JP3472933B2 - Polypropylene resin composition and extruded sheet comprising the composition - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a propylene resin composition which is lighter in weight than conventional propylene resin compositions and which gives a molded article excellent in rigidity, and an extruded sheet comprising the composition. is there.

[0002]

BACKGROUND OF THE INVENTION Crystalline polypropylene has been conventionally molded by various molding methods because of its excellent mechanical strength such as rigidity and impact resistance, high transparency, and excellent heat resistance. Is used for. For example, it is formed into a sheet, a film, a pipe, a hose, a wire coating, a monofilament, etc. by an extrusion molding method.

By the way, crystalline polypropylene is often used as a resin composition containing other resins and fillers, and such a resin composition has improved mechanical strength when the amount of the fillers is increased. It is known.

However, the specific gravity of the filler is usually 2.5.
Therefore, if the compounding amount of the filler is increased to obtain higher mechanical strength, the weight of the molded product becomes heavy.

Nowadays, in many fields, there is a demand for weight reduction and size reduction of products, and resin products used therein are also required for weight reduction and thickness reduction for size reduction. Therefore, it is desired to develop a polypropylene resin composition that can reduce the weight or the thickness of a molded body without lowering the mechanical strength.

As a result of intensive studies in view of such circumstances, the present inventors have found that a specific propylene polymer having a melt flow rate (MFR) in a specific range, high stereoregularity and high crystallinity. And an olefin elastomer,
The polypropylene resin composition prepared by blending a filler,
The present invention has been completed by finding that the above requirements are satisfied.

[0007]

It is an object of the present invention to provide a polypropylene resin composition which is lighter in weight than conventional polypropylene compositions and which gives a molded article excellent in rigidity. It is intended to provide an extruded sheet of

[0008]

SUMMARY OF THE INVENTION The polypropylene resin composition according to the present invention has (A) a melt flow rate (MFR) at 230 ° C. under a load of 2.16 kg in the range of 0.1 to 500 g / 10 minutes, and a boiling heptane-insoluble component. The value of the stereoregularity index [M ₅ ] determined by the following formula (1) from the absorption intensities of Pmmmm and Pw in the ¹³ C-NMR spectrum is 0.970.
It is in the range of ~ 0.995,
Pmmrm and Pmr in ¹³ C-NMR spectrum
mr, Pmrrr, Prmrr, Prmmr, Prrr
The value of the stereoregularity index [M ₃ ] calculated from the absorption intensities of r and Pw by the following formula (2) is 0.0020 to 0.00.
Propylene polymer having a crystallinity of the boiling heptane-insoluble component of 60% or more in the range of 50: 45 to 85 % by weight
And (B) an olefin elastomer composed of two or more structural units derived from a monomer selected from an olefin having 2 to 20 carbon atoms: 2 to 27.5 % by weight, and (C) a filler: 5 to 27. It is characterized by comprising 5 % by weight.

[0009]

[Equation 5]

(In the formula, [Pmmmm]: absorption intensity derived from the methyl group of the third unit at the site where five propylene units are continuously isotactically bonded, and [Pw]: derived from the methyl group of the propylene unit. It is the absorption intensity.)

[0011]

[Equation 6]

The extruded sheet according to the present invention comprises: (A) propylene polymer: 45 to 85 % by weight, (B) olefin elastomer: 2 to 27.5 % by weight, and (C) filler: 5 to 27.5 wt% and has a melt flow rate (MFR) of 0.1 to 100 g / 10
It is characterized by being formed from a polypropylene resin composition in the range of minutes.

In the present invention, the propylene polymer (A) is a polymer having a constitutional unit derived from a compound represented by the following formula (i) or (ii) in an amount of 10 to 10,000 p.
It is desirable that the content is in the range of pm.

[0014]

[Chemical 3]

In the present invention, it is desirable that the (C) filler is at least one selected from the following group a. Group a: talc, calcium carbonate, barium sulfate, magnesium hydroxide, glass fiber, potassium titanate,
Magnesium sulfate whiskers.

[0016]

DETAILED DESCRIPTION OF THE INVENTION The polypropylene resin composition and the extruded sheet according to the present invention will be specifically described below.

The polypropylene resin composition according to the present invention comprises (A) a propylene polymer, (B) an olefin elastomer, and (C) a filler. First, (A) a propylene polymer used in the present invention, (B)
The olefin elastomer and the (C) filler will be sequentially described.

In the present invention, the term "polymerization" means
The term “polymer” may be used in the sense of including not only homopolymerization but also copolymerization, and the term “polymer” may be used in the sense of including not only homopolymer but also copolymer.

Propylene Polymer (A) The propylene polymer (A) used in the present invention is a propylene homopolymer.

In such a propylene polymer, 230
Melt flow rate (M
FR) is 0.1 to 500 g / 10 minutes, preferably 0.2
It is preferably in the range of 300 g / 10 minutes.

The melt flow rate (MFR) is A
Measured according to STM D1238-65T under the conditions of 230 ° C. and 2.16 kg load. The propylene polymer used in the present invention is represented by the following formula (1) from the absorption intensity of Pmmmm and Pw in the ¹³ C-NMR spectrum of the boiling heptane-insoluble component.
The value of the stereoregularity index [M ₅ ] obtained by
It is in the range of 0 to 0.995, preferably 0.980 to 0.995, and more preferably 0.982 to 0.995.

[0022]

[Equation 7]

[In the formula, [Pmmmm] is the absorption intensity derived from the methyl group of the third unit at the site where five propylene units are continuously isotactically bonded, and [Pw] is derived from the methyl group of the propylene unit. Then, the stereoregularity index [M ₅ ] used for evaluating the stereoregularity of the propylene polymer used in the present invention will be specifically described.

The propylene homopolymer can be represented, for example, by the following formula (A).

[0025]

[Chemical 4]

¹³ C derived from the methyl group (eg, Me ³ , Me ⁴ ) at the 3rd unit in the chain of 5 propylene units represented by
The absorption intensity at -NMR spectrum and Pmmmm, when the absorption intensity derived from all methyl groups ^{(Me 1, Me 2, Me} 3 ...) in the propylene unit and Pw, polymers represented by the above formula (A) The stereoregularity can be evaluated by the ratio of Pmmmm and Pw, that is, the value [M ₅ ] obtained from the above formula (1).

Therefore, the stereoregularity of the boiling heptane-insoluble component of the propylene polymer used in the present invention depends on the Pmmmm, Pw in the ¹³ C-NMR spectrum of the insoluble component.
It can be evaluated by the value of the stereoregularity index [M ₅ ] obtained from the above absorption intensity according to the formula (1).

The propylene polymer used in the present invention is
The value of the stereoregularity index [M ₅ ] of the boiling heptane-insoluble component determined by the above formula (1) is within the range of 0.970 to 0.995, and the boiling heptane-insoluble component ¹³ C-N
Pmmrm, Pmrmr, Pmrrr, Prm in MR spectrum
From the absorption intensity of rr, Prmmr, Prrrr, Pw, the following formula (2)
The value of the stereoregularity index [M ₃ ] obtained by
20-0.0050, preferably 0.0023-0.00
45, and more preferably in the range of 0.0025 to 0.0040.

[0029]

[Equation 8]

In the above equation (2), [Pmmrm], [Pmrm
r], [Pmrrr], [Prmrr], [Prmmr], [Prrr
r] is a methyl group of 5 consecutive propylene units in the chain of propylene units, 3 in the same direction, 2
It shows the absorption intensity derived from the methyl group of the third unit in the propylene unit 5 chain having a structure in which the individual units are oriented in the opposite direction (hereinafter sometimes referred to as “M ₃ structure”). That is, the value of the stereoregularity index [M ₃ ] obtained by the above formula (2) indicates the ratio of the M ₃ structure in the propylene unit chain.

The propylene polymer used in the present invention is
The stereoregularity index [M ₅ ] of the boiling heptane-insoluble component determined by the above formula (1) is in the range of 0.970 to 0.995, and the stereotype of the boiling heptane-insoluble component determined by the above formula (2). The value of the regularity index [M ₃ ] is 0.0020.
Since it is in the range of to 0.0050, it has an extremely long meso chain (a propylene unit chain in which α-methyl carbon points in the same direction).

Generally, in polypropylene, the smaller the value of the stereoregularity index [M ₃ ] is, the longer the mesochain is. However, when the value of the stereoregularity index [M ₅ ] is extremely large and the value of the stereoregularity index [M ₃ ] is very small, if the values of the stereoregularity index [M ₅ ] are almost the same, The larger the value of the regularity index [M ₃ ] is, the longer the meso chain may be.

[0033] For example a polypropylene having a structure (I) shown below, when compared with polypropylene having the structure (b), the polypropylene represented by the structure (a) having the M ₃ structure, the M ₃ structure It has a longer meso chain than the polypropylene represented by the structure (B) which does not have it. (However, the following structure (a) and structure (b) are
(All shall consist of 1003 propylene units)

[0034]

[Chemical 5]

Polypropylene represented by the above structure (a)
Stereoregularity index [M_Five] Is 0.986, and
Stereoregularity index of polypropylene represented by structure (b)
[M _Five] Is 0.985 and is represented by structure (a)
Polypropylene and polypropylene represented by the structure (b)
Ren's stereoregularity index [M_Five] Values are almost equal
is there. However, M₃Table with structure (a) with structure
In the case of polypropylene, the propylene contained in the meso chain
The average len unit is 497 units, and M₃Contains structure
In the polypropylene represented by the non-structure (b),
The average number of propylene units in the chain is 250 units.
It That is, the stereoregularity index [M_Five] Is extremely large
In the case of polypropylene, it is included in the propylene unit chain.
The ratio of the structure shown by r (racemo) is extremely small
Therefore, the structure indicated by r (racemo) is concentrated.
Polypropylene (M₃Polypropylene having a structure
The structure represented by r (racemo) exists in the
Polypropylene (M₃Polypropylene without structure
N) will have a longer meso chain.

The propylene polymer used in the present invention is
M as shown in the above structure (a) ₃High connection with structure
It is a crystalline polypropylene, and contains no components insoluble in boiling heptane.
Body regularity index [M_Five] Is in the range of 0.970 to 0.995
The stereoregularity index of boiling heptane-insoluble components [M
₃] Is in the range of 0.0020 to 0.0050. This
The reason why the propylene polymer used in the present invention is
Is not clear, but compared to conventional high crystalline polypropylene
It has high rigidity, heat resistance and moisture resistance. In addition,
Stereoregularity index of boiling heptane-insoluble component [M₃]The value of the
Is out of the range of 0.0020 to 0.0050,
The above characteristics may deteriorate.

In the present invention, the boiling heptane-insoluble component is prepared as follows. That is, in a 1 liter flask equipped with a stirrer, 3 g of a polymer sample, 20 mg of 2,6-ditert-butyl-4-methylphenol, and 500 ml of n-decane.
, And heat and dissolve on an oil bath at 145 ° C. After the polymer sample has dissolved, it is cooled to room temperature over about 8 hours and then held on a 23 ° C. water bath for 8 hours. G-4 was added to the n-decane suspension containing the precipitated polymer (decane insoluble component at 23 ° C).
(Or G-2) is separated by filtration through a glass filter, dried under reduced pressure, and 1.5 g of the polymer is Soxhlet-extracted with heptane for 6 hours or longer. A boiling heptane-insoluble component is used as a sample. The amount of the boiling heptane-insoluble component of the propylene polymer used in the present invention is usually 80% by weight or more, preferably 90% by weight or more, more preferably 94% by weight or more, further preferably 95% by weight or more, particularly preferably 96% by weight. % Or more. The amount of the boiling heptane-insoluble component is calculated on the assumption that the 23 ° C. decane-soluble component is also soluble in boiling heptane.

In the present invention, the boiling heptane-insoluble component N
The MR measurement is performed as follows, for example. That is, 0.35 g of the insoluble component was added to hexachlorobutadiene 2.
Dissolve by heating to 0 ml. This solution is filtered through a glass filter (G2), 0.5 ml of deuterated benzene is added, and the solution is placed in an NMR tube having an inner diameter of 10 mm. Then, using a JEOL GX-500 type NMR measuring device, 1
¹³ C-NMR measurement is performed at 20 ° C. The total number of times is 10,
000 times or more. The values of the stereoregularity indexes [M ₅ ] and [M ₃ ] can be determined from the peak intensities or the sum of peak intensities based on the respective structures obtained by the above measurement.

The crystallinity of the boiling heptane-insoluble component of the propylene polymer used in the present invention is 60% or more, preferably 65% or more, more preferably 70% or more.

The crystallinity is measured as follows.
That is, the sample is 1 mm thick with a pressure molding machine at 180 ° C.
Rotorflex RU3 manufactured by Rigaku Denki Co., Ltd. using a press sheet obtained by immediately cooling with water after molding into a rectangular plate
00 measuring device (output 50 kV, 250 mA). As a measuring method at this time, a transmission method is used, and the measurement is performed while rotating the sample.

The propylene polymer used in the present invention is
A polymer composed of structural units derived from a compound represented by the following formula (i) or (ii) is used in an amount of 10 to 10000 pp.
m, preferably in the range of 100 to 5000 ppm.

[0042]

[Chemical 6]

In the above formula (i), the cycloalkyl group represented by X includes a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and the like, and the aryl group includes a phenyl group, a tolyl group, a xylyl group and a naphthyl group. Groups and the like.

In the above formula (i) or (ii),
As the hydrocarbon group represented by R ¹ , R ² and R ³ ,
Examples thereof include an alkyl group such as a methyl group, an ethyl group, a propyl group and a butyl group, an aryl group such as a phenyl group and a naphthyl group, and a norbornyl group. Furthermore, R ¹ ,
The hydrocarbon group represented by R ² and R ³ may contain silicon or halogen.

Specific examples of the compound represented by the above formula (i) or (ii) include 3-methyl-1-butene and 3
-Methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-
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 , Allylnorbornane, styrene, dimethylstyrenes, vinylnaphthalene, allyltoluenes, allylbenzene, vinylcyclohexane, vinylcyclopentane, vinylcycloheptane, allyltrialkylsilanes and the like. Among these, 3-methyl-1-butene, 3-methyl-
1-pentene, 3-ethyl-1-hexene, vinylcyclohexane, allyltrimethylsilane, preferably contains dimethylstyrene and the like, 3-methyl-1-butene,
It is more preferable to contain vinylcyclohexane and allyltrimethylsilane, and it is particularly preferable to contain 3-methyl-1-butene.

The propylene polymer used in the present invention may contain a small amount of a structural unit derived from an olefin other than propylene having 20 or less carbon atoms or a diene compound having 4 to 20 carbon atoms.

As described above, even if the propylene polymer contains a small amount of a monomer component other than propylene, the value of the stereoregularity index [M ₅ ] and the value of the stereoregularity index [M ₃ ] are substantially affected. Does not give.

The propylene polymer used in the present invention is
It is desirable that the density is in the range of 0.900 to 0.936 g / cm ³ , preferably 0.910 to 0.9936 g / cm ³ .

The propylene polymer used in the present invention has a decane-soluble component amount at 23 ° C. of not more than 3.0%, preferably not more than 2.5%, more preferably not more than 2.0%, particularly preferably 1%. It is desirable that it is 0.5% or less.

The amount of the 23 ° C. decane-soluble component of the propylene polymer is measured as follows. That is,
In a 1 liter flask equipped with a stirrer, 3 g of the polymer sample,
2,6-di tert-butyl-4-methylphenol 20mg, n-
Add 500 ml of decane and heat to dissolve on an oil bath at 145 ° C. After the polymer sample has dissolved, it is cooled to room temperature over about 8 hours and then held on a 23 ° C. water bath for 8 hours.
The precipitated polymer and the n-decane suspension containing the dissolved polymer are separated by filtration with a G-4 (or G-2) glass filter. The resulting solution is dried at 10 mmHg and 150 ° C. until a constant weight is obtained, and the weight is measured to obtain the amount of the soluble component of the polymer in the mixed solvent, which is calculated as a percentage with respect to the weight of the sample polymer. .

The half-crystallization time at 135 ° C. of the boiling heptane-insoluble component of the propylene polymer used in the present invention is 5
00 seconds or less, preferably 100 seconds or less, more preferably 80 seconds or less, and particularly preferably 70 seconds or less.

The half-crystallization time at 135 ° C. of the boiling heptane-insoluble component of the propylene polymer is measured as follows. That is, by using a differential heat meter manufactured by Perkin Elmer Co., the relationship between the heating value due to the crystallization of the boiling heptane-insoluble component of the polymer at 135 ° C. and the time was measured, until the heating value reached 50% of the total heating value. The time required for crystallization is defined as the half-crystallization time.

In the propylene polymer used in the present invention, the difference between the melting point of the boiling heptane-insoluble component and the crystallization temperature is preferably 45 ° C. or less, preferably 43 ° C. or less, more preferably 40 ° C. or less.

One of the propylene polymers used in the present invention
The intrinsic viscosity [η] measured in decalin at 35 ° C. is usually 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.

Examples of the propylene polymer used in the present invention include [Ia] magnesium, titanium,
A solid titanium catalyst component (a) containing halogen and an electron donor as essential components, [II] an organometallic catalyst component (b), and [III] a silicon compound (c) represented by the following formula (iii) or during more compounds having two or more ether linkages present through the atom (d) and _{^{R a n Si (oR b)}} 4-n ... (iii) ( wherein, n is 1, 2 or 3, When n is 1, R
^a is a secondary or tertiary hydrocarbon group, and when n is 2 or 3, at least one R ^a is a secondary or tertiary hydrocarbon group, and R ^a is the same or different. R ^b is a hydrocarbon group having 1 to 4 carbon atoms,
When n is 2 or 3, R ^b may be the same or different. In the presence of an olefin polymerization catalyst formed from the above), a solid titanium catalyst component (a) preferably containing [Ib] magnesium, titanium, halogen and an electron donor as essential components, and an organometallic catalyst component (b). A prepolymerization catalyst component obtained by prepolymerizing at least one olefin selected from the olefins represented by the following formulas (i) and (ii) in the presence of

[0056]

[Chemical 7]

[II] The organometallic catalyst component (b) and [II
I] Propylene in the presence of an olefin polymerization catalyst formed from a silicon compound (c) represented by the above formula (iii) or a compound (d) having two or more ether bonds existing through a plurality of atoms, It can be produced by polymerizing.

Each component forming the olefin polymerization catalyst used for producing the propylene polymer used in the present invention will be specifically described below. The solid titanium catalyst component (a) can be prepared by contacting the following magnesium compound, titanium compound and electron donor.

Specific examples of the titanium compound used for preparing the solid titanium catalyst component (a) include a tetravalent titanium compound represented by the following formula. Ti (OR) _g X _4-g (In the formula, R is a hydrocarbon group, X is a halogen atom, and g is 0 ≦ g ≦ 4.) As such a titanium compound, specifically, , TiC
Tetrahalogenated titanium such as l ₄ , TiBr ₄ and TiI ₄ ;
Ti (OCH ₃ ) Cl ₃ , Ti (OC ₂ H ₅ ) Cl ₃ , Ti (On-C ₄ H
₉ ) Cl ₃ , Ti (OC ₂ H ₅ ) Br ₃ , Ti (O-iso-C ₄ H ₉ ) Br ₃
Trihalogenated alkoxy titanium such as; Ti (OCH ₃ )
₂ Cl ₂ , Ti (OC ₂ H ₅ ) ₂ Cl ₂ , Ti (On-C ₄ H ₉ ) ₂ Cl ₂ ,
Ti (OC ₂ H ₅₎ dihalogenated dialkoxy titanium, such as _{2 Br 2; Ti (OCH 3} ) 3 Cl, Ti (OC 2 H 5) 3 Cl, Ti
Monohalogenated trialkoxy titanium such as (On-C ₄ H ₉ ) ₃ Cl and Ti (OC ₂ H ₅ ) ₃ Br; Ti (OCH ₃ ) ₄ and Ti (O
_{C 2 H 5) 4, Ti} (On-C 4 H 9) 4, Ti (O-iso-C 4 H 9) 4,
Examples thereof include tetraalkoxy titanium such as Ti (O-2-ethylhexyl) ₄ .

Of these, halogen-containing titanium compounds are preferable, titanium tetrahalides are more preferable, and titanium tetrachloride is particularly preferable. These titanium compounds may be used alone or in combination of two or more. Further, these titanium compounds may be diluted with a hydrocarbon compound or a halogenated hydrocarbon compound.

Examples of the magnesium compound used for preparing the solid titanium catalyst component (a) include a reducing magnesium compound and a non-reducing magnesium compound.

Examples of the reducing magnesium compound include magnesium compounds having a magnesium-carbon bond or a magnesium-hydrogen bond. Specific examples of such a magnesium compound having a reducing property include dimethyl magnesium, diethyl magnesium, dipropyl magnesium,
Examples include dibutyl magnesium, diamyl magnesium, dihexyl magnesium, didecyl magnesium, ethyl magnesium chloride, propyl magnesium chloride, butyl magnesium chloride, hexyl magnesium chloride, amyl magnesium chloride, butyl ethoxy magnesium, ethyl butyl magnesium, butyl magnesium hydride. it can. These magnesium compounds may be used alone or may form a complex compound with an organic metal compound described later. Further, these magnesium compounds may be liquid, solid, or may be derived by reacting metallic magnesium with a corresponding compound. It can also be derived from metallic magnesium during catalyst preparation using the methods described above.

Specific examples of the magnesium compound having no reducing property include magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide and magnesium fluoride; magnesium methoxy chloride;
Alkoxy magnesium halides such as ethoxy magnesium chloride, isopropoxy magnesium chloride, butoxy magnesium chloride, octoxy magnesium chloride;
Allyloxy magnesium halides such as phenoxy magnesium chloride, methylphenoxy magnesium chloride;
Ethoxymagnesium, isopropoxymagnesium,
Butoxy magnesium, n-octoxy magnesium, 2-
Examples thereof include alkoxy magnesium such as ethylhexoxy magnesium; allyoxy magnesium such as phenoxy magnesium and dimethylphenoxy magnesium; magnesium carboxylates such as magnesium laurate and magnesium stearate.

The non-reducing magnesium compound may be a compound derived from the above-mentioned reducing magnesium compound or a compound derived during preparation of the catalyst component. In order to derive a non-reducing magnesium compound from a reducible magnesium compound, for example, a reductive magnesium compound can be used as a halogen, a polysiloxane compound, a halogen-containing silane compound, a halogen-containing aluminum compound, an alcohol, an ester. It may be contacted with a compound having an active carbon-oxygen bond, such as a ketone, an aldehyde or the like.

In the present invention, in addition to the above-mentioned reducing magnesium compound and non-reducing magnesium compound, the magnesium compound may be a complex compound, a complex compound or another compound of the above-mentioned magnesium compound and another metal. It may be a mixture with a metal compound. Furthermore, you may use the said compound in combination of 2 or more types.

As the magnesium compound used for the preparation of the solid titanium catalyst component (a), many magnesium compounds other than those mentioned above can be used, but in the finally obtained solid titanium catalyst component (a) , Preferably in the form of a halogen-containing magnesium compound,
Therefore, when a halogen-free magnesium compound is used, it is preferable to react it with a halogen-containing compound during the preparation.

Among the above-mentioned magnesium compounds, a magnesium compound having no reducing property is preferable, a halogen-containing magnesium compound is more preferable, and magnesium chloride, alkoxy magnesium chloride, and aryloxy magnesium chloride are particularly preferable.

The solid titanium catalyst component (a) used in the present invention is formed by bringing the above-mentioned magnesium compound into contact with the above-mentioned titanium compound and electron donor.

Specific examples of the electron donor used in the preparation of the solid titanium catalyst component (a) include the following compounds. Methylamine, ethylamine,
Dimethylamine, diethylamine, ethylenediamine,
Amines such as tetramethylenediamine, hexamethylenediamine, tributylamine, tribenzylamine;
Pyrroles such as pyrrole, methylpyrrole and dimethylpyrrole; pyrroline; pyrrolidine; indole; pyridine, methylpyridine, ethylpyridine, propylpyridine, dimethylpyridine, ethylmethylpyridine, trimethylpyridine, phenylpyridine, benzylpyridine,
Pyridines such as pyridine chloride; nitrogen-containing cyclic compounds such as piperidines, quinolines, isoquinolines; tetrahydrofuran, 1,4-cineole, 1,8-cineole, pinolfuran, methylfuran, dimethylfuran, diphenylfuran, benzofuran, Cyclic oxygen-containing compounds such as coumaran, phthalane, tetrahydropyran, pyran and ditedropyran; methanol, ethanol, propanol, pentanol, hexanol, octanol, 2-ethylhexanol, dodecanol, octadecyl alcohol,
C1-C18 alcohols such as oleyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, isopropyl alcohol, isopropylbenzyl alcohol; phenol, cresol, xylenol, ethylphenol, propylphenol,
Nonylphenol, cumylphenol, naphthol, and other phenols having 6 to 20 carbon atoms which may have a lower alkyl group; acetone, methylethylketone, methylisobutylketone, acetophenone, benzophenone, acetylacetone, benzoquinone and the like having 3 to 15 carbon atoms Ketones; aldehydes having 2 to 15 carbon atoms such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde, naphthaldehyde; methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, Ethyl propionate, methyl butyrate, ethyl valerate,
Methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzoate Acid benzyl, methyl toluate, ethyl toluate, amyl toluate, ethyl ethyl benzoate, methyl anisate, n-butyl maleate, diisobutyl methylmalonate, din-hexyl cyclohexenecarboxylic acid, diethyl nadic acid, tetrahydrophthalic acid Diisopropyl, diethyl phthalate, diisobutyl phthalate, di-n-butyl phthalate,
Di2-ethylhexyl phthalate, γ-butyrolactone, δ-
C2-30 organic acid esters such as valerolactone, coumarin, phthalide, and ethyl carbonate; acid halides having 2 to 15 carbon atoms such as acetyl chloride, benzoyl chloride, toluic acid chloride, and anisic acid chloride; methyl ether, ethyl Ether, isopropyl ether,
Butyl ether, amyl ether, anisole, diphenyl ether epoxy-p-menthane, etc. with 2 to 2 carbon atoms
0 ethers; 2-isopentyl-2-isopropyl-1,3-
Dimethoxypropane, 2,2-isobutyl-1,3-dimethoxypropane, 2,2-isopropyl-1,3-dimethoxypropane, 2-cyclohexylmethyl-2-isopropyl-1,3-dimethoxypropane, 2,2-isopentyl -1,3-dimethoxypropane, 2-isobutyl-2-isopropyl-1,3-dimethoxypropane, 2-cyclohexyl-2-isopropyl-1,3-dimethoxypropane, 2-cyclopentyl-2-isopropyl-1,
3-dimethoxypropane, 2,2-dicyclopentyl-1,3-dimethoxypropane, 1,2-bis-methoxymethyl-bicyclo
-[2,2,1] -Heptane, diphenyldimethoxysilane, isopropyl-t-butyldimethoxysilane, 2,2-diisobutyl-1,3-dimethoxycyclohexane, 2-isopentyl-
Diethers such as 2-isopropyl-1,3-dimethoxycyclohexane; Acid amides such as acetic acid amide, benzoic acid amide, toluic acid amide; Nitriles such as acetonitrile, benzonitrile, tolunitrile; Acetic anhydride, phthalic anhydride, anhydrous An acid anhydride such as benzoic acid is used.

As the electron donor, a silicon compound represented by the general formula (iii) described below can be used. When the titanium compound, the magnesium compound and the electron donor as described above are brought into contact with each other, the carrier compound as described below can be used to prepare the carrier-supported solid titanium catalyst component (a).

Examples of such carrier compounds include Al
₂ O ₃ , SiO ₂ , B ₂ O ₃ , MgO, CaO, TiO ₂ , Z
Examples thereof include resins such as nO, ZnO ₂ , SnO ₂ , BaO, ThO, and a styrene-divinylbenzene copolymer. Among these carrier compounds, SiO ₂ , Al ₂ O ₃ , MgO, ZnO, ZnO _{2 and the} like are preferable.

The above components may be contacted in the presence of other reaction agents such as silicon, phosphorus and aluminum. The solid titanium catalyst component (a) can be produced by bringing the above titanium compound, magnesium compound and electron donor into contact with each other, and any known method can be adopted. it can.

A few specific examples of the method for producing the solid titanium catalyst component (a) will be briefly described below. (1) A method in which a solution of a magnesium compound, an electron donor and a hydrocarbon solvent is contact-reacted with an organometallic compound to precipitate a solid, or while being precipitated, a titanium compound is contact-reacted.

(2) A method in which a complex consisting of a magnesium compound and an electron donor is brought into contact with an organometallic compound to cause a reaction, and then a titanium compound is brought into a catalytic reaction. (3) For the contact product between the inorganic carrier and the organic magnesium compound,
A method of catalytically reacting a titanium compound and preferably an electron donor. At this time, the contact product may be previously contact-reacted with a halogen-containing compound and / or an organometallic compound.

(4) A magnesium compound-supported inorganic or organic carrier is obtained from a mixture of a solution containing a magnesium compound, an electron donor, and optionally a hydrocarbon solvent, and an inorganic or organic carrier. How to contact.

(5) magnesium compound, titanium compound,
A method for obtaining a solid titanium catalyst component carrying magnesium and titanium by contacting a solution containing an electron donor, and optionally a hydrocarbon solvent, with an inorganic or organic carrier.

(6) A method of reacting an organomagnesium compound in a liquid state with a halogen-containing titanium compound in a catalytic reaction. At this time, the electron donor is used at least once. (7) A method of contacting a titanium compound after a liquid reaction of an organomagnesium compound with a halogen-containing compound.
At this time, the electron donor is used at least once.

(8) A method of catalytically reacting an alkoxy group-containing magnesium compound with a halogen-containing titanium compound. At this time, the electron donor is used at least once. (9) A method of reacting a complex of an alkoxy group-containing magnesium compound and an electron donor with a titanium compound.

(10) A method of bringing a complex consisting of an alkoxy group-containing magnesium compound and an electron donor into contact with an organometallic compound and then reacting with the titanium compound. (11) A method of contacting and reacting a magnesium compound, an electron donor, and a titanium compound in any order. In this reaction, each component may be pretreated with an electron donor and / or a reaction aid such as an organometallic compound or a halogen-containing silicon compound. In this method, it is preferable to use the electron donor at least once.

(12) A method of reacting a liquid magnesium compound having no reducing ability with a liquid titanium compound, preferably in the presence of an electron donor, to precipitate a solid magnesium-titanium complex.

(13) A method of further reacting the reaction product obtained in (12) with a titanium compound. (14) A method of further reacting the reaction product obtained in (11) or (12) with an electron donor and a titanium compound.

(15) A method of treating a solid material obtained by pulverizing a magnesium compound, preferably an electron donor, and a titanium compound with any of halogen, a halogen compound and an aromatic hydrocarbon. In this method,
It may include a step of pulverizing only the magnesium compound, the complex compound consisting of the magnesium compound and the electron donor, or the magnesium compound and the titanium compound. Further, after pulverization, pretreatment with a reaction auxiliary agent and then treatment with halogen or the like may be performed. Examples of the reaction aid include organic metal compounds and halogen-containing silicon compounds.

(16) A method of crushing a magnesium compound and then contacting and reacting with a titanium compound. At this time, it is preferable to use an electron donor or a reaction aid during pulverization and / or contact / reaction.

(17) A method of treating the compound obtained in (11) to (16) above with halogen or a halogen compound or an aromatic hydrocarbon. (18) A method of bringing a contact reaction product of a metal oxide, an organomagnesium and a halogen-containing compound into contact with an electron donor and a titanium compound.

(19) A method of reacting a magnesium compound such as a magnesium salt of an organic acid, alkoxy magnesium or aryloxy magnesium with a titanium compound and / or a halogen-containing hydrocarbon and preferably an electron donor.

(20) A method of bringing a hydrocarbon solution containing at least a magnesium compound and alkoxytitanium into contact with a titanium compound and / or an electron donor. At this time, it is preferable to coexist with a halogen-containing compound such as a halogen-containing silicon compound.

(21) A magnesium compound in the liquid state having no reducing ability is reacted with an organometallic compound to precipitate a solid magnesium-metal (aluminum) complex,
Then, a method of reacting an electron donor and a titanium compound.

The amount of each of the above components used in preparing the solid titanium catalyst component (a) varies depending on the preparation method and cannot be specified unconditionally. For example, the amount of electron donor is 0.01 per mol of the magnesium compound. It is used in an amount of -10 to 10 mol, preferably 0.1 to 5 mol, and the titanium compound is used in an amount of 0.01 to 1000 mol, preferably 0.1 to 200 mol.

The solid titanium catalyst component (a) thus obtained contains magnesium, titanium, halogen and an electron donor as essential components. In this solid titanium catalyst component (a), the halogen / titanium (atomic ratio) is in the range of about 2-200, preferably about 4-100, and the electron donor / titanium (molar ratio) is about 0.0.
1 to 100, preferably about 0.02 to 10, magnesium / titanium (atomic ratio) is about 1 to 100,
It is desirable that it is preferably in the range of about 2 to 50.

Such solid titanium catalyst component (a)
(Catalyst component [Ia]) is a [Ib] prepolymerization catalyst component obtained by prepolymerizing an olefin in the presence of the solid titanium catalyst component (a) and the following organometallic catalyst component (b). It is desirable to use it for polymerization.

[Ib] As the organometallic catalyst component (b) used for preparing the prepolymerization catalyst component, an organometallic compound of Group I to Group III metal of the periodic table is used, and specifically, Compounds such as

(B-1) General formula R ¹ _m Al (OR ² ) _n H _p X _q (In the formula, R ¹ and R ² are carbonized usually containing 1 to 15, preferably 1 to 4 carbon atoms. Hydrogen groups, which may be the same or different, X represents a halogen atom,
0 <m ≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, and q is 0
≦ q <3, and m + n + p + q = 3. ) An organoaluminum compound represented by.

[0093] (b-2) the general formula M ¹ AlR ¹ ₄ (wherein, M ¹ is Li, Na, a K, R ¹ is as defined above.) Group I metals and aluminum represented by Complex alkylated with.

(B-3) General formula R ¹ R ² M ² (wherein R ¹ and R ² are the same as above, and M ² is M
g, Zn or Cd. ) A dialkyl compound of Group II or Group III represented by:

Examples of the organoaluminum compound belonging to the above (b-1) include the following compounds. It is represented by the general formula R ¹ _m Al (OR ² ) _3-m (wherein R ¹ and R ² are the same as defined above, and m is preferably a number of 1.5 ≦ m ≦ 3). A compound, a compound represented by the general formula R ¹ _m AlX _3-m (wherein R ¹ is the same as defined above, X is a halogen, and m is preferably 0 <m <3), Formula R ¹ _m AlH _3-m (In the formula, R ¹ is as defined above, and m is preferably 2 ≦
m <3. ), A compound represented by the general formula R ¹ _m Al (OR ² ) _n X _q (wherein R ¹ and R ² are the same as defined above, X is halogen, 0 <m ≦ 3, 0 ≦ n < 3, 0 ≦ q <3, and m + n + q = 3).

Specific examples of the aluminum compound belonging to (b-1) include trialkylaluminums such as triethylaluminum and tributylaluminum; trialkenylaluminums such as triisoprenylaluminum; diethylaluminum ethoxide and dibutylaluminum butoxide. Dialkyl aluminum alkoxides such as; ethyl aluminum sesquiethoxide,
Butyl aluminum sesquibutoxide and other alkyl aluminum sesquialkoxides; R ¹ _2.5 Al (OR ² )
Partially alkoxylated alkyl aluminum having an average composition represented by _0.5, etc .; Dialkyl aluminum halides such as diethyl aluminum chloride, dibutyl aluminum chloride, diethyl aluminum bromide; ethyl aluminum sesquichloride, butyl aluminum sesquichloride, ethyl aluminum sesqui Alkyl aluminum sesquihalides such as bromide;
Partially halogenated alkyl aluminum such as alkyl aluminum dihalide such as ethyl aluminum dichloride, propyl aluminum dichloride, butyl aluminum dibromide; Dialkyl aluminum hydride such as diethyl aluminum hydride, dibutyl aluminum hydride; ethyl aluminum dihydride, propyl aluminum Alkyl aluminums such as dihydrides Other partially hydrogenated alkyl aluminums such as dihydrides; Can be mentioned.

Examples of the compound similar to (b-1) include an organoaluminum compound in which two or more aluminum atoms are bound via an oxygen atom or a nitrogen atom. Examples of such a compound include (C ₂ H ₅ ) ₂ Al
_{OAl (C 2 H 5) 2} , (C 4 H 9) 2 AlOAl (C
_{4 H 9) 2, (C} 2 H 5) 2 AlN (C 2 H 5) Al (C
_{In addition to 2} H ₅ ) _{2 and the} like, aluminoxanes such as methylaluminoxane can be mentioned.

Compounds belonging to the above (b-2) include Li
Examples thereof include Al (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ .

Of these, organoaluminum compounds are preferably used. As the olefin used for preparing the prepolymerization catalyst component [Ib], the compound represented by the above formula (i) or (ii) is preferably used, and specifically, 3-methyl-1-butene, 3-methyl -1-pentene, 3-ethyl-1-pentene, 4-methyl-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,
Examples thereof include olefins having a branched structure such as vinylnaphthalene, allyltoluene, allylbenzene, vinylcyclohexane, vinylcyclopentane, vinylcycloheptane, and allyltrialkylsilanes. Among these, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-hexene, vinylcyclohexane, allyltrimethylsilane, dimethylstyrene and the like are preferable, and 3-methyl-1-butene and vinyl are preferable. Cyclohexyne and allyltrimethylsilane are more preferable, and 3-methyl-1-butene is particularly preferable.

In addition to these, linear olefins such as ethylene, propylene, 1-butene, 1-octene, 1-hexadecene and 1-eicosene can be used in combination. In the prepolymerization, the catalyst can be used at a much higher concentration than the catalyst concentration in the system in the main polymerization of propylene.

The concentration of the solid titanium catalyst component (a) in the prepolymerization is usually about 0.01-200 mmol, preferably about 0.05-0.5, in terms of titanium atom, per liter of an inert hydrocarbon medium described later. It is preferably in the range of 100 mmol.

The amount of the organometallic catalyst component (b) may be such that 0.1 to 1000 g, preferably 0.3 to 500 g of polymer is produced per 1 g of the solid titanium catalyst component (a). The amount is usually about 0.1 to 100 mmol, preferably about 0.5 to 50 mmol, per mol of titanium atom in the solid titanium catalyst component (a).

When carrying out the prepolymerization, an electron donor (e) may be used in addition to the solid titanium catalyst component (a) and the organometallic catalyst component (b). As the electron donor (e), specifically, the electron donor previously used in preparing the solid titanium catalyst component (a), the silicon compound (c) represented by the formula (iii) described later, and A compound (d) having two or more ether bonds existing through a plurality of atoms,
Further, an organic silicon compound represented by the following formula (ci) can be given.

R _n Si (OR ′) _4-n ... (ci) (wherein R and R ′ are hydrocarbon groups, and 0 <n <4
It should be noted that the organosilicon compound represented by the formula (ci) does not include the silicon compound (c) represented by the formula (iii) described later.

Specific examples of the organosilicon compound represented by the general formula (ci) include trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diisopropyldimethoxysilane, diphenyldimethoxysilane, Phenylmethyldimethoxysilane, diphenyldiethoxysilane, bis o-tolyldimethoxysilane, bis m-tolyldimethoxysilane, bis p-tolyldimethoxysilane, bis p-tolyldiethoxysilane, bisethylphenyldimethoxysilane, ethyltrimethoxysilane, Ethyltriethoxysilane, vinyltrimethoxysilane, methyltrimethoxysilane, n-propyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane,
Phenyltrimethoxysilane, γ-chloropropyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, n-butyltriethoxysilane, phenyltriethoxysilane,
γ-aminopropyltriethoxysilane, chlorotriethoxysilane, ethyltriisopropoxysilane, vinyltributoxysilane, ethyl silicate, butyl silicate,
Trimethylphenoxysilane, methyltriaryloxy (a
llyloxy) silane, vinyltris (β-methoxyethoxysilane), vinyltriacetoxysilane, dimethyltetraethoxydisiloxane and the like.

These electron donors (e) can be used alone or in combination of two or more kinds. The electron donor (e) is used in an amount of 0.1 to 50 mol, preferably 0.5 to 3 mol, per mol of titanium atom in the solid titanium catalyst component (a).
It is used in an amount of 0 mol, more preferably 1 to 10 mol.

The prepolymerization is preferably carried out under mild conditions by adding the olefin represented by the above formula (i) or (ii) and the above catalyst component to an inert hydrocarbon medium. Examples of the inert hydrocarbon medium used at this time include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane, methylcyclopentane, etc. Alicyclic hydrocarbons; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride and chlorobenzene; and contact products thereof. Of these inert hydrocarbon media, it is particularly preferable to use aliphatic hydrocarbons.

The reaction temperature in the prepolymerization may be a temperature at which the prepolymer to be produced is not substantially dissolved in the inert hydrocarbon medium, and is usually about -20 to + 100 ° C, preferably about-. 20 to + 80 ° C, more preferably 0 to +
It is preferably in the range of 40 ° C. In the prepolymerization, a molecular weight modifier such as hydrogen can be used.

It is desirable that the prepolymerization is carried out so that about 0.1 to 1000 g, preferably about 0.3 to 500 g of a polymer is produced per 1 g of the solid titanium catalyst component (a) as described above. If the prepolymerization amount is too large, the production efficiency of the (co) polymer in the main polymerization may decrease, and fish eyes are likely to occur when a film or the like is formed from the obtained (co) polymer. There is.

Such prepolymerization can be carried out batchwise or continuously. The olefin polymerization catalyst used for producing the propylene polymer used in the present invention has the above-mentioned [I
a] solid titanium catalyst component or [Ib] prepolymerization catalyst component, [II] organometallic catalyst component, [III] silicon compound (c) or two or more ether bonds present through a plurality of atoms. And the compound (d) having.

As the [II] organometallic catalyst component, the same as the (b) organometallic catalyst component used in the preparation of the above-mentioned [Ib] prepolymerization catalyst component can be used. The [III] silicon compound (c) is a compound represented by the following formula (iii).

[0112] In _{^{R a n -Si- (OR b)}} 4-n ... (iii) ( wherein, n is 1, 2 or 3, when n is 1, R
^a is a secondary or tertiary hydrocarbon group, and when n is 2 or 3, at least one R ^a is a secondary or tertiary hydrocarbon group, and R ^a is the same or different. R ^b is a hydrocarbon group having 1 to 4 carbon atoms,
When n is 2 or 3, R ^b may be the same or different. ) In the silicon compound (c) represented by the formula (iii), the secondary or tertiary hydrocarbon group is a cyclopentyl group, a cyclopentenyl group, a cyclopentadienyl group, a group having these substituents or Si. And a hydrocarbon group in which the carbon adjacent to is a secondary or tertiary carbon group.
More specifically, the substituted cyclopentyl group, 2-methylcyclopentyl group, 3-methylcyclopentyl group, 2-ethylcyclopentyl group, 2-n-butylcyclopentyl group,
2,3-dimethylcyclopentyl group, 2,4-dimethylcyclopentyl group, 2,5-dimethylcyclopentyl group, 2,3-diethylcyclopentyl group, 2,3,4-trimethylcyclopentyl group, 2,3,5-trimethylcyclopentyl group Examples thereof include a cyclopentyl group having an alkyl group such as a group, a 2,3,4-triethylcyclopentyl group, a tetramethylcyclopentyl group, and a tetraethylcyclopentyl group.

The substituted cyclopentenyl group includes 2-methylcyclopentenyl group, 3-methylcyclopentenyl group,
2-ethylcyclopentenyl group, 2-n-butylcyclopentenyl group, 2,3-dimethylcyclopentenyl group, 2,4-dimethylcyclopentenyl group, 2,5-dimethylcyclopentenyl group, 2,3,4-trimethyl Examples include cyclopentenyl group, cyclopentenyl group having an alkyl group such as 2,3,5-trimethylcyclopentenyl group, 2,3,4-triethylcyclopentenyl group, tetramethylcyclopentenyl group, and tetraethylcyclopentenyl group. it can.

Examples of the substituted cyclopentadienyl group include 2-
Methylcyclopentadienyl group, 3-methylcyclopentadienyl group, 2-ethylcyclopentadienyl group, 2-n-butylcyclopentenyl group, 2,3-dimethylcyclopentadienyl group, 2,4-dimethyl Cyclopentadienyl group, 2,5-
Dimethylcyclopentadienyl group, 2,3-diethylcyclopentadienyl group, 2,3,4-trimethylcyclopentadienyl group, 2,3,5-trimethylcyclopentadienyl group, 2,
3,4-triethylcyclopentadienyl group, 2,3,4,5-tetramethylcyclopentadienyl group, 2,3,4,5-tetraethylcyclopentadienyl group, 1,2,3,4, Examples thereof include a cyclopentadienyl group having an alkyl group such as a 5-pentamethylcyclopentadienyl group and a 1,2,3,4,5-pentaethylcyclopentadienyl group.

Examples of the hydrocarbon group in which the carbon adjacent to Si is secondary carbon include i-propyl group, s-butyl group, s-amyl group and α-methylbenzyl group. Examples of the hydrocarbon group whose carbon adjacent to is a tertiary carbon include a t-butyl group, a t-amyl group, an α, α′-dimethylbenzyl group, and an admantyl group.

When n is 1, the silicon compound (c) represented by the formula (iii) includes cyclopentyltrimethoxysilane, 2-methylcyclopentyltrimethoxysilane and 2,3-dimethylcyclopentyltrimethoxysilane. Trialkoxysilanes such as silane, cyclopentyltriethoxysilane, iso-butyltriethoxysilane, t-butyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 2-norbornanetrimethoxysilane, 2-norbornanetriethoxysilane Is exemplified.

When n is 2, dicyclopentyldiethoxysilane, t-butylmethyldimethoxysilane,
Examples of dialkoxysilanes include t-butylmethyldiethoxysilane, t-amylmethyldiethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, and 2-norbornanemethyldimethoxysilane.

When n is 2, the silicon compound (c) represented by the formula (iii) is preferably a dimethoxy compound represented by the following formula (iv).

[0119]

[Chemical 8]

In the formula, R ^a and R ^c are each independently a cyclopentyl group, a substituted cyclopentyl group, a cyclopentenyl group, a substituted cyclopentenyl group, a cyclopentadienyl group, a substituted cyclopentadienyl group, or
A hydrocarbon group in which the carbon adjacent to Si is secondary carbon or tertiary carbon is shown.

Examples of the silicon compound represented by the formula (iv) include dicyclopentyldimethoxysilane, dicyclopentenyldimethoxysilane, dicyclopentadienyldimethoxysilane, di-t-butyldimethoxysilane, and di (2- Methylcyclopentyl) dimethoxysilane, di (3-methylcyclopentyl) dimethoxysilane, 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) dimethoxysilane, di (2,3,5-trimethylcyclopentyl) dimethoxysilane, di (2,3,4-triethylcyclopentyl) dimethoxysilane, di (tetramethylcyclopentyl) dimethoxysilane , Di (tetraethylcyclopentyl) dimethoxysilane, di (2-methylcyclopentenyl) dimethoxysilane, di (3-methylcyclopentenyl) dimethoxysilane, di (2-ethylcyclopentenyl) dimethoxysilane, di (2-n-butylcyclo) Pentenyl) dimethoxysilane, di (2,3-dimethylcyclopentenyl) dimethoxysilane, di (2,4-dimethylcyclopentenyl) dimethoxysilane, di (2,5-dimethylcyclopentenyl) dimethoxysilane, di (2,3, 4-trimethylcyclopentenyl)
Dimethoxysilane, di (2,3,5-trimethylcyclopentenyl) dimethoxysilane, di (2,3,4-triethylcyclopentenyl) dimethoxysilane, di (tetramethylcyclopentenyl) dimethoxysilane, di (tetraethylcyclopentenyl) dimethoxy Silane, di (2-methylcyclopentadienyl) dimethoxysilane, di (3-methylcyclopentadienyl) dimethoxysilane, di (2-ethylcyclopentadienyl) dimethoxysilane, di (2-n-butylcyclopentenyl) ) Dimethoxysilane, di (2,3-dimethylcyclopentadienyl) dimethoxysilane, di (2,4-dimethylcyclopentadienyl) dimethoxysilane, di (2,5-dimethylcyclopentadienyl) dimethoxysilane, di (2,3-diethylcyclopentadienyl) dimethoxysilane, di (2,3,4-trimethyl) Dicyclopentadienyl) dimethoxysilane, di (2,3,5-trimethylcyclopentadienyl) dimethoxysilane, di (2,3,4-triethylcyclopentadienyl) dimethoxysilane, di (2,3,4 , 5-Tetramethylcyclopentadienyl) dimethoxysilane, di (2,3,4,5-tetraethylcyclopentadienyl) dimethoxysilane, di (1,2,3,4,5-pentamethylcyclopentadienyl) ) Dimethoxysilane, di (1,2,
3,4,5-Pentaethylcyclopentadienyl) dimethoxysilane, di-t-amyl-dimethoxysilane, di (α, α'-dimethylbenzyl) dimethoxysilane, di (admantyl) dimethoxysilane, admantyl-t-butyldimethoxy Examples thereof include silane, cyclopentyl-t-butyldimethoxysilane, diisopropyldimethoxysilane, dis-butyldimethoxysilane, dis-amyldimethoxysilane, and isopropyl-s-butyldimethoxysilane.

When n is 3, tricyclopentylmethoxysilane, tricyclopentylethoxysilane, dicyclopentylmethylmethoxysilane, dicyclopentylethylmethoxysilane, dicyclopentylmethylethoxysilane, cyclopentyldimethylmethoxysilane, cyclopentyldiethylmethoxysilane, Examples include monoalkoxysilanes such as cyclopentyldimethylethoxysilane.

Of these, dimethoxysilanes, particularly dimethoxysilane represented by the formula (iv), are preferable, and specifically, dicyclopentyldimethoxysilane, di-t-butyldimethoxysilane, di (2-methylcyclopentyl) dimethoxysilane. , Di (3-methylcyclopentyl) dimethoxysilane and di-t-amyldimethoxysilane are preferable.

Two or more kinds of these silicon compounds (c) can be used in combination. In the compound (d) having two or more ether bonds existing via a plurality of atoms used in the present invention (hereinafter sometimes referred to as a polyether compound), the atoms existing between these ether bonds are carbon and silicon. , At least one selected from the group consisting of oxygen, sulfur, phosphorus, and boron, and the number of atoms is 2 or more. Of these, a relatively bulky substituent at an atom between ether bonds, specifically, a substituent having 2 or more carbon atoms, preferably 3 or more, having a linear, branched or cyclic structure, and more preferably a branched substituent. Those in which a substituent having a ring-like or cyclic structure is bonded are desirable. Further, a compound in which a plurality of carbon atoms, preferably 3 to 20, more preferably 3 to 10 and particularly preferably 3 to 7 carbon atoms are contained in an atom existing between two or more ether bonds is preferable.

As such a polyether compound,
For example, a compound represented by the following formula can be given.

[0126]

[Chemical 9]

In the formula, n is an integer of 2 ≦ n ≦ 10, and R
^{1 to} R ²⁶ are carbon, hydrogen, oxygen, halogen, nitrogen, sulfur,
At least one selected from phosphorus, boron and silicon
R ^{1 to} R ²⁶ , preferably R ^{1 to} R ²ⁿ , which are substituents having a certain element, may jointly form a ring other than a benzene ring, and an atom other than carbon in the main chain. May be included.

As the polyether compound as described above,
Specifically, 2- (2-ethylhexyl) -1,3-dimethoxypropane, 2-isopropyl-1,3-dimethoxypropane, 2
-Butyl-1,3-dimethoxypropane, 2-s-butyl-1,3-dimethoxypropane, 2-cyclohexyl-1,3-dimethoxypropane, 2-phenyl-1,3-dimethoxypropane, 2-cumyl-1 , 3-Dimethoxypropane, 2- (2-phenylethyl) -1,3-dimethoxypropane, 2- (2-cyclohexylethyl) -1,3-dimethoxypropane, 2- (p-chlorophenyl) -1,3- Dimethoxypropane, 2- (diphenylmethyl) -1,3-dimethoxypropane, 2- (1-naphthyl) -1,3-
Dimethoxypropane, 2- (2-fluorophenyl) -1,3-
Dimethoxypropane, 2- (1-decahydronaphthyl) -1,3
-Dimethoxypropane, 2- (pt-butylphenyl) -1,3-
Dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, 2,2-dicyclopentyl-1,3-dimethoxypropane, 2,2-diethyl-1,3-dimethoxypropane,
2,2-dipropyl-1,3-dimethoxypropane, 2,2-diisopropyl-1,3-dimethoxypropane, 2,2-dibutyl-1,3-
Dimethoxypropane, 2-methyl-2-propyl-1,3-dimethoxypropane, 2-methyl-2-benzyl-1,3-dimethoxypropane, 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-dimethoxypropane, 2-methyl-2-isobutyl-1,3-dimethoxypropane, 2-methyl-2- (2-ethylhexyl) -1,3-dimethoxypropane, 2 , 2-Diisobutyl-1,3-dimethoxypropane, 2,2-diphenyl-1,3-dimethoxypropane, 2,2-dibenzyl-1,3-dimethoxypropane, 2,2-bis (cyclohexylmethyl) -1, 3-dimethoxypropane, 2,2-diisobutyl-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-methylbutyl) -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-dimethoxypropane, 2-phenyl-2-benzyl-1,3-dimethoxypropane, 2-cyclopentyl-2-isopropyl-1,3-dimethoxypropane, 2-Cyclopentyl-2-s-butyl-1,3-
Dimethoxypropane, 2-cyclohexyl-2-isopropyl-1,3-dimethoxypropane, 2-cyclohexyl-2-s-butyl-1,3-dimethoxypropane, 2-isopropyl-2-s-butyl-1,3-dimethoxy Propane, 2-cyclohexyl-2-cyclohexylmethyl-1,3-dimethoxypropane, 2,3-diphenyl-1,4-diethoxybutane, 2,3-dicyclohexyl-1,4-diethoxybutane, 2,2- Dibenzyl-1,4-diethoxybutane, 2,3-dicyclohexyl-1,4-diethoxybutane, 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-dimethoxybutane, 2,4-diphenyl-1,5-dimethoxypentane, 2,5-diphenyl-1,5-dimethoxyhexane, 2,4-diisopropyl -1,5-dimethoxypentane, 2,4-diisobutyl-1,5-dimethoxypentane, 2,4-diisoamyl-1,5-dimethoxypentane, 3-methoxymethyltetrahydrofuran, 3-methoxymethyldioxane, 1,3- Diisobutoxypropane, 1,2-diisobutoxypropane, 1,2-diisobutoxyethane, 1,3-diisoamyloxypropane, 1,3-diisoneopentyloxyethane, 1,3-dineopentyloxypropane , 2,2-tetramethylene-1,3-dimethoxypropane, 2,2
-Pentamethylene-1,3-dimethoxypropane, 2,2-hexamethylene-1,3-dimethoxypropane, 1,2-bis (methoxymethyl) cyclohexane, 2,8-dioxaspiro [5,
5] undecane, 3,7-dioxabicyclo [3,3,1] nonane, 3,7-dioxabicyclo [3,3,0] octane, 3,3-diisobutyl-1,5-oxononane, 6, 6-diisobutyldioxyheptane, 1,1-dimethoxymethylcyclopentane,
1,1-bis (dimethoxymethyl) cyclohexane, 1,1-bis (methoxymethyl) bicyclo [2,2,1] heptane, 1,1
-Dimethoxymethylcyclopentane, 2-methyl-2-methoxymethyl-1,3-dimethoxypropane, 2-cyclohexyl-
2-ethoxymethyl-1,3-diethoxypropane, 2-cyclohexyl-2-methoxymethyl-1,3-dimethoxypropane,
2,2-diisobutyl-1,3-dimethoxycyclohexane, 2-
Isopropyl-2-isoamyl-1,3-dimethoxycyclohexane, 2-cyclohexyl-2-methoxymethyl-1,3-dimethoxycyclohexane, 2-isopropyl-2-methoxymethyl-1,3-dimethoxycyclohexane, 2-isobutyl-2 -Methoxymethyl-1,3-dimethoxycyclohexane, 2-cyclohexyl-2-ethoxymethyl-1,3-diethoxycyclohexane, 2-cyclohexyl-2-ethoxymethyl-1,3-dimethoxycyclohexane, 2-isopropyl-2- Ethoxymethyl-1,3-diethoxycyclohexane, 2-isopropyl-
2-ethoxymethyl-1,3-dimethoxycyclohexane, 2-
Isobutyl-2-ethoxymethyl-1,3-diethoxycyclohexane, 2-isobutyl-2-ethoxymethyl-1,3-dimethoxycyclohexane, tris (p-methoxyphenyl) phosphine, methylphenylbis (methoxymethyl) silane, diphenyl Bis (methoxymethyl) silane, methylcyclohexylbis (methoxymethyl) silane, di-t-
Butylbis (methoxymethyl) silane, cyclohexyl
-t-butylbis (methoxymethyl) silane, i-propyl-
Examples thereof include t-butylbis (methoxymethyl) silane.

Of these, 1,3-diethers are preferably used, particularly 2,2-diisobutyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2, 2-dicyclohexyl-1,3-dimethoxypropane and 2,2-bis (cyclohexylmethyl) -1,3-dimethoxypropane are preferably used.

These polyether compounds (d) can be used in combination of two or more kinds. Next, a method for producing the propylene polymer used in the present invention will be described. The propylene polymer used in the present invention includes, for example, the above-mentioned [Ia] solid titanium catalyst component, [II] organometallic catalyst component, [III] silicon compound (c) or polyether represented by the above formula (iii). In the presence of an olefin polymerization catalyst formed with the compound (d), the above [I
b] a prepolymerization catalyst component, [II] an organometallic catalyst component,
[III] Polymerization of propylene (main polymerization) in the presence of an olefin polymerization catalyst formed from the silicon compound (c) represented by the above formula (iii) or the polyether compound (d).
Can be obtained by performing.

When propylene is polymerized, a small amount of an olefin other than propylene or a small amount of a diene compound may be allowed to coexist in the polymerization system in addition to propylene.

Other olefins other than propylene include ethylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-
Examples thereof include olefins having 3 to 8 carbon atoms such as octene and 3-methyl-1-butene.

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-methyl-1,6-octadiene, 7-methyl-1,6-octadiene,
6-ethyl-1,6-octadiene, 6-propyl-1,6-octadiene, 6-butyl-1,6-octadiene, 6-methyl-1,6-nonadiene, 7-methyl-1,6-nonadiene, 6-ethyl-1,6-nonadiene, 7-ethyl-1,6-nonadiene, 6-methyl-1,6-decadiene, 7-methyl-1,6-decadiene, 6-methyl-1,6-undecadiene, Examples thereof include diene compounds having 4 to 20 carbon atoms such as 1,7-octadiene, 1,9-decadiene, isoprene, butadiene, ethylidene norbornene, vinyl norbornene and dicyclopentadiene.

Polymerization of propylene is usually carried out in a gas phase or a liquid phase. When the polymerization takes the reaction form of slurry polymerization or solution polymerization, the above-mentioned [Ib] is used as the reaction solvent.
Inert hydrocarbons similar to the inert hydrocarbons used to prepare the prepolymerization catalyst component can be used.

In the polymerization system, the above-mentioned [Ia] solid titanium catalyst component or [Ib] prepolymerization catalyst component is the titanium atom in the [Ia] solid titanium catalyst component or [Ib] prepolymer per 1 liter of polymerization volume. It is generally used in an amount of about 0.0001 to 50 mmol, preferably about 0.001 to 10 mmol, calculated as titanium atoms in the polymerization catalyst component. In the [II] organometallic catalyst component, the metal atom contained in the [II] organometallic catalyst component is usually about 1 to 2000 mol, preferably about 2 to 500 mol, relative to 1 mol of the titanium atom in the polymerization system. Used in such an amount that Further, the [III] silicon compound (c) or the polyether compound (d) is usually about 0.001 to 50 mol, preferably about 0.001 mol per mol of the metal atom in the [II] organometallic catalyst component.
It is used in an amount such that it is from 01 to 20 mol.

When hydrogen is used during the polymerization, a propylene polymer having a high melt flow rate is obtained, and the molecular weight of the propylene polymer obtained can be adjusted by adjusting the hydrogenation amount. Even in this case, in the present invention, the crystallinity and stereoregularity index of the obtained propylene polymer do not decrease, and the catalytic activity does not decrease.

In the present invention, the polymerization temperature of propylene is usually about -50 to 200 ° C, preferably about 20 to 1
The temperature is 00 ° C., and the pressure is usually atmospheric pressure to 100 kg / cm.
² , preferably about ² to 50 kg / cm ² . The polymerization can be carried out by any of batch method, semi-continuous method and continuous method.

When the propylene polymer is produced in this manner, the yield of the propylene polymer per unit amount of the solid catalyst component can be increased, so that the catalyst residue, especially the halogen content in the propylene polymer can be relatively increased. Can be reduced to Therefore, the operation of removing the catalyst in the propylene polymer can be omitted, and at the time of molding a molded product using the obtained propylene polymer, rusting of the mold can be easily prevented.

Further, such a propylene polymer has a very small amount of amorphous components and therefore a small amount of hydrocarbon-soluble components, and a film formed from this propylene polymer has a low surface tackiness.

The propylene polymer used in the present invention can be produced in two or more stages by changing the reaction conditions. In this case, it is carried out in a gas phase or a liquid phase using 2 to 10 polymerization vessels.

When the polymerization takes the reaction form of slurry polymerization or solution polymerization, an inert hydrocarbon similar to the inert hydrocarbon used in the preparation of the above-mentioned [Ib] prepolymerization catalyst component is used as a reaction solvent. it can.

In such a polymerization method, propylene is polymerized in at least one or more of the above-mentioned two or more polymerization vessels (hereinafter, this polymerization may be referred to as "A polymerization"). Intrinsic viscosity [η] is 3-40
dl / g, preferably 5 to 30 dl / g, particularly preferably 7
~ 25 dl / g polymer is produced.

The isotactic pentad value ([M ₅ ]) determined by NMR measurement of the boiling heptane-insoluble component of the polymer obtained by this A-polymerization was 0.960 to 0.995,
Preferably 0.970 to 0.995, more preferably 0.9.
980-0.995, more preferably 0.982-0.
It is preferably 995.

The amount of the boiling heptane-insoluble component in the polymer is 80% or more, preferably 90% or more, more preferably 94% or more, further preferably 95% or more, particularly preferably 96% or more. .

The polymer obtained by the above A polymerization is
0.1 to 55 in the propylene polymer finally obtained
%, Preferably 2-35%, particularly preferably 5-30%
It is desirable to be manufactured so that it is present in the ratio of.

When the propylene polymer is produced by using two or more polymerization vessels, propylene is polymerized in the remaining two or more polymerization vessels (hereinafter referred to as "B polymerization"). As a final product, a propylene polymer having a melt flow rate of 0.1 to 500 g / 10 min is obtained.

In the polymerization system of A polymerization and B polymerization, the solid titanium catalyst component [Ia] or [Ib] is used.
The prepolymerization catalyst component is [Ia] per liter of polymerization volume.
Converted to titanium atoms in the solid titanium catalyst component or titanium atoms in the [Ib] prepolymerization catalyst component, it is usually about 0.0001-50 mmol, preferably about 0.001-.
Used in an amount of 10 mmol. Further, the [II] organometallic catalyst component is [I] based on 1 mol of titanium atom in the polymerization system.
I] The metal atom contained in the organometallic catalyst component is usually about 1
~ 2000 mol, preferably about 2-500 mol. Further, the [III] silicon compound (c) or the polyether compound (d) is usually about 0.000 per mol of the metal atom in the [II] organometallic catalyst component.
It is used in an amount of 1 to 50 mol, preferably about 0.01 to 20 mol.

If necessary, in any polymerization vessel, [Ia] solid titanium catalyst component or [Ib] prepolymerization catalyst component, [II] organometallic catalyst component, [III] silicon compound (c) or The polyether compound (d) may be supplied. Further, the electron donor used when preparing the solid titanium catalyst component (a) and / or the organosilicon compound represented by the above formula (ci) may be supplied to any of the polymerization vessels.

In both the A-polymerization and the B-polymerization, the molecular weight of the polymer obtained by supplying or removing hydrogen can be easily adjusted. In this case, in the present invention, the crystallinity and stereoregularity index of the obtained propylene polymer do not decrease, and the catalytic activity does not decrease. The supply amount of hydrogen varies depending on various conditions, but may be such that the melt flow rate of the polymer finally obtained is in the range of 0.1 to 500 g / 10 minutes.

The value of [M ₅ ] of the boiling heptane-insoluble component is 0.975 to 0.995, preferably 0.980.
It is in the range of 0.995, more preferably 0.982 to 0.995, and the value of [M ₃ ] is 0.0020 to 0.005.
It may be set to 0, preferably 0.0023 to 0.0045, and more preferably 0.0025 to 0.0040.

The polymerization temperature of 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 ° C.
The pressure is set to 0 kg / cm ² , preferably ² to 50 kg / cm ² . The polymerization can be carried out by any of batch method, semi-continuous method and continuous method.

The propylene polymer used in the present invention is
A nucleating agent as described below may be blended. By blending the core material with the propylene polymer, the crystal grains can be made finer, the crystallization rate can be improved, and high-speed molding can be performed.

As the nucleating agent, various conventionally known nucleating agents can be used without particular limitation. Among them, as preferable nucleating agents, the following nucleating agents can be exemplified.

[0154]

[Chemical 10]

(In the formula, R ¹ is oxygen, sulfur, or a hydrocarbon group having 1 to 10 carbon atoms, R ² and R ³ are hydrogen or a hydrocarbon group having 1 to 10 carbon atoms, and R ² , R ^{3 s} may be the same or different, R ^{2 s} , R ^{3 s,} or R ^{2 s} and R ^{3 s} may be bonded to form a ring, and M is
It is a monovalent metal atom, and n is an integer of 1 to 3. ) Specifically, sodium-2,2'-methylene-bis (4,6-di-
t-Butylphenyl) phosphate, sodium-2,2'-
Ethylidene-bis (4,6-di-t-butylphenyl) phosphate, lithium-2,2'-methylene-bis- (4,6-di-t-butylphenyl) phosphate, lithium-2,2 ' -Ethylidene-bis (4,6-di-t-butylphenyl) phosphate, sodium-2,2'-ethylidene-bis (4-i-propyl-
6-t-Butylphenyl) phosphate, lithium-2,2'-
Methylene-bis (4-methyl-6-t-butylphenyl) phosphate, lithium-2,2'-methylene-bis (4-ethyl-6-
t-Butylphenyl) phosphate, calcium-bis [2,2'-thiobis (4-methyl-6-t-butylphenyl) phosphate], calcium-bis [2,2'-thiobis (4-ethyl-6) -t-butylphenyl) phosphate], calcium-bis [2,2'-thiobis- (4,6-di-t-butylphenyl) phosphate], magnesium-bis [2,2'-thiobis (4, 6-di-t-butylphenyl) phosphate],
Magnesium-bis [2,2'-thiobis- (4-t-octylphenyl) phosphate], sodium-2,2'-butylidene-bis (4,6-di-methylphenyl) phosphate, sodium-2, 2'-butylidene-bis (4,6-di-t-butylphenyl) phosphate, sodium-2,2'-t-octylmethylene-bis (4,6-di-methylphenyl) phosphate, sodium-2 , 2'-t-octylmethylene-bis (4,6-
Di-t-butylphenyl) phosphate, calcium-
Bis- (2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate), magnesium-bis [2,2'-methylene-bis (4,6-di-t-butylphenyl) ) Phosphate], barium-bis [2,2'-methylene-bis (4,6-di-t-
Butylphenyl) phosphate], sodium-2,2'-
Methylene-bis (4-methyl-6-t-butylphenyl) phosphate, sodium-2,2'-methylene-bis (4-ethyl-
6-t-Butylphenyl) phosphate, sodium (4,
4'-dimethyl-5,6'-di-t-butyl-2,2'-biphenyl) phosphate, calcium-bis [(4,4'-dimethyl-6,6'-
Di-t-butyl-2,2'-biphenyl) phosphate], sodium-2,2'-ethylidene-bis (4-m-butyl-6-t-butylphenyl) phosphate, sodium-2,2 ' -Methylene-bis (4,6-di-methylphenyl) phosphate, sodium-2,2'-methylene-bis (4,6-di-ethylphenyl) phosphate, potassium-2,2'-ethylidene-bis (4,6-Di-t-butylphenyl) phosphate, calcium-bis [2,2'-ethylidene-bis (4,6-di-t-butylphenyl) phosphate], magnesium-bis [2,2 ' -
Ethylidene-bis (4,6-di-t-butylphenyl) phosphate], barium-bis [2,2'-ethylidene-bis (4,6
-Di-t-butylphenyl) phosphate], aluminum-tris [2,2'-methylene-bis (4,6-di-t-butylfel) phosphate] and aluminum-tris [2,
2′-Ethylidene-bis (4,6-di-t-butylphenyl) phosphate] and mixtures of two or more thereof. Particularly preferred is sodium-2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate.

[0156]

[Chemical 11]

(In the formula, R ⁴ is hydrogen or a carbon number of 1 to 1.
It is a hydrocarbon group of 0, M is a metal atom with a valence of 1 to 3, and n is an integer of 1 to 3. ) Specifically, sodium-bis (4-t-butylphenyl)
Phosphate, sodium-bis (4-methylphenyl) phosphate, sodium-bis (4-ethylphenyl) phosphate, sodium-bis (4-i-propylphenyl) phosphate, sodium-bis (4-t-
Octylphenyl) phosphate, potassium-bis (4
-t-Butylphenyl) phosphate, calcium-bis (4-t-butylphenyl) phosphate, magnesium
-Bis (4-t-butylphenyl) phosphate, lithium-bis (4-t-butylphenyl) phosphate, aluminum-bis (4-t-butylphenyl) phosphate and mixtures of two or more thereof can do. Particularly, sodium-bis (4-t-butylphenyl) phosphate is preferable.

[0158]

[Chemical 12]

(In the formula, R ⁵ is hydrogen or has 1 to 1 carbon atoms.
It is a hydrocarbon group of 0. ) Specifically, 1,3,2,4-dibenzylidene sorbitol, 1,
3-benzylidene-2,4-p-methylbenzylidene sorbitol, 1,3-benzylidene-2,4-p-ethylbenzylidene sorbitol, 1,3-p-methylbenzylidene-2,4-benzylidene sorbitol, 1,3- p-Ethylbenzylidene-2,4-benzylidene sorbitol, 1,3-p-methylbenzylidene-2,4
-p-ethylbenzylidene sorbitol, 1,3-p-ethylbenzylidene-2,4-p-methylbenzylidene sorbitol,
1,3,2,4-di (p-methylbenzylidene) sorbitol, 1,
3,2,4-di (p-ethylbenzylidene) sorbitol, 1,3,
2,4-di (pn-propylbenzylidene) sorbitol, 1,
3,2,4-di (pi-propylbenzylidene) sorbitol,
1,3,2,4-di (pn-butylbenzylidene) sorbitol,
1,3,2,4-di (ps-butylbenzylidene) sorbitol,
1,3,2,4-di (pt-butylbenzylidene) sorbitol,
1,3,2,4-di (2 ', 4'-dimethylbenzylidene) sorbitol, 1,3,2,4-di (p-methoxybenzylidene) sorbitol, 1,3,2,4-di (p- Ethoxybenzylidene) sorbitol, 1,3-benzylidene-2-4-p-chlorobenzylidene sorbitol, 1,3-p-chlorobenzylidene-2,4-benzylidene sorbitol, 1,3-p-chlorobenzylidene-2,4- p-methylbenzylidene sorbitol, 1,3-p-chlorobenzylidene-2,4-p-ethylbenzylidene sorbitol, 1,3-p-
Methylbenzylidene-2,4-p-chlorobenzylidene sorbitol, 1,3-p-ethylbenzylidene-2,4-p-chlorobenzylidene sorbitol and 1,3,2,4-di (p-chlorobenzylidene) sorbitol and these And a mixture of two or more of 1,3,2,4-dibenzylidene sorbitol, 1,3,2,4-di (p-methylbenzylidene) sorbitol, 1,3,2,4-di ( p-Ethylbenzylidene) sorbitol, 1,3-p-chlorobenzylidene-2,4-p-methylbenzylidenesorbitol, 1,3,2,4-di (p-chlorobenzylidene) sorbitol, and mixtures of two or more thereof. Is preferred.

Examples of other nucleating agents include metal salts of aromatic carboxylic acids and aliphatic carboxylic acids.
Aluminum benzoate, aluminum pt-butylbenzoate, sodium adipate, sodium thiophenecarboxylate, sodium pyrrolecarboxylate and the like can be mentioned.

In the propylene polymer used in the present invention, the nucleating agent is 0.001 to 10 parts by weight, preferably 0.01 to 10 parts by weight, based on 100 parts by weight of the propylene polymer.
5 parts by weight, particularly preferably 0.1 to 3 parts by weight is desirable.

By blending the nucleating agent in the above amount in the propylene polymer, a propylene polymer having fine crystal particles and further improved crystallinity can be obtained without impairing the excellent properties originally possessed by the propylene polymer. can get.

Olefin-based elastomer (B) Olefin-based elastomer (B) used in the present invention
Is a (co) polymer of an olefin having 2 to 20 carbon atoms and has a density of 0.900 g / cm ³ or less, preferably 0.8.
It is in the range of 60 to 0.900 g / cm ³ , 230 ° C,
Melt flow rate under 2.16 kg load (MF
R) is 0.01 to 100 g / 10 minutes, preferably 0.05
It is desirable to be in the range of 50 g / 10 minutes. It is desirable that such an olefin-based elastomer has a crystallinity of less than 30% as measured by an X-ray diffraction method or is amorphous.

Examples of the olefin having 2 to 20 carbon atoms include ethylene, propylene, 1-butene, 1-pentene,
1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 3-methyl-1-butene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1- Octadecene, 1-eicosene, cyclopentene, cycloheptene, norbornene, 5-ethyl-2-norbornene, tetracyclododecene, 2-ethyl-1,4,5,8-dimethano-1,2,3,4,
Mention may be made of 4a, 5,8,8a-octahydronaphthalene and mixtures thereof. Of these, it is particularly preferable to use an olefin having 2 to 10 carbon atoms.

The olefin elastomer used in the present invention may contain a component unit other than a component unit derived from an olefin, for example, a component unit derived from a diene compound, within a range not impairing its properties. Examples of component units that are allowed to be contained in the olefin-based elastomer used in the present invention include, for example, 1,4-hexadiene, 1,6-octadiene, 2-methyl-1,5-hexadiene, and 6-methyl-1. Chain non-conjugated dienes such as 2,5-heptadiene and 7-methyl-1,6-octadiene; cyclohexadiene, dicyclopentadiene, methyltetrahydroindene, 5-vinylnorbornene, 5-ethylidene-2-norbornene, 5-methylene Cyclic non-conjugated dienes such as -2-norbornene, 5-isopropylidene-2-norbornene, 6-chloromethyl-5-isopropenyl-2-norbornene; 2,3-diisopropylidene-5-norbornene, 2-ethylidene -3-Isopropylidene-5-norbornene, 2-propenyl-2,2-norbornadiene and the like can be mentioned a component unit derived from a diene compound.

Such diene components can be used alone or in combination, and the content of the diene components is usually 10 mol% or less, preferably 0 to 5 mol%.
Is.

Specific examples of the olefinic elastomer used in the present invention include a component unit derived from ethylene of 0 to 95 mol%, preferably 30 to 92 mol%, and more preferably 50 to 90 mol%. In an amount of 1 to 100 mol%, preferably 4 to 70 mol%, more preferably 8 to 50 mol%, and the component unit derived from an olefin having 3 to 20 carbon atoms is contained in the diene component. Mention may be made of (co) polymers in which the derived component units are contained in an amount of 0 to 10 mol, preferably 0 to 5 mol%, more preferably 0 to 3 mol%.

Filler (C) The filler (C) used in the present invention includes silica, diatomaceous earth, alumina, titanium oxide, magnesium oxide, pumice powder, pumice balloon, aluminum hydroxide, magnesium hydroxide, base. Magnesium carbonate, calcium carbonate,
Dolomite, calcium sulfate, potassium titanate, barium sulfate, calcium sulfite, talc, clay, mica, asbestos, magnesium sulfate whiskers, glass fiber, glass flakes, glass beads, calcium silicate, montmorillonite, bentonite, graphite,
Examples thereof include aluminum powder, molybdenum sulfide, boron fiber, silicon carbide fiber, polyethylene fiber, polypropylene fiber, polyester fiber, and polyamide fiber.

Among these, talc, calcium carbonate,
It is preferable to use barium sulfate, magnesium hydroxide, glass fiber, potassium titanate, and magnesium sulfate whiskers.

Polypropylene Resin Composition The polypropylene resin composition according to the present invention is formed from the propylene polymer, the olefin elastomer and the filler.

In this polypropylene resin composition, the propylene polymer is 30 to 98.9% by weight, preferably 4% by weight.
5-97.5% by weight, the olefinic elastomer is 1-30% by weight, preferably 2-27.5%.
It is desirable that the filler is included in an amount of 0.1% by weight, and the filler is included in an amount of 0.1 to 30% by weight, preferably 0.5 to 27.5% by weight.

The polypropylene resin composition used in the present invention is a known olefin-based (co) polymer such as homopolypropylene other than the propylene polymer, propylene-based block copolymer, propylene-based random copolymer and the like.
The polymer may be contained in an amount of 0 to 25% by weight.

In such a polypropylene resin composition, the melt flow rate (MFR) is 0.1 to 200 g.
/ 10 minutes, preferably 0.3 to 100 g / 10 minutes.

Further, this polypropylene resin composition contains a heat resistance stabilizer, a weather resistance stabilizer, an antistatic agent, a slip agent, an antiblocking agent, a viscosity adjusting agent, an anti-coloring agent,
Antifogging agents, lubricants, dyes, pigments, natural oils, synthetic oils, waxes and the like can be added, and the mixing ratio is an appropriate amount.

The polypropylene resin composition of the present invention can be manufactured by utilizing a known method. For example, a propylene polymer, an olefin elastomer, a filler, and optionally other components are added. , An extruder, a kneader, etc., for mechanically blending.

The (A) propylene polymer used in such a polypropylene resin composition is superior in rigidity to conventional polypropylene. For this reason, the rigidity equivalent to that of the conventional resin composition using polypropylene can be obtained with a small amount of the filler compounded, so that the specific gravity of the molded body can be reduced and the weight of the molded body can be reduced. In addition, since the rigidity is higher than that of the conventional molded product made of a resin composition using polypropylene with the same amount of the filler compounded, the molded product can be made thinner and the molded product can be made lighter. Furthermore, since the crystallization speed is high, the molding cycle can be shortened and high speed molding can be performed.

Such a polypropylene resin composition is
For example, it is preferably used for an extruded sheet or an injection molded body as described below. A conventionally known injection molding machine can be used for manufacturing the injection molded body, and conventionally well known injection molding conditions can be adopted.

Extruded Sheet The extruded sheet according to the present invention is formed from the polypropylene resin composition. The melt flow rate (MFR) of this polypropylene resin composition is 0.1 to 100.
g / 10 minutes, preferably in the range of 0.3 to 85 g / 10 minutes.

In order to produce the extruded sheet according to the present invention from the polypropylene resin composition as described above, a conventionally known extruder can be used. For example, a single screw extruder, a kneading extruder, a ram extruder, a gear extruder or the like can be used to produce the molten polypropylene resin composition by extruding it from a T die or the like.

As the molding conditions, conventionally known conditions can be adopted. In the present invention, it is preferable to manufacture a molded product under the following conditions even under such molding conditions.

For example, using an extruder equipped with a T-die, the resin temperature is 190 to 300 ° C., preferably 200 to 2
85 ° C., T-die temperature 180-270 ° C., preferably 1
Examples include a method of forming a sheet at 95 to 240 ° C. In addition to using water for cooling the formed body, there is also a method of using an air knife or a cooling roll when forming a sheet.

The extruded sheet according to the present invention can be made into artificial leather, waterproof cloth, and various laminated products by feeding paper or cloth onto the roll during sheet forming. Further, it can be used as a multi-layer sheet by laminating it with various sheets such as a polyamide sheet and a polyester sheet.

The extruded sheet according to the present invention is formed from the polypropylene resin composition. Since this extruded sheet is formed from the polypropylene resin composition, as compared with an extruded sheet made of a conventional resin composition,
The specific gravity or the thickness can be reduced without lowering the rigidity of the molded body, and the weight of the molded body can be reduced. Further, by thinning the molded body, the cooling time of the molded body can be shortened and the productivity can be improved.

[0184]

EFFECTS OF THE INVENTION The polypropylene resin composition according to the present invention can reduce the weight of the molded product without lowering the rigidity, as compared with the conventional polypropylene resin compositions.

The extruded sheet according to the present invention can be made lighter than the extruded sheet made of the conventional polypropylene resin composition without lowering the rigidity.

[0186]

The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited to these examples.

The molding conditions for the extruded sheet and the methods for measuring the physical properties of the molded product are as follows. [Molding conditions of extruded sheet] Extrusion conditions: screw diameter / 65 mmφ, set temperature / 24
5 ° C Die temperature: 235 ° C Cooling condition: 3-roll system, roll temperature 80/90 /
80 ° C. [specific gravity] Measured by a water substitution method.

[Initial Flexural Modulus] The elastic modulus was measured according to ASTM D790. [Izod impact strength (with notch)] ASTM D6
It measured based on 28.

[0189]

[Production example]

[Preparation of solid titanium catalyst component] A 4.5 m ³ reactor was charged with 240 kg of anhydrous magnesium chloride, 1100 liters of decane and 990 kg of 2-ethylhexyl alcohol and heated at 130 ° C. to obtain a uniform solution. 54 kg of phthalic anhydride was added to, and the mixture was further stirred at 130 ° C. to dissolve phthalic anhydride. The homogeneous solution thus obtained was cooled to room temperature and then added dropwise to 6.7 m ^{3 of} titanium tetrachloride kept at −25 ° C. with stirring. The temperature after completion of charging was about -20 ° C.

Next, the temperature of this mixed solution is kept at 1 for 4 hours.
The temperature was raised to 10 ° C, and when it reached 110 ° C, 13 kg of diisobutyl phthalate (DIBP) was added.
The mixture was kept under stirring at the same temperature for a time. After completion of the reaction for 2 hours, a solid portion was collected by hot filtration, and the solid portion was resuspended in 7.3 m ³ of titanium tetrachloride, and then again at 110 ° C. for 2 hours.
A heating reaction was performed.

After the completion of the reaction, the solid portion was again collected by hot filtration and washed sufficiently with decane and hexane at 110 ° C. until no free titanium compound was detected in the solution.
Through the above operation, a solid titanium catalyst component [A] was obtained.

The composition of the obtained solid titanium catalyst component [A] was titanium: 2.2% by weight, chlorine: 61% by weight, magnesium: 19% by weight, DIBP: 12.7% by weight.

[Preparation of prepolymerization catalyst [B]] In a reactor equipped with a stirrer of 80 liters, under a nitrogen atmosphere, 40 liters of purified hexane, 3.0 mol of triethylaluminum, 3.0 mol of trimethylmethoxysilane and the above solid state were prepared. After adding 0.3 mol of the titanium catalyst component [A] in terms of titanium atom, 3-methyl-1-butene (3MB-
1) 1.0 kg was supplied to the reactor and prepolymerization was carried out for 2 hours.

After completion of the reaction, the inside of the reactor was replaced with nitrogen, and a washing operation consisting of removal of the supernatant and addition of purified hexane was repeated 3 times to obtain a prepolymerized catalyst [B]. This prepolymerized catalyst [B] was resuspended in purified hexane and stored.

[Polymerization] A reactor equipped with a stirrer and having an internal volume of 1,000 liters was charged with 450 liters of purified n-hexane, and at 60 ° C. in a propylene atmosphere, 500 mmol of triethylaluminum, 500 mmoles of dicyclopentyldimethoxysilane and prepolymerization. The catalyst [B] was charged in an amount of 10 mmol Ti in terms of titanium atom.

After introducing 100 liters of hydrogen and raising the temperature to 80 ° C., this was kept for 5 hours to carry out propylene polymerization. The pressure during the polymerization was kept at 6 kg / cm ² -G. After the polymerization is completed, the pressure is released, the slurry containing the produced solid is centrifuged,
White powder polymer 190 by drying with a dryer
I got kg.

The MFR of this polymer was 0.5 g / 10 min, and the stereoregularity index [M ₅ ] of the boiling heptane-insoluble component was obtained.
Value of 0.974, the stereoregularity index [M ₃ ] of the boiling heptane-insoluble component is 0.0032, the crystallinity of the boiling heptane-insoluble component is 70.5%, and 3MB-1 polymer Content was 200 ppm.

[0198]

[Comparative production example]

[Polymerization] A reactor equipped with a stirrer and having an internal volume of 1000 liters was charged with 450 liters of purified n-hexane,
Triethylaluminum 500 mmol, cyclohexylmethyldimethoxysilane 100 in propylene atmosphere
10 mmol Ti in terms of titanium atom was charged with mmol and the prepolymerization catalyst [B].

After introducing 40 liters of hydrogen and raising the temperature to 80 ° C., this was kept for 5 hours to carry out propylene polymerization. The pressure during the polymerization was kept at 6 kg / cm ² -G. After the polymerization is completed, the pressure is released, the slurry containing the produced solid is centrifuged,
White powder polymer 200 by drying with a dryer
I got kg.

The MFR of this polymer was 0.5 g / 10 min, and the stereoregularity index [M ₅ ] of the boiling heptane-insoluble component was obtained.
Value is 0.948, the stereoregularity index [M ₃ ] of the boiling heptane-insoluble component is 0.0039, the crystallinity of the boiling heptane-insoluble component is 63.5%, and 3MB-1 polymer Content was 200 ppm.

[0201]

Example 1 75 parts by weight of the propylene polymer obtained in the above production example, 15 parts by weight of olefin elastomer “Toughmer S-4020” (trade name: manufactured by Mitsui Petrochemical Industry Co., Ltd.), and talc : 10 parts by weight of a polypropylene resin composition. An extruded sheet having a thickness of 2 mm was prepared.

Each physical property was measured using a sample cut from the obtained extruded sheet. The results are shown in Table 1.

[0203]

Example 2 In Example 1, the propylene polymer was mixed with 8
An extruded sheet was prepared in the same manner as in Example 1 except that 5 parts by weight, 10 parts by weight of the olefin elastomer and 5 parts by weight of talc were used.

Each physical property was measured using a sample cut from the obtained extruded sheet. The results are shown in Table 1.

[0205]

Comparative Example 1 An extruded sheet was prepared in the same manner as in Example 1 except that the propylene polymer obtained in Comparative Production Example was used.

Each physical property was measured using a sample cut from the obtained extruded sheet. The results are shown in Table 1.

[0207]

Comparative Example 2 In Comparative Example 1, the propylene polymer was added
An extruded sheet was prepared in the same manner as in Comparative Example 1 except that 5 parts by weight, 10 parts by weight of olefin elastomer and 5 parts by weight of talc were used.

Each physical property was measured using a sample cut out from the obtained extruded sheet. The results are shown in Table 1.

[0209]

[Table 1]

─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Mamoru Oka 6-1-2 Waki, Waki-cho, Kuga-gun, Yamaguchi Mitsui Petrochemical Co., Ltd. (56) Reference JP-A-1-306448 (JP, A) JP 61-16943 (JP, A) JP 5-51498 (JP, A) JP 3-170512 (JP, A) JP 4-96911 (JP, A) JP 3 -294304 (JP, A) JP-A-3-163115 (JP, A) JP-A-4-202505 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08L 23/00- 23/36 C08K 3/00-13/08 C08J 5/18

Claims (6)

(57) [Claims] 1. A melt flow rate (MFR) at 230 ° C. under a load of 2.16 kg is 0.1 to 500 g.
The value of the stereoregularity index [M ₅ ] determined by the following formula (1) from the absorption intensity of Pmmmm and Pw in the ¹³ C-NMR spectrum of the boiling heptane-insoluble component is 0.970.
In the range of 0.995 to 0.995, Pmmrm, Pmrmr, Pmrrr, Prmr in ¹³ C-NMR spectrum of boiling heptane-insoluble component
The value of the stereoregularity index [M ₃ ] obtained by the following formula (2) from the absorption intensities of r, Prmmr, Prrrr, and Pw is in the range of 0.0020 to 0.0050, and the crystallinity of the boiling heptane-insoluble component is Propylene polymer having a content of 60% or more: 45 to 85 % by weight, and (B) an olefin elastomer composed of two or more constituent units derived from a monomer selected from olefins having 2 to 20 carbon atoms: 2 to 27. 5 % by weight and (C) filler: 5 to 27.5 % by weight, a polypropylene resin composition characterized by the following: (In the formula, [Pmmmm]: absorption intensity derived from the methyl group of the third unit in the site where five propylene units are continuously isotactically bonded, and [Pw]: absorption intensity derived from the methyl group of the propylene unit. (2) 2. The propylene polymer has the following formula (i):
Alternatively, the polypropylene resin composition according to claim 1, which contains a polymer composed of a structural unit derived from the compound represented by (ii) in an amount in the range of 10 to 10,000 ppm; 3. The polypropylene resin composition according to claim 1, wherein the filler is at least one selected from the following group a: group a: talc, calcium carbonate, barium sulfate, magnesium hydroxide, glass fiber , Potassium titanate,
Magnesium sulfate whiskers. 4. (A) Melt flow rate (MFR) at 230 ° C. and 2.16 kg load is 0.1 to 500 g.
The stereoregularity index [M _{5 in} the range of / 10 min, obtained from the absorption intensity of Pmmmm and Pw in the ¹³ C-NMR spectrum of the boiling heptane-insoluble component according to the formula (1) of claim 1. ] In the range of 0.970 to 0.995, and Pmmrm, Pmrmr, Pmrrr, Prmr in the ¹³ C-NMR spectrum of the boiling heptane-insoluble component.
billing r, Prmmr, Prrrr, from the absorption intensity of Pw
Propylene having a stereoregularity index [M ₃ ] value of 0.0020 to 0.0050 determined by the formula (2) described in Item 1 and a crystallinity of a boiling heptane-insoluble component of 60% or more. Polymer : 45 to 85 % by weight, (B) Olefin-based elastomer comprising 2 or more constituent units derived from a monomer selected from olefins having 2 to 20 carbon atoms: 2 to 27.5 % by weight, and (C ) Filler: composed of 5 to 27.5 % by weight and having a melt flow rate (MFR) of 0. Extruded sheet, characterized in that it is formed from a polypropylene resin composition in the range of 1 to 100 g / 10 min. 5. The propylene polymer described in claim 2.
The polymer composed of the constitutional unit derived from the compound represented by the formula (i) or (ii) is 10 to 10,000 pp.
extrusion sheet according to claim 4 in an amount ranging from m. 6. The extruded sheet according to claim 4, wherein the filler is at least one selected from the following group a: group a: talc, calcium carbonate, barium sulfate, magnesium hydroxide, glass fiber, Potassium titanate,
Magnesium sulfate whiskers.