out. In addition,
When the content of structural units derived from ren increases,
The amount of the soft resin component in the polymer tends to increase, and the film
This may cause a decrease in the rigidity of the tire. The α-olefin having 4 or more carbon atoms includes 1
-Butene, 1-pentene, 1-hexene, 4-methyl-1-pente
And 1-butene is particularly preferred. Propyle
Content of α-Olefin Units in Random Copolymers
Was determined from the mass balance at the time of polymerization. Also contains 1-butene
The amount was further determined using an infrared spectrophotometer at 770 c
m^-1From the characteristic absorption of
Was. In addition, measurement with an infrared spectrophotometer
About Butene Copolymer¹³To quantitative value by C-NMR
A calibration curve was prepared and quantified. Further, the propylene-based random copolymer
The content of the styrene unit was determined from the material balance at the time of polymerization.
732 cm using an infrared spectrophotometer^-1, 720c
m^-1From the characteristic absorption of
Was. In addition, measurement with an infrared spectrophotometer¹⁴Label with C
Of ethylene copolymer by radiation measurement
A calibration curve was prepared and quantified. The propylene random used in the present invention
The copolymer preferably has a small amount of the soft resin component.
It is preferable that the content of n-decane-soluble components at 23 ° C is 10% by weight or less.
Or less than 7% by weight. 23 ° C. When the amount of n-decane-soluble components increases,
The rigidity of the film is reduced, and the film is resistant to blocking.
May deteriorate. The amount of n-decane soluble components is
Ask as below. That is, 10 g of the copolymer was n-
Dissolve in 1.0 liter of decane, then slowly cool to room temperature
You. This was left in a bath at 23 ° C. for 6 hours, and then filtered.
The filtrate is concentrated, dried, dried and weighed to obtain a copolymer.
The amount of the dissolved component is the percentage based on the weight of the sample copolymer.
And calculate. Further, the propylene lane used in the present invention
The random copolymer has a melting point of 145 ° C. or less, preferably 1
It is desirable that the temperature be 40 ° C. or lower. Melting point as above
Propylene random copolymer in the range
Excellent rollability. Such a propylene random copolymer
Can be obtained by methods such as gas phase polymerization, solution polymerization (solution polymerization), etc.
It can be manufactured by the so-called slurry polymerization method.
Is desirable. A propylene-based lander is prepared by a slurry polymerization method.
Low-melting in inert hydrocarbon solvents
Since the low molecular weight soft resin component dissolves,
The components are less likely to be incorporated into the copolymer,
High propylene random copolymer can be obtained
You. The propylene polymer used in the present invention
[A] and a propylene-based random copolymer [B]
Compounding rubber components to improve impact strength,
Heat stabilizers, weather stabilizers, antistatic agents, slip agents,
Antiblocking agent, antifogging agent, lubricant, dye, pigment, natural
Oil, synthetic oil, wax, etc. can be compounded.
The mixing ratio is an appropriate amount. [0170] In addition, within the range that does not impair the object of the present invention,
Ropyrene polymer [A] and propylene-based random copolymer
Combine [B] with silica, diatomaceous earth, alumina, titanium oxide
, Magnesium oxide, pumice powder, pumice balloon, hydroxide
Aluminum, magnesium hydroxide, basic magnesium carbonate
Cium, dolomite, calcium sulfate, potassium titanate
, Barium sulfate, calcium sulfite, talc, clay
ー, mica, asbestos, glass fiber, glass fray
, Glass beads, calcium silicate, montmorillonii
, Bentonite, graphite, aluminum powder, sulfuric acid
Molybdenum fluoride, boron fiber, silicon carbide fiber, polyethylene
Fiber, polypropylene fiber, polyester fiber,
A filler such as lamide fiber may be blended. [0171]Polypropylene multilayer film The polypropylene multilayer film according to the present invention is characterized in that
A base material layer comprising a pyrene polymer [A];
And a sealing material layer comprising a random copolymer [B].
ing. Such polypropylene multilayer films are
The base layer composed of the propylene polymer [A] and the outermost layer
Sheet comprising the propylene-based random copolymer [B]
If the propylene polymer [A] is used,
Layer and / or propylene random copolymer
Even a multilayer film having a plurality of layers consisting of [B]
A multi-layer film containing layers made of other resins.
You may. In the present invention, a polypropylene multilayer film
Is a base material layer and a sealing material provided on one surface of the base material layer
Two layers, or a base layer and both sides of the base layer
A three-layer structure consisting of the provided sealing material layer
Is preferred. The thickness of this polypropylene multilayer film is
Although not particularly limited, it is usually 10 to 150 μm. Ma
Ratio of the thickness of the sealing material layer to the total thickness of the film.
(Thickness of sealing material layer / total thickness of film) is 0.03 to
0.4, preferably in the range of 0.05 to 0.3.
desirable. The thickness of the sealing material layer is defined as the sealing material layer.
If the seal is provided on both sides of the film,
It is the total thickness of the material layer. Further, the sealing material layer is a base material layer.
When provided on both sides, the thickness of each sealing material layer is almost
It is desirable that they be the same. The thickness of the sealing material layer is larger than the above range.
May cause insufficient rigidity of the film.
If the thickness of the metal layer is less than the above range,
Heat sealability may be insufficient. The polypropylene multilayer film of the present invention comprises:
A base layer made of a propylene polymer having excellent rigidity;
From a propylene-based random copolymer with excellent sealability
And a thickness of the sealing material layer,
Since the ratio to the total thickness of the film is within a certain range, rigidity
And it has excellent heat sealability. Also, this polyp
Lopylene multilayer film is transparent and blocking resistant
Excellent transparency and little deterioration of transparency over time. Further substrate
Excellent adhesion between the layer and the sealing material layer. Such a polypropylene multilayer film is
As a manufacturing method, a T-die using a multilayer die is used.
Adopt co-extrusion method such as casting method and water-cooled inflation method
can do. [0176] EFFECT OF THE INVENTION Polypropylene multilayer fill according to the present invention
System consists of a base layer made of a specific propylene polymer and a specific
A sealing material layer comprising a propylene-based random copolymer of
Has a thickness of the sealing material layer, the total thickness of the film
In contrast, it is in the range of 0.03-0.4, so it is rigid and transparent
Excellent heat resistance and blocking resistance
Excellent in properties. [0177] The present invention will be described in more detail with reference to the following examples.
However, the present invention is not limited to these examples.
Not. In the present invention, the physical properties of the film are as follows:
Was measured as follows. [Tensile Young's modulus] Based on ASTM D-882.
(Pulling speed: 200 mm / min) [Haze value] Based on ASTM D-1003. [Heat seal strength] Heat manufactured by Toyo Seiki
Using a sealer at a predetermined temperature for 1 second, seal pressure 2
kg / cm^Two, Seals with a seal width of 5 mm to create test pieces
I do. Using an Instron type universal material testing machine, 1
The test piece having a width of 5 mm was placed on the cross
Peeling at a pad speed of 300 mm / min and heat sealing
Measure strength. [0181] [Production example] [Preparation of solid titanium catalyst component] 4.5 m^ThreeThe reactor
240 kg of anhydrous magnesium chloride, 1100 liters of decane
Tol and 2-ethylhexyl alcohol 990 kg
And heated at 130 ° C. to make a homogeneous solution.
54 kg of phthalic anhydride was added to
To dissolve the phthalic anhydride. Like this
After cooling the obtained homogeneous solution to room temperature, it is kept at -25 ° C.
6.7m of titanium tetrachloride^ThreeWhile stirring this uniform
The solution was charged dropwise. The temperature after charging is about -20 ° C
there were. Next, the temperature of the mixed solution was raised to 1 over 4 hours.
When the temperature was raised to 10 ° C and reached 110 ° C, diphthalic acid
Add 13 kg of isobutyl (DIBP) and add 2 kg
Stirring was maintained at the same temperature for a period of time. After 2 hours reaction, heat
A solid part was collected by filtration, and this solid part was 7.3 m^ThreeFour
After resuspending in titanium chloride, again at 110 ° C. for 2 hours,
A heating reaction was performed. After completion of the reaction, a solid portion was collected again by hot filtration.
And released into solution with decane and hexane at 110 ° C
The washing was sufficiently performed until no titanium compound was detected.
Through the above operation, a solid titanium catalyst component [A] was obtained.
Was. Set of the obtained solid titanium catalyst component [A]
Composition: titanium; 2.2% by weight, chlorine; 61% by weight, mug
Nesium: 19% by weight, DIBP: 12.7% by weight
Was. [Preparation of Preliminary Polymerization Catalyst [B]] 80 l
Hexane in a reactor equipped with a stirrer under nitrogen atmosphere.
40 liters, 3.0 mol of triethylaluminum,
3.0 mol of trimethylmethoxysilane and the solid
0.3 mol of a tan catalyst component [A] is added in terms of titanium atom.
After that, 3-methyl-1-butene (3 MB-
1) Supply 1.5 kg to the reactor and conduct pre-polymerization for 2 hours
Was. After the completion of the reaction, the inside of the reactor was replaced with nitrogen.
Washing operation consisting of removing the supernatant and adding purified hexane
Was performed three times to obtain a preliminary polymerization catalyst [B]. This pre-polymerization contact
The medium [B] was resuspended in purified hexane and stored. [Polymerization] Stirring with an internal volume of 1000 liters
Charged 450 liters of purified n-hexane into a reactor equipped with a vessel
And triethylaluminum in a propylene atmosphere at 60 ° C.
500 mmol, dicyclopentyldimethoxysila
500 mmol and the prepolymerized catalyst [B]
10 mmol Ti was added in terms of the number of particles. 500 liters of hydrogen were introduced, and the temperature was raised to 80 ° C.
After heating, this was held for 3 hours to perform propylene polymerization.
Was. The pressure during the polymerization is 6 kg / cm^Two-Keep it at G. Polymerization end
After that, depressurize and centrifuge the slurry containing the produced solid,
Dry with a dryer to obtain a white powdery polymer 200
kg. The MFR of this polymer was 6.0 g / 10 min.
Yes, stereoregularity index of boiling heptane-insoluble component [M_Five]
Is 0.986, the stereoregularity of boiling heptane-insoluble components
Index [M_Three] Is 0.0030, and boiling heptane
The crystallinity of the soluble component is 78.5%, and 3MB-1 polymerization
The body content is 300ppm and the density is 0.920g
/ Cm^ThreeMet. [0190] [Comparative manufacturing example] [Polymerization] Reactor with a stirrer of 1000 liters inner
Was charged with 450 liters of purified n-hexane at 60 ° C.
500 ml of triethyl aluminum in propylene atmosphere
Limol, cyclohexylmethyldimethoxysilane 100
Mmol and prepolymerized catalyst [B] in terms of titanium atoms
10 mmol Ti were charged. 200 liters of hydrogen were introduced, and the temperature was raised to 80 ° C.
After heating, this was held for 3 hours to perform propylene polymerization.
Was. The pressure during the polymerization is 6 kg / cm^Two-Keep it at G. Polymerization end
After that, depressurize and centrifuge the slurry containing the produced solid,
Dry with a dryer to obtain a white powdery polymer 200
kg. The MFR of this polymer was 6.0 g / 10 min.
Yes, stereoregularity index of boiling heptane-insoluble component [M_Five]
Is 0.952, and the solid of the boiling heptane insoluble component is
Regularity index [M_ThreeIs 0.0037 and the boiling point
The crystallinity of the tan-insoluble component is 64.0%, and 3 MB-
The content of one polymer was 300 ppm and the density was 0.9.
02g / cm^ThreeMet. [0193] Example 1 Propylene polymer obtained in the above production example
And a 1-butene unit content of 5 mol% and ethylene unit
Content is 2 mol% and the melting point measured by DSC is 1
33 ° C. and MFR of 6.0 g / 10 min.
Using a random random copolymer, two kinds and three layers of a multi-layer T-da
Extrusion temperature 230 ° C, die temperature
220 ° C, 35 ° C cooling roll temperature, propylene
Base layer made of polymer and propylene random copolymer
25 μm thick formed from a body sealing material layer
A multilayer film was manufactured. The composition ratio of each layer of the multilayer film is 1 /
8/1 (seal material layer / base material layer / seal material layer).
Physical properties of the obtained polypropylene multilayer film
Table 1 shows the measurement results. [0195] Example 2 The composition ratio of each layer of the multilayer film was 1/18 /
1 (seal material layer / base material layer / seal material layer)
A multilayer film having a thickness of 25 μm was produced in the same manner as in Example 1.
Built. The obtained polypropylene multilayer film
Table 1 shows the results of measurement of each physical property. [0197] Example 3 In Example 1, a propylene-based random copolymer was used.
As a polymer, the 1-butene unit content is 7 mol%,
The melting point measured by DSC is 135 ° C., and the MFR is 6.
Using a propylene random copolymer of 5 g / 10 min
Except for the difference, the same as in Example 1
A film was produced. The obtained polypropylene multilayer film
Table 1 shows the results of measurement of each physical property. [0199] Comparative Example 1 Propylene similar to that used in Example 1
Extrusion temperature using T-die cast molding machine using polymer
Temperature 230 ° C, die temperature 220 ° C, cooling roll 35 ° C
Under the conditions, a single-layer film having a thickness of 25 μm was produced. The resulting polypropylene single-layer film
Table 1 shows the results of measurement of each physical property. [0201] Comparative Example 2 A propylene polymer was used in Example 2.
Therefore, the propylene polymer obtained in Comparative Production Example was used
Outside is the same as in Example 2, except that the thickness of the multilayer film is 25 μm.
Manufactured. The resulting polypropylene multilayer film
Table 1 shows the results of measurement of each physical property. [0203] [Comparative Example 3]
As a polymer, the ethylene unit content is 7 mol%,
The MFR is 6.0 g / 10 min and the fusion measured by DSC
Using a propylene-based random copolymer with a point of 132 ° C
Except for the difference, the same as in Example 1
A film was produced. [0204] The obtained polypropylene multilayer film
Table 1 shows the results of measurement of each physical property. [0205] [Table 1]

──────────────────────────────────────────────────続 き Continuation of front page (72) Inventor Mamoru Kioka 1-2-1, Waki, Waki-machi, Kuga-gun, Yamaguchi Prefecture Inside Mitsui Petrochemical Industry Co., Ltd. (56) References JP-A-2-84404 (JP, A) JP-A-52-11281 (JP, A) JP-A-60-166455 (JP, A) JP-A-61-89041 (JP, A) JP-A-59-212263 (JP, A) JP-A-55 -17542 (JP, A) JP-A-53-114887 (JP, A) JP-A-54-66990 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) B32B 1/00- 35/00

Claims (1)

(57) [Claim 1] A multilayer film having a base material layer made of a propylene polymer [A] and a sealing material layer made of a propylene random copolymer [B], The propylene polymer [A] has a melt flow rate (MFR) at 230 ° C. and a load of 2.16 kg in the range of 0.1 to 500 g / 10 min, and has a Pmmmm in a ¹³ C-NMR spectrum of a boiling heptane-insoluble component. the value of the pentad isotacticity [M _5] of the absorption intensity of Pw obtained by the following formula (1) is 0.970 to 0.9
95, Pmmrm, Pmrmr, Pmrrr, Prmrr, Prmmr, Prrrr, in the ¹³ C-NMR spectrum of the boiling heptane-insoluble component.
The value of the stereoregularity index [M ₃ ] obtained from the absorption intensity of Pw by the following formula (2) is in the range of 0.0020 to 0.0050, and the crystallinity of the boiling heptane-insoluble component is 60% or more. The following formula (i) or (ii) H ₂ C = CH-X (i) H ₂ C ＝ CH—CH ₂ —X (ii) A propylene polymer containing a polymer consisting of structural units derived from the compound represented by the formula at a ratio of 10 to 10000 ppm, wherein the propylene-based random copolymer [B] is an α-olefin having 4 or more carbon atoms 2 to 15 mol% of a structural unit derived from ethylene, 5 mol% or less of a structural unit derived from ethylene, a melting point of 145 ° C or less, and a 23 ° C n-decane-soluble component. A random copolymer of propylene having an amount of 10% by weight or less and an α-olefin having 4 or more carbon atoms, or a random copolymer of propylene, an α-olefin having 4 or more carbon atoms and ethylene, and The ratio of the thickness of the sealing material layer to the total thickness of the film (the thickness of the sealing material layer / the total thickness of the film) is 0.03.
A multilayer polypropylene film characterized by being in the range of ~ 0.4; (Where [Pmmmm] is the absorption intensity derived from the methyl group of the third unit at the site where 5 units of propylene units are continuously bonded isotactically, and [Pw] is the absorption intensity derived from the methyl group of the propylene unit. (2)