JPH07278375A - Propylenic resin composition and its use - Google Patents

Abstract

PURPOSE:To obtain the subject composition comprising specific propylene polymer and a thioether stabilizer in a specified ratio, excellent in thermal stability, and useful for sheets, etc. CONSTITUTION:This composition comprises (A) 100 pts.wt. of propylene polymer, (B) 0.001-10 pts.wt. of a thioether stabilizer such as dilaurylthiodipropionate, and further preferably (C) 0.001-10 pts.wt. of one or more compounds selected from a hindered amine stabilizer and a higher fatty acid metal salt. The propylene polymer A has a MFR of 0.1-500g/10min, a stereoregularity index [M5] value of 0.970-0.995 determined by an equation I from the absorption strengths of Pmmmm, Pw in the <13>C-NMR spectrum of boiling heptane-insoluble components, a stereoregularity index [M3] value of 0.0020-0.0050 determined by an equation II from the absorption strengths of Pmmrm, Pmrmr, Pmrrr, Prmrr, Prmmr, Prrrr, Pw in the <13>C-NMR spectrum of boiling heptane-insoluble components, and a boiling heptane-insoluble component crystallinity of >=60%.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a propylene-based polymer composition and its use, and more specifically, a propylene-based polymer composition comprising a propylene polymer or a propylene-based block copolymer and a specific stabilizer. And its uses.

[0002]

BACKGROUND OF THE INVENTION Crystalline polyolefins such as crystalline polypropylene are composed of compounds of transition metals of Groups IV to VI of the periodic table and organometallic compounds of metals of groups I to III of the periodic table. It is well known that it can be obtained by polymerizing an olefin using a so-called Ziegler-Natta catalyst. A method for obtaining a highly stereoregular crystalline polyolefin with high polymerization activity using such a catalyst has been studied.

For example, JP-A-61-209207, JP-A-62-104810, JP-A-62-104811, JP-A-62-104810.
-104812, JP 62-104813, JP 1-3111
JP-A No. 06-180180, JP-A No. 1-318011, JP-A No. 2-166104, etc., formed from a titanium-containing solid catalyst component containing titanium, magnesium, halogen and an electron donor, an organoaluminum compound and an electron donor. It is disclosed that when an olefin is polymerized with the catalyst, a polyolefin having high polymerization activity and high stereoregularity can be obtained.

Further, the present applicant has already made many proposals as described below for an olefin polymerization catalyst and an olefin polymerization method for obtaining a highly stereoregular crystalline polyolefin with high polymerization activity. (For example, JP-A-50-108385, JP-A-50-126590, JP-A-50-126590
51-20297, JP-A-51-28189, JP-A-51-645
86, JP-A-51-92885, JP-A-51-136625, JP-A-52-87489, JP-A-52-100596, JP-A-52-147688, JP-A-52-104593,
JP-A-53-2580, JP-A-53-40093, JP-A-5
3-40094, JP-A-53-43094, JP-A-55-1351
02, JP-A-55-135103, JP-A-55-152710, JP-A-56-811, JP-A-56-11908, JP-A-56-18606, JP-A-58-83006, JP-A-58
-138705, JP-A-58-138706, JP-A-58-138
707, JP 58-138708, JP 58-138709
Publication, JP-A-58-138710, JP-A-58-138715, JP-A-58-138720, JP-A-58-138721,
JP-A-58-215408, JP-A-59-47210, JP-A-59-117508, JP-A-59-117509, JP-A-59
-207904, JP 59-206410, JP 59-206
408, JP 59-206407 JP, JP 61-69815 JP, JP 61-69821 JP, JP 61-69822 JP,
JP 61-69823 JP, JP 63-22806 JP, JP Sho
63-95208, JP-A-63-199702, JP-A-63-19
9703, JP 63-202603, JP 63-202604
Publication, JP-A-63-223008, JP-A-63-223009, JP-A-63-264609, JP-A-64-87610,
JP 64-156305 A, JP 2-77407 A, JP
2-84404 JP, JP2-229807 JP, JP2-22980
By the way, since crystalline polypropylene has high rigidity and generally has high heat distortion temperature, melting point, and crystallization temperature, it exhibits excellent heat resistance and has a high crystallization rate. , Shows excellent properties such as high transparency. Therefore, it is preferably used for various applications such as containers and films.

Further, since the crystalline polypropylene has higher rigidity and heat resistance when the crystallinity is increased, the crystalline polypropylene having high crystallinity can be used in applications requiring higher rigidity and heat resistance. When used for conventional applications, the product can be made thinner and the amount of filler such as talc added can be reduced, so that the weight can be reduced.

Conventionally, in such crystalline polypropylene, the crystallinity has been increased by adding a core material or the like, but the conventional crystalline polypropylene has an isotactic pentad value of 90 to 95 measured by NMR. %, And improvement in rigidity, heat resistance, etc. was limited.

In the case of molding the above-mentioned crystalline polypropylene, if the melt viscosity of the resin is low, the moldability is improved. Therefore, the method of increasing the resin temperature to lower the melt viscosity of the resin is usually adopted. . However, when the resin is heated to a high temperature in this way and molded, the resin is thermally decomposed or deteriorated, and the resulting molded product becomes colored, cracks occur, and the long-term heat stability and weather resistance deteriorate. In addition, the rigidity and heat resistance may decrease.

Further, conventional sheets and films made of crystalline polypropylene do not necessarily have sufficient moisture resistance depending on the use, and crystalline polypropylene excellent in rigidity and heat resistance as well as moisture resistance has emerged. Is desired.

As a result of studies to solve such a problem, the present inventors have found that a meso-chain having a higher stereoregularity than ever before and an extremely long meso-chain (a propylene unit in which α-methyl carbons are oriented in the same direction). Chain), a propylene-based polymer composition comprising a propylene polymer or a propylene-based block copolymer and a specific stabilizer has a thermal stability at the time of molding and a molding stability higher than those of conventional crystalline polypropylene. The inventors have found that the body is excellent in long-term heat resistance stability, weather resistance, and the like, and that it has high rigidity, heat resistance, and moisture resistance, and has completed the present invention.

[0010]

An object of the present invention is to provide a propylene-based polymer composition which is excellent in thermal stability during molding, long-term heat stability, weather resistance and the like, as well as a molded article excellent in rigidity, heat resistance and moisture resistance. It is intended to provide a product and its use.

[0011]

SUMMARY OF THE INVENTION The first propylene polymer composition according to the present invention has [A] a melt flow rate (MFR) at 230 ° C. and a load of 2.16 kg of 0.1 to 500 g / 10 minutes. The value of the stereoregularity index [M ₅ ] obtained from the absorption intensity of Pmmmm and Pw in the ¹³ C-NMR spectrum of the boiling heptane-insoluble component by the following formula (1) is 0.970.
It is in the range of up to 0.995, and the boiling heptane-insoluble component is ¹³
Pmmrm, Pmrmr, Pmrr in C-NMR spectrum
The stereoregularity index [M ₃ ] obtained from the absorption intensities of r, Prmrr, Prmmr, Prrrr, and Pw by the following formula (2) is in the range of 0.0020 to 0.0050, and crystals of boiling heptane-insoluble component Propylene polymer having a degree of conversion of 60% or more and [B] thioether-based stabilizer: the propylene polymer 1
It is characterized by comprising 0.001 to 10 parts by weight with respect to 00 parts by weight.

[0012]

[Equation 9]

(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.)

[0014]

[Equation 10]

The second propylene polymer composition according to the present invention comprises [A] the propylene polymer and [B] a thioether stabilizer: the propylene polymer 1
0.001 to 10 parts by weight with respect to 00 parts by weight, at least one compound selected from the group consisting of [C] (C-1) hindered amine stabilizers and (C-2) metal salts of higher fatty acids: It is characterized by comprising 0.001 to 10 parts by weight with respect to 100 parts by weight of the propylene polymer.

The third propylene-based polymer composition according to the present invention has a [A] melt flow rate (MFR) at 230 ° C. and a load of 2.16 kg in the range of 0.1 to 500 g / 10 minutes and boils. Pmmmm, Pw, Sαγ, Sαδ ⁺ , Tδ ⁺ δ ⁺ in ¹³ C-NMR spectrum of heptane-insoluble component
The value of the stereoregularity index [M ₅ ] determined from the absorption intensity of the formula (1A) below is in the range of 0.970 to 0.995, and Pmmrm and Pmrmr in the ¹³ C-NMR spectrum of the boiling heptane-insoluble component, Pmrrr, Prmrr, Prmmr, P
Stereoregularity index [M obtained by the following formula (2A) from the absorption intensities of rrrr, Pw, Sαγ, Sαδ ⁺ , Tδ ⁺ δ ⁺
_[3 ] value in the range of 0.0020 to 0.0050, and the crystallinity of the boiling heptane-insoluble component is 60% or more, and [B] thioether stabilizer: the propylene-based stabilizer. It is characterized by comprising 0.0001 to 10 parts by weight with respect to 100 parts by weight of the block copolymer.

[0017]

[Equation 11]

(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. [Sαγ]: a secondary carbon in the main chain, one of the two tertiary carbons closest to the secondary carbon being in the α-position,
The other is the absorption intensity derived from the secondary carbon in the γ position, and [Sαδ ⁺ ]: the secondary carbon in the main chain, of the two tertiary carbons closest to the secondary carbon. , One is at the α-position and the other is at the δ-position or the absorption intensity derived from a secondary carbon located at a position distant from the δ-position, and [Tδ ⁺ δ ⁺ ] is a tertiary carbon in the main chain. Of the two tertiary carbons closest to the tertiary carbon, one of them is at the δ position or a position away from the δ position and the other is at a position of the δ position or away from the δ position. Is the absorption intensity derived from. )

[0019]

[Equation 12]

(Where [Pmmrm], [Pmrmr], [Pmr]
rr], [Prmrr], [Prmmr], [Prrrr] and [P
w] is the same as the above formula (1A), and [Sαγ],
[Sαδ ⁺ ] and [Tδ ⁺ δ ⁺ ] are the same as in the above formula (1A). ) The fourth propylene-based polymer composition according to the present invention is [A] the propylene-based block copolymer, and [B] thioether-based stabilizer: 0 relative to 100 parts by weight of the propylene-based block copolymer. 0.001 to 10 parts by weight, and at least one compound selected from the group consisting of [C] (C-1) hindered amine stabilizer and (C-2) metal salt of higher fatty acid: the propylene block copolymer 100. It is characterized by comprising 0.001 to 10 parts by weight with respect to parts by weight.

The propylene polymer used in the first and second propylene polymer compositions according to the present invention and the propylene block used in the third and fourth propylene polymer compositions according to the present invention The polymer preferably contains a structural unit derived from a compound represented by the following formula (i) or (ii) in an amount of 10 to 10,000 ppm.

[0022]

[Chemical 3]

The extruded sheet according to the present invention is characterized by comprising the above propylene polymer composition. The unstretched film according to the present invention is characterized by comprising the above-mentioned propylene polymer composition.

The stretched film according to the present invention is characterized by comprising the above-mentioned propylene polymer composition. The filament according to the present invention is characterized by being composed of the propylene polymer composition.

The injection-molded article according to the present invention is characterized by comprising the above-mentioned propylene polymer composition. The blow-molded article according to the present invention is characterized by comprising the propylene-based polymer composition.

The press-through pack according to the present invention is characterized by using the above propylene polymer composition. A mold stamping molding according to the present invention is characterized by using the above-mentioned propylene polymer composition.

[0027]

DETAILED DESCRIPTION OF THE INVENTION The propylene polymer composition according to the present invention and its use will be described in detail below.

In the present invention, the term "polymerization" means
The term "polymer" may be used to mean not only homopolymerization but also copolymerization, and the term "polymer" may be used to include not only homopolymer but also copolymer.

First, the propylene polymer and the propylene-based block copolymer used in the present invention (hereinafter, these may be collectively referred to as "propylene-based polymer") will be specifically described.

The propylene polymer used in the present invention is
It is a homopolymer of propylene. Such a propylene polymer has a melt flow rate (MFR) at 230 ° C. and a load of 2.16 kg of 0.1 to 500 g / 10.
Min, preferably 0.2 to 300 g / 10 min.

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 block copolymer used in the present invention is a structural unit 0 to 20 derived from ethylene and / or an olefin having 4 to 10 carbon atoms.
Low crystalline copolymer part or amorphous containing a crystalline polypropylene part consisting of mol% and a constitutional unit derived from propylene and two or more constitutional units derived from an olefin having 2 to 20 carbon atoms. It is a block copolymer comprising a sex copolymer part.

This propylene-based block copolymer has a constitutional unit derived from propylene of 50 to 98 mol%,
Preferably, it is contained in an amount of 60 to 97 mol%, and the structural unit derived from ethylene and / or an olefin having 4 to 20 carbon atoms is contained in an amount of 50 to 2 mol%, preferably 40 to 3 mol%. Is desirable.

Specific examples of the olefin having 4 to 20 carbon atoms include 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-
Examples thereof include ethyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene. 4 to 2 carbon atoms
Two or more constituent units derived from 0 olefin or ethylene may be contained.

Such a propylene block copolymer has a melt flow rate (MFR) at 230 ° C. under a load of 2.16 kg of 0.1 to 500 g / 10 minutes, preferably 0.2 to 300 g / 10 minutes. Is desirable.

The propylene polymer used in the present invention is
The value of the stereoregularity index [M ₅ ] obtained from the absorption intensity of Pmmmm and Pw in the ¹³ C-NMR spectrum of the boiling heptane-insoluble component is 0.970 to 0.9.
95, preferably 0.980 to 0.995, more preferably 0.982 to 0.995.

[0036]

[Equation 13]

(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. The propylene-based block copolymer used in the present invention is
The value of the stereoregularity index [M ₅ ] determined by the following formula (1A) from the absorption intensities of Pmmmm, Pw, Sαγ, Sαδ ⁺ and Tδ ⁺ δ ⁺ in the ¹³ C-NMR spectrum of the boiling heptane insoluble component is 0.970. ~ 0.995, preferably 0.9
80-0.995, more preferably 0.982-0.99
It is in the range of 5.

[0038]

[Equation 14]

(In the formula, [Pmmmm] and [Pw] are as described above.
Same as in formula (1), [Sαγ]: secondary carbon in the main chain
One of the two tertiary carbons closest to
And the absorption strength derived from secondary carbon such that the other is in the γ position
Degree, [Sαδ⁺]: Secondary carbon in the main chain, said secondary carbon
One of the two tertiary carbons closest to
And the other is at the δ position or at a position distant from the δ position.
Absorption intensity derived from secondary carbon, [Tδ⁺δ⁺]: Tertiary carbon in the main chain, said tertiary carbon
Of the two tertiary carbons closest to the element, one is in the δ position or
Is distant from the δ position, and the other is δ position or δ position.
Absorption strength derived from tertiary carbon that is located far away
Is. ) Next, the propylene polymer and propylene used in the present invention
Stereochemistry of boiling heptane-insoluble components of ren block copolymers.
Stereoregularity index [M used to evaluate regularity _Five]
Will be described in detail.

When the boiling heptane insoluble component is a homopolymer of propylene, the insoluble component can be represented by, for example, the following formula (A).

[0041]

[Chemical 4]

¹³ C derived from the methyl group (eg, Me ³ , Me ⁴ ) at the third 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, boiling heptane-insoluble represented by the above formula (A) The stereoregularity of the components is Pmmmm and P
The ratio with w, that is, the value [M
₅ ] can be evaluated.

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 by the following formula (1) from the absorption intensity of

[0044]

[Equation 15]

When the boiling heptane-insoluble component contains a small amount of a structural unit derived from an olefin other than the propylene unit, for example, an ethylene unit, the insoluble component is represented by the following formula (B-1) or (B-2). ) Can be expressed as. The formula (B-1) shows the case where one ethylene unit is contained in the propylene unit chain, and the formula (B-2)
Shows the case where the propylene unit chain contains an ethylene unit chain composed of two or more ethylene units.

[0046]

[Chemical 5]

In such a case, a methyl group other than the methyl group at the third unit in the chain of 5 propylene units (the above formula (B-
In 1) and (B-2), the absorption intensity derived from Me ⁴ , Me ⁵ , Me ⁶ and Me ⁷ ) should be excluded in principle when evaluating stereoregularity. However, the absorption of these methyl groups is observed to overlap with the absorption of other methyl groups, so it is difficult to quantify.

Therefore, the boiling heptane-insoluble component is represented by the formula (B-
In the case as shown in 1), ¹³ C derived from the secondary carbon in the ethylene unit and the secondary carbon (C ¹ ) bonded to the tertiary carbon (C ^a ) in the propylene unit. -NMR
Absorption intensity (Sαγ) in the spectrum, and absorption intensity (Sαγ derived from the secondary carbon (C ³ ) in the propylene unit, which is bonded to the secondary carbon (C ² ) in the ethylene unit. ) To exclude this.

That is, a secondary carbon in the main chain,
Secondary carbon (C¹Or C³) The closest two tertiary coals
One of the primes (C^aOr C^b) Is in alpha position, while
(C ^bOr C^a) Is derived from secondary carbon such as γ position
The absorption intensity (Sαγ) doubled is subtracted from Pw
As a result, the 3rd unit of the propylene unit 5 chain
Methyl groups other than^Four, Me^Five, Me⁶And Me⁷) To
Exclude the derived absorption intensity.

Further, the boiling heptane-insoluble component is represented by the formula (B-2).
In the case where the secondary carbon is a secondary carbon in an ethylene unit chain composed of two or more ethylene units and is bonded to a tertiary carbon (C ^d ) in the propylene unit (C ⁴ ) -Derived ¹³ C-NMR spectrum absorption intensity (Sαδ ⁺ ), and a secondary carbon in the propylene unit, which is bonded to a secondary carbon (C ⁵ ) in a chain of two or more ethylene units. This is excluded by using the absorption intensity (Sαδ ⁺ ) derived from the primary carbon (C ⁶ ).

That is, a secondary carbon in the main chain,
Secondary carbon (C^FourOr C⁶) The closest two tertiary coals
One of the primes (C^dOr C^e) Is in alpha position, while
(C ^eOr C^d) Is at δ position or at a position distant from δ position
Absorption intensity derived from secondary carbon (Sαδ⁺)
By subtracting the doubled value from Pw,
Methyl groups other than the third methyl group in the 5-position chain (M
e^Four, Me^Five, Me⁶And Me⁷Excludes absorption intensity derived from
To do.

Therefore, the stereoregularity of the boiling heptane-insoluble component represented by the above formulas (B-1) and (B-2) can be evaluated by the value obtained from the following formula (1B).

[0053]

[Equation 16]

Further, when the boiling heptane-insoluble component contains a small amount of ethylene unit and one ethylene unit chain is contained in the ethylene unit chain, the insoluble component is represented by the following formula (C). Can be represented.

[0055]

[Chemical 6]

In such a case, if the above formula (1B) is applied as it is, five methyl groups to be excluded (Me ⁴ , M ⁴ ) are excluded.
e ⁵ , Me ⁶ , Me ⁷ and Me ⁸ ) but S
Since there are four methyl groups corresponding to αγ or Sαδ ⁺ , three more methyl groups other than the central methyl group in the propylene unit 5 chain will be excluded, and further correction is required.

Therefore, the pro units contained in the ethylene unit chain
Derived from the tertiary carbon in the pyrene unit ¹³C-NMR spectrum
Correct this using the absorption intensity in torr. Sanawa
The tertiary carbon in the main chain, which is the closest to the tertiary carbon
Two tertiary carbons (C^f, C^g), One (C^f)But
δ position or a position away from δ position, while the other (C^g)But
Tertiary carbon at or at a position delta
(C⁷) -Derived absorption intensity (Tδ⁺δ⁺) Is also tripled
This is corrected by adding to Pw.

Thus, the stereoregularity of the boiling heptane-insoluble component represented by the above formula (C) can be evaluated by the value of the stereoregularity index [M ₅ ] obtained by the following formula (1A).

Therefore, the stereoregularity of the boiling heptane-insoluble component of the propylene block copolymer used in the present invention can be evaluated by the value of the stereoregularity index [M ₅ ] obtained by the following formula (1A). it can.

[0060]

[Equation 17]

The equations (1) and (1B) are (1
It is not different from the formula (A), and is regarded as a special case of the formula (1A). Further, the above correction may not be necessary depending on the type of constitutional unit other than the propylene unit contained in the boiling heptane-insoluble component.

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.

[0063]

[Equation 18]

The propylene block copolymer used in the present invention has a stereoregularity index [M ₅ ] of 0.970 calculated from the above formula (1A) of the boiling heptane-insoluble component.
In the range of 0.195 to 0.995, and Pmmrm and Pmrm in the ¹³ C-NMR spectrum of the boiling heptane-insoluble component.
r, Pmrrr, Prmrr, Prmmr, Prrrr, Pw, Sαγ,
The value of the stereoregularity index [M ₃ ] calculated from the absorption intensities of Sαδ ⁺ and Tδ ⁺ δ ^{+ by} the following formula (2A) is 0.0020.
~ 0.0050, preferably 0.0023 to 0.004
5, more preferably in the range of 0.0025 to 0.0040.

[0065]

[Formula 19]

(In the formula, [Pmmrm], [Pmrmr], [Pmr]
rr], [Prmrr], [Prmmr], and [Prrrr] are the same as in the above equation (2), and [Pw], [Sαγ], and [S
[alpha] [delta] ⁺ ] and [T [delta] ⁺ [delta] ⁺ ] are the same as in the above formula (1A). ) In the above formulas (2) and (2A), [Pmmrm], [Pmr
mr], [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
The absorption intensity derived from the methyl group of the third unit derived from 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”) is shown.
That is, the value of the above formula stereoregularity index determined by (2) [M _3] represents the ratio of M ₃ structure in the propylene unit in the chain, stereoregularity index determined by the above formula (2A) [M _3] The value of is M ₃ in the propylene unit chain containing a small amount of monomer units other than propylene units.
The percentage of structure is shown.

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 ~ 0.0050, it has an extremely long meso chain (a propylene unit chain in which α-methyl carbons are oriented in the same direction).

The propylene block copolymer used in the present invention has a stereoregularity index [M ₅ ] of 0.970, which is obtained by the above formula (1A) of the boiling heptane-insoluble component.
The stereoregularity index [M ₃ ] of the boiling heptane-insoluble component determined by the above formula (2A) is in the range of
Since the value of is in the range of 0.0020 to 0.0050, the crystalline polypropylene part of the propylene block copolymer has an extremely long meso chain.

In general, polypropylene has a longer meso chain when the value of the stereoregularity index [M ₃ ] is smaller. 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.

[0070] 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)

[0071]

[Chemical 7]

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. Na
Oh, stereoregularity index of boiling heptane insoluble component [M₃]of
The value is out of the range from 0.0020 to 0.0050
If so, the above characteristics may be deteriorated.

The propylene block copolymer used in the present invention contains a highly crystalline polypropylene part having an M ₃ structure as shown in the above structure (a) and has a stereoregularity index [M of the insoluble component of boiling heptane]. ₅ ] value is 0.970
It is in the range of 0.0095, and the value of the stereoregularity index [M ₃ ] of the boiling heptane-insoluble component is in the range of 0.0020 to 0.0050. The propylene block copolymer used in the present invention is excellent in balance of rigidity, heat resistance and impact resistance as compared with the conventional high crystalline polypropylene, though the reason is not clear. The value of the stereoregularity index [M ₃ ] of the boiling heptane-insoluble component is 0.0020 to 0.00.
If it deviates from the range of 0050, the above characteristics may be deteriorated.

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 according to the present invention is usually 80% by weight or more, preferably 9% by weight.
0 wt% or more, more preferably 94 wt% or more, further preferably 95 wt% or more, particularly preferably 96 wt%
That is all.

The amount of the boiling heptane-insoluble component of the propylene-based block copolymer according to the present invention depends largely on the amount of the decane-soluble component at 23 ° C. and cannot be specified, but at 23 ° C.
The amount of the boiling heptane-insoluble component in the decane-insoluble part is usually 80
% Or more, preferably 85% or more, more preferably 90% or more, further preferably 93% or more,
It is particularly preferably 94% by weight or more.

The amount of the above-mentioned insoluble component in boiling heptane is
The 23 ° C. decane-soluble component is calculated assuming that it is also soluble in boiling heptane. In the present invention, the NMR measurement of the boiling heptane-insoluble component is carried out, for example, as follows. That is, 0.35 g of the insoluble component is heated and dissolved in 2.0 ml of hexachlorobutadiene. 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, ¹³ C-NMR measurement is performed at 120 ° C. using a GX-500 type NMR measuring device manufactured by JEOL Ltd. The number of times of integration is 10,000 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 according to the present invention is 60% or more, preferably 6
It is desirable to be 5% or more, and more preferably 70% or more.

The crystallinity of the boiling heptane-insoluble component of the propylene block copolymer according to the present invention is preferably 60% or more, preferably 65% or more, more preferably 68% 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 and the propylene-based block copolymer used in the present invention are 10 to 10000 ppm, preferably a polymer comprising a constitutional unit derived from a compound represented by the following formula (i) or (ii). Is 10
It is desirable that the content is in the range of 0 to 5000 ppm.

[0083]

[Chemical 8]

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, 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 and having 20 or less carbon atoms, or a diene compound having 4 to 20 carbon atoms.

The propylene-based block copolymer used in the present invention is 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, Composition derived from diene compounds having 4 to 20 carbon atoms such as 6-methyl-1,6-undecadiene, 1,7-octadiene, 1,9-decadiene, isoprene, butadiene, ethylidene norbornene, vinyl norbornene and dicyclopentadiene The unit may be contained in an amount of 5 mol% or less.

The propylene polymer used in the present invention preferably has a density in the range of 0.900 to 0.936 g / cm ³ , preferably 0.910 to 0.9936 g / cm ³ . The propylene-based block copolymer used in the present invention has a density of 0.900 to 0.936 g / cm ³ ,
It is preferably in the range of 0.910 to 0.936 g / cm ³ .

In the propylene polymer used in the present invention, the amount of the decane-soluble component at 23 ° C. is 3.0% or less, preferably 2.5% or less, more preferably 2.0% or less, particularly preferably 1. It is preferably 5% or less. The propylene block copolymer used in the present invention has a temperature of 23 ° C.
The amount of decane-soluble component is 50% or less, preferably 30% or less, more preferably 20% or less, particularly preferably 15%.
The following is desirable.

The amount of decane-soluble component at 23 ° C. of the propylene polymer and the propylene-based block copolymer is measured as follows. That is, in a 1-liter flask equipped with a stirrer, 3 g of the polymer sample and 2,6-di-tert-butyl were added.
-4-Methylphenol (20 mg) and n-decane (500 ml) were added, and the mixture was heated and dissolved 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,
N-decane suspension containing dissolved polymer and G-4 (or G-
Filter and separate with the glass filter of 2). The obtained solution is dried at 10 mmHg and 150 ° C. until a constant weight is obtained,
The weight of the polymer is measured to obtain the amount of the soluble component of the polymer in the mixed solvent, which is calculated as a percentage of 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 of the propylene block copolymer used in the present invention for the 23 ° C. decane-insoluble component at 135 ° C. is 500 seconds or less, preferably 100 seconds or less, more preferably 80 seconds or less, and particularly preferably 70 seconds. The following is desirable.

The boiling heptane-insoluble component of the propylene polymer and the propylene block copolymer was 135 ° C.
The half-crystallization time at is measured as follows. That is, using a differential heat meter manufactured by Perkin Elmer, 135
The relationship between the amount of heat generated by crystallization of the boiling heptane-insoluble component of the polymer at 0 ° C. and the time is measured, and the time required for the amount of heat generated to reach 50% of the total amount of heat generated is taken 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. In the propylene block copolymer used in the present invention, it is desirable that the difference between the melting point of the boiling heptane-insoluble component and the crystallization temperature is 45 ° C or lower, preferably 43 ° C or lower, and more preferably 40 ° C or lower.

One of the propylene polymers used in the present invention
The intrinsic viscosity [η] measured in decalin at 35 ° C. is usually 30 to 0.001 dl / g, preferably 10 to 0.01 dl.
/ G, particularly preferably in the range of 5 to 0.05 dl / g. The propylene block copolymer used in the present invention has an intrinsic viscosity [η] measured in decalin at 135 ° C. of usually 30 to 0.001 dl / g, preferably 10 to 0.01 dl / g, and particularly preferably. 8 to 0.05 dl
It is preferably in the range of / 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 formula (i) or (ii) in the presence of

[0097]

[Chemical 9]

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

The propylene block copolymer used in the present invention includes, for example, a solid titanium catalyst component (a) containing [Ia] magnesium, titanium, halogen and an electron donor as essential components, and [II] organic compound. A metal catalyst component (b) and [III] 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. In the presence of an olefin polymerization catalyst, preferably [Ib]
A solid titanium catalyst component (a) containing magnesium, titanium, halogen and an electron donor as essential components;
A prepolymerization catalyst component obtained by prepolymerizing at least one olefin selected from the olefins represented by the above formulas (i) or (ii) in the presence of the organometallic catalyst component (b), [II] It is formed from an organometallic catalyst component (b) and [III] 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. In the first polymerization step, propylene is homopolymerized in the presence of an olefin polymerization catalyst, or propylene is copolymerized with ethylene and / or an olefin having 4 to 10 carbon atoms to obtain a crystalline polymer. A polymer (crystalline polypropylene part) is produced, and ethylene and carbon atoms are 3 in the second polymerization step.
Copolymer of two or more kinds selected from olefins of 20 to 20 to give a low crystalline copolymer (low crystalline copolymer part)
Alternatively, it can be obtained by producing an amorphous copolymer (amorphous copolymer part).

1 and 2 show the steps for preparing the olefin polymerization catalyst used for producing the propylene polymer and the propylene block copolymer used in the present invention. Each component forming the olefin polymerization catalyst used in the production of the propylene polymer and the propylene block copolymer used in the present invention will be specifically described below.

The solid titanium catalyst component (a) can be prepared by bringing the following magnesium compound, titanium compound and electron donor into contact with each other. 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 (On
_{-C 4 H 9) 3 Cl,} Ti (OC 2 H 5) 3 monohalogenated trialkoxy titanium such as _{Br; Ti (OCH 3) 4} , Ti (OC 2 H
_{5) 4, Ti (On-} C 4 H 9) 4, Ti (O-iso-C 4 H 9) 4, Ti (O
Examples thereof include tetraalkoxy titanium such as -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 magnesium compound having a reducing property and a magnesium compound having no reducing property.

Examples of the reducing magnesium compound include a magnesium compound 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 magnesium metal using the above method during catalyst preparation.

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 magnesium compound having reducibility and the magnesium compound having no reducibility, the magnesium compound may be a complex compound, a complex compound or another compound of the above-mentioned magnesium compound with 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.

Further, as the electron donor, a silicon compound (c) represented by the general formula (iii) described below can also 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-mentioned 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 contact-reacted with an organometallic compound and then a titanium compound is contact-reacted. (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 in which an organomagnesium compound in a liquid state is subjected to a catalytic reaction with a halogen-containing titanium compound. 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 a titanium compound with the reaction product obtained in (12). (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 substance 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 pulverizing a magnesium compound and then contacting and reacting with the 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 liquid magnesium compound 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.

(B-2) Group I metal represented by the general formula M ¹ AlR ¹ ₄ (wherein M ¹ is Li, Na and K, and R ¹ is the same as above) and aluminum. 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 trialkyl aluminum such as triethyl aluminum and tributyl aluminum; trialkenyl aluminum such as triisoprenyl aluminum; diethyl aluminum ethoxide and dibutyl aluminum 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; Partially alkoxylated and halogenated alkyl aluminums such as ethyl aluminum ethoxy chloride, butyl aluminum butoxycyclolide, ethyl aluminum ethoxy bromide 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 AlO
Al (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 ₂ H ₅ ) _{2 and the} like, as well as aluminoxanes such as methylaluminoxane.

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, allylnorbornane, styrene, dimethylstyrenes, vinylnaphthalene, allyltoluenes, allylbenzene, vinylcyclohexane, vinylcyclopentane, vinylcycloheptane, allyltrialkylsilanes, etc. And an olefin having Among these, 3-methyl-1-butene, 3-methyl-
1-Pentene, 3-ethyl-1-hexene, vinylcyclohexane, allyltrimethylsilane, dimethylstyrene and the like are preferable, 3-methyl-1-butene, vinylcyclohexyne and allyltrimethylsilane are more preferable, and 3-methyl
-1-Butene is particularly preferred.

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 used in the preparation of 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 30 mol, more preferably 1 to 10 mol, per 1 mol of titanium atom in the solid titanium catalyst component (a). To be

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. Specific 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 resulting prepolymer 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.

The prepolymerization is desirably 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 amount of prepolymerization 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 in the production of the propylene polymer and the propylene block copolymer used in the present invention includes the solid titanium catalyst component [Ia] or the prepolymerization catalyst component [Ib] and the organometallic catalyst [II]. It is formed from the component and the [III] silicon compound (c) or the compound (d) having two or more ether bonds existing through a plurality of atoms.

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).

[0155] 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 is a 2-methylcyclopentenyl group, a 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) is as follows: cyclopentyltrimethoxysilane, 2-methylcyclopentyltrimethoxysilane, 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).

[0162]

[Chemical 10]

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 dimethoxysilanes represented by the formula (iv), are preferable. 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 through 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.

[0169]

[Chemical 11]

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

Two or more kinds of these polyether compounds (d) can be used in combination. Next, a method for producing the propylene polymer and the propylene block copolymer used in the present invention will be described.

The propylene polymer used in the present invention is
For example, the solid titanium catalyst component [Ia] and [II]
In the presence of an olefin polymerization catalyst formed from an organometallic catalyst component and [III] the silicon compound (c) or the polyether compound (d) represented by the above formula (iii), preferably the above [Ib] prepolymerization Propylene in the presence of an olefin polymerization catalyst formed from a catalyst component, [II] an organometallic catalyst component, and [III] a silicon compound (c) or a polyether compound (d) represented by the above formula (iii). It can be obtained by carrying out the polymerization (main polymerization) of.

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

As other olefins other than propylene, 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 the 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.

At the time of polymerization, the electron donor used in preparing the solid titanium catalyst component (a) and / or the organosilicon compound represented by the above formula (ci) can be used in combination.

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 a 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 is 0.960 to 0995, preferably 0.970 to 0. .995, more preferably 0.9
80-0.995, and more preferably 0.982-0.9.
95 is desirable.

The amount of the boiling heptane-insoluble component in the polymer is 80% or more, preferably 90% or more, more preferably 94% by weight or more, further preferably 95% by weight or more,
Particularly preferably, it is desirable that it is 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 a propylene polymer is produced by using two or more polymerization vessels, propylene is polymerized in the remaining polymerization vessels of the 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 the A polymerization and the B polymerization, the solid titanium catalyst component [Ia] or [Ib]
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 B polymerization is usually about -50 to 200 ° C, preferably 20 to 100 ° C, and the pressure is usually atmospheric 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 block copolymer used in the present invention includes, for example, the above-mentioned [Ia] solid titanium catalyst component, [II] organometallic catalyst component, and [III] the above formula (ii).
In the presence of an olefin polymerization catalyst formed from the silicon compound (c) or the polyether compound (d) represented by i), preferably [Ib] the prepolymerization catalyst component,
First polymerization step in the presence of an olefin polymerization catalyst formed from [II] an organometallic catalyst component and [III] a silicon compound (c) or a polyether compound (d) represented by the above formula (iii). In the above, homopolymerization of propylene or copolymerization of propylene with ethylene and / or olefin having 4 to 10 carbon atoms is carried out to produce a crystalline polymer (crystalline polypropylene part), and
In the polymerization step, copolymerization of two or more kinds of monomers selected from ethylene and an olefin having 3 to 20 carbon atoms is carried out to obtain a low crystalline copolymer (low crystalline copolymer part) or an amorphous copolymer. It can be obtained by producing a polymer (amorphous copolymer part).

In producing the propylene block copolymer, first, in the first polymerization step, propylene homopolymerization is carried out, or propylene is copolymerized with ethylene and / or an olefin having 4 to 20 carbon atoms. I do.

Examples of the olefin having 4 to 20 carbon atoms include 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-methyl-2-norbornene, tetracyclododecene, 2-methyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a -
Examples include octahydronaphthalene.

The first polymerization step is usually carried out in a gas phase or a liquid phase. When the polymerization takes a reaction form of slurry polymerization or solution polymerization, an inert hydrocarbon similar to the inert hydrocarbon used for preparing the above-mentioned [Ib] prepolymerization catalyst component can be used as a reaction solvent.

In the first polymerization system, the above [Ia]
The solid titanium catalyst component or the [Ib] prepolymerization catalyst component is usually converted into titanium atom in the [Ia] solid titanium catalyst component or titanium atom in the [Ib] prepolymerization catalyst component per liter of the polymerization volume, Is about 0.0001 to 50
It is used in an amount of mmol, preferably about 0.001 to 10 mmol. 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 Furthermore, the [III] silicon compound (c) or the polyether compound (d) is usually about 0.001 to 50 mol, preferably about 0.01 to 20 mol, per 1 mol of the metal atom in the [II] organometallic catalyst component. It is used in a molar amount.

If hydrogen is used in the first polymerization, the molecular weight of the resulting polymer can be adjusted. In the first polymerization step, the polymerization temperature is usually about -50 to 200.
° C., preferably about 20 to 100 ° C., the pressure is usually normal pressure to 100 kg / cm ^2, preferably about 2 to 50
It is set to kg / cm ² . Polymerization is batch type, semi-continuous type,
It can be carried out by any of the continuous methods. It is also possible to use two or more polymerization vessels.

In the polymer obtained in the first polymerization step as described above, the content of the constituent units derived from ethylene and / or an olefin having 4 to 10 carbon atoms is 0 to 20 mol%, preferably It is desirable that the content is 0 to 15 mol%, particularly preferably 0 to 10 mol%.

The intrinsic viscosity [η] of the polymer obtained in the first polymerization step measured in decalin at 135 ° C.
40-0.001 dl / g, preferably 30-0.01 dl /
g, particularly preferably 20 to 0.05 dl / g is desirable.

In the first polymerization step, a small amount of a diene compound is added to the polymerization system in addition to propylene and the above-mentioned ethylene and / or olefin having 4 to 20 carbon atoms to derive from the diene compound. The structural unit may be introduced into the polymer obtained in the first polymerization step.

Examples of the diene compound include the same diene compounds as those used in the above-mentioned propylene polymer polymerization. Of these, 1,4-hexadiene, 1,5-hexadiene and 4-methyl- It is preferable to use diene compounds having 5 to 12 carbon atoms such as 1,4-hexadiene, 5-methyl-1,4-hexadiene, 7-methyl-1,6-octadiene, ethylidene norbornene and vinyl norbornene.

In the production of the propylene-based block copolymer used in the present invention, for example, in the presence of the polymer obtained in the first polymerization step, ethylene and the number of carbon atoms are increased after the first polymerization step. There is a method of copolymerizing two or more kinds of monomers selected from 2 to 20 olefins.

Examples of the olefin having 2 to 20 carbon atoms include ethylene, propylene, and the olefin having 4 to 20 carbon atoms used in the first polymerization step. Among them, the olefin having 3 to 12 carbon atoms is used. It is preferable.

The second polymerization step is usually carried out in the gas phase or the liquid phase. When the polymerization takes a reaction form of slurry polymerization or solution polymerization, an inert hydrocarbon similar to the inert hydrocarbon used for preparing the above-mentioned [Ib] prepolymerization catalyst component can be used as a reaction solvent. It is also possible to use two or more polymerization vessels.

In the second polymerization system, [Ia] solid titanium catalyst component or [Ib] prepolymerization catalyst component, [II] organometallic catalyst component, [III] silicon compound (c) or A polyether compound (d) can be added, and [Ia] solid titanium catalyst component or [Ia]
b] The prepolymerization catalyst component is added in an amount of [I
a] Titanium atom in the solid titanium catalyst component or [I
b] Converted to titanium atoms in the prepolymerization catalyst component, usually about 0.0001 to 50 mmol, preferably about 0.00
Amounts of 1-10 mmol can be added. Also,
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 1 mol of the titanium atom added to the polymerization system.
An amount can be added such that the amount is 500 mol. Further, the [III] silicon compound (c) or the polyether compound (d) is usually about 0.001 to 50 mol, preferably about 0.01 per 1 mol of the metal atom in the added [II] organometallic catalyst component. It can be used in an amount such that it is up to 20 mol.

When hydrogen is used in the second polymerization system, the molecular weight of the low crystalline copolymer portion or the amorphous copolymer portion can be adjusted by adjusting the hydrogenation amount. In the second polymerization step, the polymerization temperature is usually about −50 to 200 ° C., preferably about 20 to 100 ° C., and the pressure is usually atmospheric pressure to 1
The pressure is set to 00 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.

Also in the second polymerization step, a small amount of the diene compound may be introduced into the reaction system as in the above-mentioned first polymerization step. Further, in both the first and second polymerization steps, the electron donor used in preparing the solid titanium catalyst component (a) and / or the above formula (c-
An organosilicon compound represented by i) may be supplied.

When the propylene-based block copolymer is produced in this way, the yield of the propylene-based block copolymer per unit amount of the solid catalyst component can be increased, so that the propylene-based block copolymer The content of catalyst residues, especially halogen, can be reduced relatively. Therefore, the operation of removing the catalyst in the propylene-based block copolymer can be omitted, and it becomes easy to prevent rusting of the mold when molding a molded product using the obtained propylene-based block copolymer. .

In the propylene block copolymer obtained by the above production method, the content of propylene units is 50 to 98 mol%, preferably 60 to 97.
Mol%.

The amount of the decane-soluble component of the propylene-based block copolymer is 50% or less, and the decane-soluble component mainly contains the copolymer obtained in the second polymerization step. There is. The composition of this copolymer cannot be unconditionally specified because it depends on the type of olefin used, but when copolymerizing ethylene and propylene, for example, the propylene unit is 20 to 80 mol%, preferably 25 to 75 mol%. , Particularly preferably 30 to 70 mol%. The intrinsic viscosity of the decane-soluble component measured in decalin at 135 ° C. is 0.5 to 20 dl / g, preferably 1 to 15 dl / g, more preferably 2 to 12 dl / g,
Particularly preferably, it is 2.5 to 10 dl / g. In addition, the MFR of the propylene block copolymer is
0.1-500 g / 10 minutes, preferably 0.2-300 g
/ 10 minutes, and can be freely adjusted depending on conditions such as the amount of hydrogen added in the first and second polymerizations and the polymerization temperature.

The propylene polymer and the propylene block copolymer used in the present invention may be blended with a nucleating agent as described below. By blending a propylene polymer and a propylene-based block copolymer with a core material, 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 are used without particular limitation. Among them, as preferable nucleating agents, the following nucleating agents can be exemplified.

[0218]

[Chemical 12]

(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, 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.

[0220]

[Chemical 13]

(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.

[0222]

[Chemical 14]

(In the formula, R ⁵ is hydrogen or a carbon number of 1 to 1.
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 the other nucleating agent 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.

Further, an inorganic compound such as talc described later can also be exemplified. In the propylene polymer used in the present invention, the nucleating agent is the propylene polymer 1
It is desirable that it is blended in a ratio of 0.001 to 10 parts by weight, preferably 0.01 to 5 parts by weight, and particularly preferably 0.1 to 3 parts by weight with respect to 00 parts by weight. By blending the nucleating agent in the above amount in the propylene polymer, without impairing the excellent properties originally possessed by the propylene polymer,
A propylene polymer having fine crystal particles and improved crystallinity can be obtained.

In the propylene-based block copolymer used in the present invention, the nucleating agent is 0.001-1 with respect to 100 parts by weight of the propylene-based block copolymer.
It is desirable that the amount is 0 parts by weight, preferably 0.01 to 5 parts by weight, and particularly preferably 0.1 to 3 parts by weight. By blending the nucleating agent in the above amount in the propylene-based block copolymer, the propylene-based block copolymer has fine crystal particles and improved crystallinity without impairing the excellent properties originally possessed by the propylene-based block copolymer. A block copolymer is obtained.

Next, the propylene polymer composition according to the present invention will be described. The first propylene polymer composition according to the present invention comprises the above-mentioned [A] propylene polymer and [B] thioether stabilizer: the above-mentioned propylene polymer 1
0.001 to 10 parts by weight, preferably 0.003 to 5 parts by weight, more preferably 0.005 parts by weight based on 00 parts by weight.
.About.3 parts by weight.

The second propylene polymer composition according to the present invention comprises the above [A] propylene polymer and [B] thioether stabilizer: the above propylene polymer 1
0.001 to 10 parts by weight, preferably 0.003 to 5 parts by weight, more preferably 0.005 parts by weight based on 00 parts by weight.
To 3 parts by weight, and at least one compound selected from the group consisting of [C] (C-1) hindered amine stabilizer and (C-2) metal salt of higher fatty acid: 100 parts by weight of the propylene polymer 0.001 to 10 parts by weight, preferably 0.003 to 5 parts by weight
Parts by weight, more preferably 0.005 to 3 parts by weight.

A third propylene polymer composition according to the present invention comprises the above [A] propylene block copolymer and [B] thioether stabilizer: 100 parts by weight of the above propylene block copolymer. The amount is 0.001 to 10 parts by weight, preferably 0.003 to 5 parts by weight, and more preferably 0.005 to 3 parts by weight.

The fourth propylene polymer composition according to the present invention comprises the above [A] propylene block copolymer and [B] thioether stabilizer: 100 parts by weight of the above propylene block copolymer. 0.001 to 10 parts by weight, preferably 0.003 to 5 parts by weight, more preferably 0.005 to 3 parts by weight, based on parts by weight, and [C] (C-1) hindered amine-based stabilizer as described later. Agent, (C-2) at least one compound selected from the group consisting of metal salts of higher fatty acids: 0.001 to 10 parts by weight based on 100 parts by weight of a propylene block copolymer,
Preferably 0.003 to 5 parts by weight, more preferably 0.0
It is formed from 05 to 3 parts by weight.

The content of the thioether stabilizer [B] is
When the amount is within the above range with respect to 100 parts by weight of the propylene polymer or the propylene-based block copolymer [A], the effect of improving the heat resistance is high, and the cost of the stabilizer can be suppressed at a low price. The properties of the united material, such as tensile strength, are not reduced.

Further, the content of at least one compound [C] selected from (C-1) and (C-2) is such that the propylene polymer or propylene block copolymer [A] 10
Within the above range relative to 0 parts by weight, the effect of improving the heat resistance is high, the cost of the stabilizer is kept low, and the properties of the propylene polymer, such as tensile strength, are reduced. Nor.

Furthermore, when the content of the metal salt (C-2) of higher fatty acid is within the above range with respect to 100 parts by weight of the propylene polymer or the propylene block copolymer [A], Residual chlorine derived from the catalyst in the polymer can be sufficiently absorbed, and the characteristics of the propylene polymer are not deteriorated.

In the propylene-based polymer composition of the present invention, [B] thioether-based stabilizer: 0.005 to 2 parts by weight based on 100 parts by weight of the propylene polymer or propylene-based block copolymer [A]. (C-1) hindered amine stabilizer; 0.005 to 2 parts by weight (C-2) metal salt of higher fatty acid;

The [B] thioether stabilizer, (C-1) hindered amine stabilizer and (C-2) higher fatty acid metal salt used in the present invention will be sequentially described below. [B] Thioether-based Stabilizer As the thioether-based stabilizer, conventionally known ones are used without particular limitation, and specifically, the following compounds are used.

Dialkylthiodipropionates such as dilauryl-, dimyristyl-, distearyl- and polyhydric alcohols of alkylthiopropionic acids such as butyl-, octyl-, lauryl-, stearyl- (eg glycerin, trimethylolethane, trimethylol) Propane, pentaerythritol, trishydroxyethyl isocyanurate) ester (for example, pentaerythritol tetralauryl thiopropionate). More specifically, dilauryl thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate, lauryl stearyl thiodipropionate, distearyl thiodibutyrate, etc.

These thioether stabilizers may be used alone or in combination. (C-1) Hindered Amine Stabilizer The hindered amine stabilizer is particularly limited to a compound having a structure in which all the hydrogens bonded to the carbons at the 2- and 6-positions of the conventionally known piperidine are replaced with methyl groups. Although it is used without any treatment, specifically, the following compounds are used. (1) Bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, (2) Dimethyl-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-succinate Tetramethylpiperidine polycondensate, (3) poly [[6- (1,1,3,3-tetramethylbutyl) imino-1,3,5-triazine-2-4-diyl]
[(2,2,6,6-Tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]], (4) Tetrakis (2,2 , 6,6-Tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, (5) 2,2,6,6-tetramethyl-4-piperidinylbenzoate, (6) Bis- (1,2,6,6-pentamethyl-4-
Piperidinyl) -2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonate, (7) bis- (N-methyl-2,2,6,6-tetramethyl -4-piperidinyl) sebacate, (8) 1,1 '-(1,2-ethanediyl) bis (3,3,5,5-
Tetramethylpiperazinone), (9) (mixed 2,2,
6,6-Tetramethyl-4-piperidyl / tridecyl) -1,2,3,
4-Butane tetracarboxylate, (10) (mixed
1,2,2,6,6-pentamethyl-4-piperidyl / tridecyl)-
1,2,3,4-butanetetracarboxylate, (11) mixed {2,2,6,6-tetramethyl-4-piperidyl / β, β,
β ', β'-tetramethyl-3-9- [2,4,8,10-tetraoxaspiro (5,5) undecane] diethyl} -1,2,3,4-butanetetracarboxylate, (12 ) Mixed {1,2,2,6,6-
Pentamethyl-4-piperidyl / β, β, β ', β'-tetramethyl-3-9- [2,4,8,10-tetraoxaspiro (5,5) undecane] diethyl} -1,2,3 , 4-Butane tetracarboxylate, (13) N, N'-bis (3-aminopropyl) ethylenediamine-2-4-bis [N-butyl N- (1,2,2,6,6-pentamethyl-4 -Piperidyl) amino] -6-chloro-1,3,5-triazine condensate, (14) poly [[6-N-morpholyl-1,3,5-
Triazine-2-4-diyl] [(2,2,6,6-tetramethyl-4-
Piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]], (15) N, N'-bis (2,2,6,6-tetramethyl-4- Piperidyl) hexamethylenediamine and 1,2-dibromoethane condensate, (16)
[N- (2,2,6,6-tetramethyl-4-piperidyl) -2-methyl
-2- (2,2,6,6-tetramethyl-4-piperidyl) imino] propionamide and the like.

Among them, the above (1), (2), (3), (4),
The compounds (8), (10), (11), (14) and (15) are preferably used. These hindered amine stabilizers may be used alone or in combination.

(C-2) Metal salt of higher fatty acid Examples of the metal salt of higher fatty acid include stearic acid, oleic acid, lauric acid, capric acid, arachidic acid, palmitic acid, behenic acid, 12-hydroxystearic acid and ricinoleic acid. , Higher fatty acid magnesium salts such as montanic acid, calcium salts, alkaline earth metal salts such as barium salts, cadmium salts, zinc salts, lead salts, sodium salts, potassium salts, alkali metal salts such as lithium salts, etc. . Specifically, the following compounds are used.

Magnesium stearate, magnesium laurate, magnesium palmitate, calcium stearate, calcium oleate, calcium laurate, barium stearate, barium oleate, barium laurate, barium arachidate, barium behenate, zinc stearate, olein. Zinc acid, zinc laurate, lithium stearate, sodium stearate, sodium palmitate, sodium laurate, potassium stearate, potassium laurate, 12-
Calcium hydroxystearate, calcium montanate, etc.

The metal salts of these higher fatty acids may be used alone or in combination. Since the metal salt of higher fatty acid as described above has an effect as a lubricant and a rust preventive agent, a propylene-based polymer composition containing such a metal salt of higher fatty acid is excellent in moldability and can be used in a molding machine or the like. It is effective in preventing rust.

The propylene-based polymer composition according to the present invention includes the above-mentioned propylene polymer or propylene-based block copolymer [A], thioether-based stabilizer [B], hindered amine-based stabilizer (C-1), Metal salts of higher fatty acids (C
-In addition to at least one compound [C] selected from 2), a rubber component for improving impact strength is blended, a heat resistance stabilizer, a weather resistance stabilizer, an antistatic agent, a slip agent, an antiblocking 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.

Further, in the present invention, as long as the object of the present invention is not impaired, silica, diatomaceous earth, alumina, titanium oxide, magnesium oxide, pumice powder, pumice stone balloon, aluminum hydroxide, water is added to the propylene polymer composition. Magnesium oxide, basic magnesium carbonate, dolomite, calcium sulfate, potassium titanate, barium sulfate, calcium sulfite, talc, clay, mica, asbestos, glass fiber, glass flakes, glass beads, calcium silicate, montmorillonite, bentonite, graphite, Fillers such as aluminum powder, molybdenum sulfide, boron fibers, silicon carbide fibers, polyethylene fibers, polypropylene fibers, polyester fibers and polyamide fibers may be blended.

The propylene-based polymer composition of the present invention can be used without particular limitation in the field where polypropylene has been conventionally used, but particularly extruded sheet, unstretched film, stretched film, filament, injection molded article. ,
It is preferably used for applications such as blow molding.

The shape and product type of the extruded product comprising the propylene-based polymer composition of the present invention are not particularly limited, but specifically, a sheet, a film (unstretched film), a pipe, a hose, an electric wire coating, Examples thereof include filaments, which are particularly suitably used as sheets, films (unstretched films), filaments, and the like.

[0246] When producing an extruded product such as a sheet or a film (unstretched film) from the propylene polymer composition of the present invention, a conventionally known extruding device can be used. For example, single screw extruder, kneading extruder,
It can be produced by extruding the molten propylene-based polymer composition from a T-die using a ram extruder, a gear extruder or the like. Further, as the molding conditions, conventionally known conditions can be adopted.

Such an extruded sheet or film (unstretched film) is excellent in rigidity and heat resistance as well as in moisture resistance. The stretched film can be produced by a conventionally known stretching device using a sheet or film made of the propylene polymer composition as described above.
For example, a tenter method (longitudinal and transverse stretching, transverse and longitudinal stretching), simultaneous biaxial stretching method, uniaxial stretching method and the like can be mentioned. The stretching ratio of the stretched film is usually 20 in the case of a biaxially stretched film.
˜70 times, and usually 2 to 10 times in the case of a uniaxially stretched film. Further, the thickness of the stretched film is usually preferably 5 to 200 μm.

Such a stretched film is excellent in rigidity and heat resistance as well as in moisture resistance. An inflation film can also be produced from the propylene-based polymer composition of the present invention.

The sheet, unstretched film and stretched film made of the propylene polymer composition of the present invention have heat resistance,
Since it has excellent transparency, transparency, gloss, rigidity, moisture resistance, and gas barrier property, it can be widely used for packaging films and the like. In particular, since it has excellent moisture resistance, it is suitable for press through packs used for packaging tablets, capsules, etc. of chemicals.

The filament made of the propylene polymer composition of the present invention can be produced, for example, by extruding a molten propylene polymer composition through a spinneret. The filament thus obtained may be further stretched. The extent of this stretching is
It may be performed to such an extent that the propylene-based polymer is effectively imparted with at least uniaxial molecular orientation, and the stretching ratio is usually preferably 5 to 10 times.

Such filaments are excellent in rigidity and heat resistance. The injection-molded article made of the propylene-based polymer composition of the present invention can be produced by a conventionally known injection-molding apparatus. Further, as the molding conditions, conventionally known conditions can be adopted.

Such an injection molded product has rigidity, heat resistance,
It has excellent impact resistance, surface gloss, chemical resistance, and abrasion resistance, and can be widely used for automobile interior trim materials, automobile exterior materials, home appliances housings, and containers.

The blow-molded article comprising the propylene polymer composition of the present invention can be produced by a conventionally known blow-molding apparatus. Further, as the molding conditions, conventionally known conditions can be adopted. For example, in the case of extrusion blow molding, a tubular parison is extruded from a die at a resin temperature of 100 ° C. to 300 ° C. in a molten state, and then the parison is held in a mold having a shape to be applied. After that, air is blown in to make the resin temperature 130 ° C to 30
It is attached to a mold at 0 ° C to obtain a hollow molded article. The draw ratio is
It is preferably 1.5 to 5 times in the lateral direction.

In the case of injection blow molding, the resin temperature is 10
The propylene-based polymer composition is injected into a mold at 0 ° C to 300 ° C to form a parison, and then the parison is held in a mold having a shape to be imparted, and then air is blown into the mold to obtain a resin temperature of 120 ° C to 300 ° C. It is attached to a mold at ℃ to obtain a hollow molded article. The stretching ratio is preferably 1.1 to 1.8 times in the machine direction and 1.3 to 2.5 times in the cross direction.

Such a blow-molded article is excellent in rigidity and heat resistance, and is also excellent in moisture resistance. The propylene-based polymer composition of the present invention can be used as a base material in a method (mold stamping molding) for producing a molded body in which both the surface material and the base material are simultaneously press-molded to form a composite and integrated body. . The mold stamping molded body obtained by this molding method is a door rim,
Rear package trim, seat back garnish,
It is preferably used as an automobile interior material such as an instrument panel.

[0256] Such a mold stamping molding has excellent rigidity and heat resistance.

[0257]

The propylene-based polymer composition of the present invention is
It has a high degree of crystallinity, high stereoregularity, and is formed from a propylene polymer or propylene block copolymer having a long meso chain and a specific stabilizer. In addition to excellent properties, long-term heat stability, weather resistance, etc., the obtained molded product is excellent in rigidity, heat resistance, and moisture resistance.

[0258]

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.

[0259]

Examples 1 to 7 and Comparative Example 1 Melt flow rate (MFR: ASTM D1238 standard, 230 ° C., 2.
16 kg load) 10 g / 10 min, boiling heptane-insoluble component [M ₅ ] = 0.992% and boiling heptane-insoluble component [M ₃ ] = 0.0027, and crystallinity of boiling heptane-insoluble component is 72.6. % Propylene polymer, various stabilizers as shown in Table 1 were added, and the screw diameter was 45 mmφ.
Extruded and pelletized at 230 ° C. using the Extruder. From the pellets, a commercially available T-die film molding machine equipped with an extruder with a diameter of 65 mm has a width of 420 mm and a thickness of 0.0
A 4 mm film was molded. Resin temperature of molding machine is 25
The draft ratio was 0.6 at 0 ° C. and a film forming speed of 20 m / min.

With respect to this film, MFR, heat aging resistance and weather resistance were evaluated. The results are shown in Table 2. It is preferable that the difference between the MFR of the heat stable film at the time of molding and the MFR of the pellet is small.

The long-term heat-resistant stable film was aged in a gear oven at 100 ° C.,
The time required for the residual tensile elongation to reach one half of the initial value was measured. The longer the time, the better the heat resistance stability.

Using a sunshine weather meter for the weather resistant film, the discharge voltage was 50 V, the discharge current was 60 A, and the conditions were 500 with rain.
Light irradiation was carried out for an hour to measure the residual tensile elongation. The greater the residual elongation rate, the better the weather resistance.

[0263]

[Table 1]

Thioether stabilizer A: dilauryl propionate (trade name: Antiox L NOF CORPORATION) B: distearyl thiodipropionate (trade name: DS
TP "Yoshitomi" Yoshitomi Pharmaceutical Co., Ltd.) C: Pentaerythrityl tetra-β-mercaptolauryl propionate (trade name: Cynox 412S, manufactured by Cypro Kasei Co., Ltd.) Hindered amine stabilizer D: Bis (2,2, 2,6,6-tetramethyl-4-piperidyl) sebacate (trade name: Sanol LS770, Sankyo Co., Ltd.) fatty acid metal salt E: calcium stearate

[0265]

[Table 2]

[Brief description of drawings]

FIG. 1 is an explanatory view showing a process for preparing an olefin polymerization catalyst used for producing a propylene polymer and a propylene block copolymer used in the present invention.

FIG. 2 is an explanatory view showing a process for preparing an olefin polymerization catalyst used for producing a propylene polymer and a propylene block copolymer used in the present invention.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C08K 5/01 KEH 5/098 KEP 5/17 KEV 5/36 C08L 53/00 LLW // B29K 23 : 00 B29L 7:00

Claims (14)

[Claims] 1. [A] Melt flow rate (MFR) at 230 ° C. and 2.16 kg load is 0.1 to 500 g /
The value of the stereoregularity index [M ₅ ] determined from the absorption intensity of Pmmmm and Pw in the ¹³ C-NMR spectrum of the boiling heptane-insoluble component in the range of 10 minutes by the following formula (1) is 0.970 to 0.9. 9
In the range of 95, Pmmrm, Pmrmr, Pmrrr, Prmrr, Prmmr, Prrrr in the ¹³ C-NMR spectrum of the boiling heptane-insoluble component
The value of stereoregularity index [M ₃ ] obtained from the absorption intensity of Pw by the following formula (2) is in the range of 0.0020 to 0.0050, and the crystallinity of the boiling heptane-insoluble component is 60% or more. Propylene Polymer and [B] Thioether Stabilizer: Propylene Polymer 1
0.001 to 10 parts by weight based on 00 parts by weight; (In the formula, [Pmmmm]: absorption intensity derived from the methyl group of the third unit at the site where 5 units of propylene units are continuously isotactically bonded, [Pw]: absorption intensity derived from the methyl group of propylene unit. (2) 2. [A] Melt flow rate (MFR) at 230 ° C. and 2.16 kg load is 0.1 to 500 g /
The value of the stereoregularity index [M ₅ ] determined from the absorption intensity of Pmmmm and Pw in the ¹³ C-NMR spectrum of the boiling heptane-insoluble component in the range of 10 minutes by the following formula (1) is 0.970 to 0.9. 9
In the range of 95, Pmmrm, Pmrmr, Pmrrr, Prmrr, Prmmr, Prrrr in the ¹³ C-NMR spectrum of the boiling heptane-insoluble component
The value of stereoregularity index [M ₃ ] obtained from the absorption intensity of Pw by the following formula (2) is in the range of 0.0020 to 0.0050, and the crystallinity of the boiling heptane-insoluble component is 60% or more. Propylene Polymer and [B] Thioether Stabilizer: Propylene Polymer 1
0.001 to 10 parts by weight per 100 parts by weight, at least one compound selected from the group consisting of [C] (C-1) hindered amine stabilizers and (C-2) metal salts of higher fatty acids: A propylene-based polymer composition, characterized by comprising 0.001 to 10 parts by weight relative to 100 parts by weight of the propylene polymer; (In the formula, [Pmmmm]: absorption intensity derived from the methyl group of the third unit in the site where 5 units of propylene units are continuously isotactic-bonded, and [Pw]: absorption intensity derived from the methyl group of propylene unit. .) [Formula 4] 3. The propylene polymer contains a structural unit derived from a compound represented by the following formula (i) or (ii) in an amount of 10 to 10,000 ppm.
Alternatively, the propylene-based polymer composition according to item 2; 4. [A] Melt flow rate (MFR) at 230 ° C. under a load of 2.16 kg is 0.1 to 500 g /
In the range of 10 minutes, Pmmmm in ¹³ C-NMR spectrum of a boiling heptane-insoluble component, Pw, Sαγ, Sαδ ^+, stereoregularity index determined by the following formula (1A) from the absorption intensities of Tδ ⁺ δ ⁺ [M ₅ ] In the range of 0.970 to 0.995, Pmmrm, Pmrmr, Pmrrr, Prmrr, Prmmr, Prrrr in the ¹³ C-NMR spectrum of the boiling heptane-insoluble component.
The stereoregularity index [M ₃ ] obtained from the absorption intensities of Pw, Sαγ, Sαδ ⁺ , and Tδ ⁺ δ ^{+ by} the following formula (2A) is in the range of 0.0020 to 0.0050, and the boiling heptane-insoluble component is And a propylene block copolymer having a crystallinity of 60% or more, and [B] thioether stabilizer: 0.001 to 10 parts by weight based on 100 parts by weight of the propylene block copolymer. A propylene-based polymer composition characterized by: (In the formula, [Pmmmm]: absorption intensity derived from the methyl group of the third unit in the site where 5 units of propylene units are continuously isotactic-bonded, and [Pw]: absorption intensity derived from the methyl group of propylene unit. [Sαγ]: a secondary carbon in the main chain, one of the two tertiary carbons closest to the secondary carbon being in the α-position,
The other is the absorption intensity derived from the secondary carbon in the γ position, and [Sαδ ⁺ ]: the secondary carbon in the main chain, of the two tertiary carbons closest to the secondary carbon. , One is at the α-position and the other is at the δ-position or the absorption intensity derived from a secondary carbon located at a position distant from the δ-position, and [Tδ ⁺ δ ⁺ ] is a tertiary carbon in the main chain. Of the two tertiary carbons closest to the tertiary carbon, one of them is at the δ position or a position away from the δ position and the other is at a position of the δ position or away from the δ position. Is the absorption intensity derived from. ) [Equation 6] [Pw], [Sαγ], [Sαδ ⁺ ] and [Tδ ⁺ δ
⁺ ] Is the same as the above formula (1A). ) 5. [A] Melt flow rate (MFR) at 230 ° C. and 2.16 kg load is 0.1 to 500 g /
In the range of 10 minutes, Pmmmm in ¹³ C-NMR spectrum of a boiling heptane-insoluble component, Pw, Sαγ, Sαδ ^+, stereoregularity index determined by the following formula (1A) from the absorption intensities of Tδ ⁺ δ ⁺ [M ₅ ] In the range of 0.970 to 0.995, Pmmrm, Pmrmr, Pmrrr, Prmrr, Prmmr, Prrrr in the ¹³ C-NMR spectrum of the boiling heptane-insoluble component.
The stereoregularity index [M ₃ ] obtained from the absorption intensities of Pw, Sαγ, Sαδ ⁺ , and Tδ ⁺ δ ^{+ by} the following formula (2A) is in the range of 0.0020 to 0.0050, and the boiling heptane-insoluble component is A propylene block copolymer having a crystallinity of 60% or more, [B] thioether stabilizer: 0.001 to 10 parts by weight relative to 100 parts by weight of the propylene block copolymer, and [C ] (C-1) at least one compound selected from the group consisting of hindered amine stabilizers and (C-2) higher fatty acid metal salts: 0.001 to 10 to 100 parts by weight of the propylene block copolymer And a propylene-based polymer composition characterized by comprising: (In the formula, [Pmmmm]: absorption intensity derived from the methyl group of the third unit in the site where 5 units of propylene units are continuously isotactic-bonded, and [Pw]: absorption intensity derived from the methyl group of propylene unit. [Sαγ]: a secondary carbon in the main chain, one of the two tertiary carbons closest to the secondary carbon being in the α-position,
The other is the absorption intensity derived from the secondary carbon in the γ position, and [Sαδ ⁺ ]: the secondary carbon in the main chain, of the two tertiary carbons closest to the secondary carbon. , One is at the α-position and the other is at the δ-position or the absorption intensity derived from a secondary carbon located at a position distant from the δ-position, and [Tδ ⁺ δ ⁺ ] is a tertiary carbon in the main chain. Of the two tertiary carbons closest to the tertiary carbon, one of them is at the δ position or a position away from the δ position and the other is at a position of the δ position or away from the δ position. Is the absorption intensity derived from. ) [Equation 8] [Pw], [Sαγ], [Sαδ ⁺ ] and [Tδ ⁺ δ
⁺ ] Is the same as the above formula (1A). ) 6. The method according to claim 4, wherein the propylene-based block copolymer contains a structural unit derived from a compound represented by the following formula (i) or (ii) in an amount of 10 to 10,000 ppm. The propylene-based polymer composition described above; 7. An extruded sheet comprising the propylene-based polymer composition according to any one of claims 1 to 6. 8. An unstretched film comprising the propylene polymer composition according to any one of claims 1 to 6. 9. A stretched film comprising the propylene-based polymer composition according to claim 1. 10. A filament comprising the propylene-based polymer composition according to any one of claims 1 to 6. 11. An injection-molded article comprising the propylene-based polymer composition according to any one of claims 1 to 6. 12. A blow molded product comprising the propylene-based polymer composition according to any one of claims 1 to 6. 13. A press-through pack comprising the propylene-based polymer composition according to any one of claims 1 to 6. 14. A mold stamping molded article comprising the propylene-based polymer composition according to claim 1. Description: