JP3330733B2 - Polypropylene resin composition and use thereof - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polypropylene resin composition comprising crystalline polypropylene having a high stereoregularity and a terpene resin containing no polar group and / or a petroleum resin containing no polar group. Film, and a multilayer stretched film having a substrate layer comprising the composition, and a polypropylene resin composition comprising a highly stereoregular crystalline polypropylene and a hydrogenated petroleum resin,
The present invention relates to a polypropylene sheet for press-through pack packaging comprising the composition, and a polypropylene multilayer sheet for press-through pack packaging having a base material layer comprising the composition.

[0002]

BACKGROUND OF THE INVENTION Polyolefins such as crystalline polypropylene are so-called Ziegler compounds comprising a compound of a transition metal belonging to Groups IV to VI of the periodic table and an organometallic compound of a metal belonging to Groups I to III of the periodic table. It is well known that it is obtained by polymerizing olefins using a Natta catalyst. A method for obtaining a highly stereoregular crystalline polyolefin with high polymerization activity using such a catalyst is disclosed in, for example, JP-A-61-209207 and JP-A-62-1048.
No. 10, JP-A-62-104811, JP-A-62-104812, JP-A-62-104813, JP-A-1-311106, JP-A-1-318011, JP-A-2 -166104.

[0003] Such a crystalline polypropylene having a high stereoregularity has high rigidity and generally has a high heat deformation temperature, melting point and crystallization temperature, so that it exhibits excellent heat resistance, a high crystallization speed, and high transparency. And excellent properties such as high. Therefore, it is suitably used for various uses such as containers and films.

A film made of crystalline polypropylene as described above has an excellent water vapor barrier property as compared with a film made of polyamide or polyester.
For example, for applications such as tobacco packaging films, the water vapor barrier properties were not always sufficient. Therefore, for applications requiring such a very high water vapor barrier property, a polypropylene biaxially stretched film (OP
P film) on the surface of polyvinylidene chloride (PVDC)
, A so-called K-OP film is used. However, since the K-OP film contains PVDC, there is a problem that chlorine gas is generated at the time of incineration, and there is a problem that PVDC has poor compatibility with polypropylene and cannot be recycled by re-extrusion. .

In order to solve such a problem, Japanese Patent Publication No.
JP-A-47177 discloses polypropylene and a petroleum resin containing no polar group or a petroleum resin containing no polar group, and a glass transition temperature (Tg) of 10 or less.
A stretched polypropylene film having a temperature of not lower than 80 ° C and not higher than 80 ° C has been proposed. However, since the water vapor barrier property of this film is inferior to that of the K-OP film, it has been difficult to use this film in applications requiring extremely high water vapor barrier properties.

The inventors of the present invention have conducted intensive studies under such circumstances, and as a result, have found that a crystalline polypropylene having a high specific stereoregularity and a terpene resin containing no polar group and / or a petroleum resin containing no polar group can be obtained. It has been found that a stretched film formed from a propylene resin composition consisting of

In recent years, as a packaging for medicines and the like, a plurality of recesses are formed on a plastic sheet by thermoforming, tablets and capsules are filled in the recesses, and these are sealed with an aluminum foil. The following “PTP
Packaging) is often used. And such a plastic sheet for PTP packaging includes:
Conventionally, a rigid vinyl chloride resin sheet has been used.
However, the rigid vinyl chloride resin sheet does not always have a sufficient steam barrier property for packaging pharmaceuticals and the like which are easily degraded by moisture such as antibiotics. Therefore, for applications requiring particularly high water vapor barrier properties, a laminated sheet in which the surface of a hard vinyl chloride resin sheet is coated with PVDC is used. However, such a laminated sheet has a problem that it is expensive. Hard vinyl chloride resin and PVDC have a problem that chlorine gas is generated during incineration.

On the other hand, conventional polypropylene sheets have no problem of generating chlorine gas during incineration, but have problems in transparency and thermoformability, and thus are rarely used for PTP packaging.

As a conventional method for improving the transparency of a polypropylene sheet, a method of adding a nucleating agent such as dibenzylidene sorbitol to polypropylene is known. However, according to this method, the heat of the sheet during PTP packaging is known. There is a problem that moldability deteriorates. Further, as a method of improving the thermoformability of a conventional polypropylene sheet, a method of blending polyethylene with polypropylene is known, but this method has a problem that the transparency of the sheet is significantly reduced.

The inventors of the present invention have conducted intensive studies in such a situation, and as a result, a sheet formed from a propylene resin composition comprising a specific highly stereoregular crystalline polypropylene and a hydrogenated petroleum resin, The inventors have found that the present invention has excellent steam barrier properties, rigidity, transparency, and thermal workability, and has completed the present invention.

[0011]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above circumstances, and a polypropylene resin composition capable of obtaining a film having excellent water vapor barrier properties, a stretched polypropylene film having excellent water vapor barrier properties, and a polypropylene. Along with the purpose of providing a multilayer stretched film, a polypropylene resin composition capable of obtaining a sheet having excellent steam barrier properties and excellent rigidity and transparency, excellent steam barrier properties, and excellent rigidity and transparency. An object is to provide an excellent polypropylene sheet for press-through pack packaging and a polypropylene multilayer sheet for press-through pack packaging.

[0012]

SUMMARY OF THE INVENTION The first polypropylene resin composition according to the present invention comprises (A) a melt flow rate at 230 ° C. under a load of 2.16 kg in the range of 0.1 to 500 g / 10 minutes, and a boiling heptane-insoluble component. The value of the stereoregularity index [M ₅ ] obtained by the following formula (1) from the absorption intensity of Pmmmm and Pw in the ¹³ C-NMR spectrum of 0.97 was 0.97.
0 to 0.995 in the range of boiling heptane insoluble components
Pmmrm, Pmrmr, Pmr in ¹³ C-NMR spectrum
The value of the stereoregularity index [M ₃ ] obtained from the absorption intensity of rr, Prrmr, Prmmr, Prrrr, and Pw by the following formula (2) is in the range of 0.0020 to 0.0050, and the boiling heptane-insoluble crystal A propylene polymer having a degree of conversion of 60% or more: 80 to 95% by weight, and (B) a terpene resin containing no polar group and / or a petroleum resin containing no polar group: 20 to 5% by weight. Features.

[0013]

(Equation 15)

(Wherein [Pmmmm] is the absorption intensity derived from the methyl group of the third unit at the site where 5 units of propylene units are continuously bonded isotactically, and [Pw] is derived from the methyl group of the propylene unit. Absorption intensity.)

[0015]

(Equation 16)

The stretched polypropylene film according to the present invention is characterized by being formed from the first polypropylene resin composition and having a glass transition temperature (Tg) in the range of 0 to 10 ° C.

The stretched polypropylene multilayer film according to the present invention comprises: [I] a base material layer comprising the first polypropylene resin composition and having a glass transition temperature (Tg) in the range of 0 to 10 ° C. II] ^{13 of} boiling heptane insoluble components
In the C-NMR spectrum, Pmmmm, Pw, Sαγ,
The value of the stereoregularity index [M ₅ ] obtained from the absorption intensity of Sαδ ⁺ and Tδ ⁺ δ ^{+ by} the following equation (3) is 0.925 to
^{13C of the} boiling heptane-insoluble component in the range of 0.975
-Pmmrm, Pmrmr, Pmrrr,
Prrmr, Prmmr, Prrrr, Pw, Sαγ, Sαδ ⁺ , T
The value of the stereoregularity index [M ₃ ] obtained from the absorption intensity of δ ⁺ δ ^{+ by} the following equation (4) is 0.0020 to 0.00.
And a surface layer made of a propylene-based polymer (C) in the range of 50, wherein the thickness of the base material layer is 80% or more of the total thickness of the film.

[0018]

[Equation 17]

(Where [Pmmmm] and [Pw] are the same as in the above formula (1), and [Sαγ] is a secondary carbon in the main chain, and the two closest carbons to the secondary carbon are Among the tertiary carbons, one is at the α-position and the other is at the γ-position, and has an absorption intensity derived from a secondary carbon. [Sαδ ⁺ ]: a 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 at a position further away from the δ-position. ⁺ δ ⁺ ]: a tertiary carbon in the main chain, one of the two tertiary carbons closest to the tertiary carbon is located at the δ-position or a position away from the δ-position, and the other is at the δ-position Or the absorption intensity derived from tertiary carbon located at a position apart from the δ position.)

[0020]

(Equation 18)

(Where [Pmmrm], [Pmrmr], [Prm
rr], [Prmmr], [Prrrr] and [Pw] are the same as in the above equation (2), and [Sαγ], [Sαδ ⁺ ],
[Tδ ⁺ δ ⁺ ] is the same as in the above formula (3). ).

In the first polypropylene resin composition, the stretched polypropylene film and the multilayer stretched polypropylene film according to the present invention, the propylene polymer (A)
A polymer comprising a structural unit derived from a compound represented by the following formula (i) or (ii): 10 to 10,000 ppm
Is desirably contained.

[0023]

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The second polypropylene resin composition according to the present invention has (A) a melt flow rate at 230 ° C. and a load of 2.16 kg in the range of 0.1 to 500 g / 10 minutes, and ¹³ % of the boiling heptane-insoluble component. C-NMR Pmmmm in the spectrum, the value of the pentad tacticity as determined by the above equation (1) from the absorption intensity [M _5] of Pw is 0.970
~ 0.995, and ^{13 of} boiling heptane-insoluble components
Pmmrm, Pmrmr, Pmrr in C-NMR spectrum
The value of the stereoregularity index [M ₃ ] obtained from the absorption intensity of r, Prrmr, Prmmr, Prrrr, and Pw by the above equation (2) is in the range of 0.0020 to 0.0050, and the crystal of the boiling heptane-insoluble component is present. A propylene polymer having a degree of conversion of 60% or more: 70 to 95% by weight, and (D) hydrogenated petroleum resin: 30 to 5% by weight.

The polypropylene sheet for press-through pack packaging according to the present invention is characterized by being formed from the second polypropylene resin composition. The polypropylene multilayer sheet for press-through pack packaging according to the present invention comprises [I] a base material layer formed from the second polypropylene resin composition, and [II] a propylene-based polymer (E).
And the ratio of the thickness of the base material layer to the total thickness of the sheet is 50% or more, and
The total thickness T (μm) of the sheet and the ratio H (%) of the thickness of the base layer to the total thickness T of the sheet are represented by 3.4 ≦ log (T × H) ≦ 5.0. It is characterized by satisfying the relationship.

In the second polypropylene resin composition, the polypropylene sheet for press-through pack packaging and the polypropylene multilayer sheet for press-through pack packaging according to the present invention, the propylene polymer (A) has the following formula (i) or (ii) It is desirable to contain a polymer consisting of structural units derived from the compound represented by the formula at a ratio of 10 to 10000 ppm.

[0027]

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[0028]

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

The first polypropylene resin composition according to the present invention comprises a propylene polymer (A) as described below and a terpene resin containing no polar group and / or a petroleum resin containing no polar group (B). Is formed. Further, the second polypropylene resin composition according to the present invention is formed from a propylene polymer (A) as described below and a hydrogenated petroleum resin (D).

First, the propylene polymer (A), the terpene resin containing no polar group, the petroleum resin containing no polar group (B), and the hydrogenated petroleum resin (D) forming the polypropylene resin composition according to the present invention are sequentially described. explain.

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

In such a propylene polymer, 230
Melt flow rate under a load of 2.16 kg at 0.1 ° C. and 0.1 to 500 g / 10 min, preferably 0.2 to 300 g
It is desirable to be in the range of / 10 minutes.

The melt flow rate is as per ASTM D1
It is measured under the conditions of 230 ° C and 2.16 kg load according to 238-65T. Propylene polymer used in the present invention,
The value of Pmmmm in ¹³ C-NMR spectrum of a boiling heptane-insoluble component, stereoregularity index determined from the absorption intensity of Pw by the following formula (1) [M _5] is from 0.970 to 0.
995, preferably 0.980 to 0.995, more preferably 0.982 to 0.995.

[0034]

[Equation 19]

(Where, [Pmmmm] is the absorption intensity derived from the methyl group of the third unit at the site where 5 units of propylene units are continuously bonded isotactically, and [Pw] is derived from the methyl group of the propylene unit. Hereinafter, the stereoregularity index [M ₅ ] used in the present invention to evaluate the stereoregularity of the propylene polymer (A) and the propylene-based polymer (C) described below will be specifically described. .

The stereoregularity index [M ₅ ] of the polymer is determined from the absorption intensity in the ¹³ C-NMR spectrum of the boiling heptane-insoluble component of the polymer. When the boiling heptane insoluble component is a propylene homopolymer, the insoluble component can be represented, for example, by the following formula (A).

[0037]

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The ^13C derived from the ^third methyl group (eg, Me ³ , Me ⁴ ) in the five propylene units represented by
Assuming that the absorption intensity in the NMR spectrum is Pmmmm and the absorption intensity derived from all the methyl groups (Me ¹ , Me ² , Me ³ ...) In the propylene unit is Pw, the boiling heptane insoluble represented by the above formula (A) is obtained. The stereoregularity of the components is Pmmmm and P
w, ie, the value [M obtained from the above equation (1)
₅ ]. Therefore, the stereoregularity of the propylene polymer (A) used in the present invention is:
Pmmmm in the ¹³ C-NMR spectrum of the insoluble component,
It can be evaluated by the value of the stereoregularity index [M ₅ ] obtained from the above formula (1) from the absorption intensity of Pw.

When the boiling heptane-insoluble component contains a small amount of a structural unit (eg, ethylene unit) derived from another olefin other than the propylene unit, the insoluble component is represented by the following formula (B-1) or (B- It can be expressed as 2). It should be noted that the formula (B-1) shows that 1
(B-2) shows the case where two ethylene units are contained.
Indicates a case where an ethylene unit chain composed of two or more ethylene units is included in the propylene unit chain.

[0040]

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In such a case, a methyl group other than the methyl group of the third unit in the five propylene units (the above-mentioned 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 steric regularity is evaluated. However, since the absorption of these methyl groups is observed overlapping with the absorption of other methyl groups, it is difficult to quantify.

Therefore, the boiling heptane-insoluble component is represented by the formula (B-
In the case shown in 1), ¹³ C derived from a secondary carbon (C ¹ ) which is ^a secondary carbon in an ethylene unit and is bonded to ^a tertiary carbon (C ^a ) in ^a propylene unit. -NMR
Absorption intensity (Sαγ) in the spectrum and absorption intensity (Sαγ) derived from the secondary carbon (C ³ ) which is the secondary carbon in the propylene unit and 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 C^Three) Two closest tertiary coals
One of the primes (C^aOr C^b) Is in the α position, while
(C ^bOr C^a) Is derived from a secondary carbon such as in the γ-position
Subtracting twice the absorption intensity (Sαγ) from Pw
As a result, the third unit in the five propylene units
Methyl groups other than^Four, Me^Five, Me⁶And Me⁷)
Exclude the absorption intensity from which it originated.

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

That is, a secondary carbon in the main chain,
Secondary carbon (C^FourOr C⁶) Two closest tertiary coals
One of the primes (C^dOr C^e) Is in the α position, while
(C ^eOr C^d) At the δ position or at a position farther from the δ position
Absorption intensity derived from a certain secondary carbon (Sαδ⁺)
By subtracting twice from Pw, propylene unit
A methyl group other than the methyl unit of the third unit in the 5th chain (M
e^Four, Me^Five, Me⁶And Me⁷Excludes absorption intensity from
I do.

Accordingly, 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).

[0047]

(Equation 20)

Further, when the boiling heptane insoluble component contains an ethylene unit and one propylene unit is contained in the ethylene unit chain, the insoluble component can be represented by the following formula (C), for example. .

[0049]

Embedded image

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

Therefore, the process contained in the ethylene unit chain is
Derived from tertiary carbon in propylene units¹³C-NMR spec
This is corrected using the absorption intensity in the vector. sand
That is, the tertiary carbon in the main chain,
Close two tertiary carbons (C^f, C^g), One of them (C^f)
Is located at the δ-position or a position separated from the δ-position, while the other (C^g )
Is a tertiary carbon such that is at the δ-position or at a distance from the δ-position
(C⁷) (Tδ)⁺δ⁺) Tripled
This is corrected by adding

Accordingly, 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 (3).

Therefore, the stereoregularity of the propylene polymer (C) described later can be evaluated by the value of the stereoregularity index [M ₅ ] obtained by the following formula (3).

[0054]

(Equation 21)

[Wherein [Pmmmm] and [Pw] are the same as those in the above formula (1), and [Sαγ] is a secondary carbon in the main chain, and the two closest carbons from the secondary carbon Among the tertiary carbons, one is at the α-position and the other is at the γ-position, and has an absorption intensity derived from a secondary carbon, [Sαδ ⁺ ]: a 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 at a position further away from the δ-position. ⁺ δ ⁺ ]: a tertiary carbon in the main chain, one of the two tertiary carbons closest to the tertiary carbon is located at the δ-position or a position away from the δ-position, and the other is at the δ-position Alternatively, the absorption intensity is derived from tertiary carbon located at a position apart from the δ position.) Note that the expressions (1) and (1B) are different from the expression (3). Ku, is positioned as (3) of the special case. In addition, the above correction may not be necessary depending on the type of the structural unit other than the propylene unit contained in the boiling heptane-insoluble component.

The propylene polymer (A) used in the present invention has a value of the stereoregularity index [M ₅ ] of the boiling heptane-insoluble component of 0.970 or less, which is determined by the above formula (1).
Pmmrm, Pmrmr, ¹³ C-NMR spectrum of the insoluble component in the boiling heptane within the range of 0.995.
Stereoregularity index [M ₃ ] obtained from the absorption intensity of Pmrrr, Prrmr, Prmmr, Prrrr, Pw by the following equation (2)
0.0020 to 0.0050, preferably 0.0
023 to 0.0045, more preferably 0.0025 to
It is in the range of 0.0040.

[0057]

(Equation 22)

When the boiling heptane-insoluble component is a propylene homopolymer as described above, the value of the stereoregularity index [M ₃ ] can be obtained by the above equation (2). When a small amount of a monomer unit other than the propylene unit is contained, the value of the stereoregularity index [M ₃ ] is determined by the following equation (4).

[0059]

(Equation 23)

(Where [Pmmrm], [Pmrmr], [Pmr
rr], [Prmrr], [Prmmr], [Prrrr], [Pw
 ], [Sαγ], [Sαδ⁺], [Tδ⁺δ⁺Is the above
This is the same as Expressions (2) and (3). ) In the above equations (2) and (4), [Pmmrm], [Pmrm
r], [Pmrrr], [Prmrr], [Prmmr], [Prrr
r] is a sequence of five consecutive
Of the methyl groups in the propylene unit, three are in the same direction,
Structure in which the individual faces in the opposite direction (hereinafter “M_ThreeStructure "
The third unit in the five propylene units having
It shows the absorption intensity derived from the methyl group of the eye. Sand
The stereoregularity index determined by the above equation (2)
[M_Three] Is the value of M in the propylene unit chain._ThreeStructure
Indicates the ratio of the structure, and the three-dimensional rule calculated by the above equation (4).
Regularity index [M _Three] Is for monomers other than propylene units.
In a propylene unit chain containing a small amount of_ThreeStructure
The ratio of the structure is shown.

The propylene polymer (A) used in the present invention has a stereoregularity index [M ₅ ] of the boiling heptane-insoluble component determined by the above formula (1) of from 0.970 to 0.970.
Since the value of the stereoregularity index [M ₃ ] of the boiling heptane-insoluble component obtained by the above equation (2) is in the range of 0.0020 to 0.0050, the extremely long meso-chain (α) A propylene unit chain with the methyl carbon oriented in the same direction).

In general, the smaller the value of the stereoregularity index [M ₃ ], the longer the meso-chain of polypropylene. However, when the value of the stereoregularity index [M ₅ ] is extremely large and the value of the stereoregularity index [M ₃ ] is extremely small, if the value of the stereoregularity index [M ₅ ] is almost the same, When the value of the regularity index [M ₃ ] is larger, the meso-chain may be longer.

[0063] 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 polypropylene represented by the structure (b) not having. (However, the following structure (a) and structure (b)
Each of them is assumed to be composed of 1003 propylene units. )

[0064]

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[0065] The value of the structure (b) stereoregularity index of the polypropylene represented by [M _5] is 0.986, stereospecificity index of polypropylene represented by the structure (b) [M _5] Is 0.985, and the values of the stereoregularity index [M ₅ ] of the polypropylene represented by the structure (a) and the polypropylene represented by the structure (b) are substantially equal. However, a structure having an M ₃ structure (a)
In the polypropylene represented by the formula, the propylene unit contained in the meso chain has an average of 497 units, and in the polypropylene represented by the structure (b) containing no M ₃ structure, the propylene unit contained in the meso chain has an average of 250 Unit. That is, in a polypropylene having an extremely large value of the stereoregularity index [M ₅ ], the ratio of the structure represented by r (racemo) contained in the propylene unit chain is extremely small. polypropylene present concentrate on (polypropylene having a M ₃ structure) will have a longer mesochain r (polypropylene having no M ₃ structure) polypropylene structure is present dispersed represented by (Racemo).

The propylene polymer (A) used in the present invention is a highly crystalline polypropylene having an M ₃ structure as shown in the above structure (a), and has a stereoregularity index [M ₅ Is 0.970-
In the range of 0.995, the value of the pentad tacticity the boiling heptane-insoluble component [M _3] is from 0.0020 to 0.0050
In the range. Such a propylene polymer (A)
Although the reason is not clear, it has higher rigidity, heat resistance and moisture resistance than conventional high crystalline polypropylene. The value of the pentad tacticity [M _3] of the boiling heptane-insoluble component is deviates from the range of 0.0020 to 0.0050, the above-mentioned characteristics may be lowered.

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

In the present invention, the boiling heptane-insoluble component N
The MR measurement is performed, for example, as follows. That is, 0.35 g of the insoluble component is dissolved by heating in 2.0 ml of hexachlorobutadiene. This solution was filtered through a glass filter (G2), and then deuterated benzene 0.5 m
Add l and charge into an NMR tube with an inner diameter of 10 mm.
Then, ¹³ C-NMR measurement is carried out at 120 ° C. by using a JEOL GX-500 type NMR measuring apparatus. The number of integrations is
10,000 times or more. The values of the stereoregularity indexes [M ₅ ] and [M ₃ ] can be determined from the peak intensities or the sum of the peak intensities based on the respective structures obtained by the above measurement.

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

The degree of crystallinity is measured as follows.
That is, the sample was 1 mm thick with a 180 ° C. pressure molding machine.
After being formed into a rectangular plate, a water-cooled press sheet was used, and a rotor flex RU3 manufactured by Rigaku Corporation was used.
It is determined by measuring using a 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 (A) used in the present invention is a polymer comprising a structural unit derived from a compound represented by the following formula (i) or (ii):
It is desirable to contain it in an amount of 00 ppm, preferably 100 to 5000 ppm.

[0072]

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

In the above formula (i) or (ii),
The hydrocarbon groups represented by R ¹ , R ² and R ³ include:
Examples 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 groups represented by R ² and R ³ may contain silicon and 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, vinylnaphthalenes, 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, etc., 3-methyl-1-butene,
More preferably, vinylcyclohexane and allyltrimethylsilane are contained, and particularly preferably, 3-methyl-1-butene is contained.

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

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

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

The propylene polymer used in the present invention has a decane-soluble component at 23 ° C. of 3.0% or less, preferably 2.5% or less, more preferably 2.0% or less, particularly preferably 1% or less. 0.5% or less is desirable.

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

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

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

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

The propylene polymer used in the present invention 1
The intrinsic viscosity [η] measured in decalin at 35 ° C. is usually 0.001 to 30 dl / g, preferably 0.01 to 1 dl / g.
0 dl / g, particularly preferably in the range of 0.05 to 8 dl / g.

The propylene polymer used in the present invention includes, for example, [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 represents a secondary or tertiary hydrocarbon group, and when n is 2 or 3, at least one of R ^a is a secondary or tertiary hydrocarbon group, R ^a is independently identical or different R ^b is a hydrocarbon group having 1 to 4 carbon atoms,
When 4-n is 2 or 3, R ^b may be the same or different. ), A solid titanium catalyst component (a) containing preferably [Ib] magnesium, titanium, halogen and an electron donor as essential components, and an organometallic catalyst component (b) And a prepolymerization catalyst component obtained by prepolymerizing at least one olefin selected from olefins represented by the following formula (i) or (ii) in the presence of:

[0086]

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

The components forming the olefin polymerization catalyst used in the production of the propylene polymer used in the present invention will be specifically described below. The solid titanium catalyst component (a) can be prepared by contacting a magnesium compound, a titanium compound and an electron donor as described below.

Used for the preparation of the solid titanium catalyst component (a)
Specifically, for example, the following formula:
And a tetravalent titanium compound represented by the following formula: Ti (OR)_gX_4-g (Wherein, R represents a hydrocarbon group, X represents a halogen atom)
G is 0 ≦ g ≦ 4. ) Such a titanium compound
Specifically, TiCl_Four, TiBr_Four, TiI_Four
Titanium tetrahalide such as Ti (OCH_Three) C
l_Three, Ti (OC_TwoH_Five) Cl_Three, Ti (On-C_FourH₉) Cl
_Three, Ti (OC_TwoH_Five) Br_Three, Ti (O-iso-C_FourH₉) B
r_ThreeTrihalogenated alkoxytitanium such as Ti (O
CH_Three)_TwoCl_Two, Ti (OC_TwoH_Five)_TwoCl_Two, Ti (On-
C_FourH₉)_TwoCl _Two, Ti (OC_TwoH_Five)_TwoBr_TwoJiha such as
Dialkoxytitanium logen; Ti (OCH_Three)_ThreeCl,
Ti (OC_TwoH_Five)_ThreeCl, Ti (On-C_FourH₉)_ThreeCl, T
i (OC_TwoH_Five)_ThreeMonohalogenated trialco such as Br
Xtitanium; Ti (OCH_Three)_Four, Ti (OC_TwoH_Five)_Four,
Ti (On-C_FourH₉)_Four, Ti (O-iso-C_FourH₉)_Four, Ti
(O-2-ethylhexyl)_FourSuch as tetraalkoxy
And the like.

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

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

Here, examples of the magnesium compound having a reducing property include a magnesium compound having a magnesium-carbon bond or a magnesium-hydrogen bond. Specific examples of such a reducing magnesium compound include dimethyl magnesium, diethyl magnesium, dipropyl magnesium,
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, and the like. it can. These magnesium compounds may be used alone or may form a complex compound with an organometallic compound described later. Further, these magnesium compounds may be liquid or solid, or may be derived by reacting metallic magnesium with a corresponding compound. Furthermore, it can be derived from metallic magnesium during the catalyst preparation using the above-mentioned method.

Specific examples of the magnesium compound having no reducing property include magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide and magnesium fluoride; methoxy magnesium chloride,
Alkoxy magnesium halides such as ethoxy magnesium chloride, isopropoxy magnesium chloride, butoxy magnesium chloride, octoxy magnesium chloride;
Allyloxymagnesium halides such as phenoxymagnesium chloride, methylphenoxymagnesium chloride;
Ethoxymagnesium, isopropoxymagnesium,
Butoxymagnesium, n-octoxymagnesium, 2-
Examples thereof include alkoxymagnesium such as ethylhexoxymagnesium; allyloxymagnesium such as phenoxymagnesium and dimethylphenoxymagnesium; and magnesium carboxylate such as magnesium laurate and magnesium stearate.

These non-reducing magnesium compounds may be compounds derived from the above-mentioned reducing magnesium compounds or compounds derived during the preparation of the catalyst component. In order to derive a non-reducing magnesium compound from a reducing magnesium compound, for example, a magnesium compound having a reducing property is converted into a halogen, a polysiloxane compound, a halogen-containing silane compound, a halogen-containing aluminum compound, an alcohol, an ester. And a compound having an active carbon-oxygen bond, such as ketone, aldehyde and the like.

In the present invention, in addition to the above-mentioned magnesium compound having a reducing property and the magnesium compound having no reducing property, a magnesium compound is a complex compound, a double compound or another compound of the above-mentioned magnesium compound and another metal. It may be a mixture with a metal compound. Further, two or more of the above compounds may be used in combination.

As the magnesium compound used for preparing the solid titanium catalyst component (a), many magnesium compounds other than those described above can be used. 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 carry out a contact reaction with a halogen-containing compound during the preparation.

Among the above-mentioned magnesium compounds, magnesium compounds having no reducing property are preferred, magnesium compounds containing halogen are more preferred, and magnesium chloride, alkoxymagnesium chloride and allyloxymagnesium chloride are particularly preferred.

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 an electron donor.

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 and 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, and isoquinolines; tetrahydrofuran, 1,4-cineole, 1,8-cineole, pinolfuran, methylfuran, dimethylfuran, diphenylfuran, benzofuran, Cyclic oxygenates such as coumaran, phthalane, tetrahydropyran, pyran, and ditedropyran; methanol, ethanol, propanol, pentanol, hexanol, octanol, 2-ethylhexanol, dodecanol, octadecyl alcohol,
Alcohols having 1 to 18 carbon atoms such as oleyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, isopropyl alcohol, isopropylbenzyl alcohol; phenol, cresol, xylenol, ethylphenol, propylphenol, nonylphenol, cumylphenol, C6-C6 which may have a lower alkyl group such as naphthol
20 phenols; acetone, methyl ethyl ketone,
C3-C15 ketones such as methyl isobutyl ketone, acetophenone, benzophenone, acetylacetone and benzoquinone; acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde,
2 carbon atoms such as tolualdehyde and naphthaldehyde
To 15 aldehydes; 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, benzoate Phenyl acid,
Benzyl benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl ethyl benzoate, methyl anisate, n-butyl maleate, diisobutyl methylmalonate, di-n-hexyl cyclohexenecarboxylate, diethyl nadicate, tetrahydrophthalate Organic compounds having 2 to 30 carbon atoms such as diisopropyl acrylate, diethyl phthalate, diisobutyl phthalate, di-n-butyl phthalate, di-2-ethylhexyl phthalate, γ-butyrolactone, δ-valerolactone, coumarin, phthalide, and ethyl carbonate Acid ester; 2 to 2 carbon atoms such as acetyl chloride, benzoyl chloride, toluic acid chloride and anisic acid chloride
15 acid halides; methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, anisole, diphenyl ether epoxy-p-
Ethers having 2 to 20 carbon atoms such as menthane; 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-2-isopropyl- Diethers such as 1,3-dimethoxycyclohexane; acid amides such as acetic acid amide, benzoic acid amide, and toluic acid amide; nitriles such as acetonitrile, benzonitrile, tolunitrile; acetic anhydride, phthalic anhydride, benzoic anhydride An acid anhydride or the like is used.

As the electron donor, a silicon compound represented by the following general formula (iii) can also be used. When the above-mentioned titanium compound, magnesium compound and electron donor are brought into contact with each other, a carrier-supported solid titanium catalyst component (a) can be prepared using the following carrier compound.

Examples of such a carrier compound include Al
₂ O ₃ , SiO ₂ , B ₂ O ₃ , MgO, CaO, TiO ₂ , Z
Resins such as nO, ZnO ₂ , SnO ₂ , BaO, ThO, and styrene-divinylbenzene copolymer can be given. Among these carrier compounds, preferably, SiO ₂ , Al ₂ O ₃ , MgO, ZnO, ZnO _{2 and the} like can be mentioned.

The above components may be brought into contact with each other in the presence of another reaction reagent such as silicon, phosphorus and aluminum. The solid titanium catalyst component (a) can be produced by, for example, bringing the titanium compound, the magnesium compound, and the electron donor into contact with each other as described above, and any method including a known method can be employed. it can.

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

(2) A method comprising bringing a complex comprising a magnesium compound and an electron donor into contact with and reacting with an organometallic compound, followed by a contact reaction with a titanium compound. (3) In the contact substance between the inorganic carrier and the organomagnesium compound,
A method in which a titanium compound and preferably an electron donor are contacted and reacted. At this time, the contacted product may be brought into contact with a halogen-containing compound and / or an organometallic compound in advance.

(4) An inorganic or organic carrier carrying a magnesium compound is obtained from a mixture of a solution containing a magnesium compound, an electron donor, and possibly a hydrocarbon solvent, and an inorganic or organic carrier. How to make contact.

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

(6) A method of contacting a liquid state organomagnesium compound with a halogen-containing titanium compound. At this time, the electron donor is used at least once. (7) A method in which a liquid state organomagnesium compound is brought into contact with a halogen-containing compound and then brought into contact with a titanium compound.
At this time, the electron donor is used at least once.

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

(10) A method comprising bringing a complex comprising an alkoxy group-containing magnesium compound and an electron donor into contact with an organometallic compound followed by a contact reaction with a titanium compound. (11) A method of contacting and reacting a magnesium compound, an electron donor, and a titanium compound in an arbitrary order. In this reaction, each component may be pretreated with an electron donor and / or a reaction auxiliary such as an organometallic compound or a halogen-containing silicon compound. In this method, the electron donor is preferably used 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 composite.

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

(15) A method in which a solid obtained by pulverizing a magnesium compound, preferably an electron donor, and a titanium compound is treated with any of a halogen, a halogen compound and an aromatic hydrocarbon. In this method,
The method may include a step of pulverizing only the magnesium compound, a complex compound composed of the magnesium compound and the electron donor, or a magnesium compound and the titanium compound. Further, after the pulverization, a preliminary treatment with a reaction aid may be performed, followed by a treatment with a halogen or the like. Examples of the reaction aid include an organometallic compound and a halogen-containing silicon compound.

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

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

(20) A method of contacting a hydrocarbon solution containing at least a magnesium compound and alkoxytitanium with a titanium compound and / or an electron donor. At this time, it is preferable to coexist 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,
Next, 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 the electron donor is 0.01 per mole of the magnesium compound. Used in an amount of from 10 to 10 mol, preferably from 0.1 to 5 mol, and from 0.01 to 1000 mol, preferably from 0.1 to 200 mol, of the titanium compound.
It is used in molar amounts.

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 to 200, preferably about 4 to 100, and the electron donor / titanium (molar ratio) is about 0.0
1-100, preferably in the range of about 0.02-10, magnesium / titanium (atomic ratio) of about 1-100,
Preferably, it is in the range of about 2 to 50.

Such a solid titanium catalyst component (a)
(Catalyst component [Ia]) is a [Ib] prepolymerization catalyst component obtained by performing an olefin prepolymerization 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 prepolymerized catalyst component, an organometallic compound of a Group I to Group III metal of the periodic table is used. Compounds such as are used.

(B-1) The general formula R ¹ _m Al (OR ² ) _{n Hp} X _q (wherein R ¹ and R ² are usually carbon atoms containing 1 to 15, preferably 1 to 4 carbon atoms. X represents a hydrogen group, 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, q is 0
≤q <3, and m + n + p + q = 3. The organoaluminum compound represented by).

[0123] (b-2) the general formula M ¹ AlR ¹ ₄ (wherein, M ¹ is Li, Na, a K, R ¹ is as defined above.) Group I metals and aluminum represented by And complex alkylated products.

(B-3) 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 group II or group III dialkyl compound represented by the formula:

As the organoaluminum compound belonging to the above (b-1), the following compounds can be exemplified. General formula R ¹ _m Al (OR ² ) _3-m (wherein R ¹ and R ² are the same as above, and m is preferably a number satisfying 1.5 ≦ m ≦ 3). A compound represented by the general formula: R ¹ _m AlX _3-m (wherein R ¹ is the same as described above, X is a halogen, and m is preferably 0 <m <3); Formula R ¹ _m AlH _3-m (wherein R ¹ is the same as above, and m is preferably 2 ≦
m <3. A compound represented by the following general formula: R ¹ _m Al (OR ² ) _n X _q (wherein R ¹ and R ² are the same as described above, X is a halogen, 0 <m ≦ 3, 0 ≦ n < 3, 0 ≦ q <3, and m + n + q = 3).

More specifically, the aluminum compounds belonging to (b-1) include trialkylaluminums such as triethylaluminum and tributylaluminum; trialkenylaluminums such as triisoprenylaluminum; diethylaluminum ethoxide and dibutylaluminum butoxide. Dialkylaluminum alkoxides such as; ethylaluminum sesquiethoxide;
Alkyl sesquichloride alkoxides such as butyl sesquichloride _{^{butoxide; R 1 2.5 Al (OR 2}} )
Partially alkoxylated alkylaluminum having an average composition represented by _0.5 or the like; dialkylaluminum halide such as diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide; ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquichloride Alkyl aluminum sesquihalides such as bromide;
Partially halogenated alkylaluminums such as alkylaluminum dihalides such as ethylaluminum dichloride, propylaluminum dichloride and butylaluminum dibromide; dialkylaluminum hydrides such as diethylaluminum hydride and dibutylaluminum hydride; ethylaluminum dihydride and propylaluminum Other partially hydrogenated alkylaluminums such as alkylaluminum dihydrides such as dihydrides; partially alkoxylated and halogenated alkylaluminums such as ethylaluminum ethoxycyclolide, butylaluminum butoxycyclolide, and ethylaluminum ethoxybromide Can be mentioned.

Examples of the compound similar to (b-1) include an organic aluminum compound in which two or more aluminum atoms are bonded via an oxygen atom or a nitrogen atom. Such compounds include, for example, (C ₂ H ₅ ) ₂ Al
OAl (C ₂ H ₅ ) ₂ , (C ₄ H ₉ ) ₂ AlOAl (C
_{4 H 9) 2, (C} 2 H 5) 2 AlN (C 2 H 5) Al (C
Besides such ₂ H _{5) 2,} it can be exemplified aluminoxanes such as methyl aluminoxane.

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

Among these, organoaluminum compounds are preferably used. [Ib] As the olefin used for preparing the prepolymerized catalyst component, a 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, vinylnaphthalenes, allyltoluenes, allylbenzene, vinylcyclohexane, vinylcyclopentane, vinylcycloheptane, allyltrialkylsilanes, etc. And an olefin having the formula: 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, 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 to 200 mmol, preferably about 0.05 to 200 mmol, in terms of titanium atom, per liter of an inert hydrocarbon medium described below. Desirably, it is in the range of 100 mmol.

The amount of the organometallic catalyst component (b) may be an amount 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 1 mol of titanium atoms in the solid titanium catalyst component (a).

In 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 preparing the solid titanium catalyst component (a), a silicon compound (c) represented by the formula (iii) described later, and A compound (d) having two or more ether bonds present through a plurality of atoms,
Further, an organosilicon compound represented by the following formula (ci) can be exemplified.

R _n Si (OR ′) _4-n (ci) (wherein R and R ′ each represent a hydrocarbon group, and 0 <n <4
The organic silicon compound represented by the formula (ci) does not include the silicon compound (c) represented by the formula (iii) described below.

Specific examples of the organosilicon compound represented by the general formula (ci) include trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diisopropyldimethoxysilane, diphenyldimethoxysilane, Phenylmethyldimethoxysilane, diphenyldiethoxysilane, bis-o-tolyldimethoxysilane, bism-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, vinyl tris (β-methoxyethoxy silane), vinyl triacetoxy silane, dimethyl tetraethoxy disiloxane and the like.

These electron donors (e) can be used alone or in combination of two or more. The electron donor (e) is used in an amount of 0.1 to 50 mol, preferably 0.5 to 50 mol, per 1 mol of titanium atom in the solid titanium catalyst component (a).
It is used in an amount of 30 mol, more preferably 1 to 10 mol.

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

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

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

Such a preliminary polymerization can be carried out in a batch system or a continuous system. The olefin polymerization catalyst used in the production of the propylene polymer used in the present invention is the above-mentioned [I]
a) a solid titanium catalyst component or [Ib] a prepolymerization catalyst component, [II] an organometallic catalyst component, and [III] a silicon compound (c) or two or more ether bonds existing through a plurality of atoms. And compound (d).

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

[0142] In _{^{R a n -Si- (OR b)}} 4-n ... (iii) ( wherein, n is 1, 2 or 3, when n is 1, R
^a represents a secondary or tertiary hydrocarbon group, and when n is 2 or 3, at least one secondary or tertiary hydrocarbon group Shimeshiri of R ^a, be R ^a is the same or different R ^b represents a hydrocarbon group having 1 to 4 carbon atoms;
When -n is 2 or 3, ^Rb may be the same or different. ) In the silicon compound (c) represented by the formula (iii), the secondary or tertiary hydrocarbon group may be a cyclopentyl group, a cyclopentenyl group, a cyclopentadienyl group, a group having a substituent, And a hydrocarbon group in which the carbon adjacent to is secondary or tertiary. More specifically, as 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, 2,3,4-triethylcyclopentyl group, A cyclopentyl group having an alkyl group such as a tetramethylcyclopentyl group and a tetraethylcyclopentyl group can be exemplified.

As the substituted cyclopentenyl group, 2-methylcyclopentenyl group, 3-methylcyclopentenyl group,
2-ethylcyclopentenyl group, 2-n-butylcyclopentenyl group, 2,3-dimethylcyclopentenyl group, 2,4-dimethylcyclopentenyl group, 2,5-dimethylcyclopentenyl group, 2,3,4-trimethyl A cyclopentenyl group having an alkyl group such as a cyclopentenyl group, a 2,3,5-trimethylcyclopentenyl group, a 2,3,4-triethylcyclopentenyl group, a tetramethylcyclopentenyl group, and a tetraethylcyclopentenyl group may be exemplified. it can.

The substituted cyclopentadienyl group includes 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,
3,4-triethylcyclopentadienyl group, 2,3,4,5-tetramethylcyclopentadienyl group, 2,3,4,5-tetraethylcyclopentadienyl group, 1,2,3,4, A cyclopentadienyl group having an alkyl group such as a 5-pentamethylcyclopentadienyl group and a 1,2,3,4,5-pentaethylcyclopentadienyl group can be exemplified.

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

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

When n is 2, dicyclopentyldiethoxysilane, t-butylmethyldimethoxysilane,
Examples include dialkoxysilanes such as 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).

[0149]

Embedded image

In the formula, R ^a and R ^c each independently represent 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 a secondary carbon or a tertiary carbon.

Examples of the silicon compound represented by the formula (iv) include, for example, dicyclopentyldimethoxysilane, dicyclopentenyldimethoxysilane, dicyclopentadienyldimethoxysilane, di-tert-butyldimethoxysilane, 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, (2,3-diethylcyclopentadienyl) dimethoxysilane, di (2,3,4-trime Lecyclopentadienyl) 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 include silane, cyclopentyl-t-butyldimethoxysilane, diisopropyldimethoxysilane, di-s-butyldimethoxysilane, di-s-amyldimethoxysilane, and isopropyl-s-butyldimethoxysilane.

When n is 3, tricyclopentylmethoxysilane, tricyclopentylethoxysilane, dicyclopentylmethylmethoxysilane, dicyclopentylethylmethoxysilane, dicyclopentylmethylethoxysilane, cyclopentyldimethylmethoxysilane, cyclopentyldiethylmethoxysilane, Monoalkoxysilanes such as cyclopentyldimethylethoxysilane are exemplified.

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

These silicon compounds (c) can be used in combination of two or more. In the compound (d) having two or more ether bonds present 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, silicon, , Oxygen, sulfur, phosphorus, and boron, and has 2 or more atoms. Of these, relatively bulky substituents on the atoms between the ether bonds, specifically those having 2 or more carbon atoms, preferably 3
As described above, a substituent having a linear, branched, or cyclic structure, more preferably, a substituent having a branched or cyclic structure is preferably bonded. Further, a compound in which an atom existing between two or more ether bonds contains a plurality of, preferably 3 to 20, more preferably 3 to 10, and particularly preferably 3 to 7 carbon atoms is preferable.

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

[0156]

Embedded image

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

As the above polyether compound,
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-
Butyl bis (methoxymethyl) silane, cyclohexyl
-t-butylbis (methoxymethyl) silane, i-propyl-
t-butylbis (methoxymethyl) silane and the like.

Among these, 1,3-diethers are preferably used, and in particular, 2,2-diisobutyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2-Dicyclohexyl-1,3-dimethoxypropane and 2,2-bis (cyclohexylmethyl) -1,3-dimethoxypropane are preferably used.

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

In the polymerization of propylene, in addition to propylene, a small amount of other olefins other than propylene or a small amount of a diene compound may coexist in the polymerization system.

Other olefins other than propylene include ethylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene,
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, vinylnorbornene, and dicyclopentadiene.

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

In the polymerization system, the above-mentioned [Ia] solid titanium catalyst component or [Ib] pre-polymerization catalyst component is composed of [Ia] titanium atom or [Ib] pre-polymerization component in [Ia] solid titanium catalyst component per liter of polymerization volume. It is used in an amount of usually about 0.0001 to 50 mmol, preferably about 0.001 to 10 mmol, in terms of titanium atom in the polymerization catalyst component. [II] The organometallic catalyst component is such that the metal atom contained in the [II] organometallic catalyst component is usually about 1 to 2000 mol, preferably about 2 to 500 mol, per 1 mol of titanium atom in the polymerization system. It is used in such an amount that [III] The silicon compound (c) or the polyether compound (d) is used in an amount of usually about 0.001 to 50 mol, preferably about 0.01 to 20 mol per mol of metal atom in the [II] organometallic catalyst component. It is used in a molar amount.

When hydrogen is used at the time of polymerization, a propylene polymer having a large melt flow rate is obtained, and the molecular weight of the propylene polymer obtained can be controlled by the amount of hydrogen added. Also 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 ° C.
00 ° C. and the pressure is usually from normal pressure to 100 kg / cm
² , preferably about ² to 50 kg / cm ² . The polymerization can be carried out in any of a batch system, a semi-continuous system and a continuous system.

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. Can be reduced. Therefore, the operation of removing the catalyst from the propylene polymer can be omitted, and rust of the mold can be easily prevented when a molded article is formed using the obtained propylene polymer.

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

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

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

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

The isotactic pentad value ([M ₅ ]) determined by NMR measurement of the boiling heptane-insoluble component of the polymer obtained in the A polymerization is 0.960 to 0.99.
5, preferably 0.970 to 0.995, more preferably 0.980 to 0.995, even more preferably 0.98
It is desirably 2 to 0.995.

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

The polymer obtained by the A polymerization is as follows:
0.1 to 55 in the finally obtained propylene polymer
%, Preferably 2 to 35%, particularly preferably 5 to 30%
Is desirably manufactured so as to be present in a proportion of

When a propylene polymer is produced using two or more polymerization reactors, propylene is polymerized in the remaining one of the two or more polymerization reactors (hereinafter referred to as “B polymerization”). And a propylene polymer having a melt flow rate of 0.1 to 500 g / 10 min as a final product.

In the polymerization system of the A polymerization and the B polymerization, the above-mentioned [Ia] solid titanium catalyst component or [Ib]
The pre-polymerization catalyst component contained [Ia] per liter of polymerization volume.
It is usually about 0.0001 to 50 mmol, preferably about 0.001 in terms of titanium atom in the solid titanium catalyst component or titanium atom in the [Ib] prepolymerization catalyst component.
It is used in an amount of 〜１０10 mmol. Further, [II] the organometallic catalyst component is added to 1 mole of titanium atom in the polymerization system.
[II] The amount of the metal atom contained in the organometallic catalyst component is usually about 1 to 2000 mol, preferably about 2 to 500 mol. [III] The silicon compound (c) or the polyether compound (d) is usually used in an amount of about 0.001 mol per mol of metal atom in the [II] organometallic catalyst component.
It is used in an amount of from 1 to 50 mol, preferably about 0.01 to 20 mol.

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

In both the A polymerization and the B polymerization, the molecular weight of the obtained polymer can be easily adjusted by supplying or excluding hydrogen. In this case, in the present invention, the crystallinity and stereoregularity index of the obtained propylene polymer do not decrease, and the catalyst activity does not decrease. The supply amount of hydrogen varies depending on various conditions, but may be any amount as long as the melt flow rate of the finally obtained polymer 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.
０．９0.995, more preferably 0.982 to 0.995
And the value of [M ₃ ] is 0.0020 to 0.0
050, preferably 0.0023 to 0.0045, and more preferably 0.0025 to 0.0040.

The polymerization temperature of propylene in the A polymerization and the B polymerization is usually about -50 to 200 ° C, preferably 20 to 100 ° C, and the pressure is usually normal pressure to 10 ° C.
0 kg / cm ² , preferably ² to 50 kg / cm ² . The polymerization can be carried out by any of batch, semi-continuous and continuous methods.

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

As the nucleating agent, various conventionally known nucleating agents can be used without any particular limitation. Among them, preferred nucleating agents include the following nucleating agents.

[0184]

Embedded image

(Wherein R¹Is oxygen, sulfur or carbon number 1
Represents 10 to 10 hydrocarbon groups;^Two, R ^ThreeIs hydrogen or charcoal
A hydrocarbon group having a prime number of 1 to 10,^Two, R^ThreeIs the same kind
Or heterogeneous, R^TwoEach other, R^ThreeBetween each other
Is R^TwoAnd R^ThreeMay be combined to form a ring,
Represents a metal atom having 1 to 3 valences, and n is an integer of 1 to 3
You. ) Specifically, sodium-2,2'-methylene-bis
(4,6-di-t-butylphenyl) phosphate, sodium
Um-2,2'-ethylidene-bis (4,6-di-t-butylphenyl
Le) phosphate, lithium-2,2'-methylene-bis-
(4,6-di-t-butylphenyl) phosphate, lithium
-2,2'-Ethylidene-bis (4,6-di-t-butylphenyl) phenyl
Phosphate, sodium-2,2'-ethylidene-bis (4-i
-Propyl-6-t-butylphenyl) phosphate, lithium
Um-2,2'-methylene-bis (4-methyl-6-t-butylphenyl
Le) phosphate, lithium-2,2'-methylene-bis (4
-Ethyl-6-t-butylphenyl) phosphate, calcium
Um-bis [2,2'-thiobis (4-methyl-6-t-butyl
Nil) phosphate], calcium-bis [2,2'-thio
Bis (4-ethyl-6-t-butylphenyl) phosphate]
 , Calcium-bis [2,2'-thiobis- (4,6-di-t-butyl
Ruphenyl) phosphate], magnesium-bis
[2,2'-thiobis (4,6-di-t-butylphenyl) phospho
), Magnesium-bis [2,2'-thiobis- (4-t-
Octylphenyl) phosphate], sodium-2,
2'-butylidene-bis (4,6-di-methylphenyl) phosph
Fate, sodium-2,2'-butylidene-bis (4,6-di-
(t-butylphenyl) phosphate, sodium-2,2'-
t-octylmethylene-bis (4,6-di-methylphenyl)
Phosphate, sodium-2,2'-t-octylmethylene-
Bis (4,6-di-t-butylphenyl) phosphate,
Lucium-bis- (2,2'-methylene-bis (4,6-di-t-butyl
Ruphenyl) phosphate), magnesium-bis [2,
2'-methylene-bis (4,6-di-t-butylphenyl) phosph
Fate], barium-bis [2,2'-methylene-bis (4,6
-Di-t-butylphenyl) phosphate], sodium
-2,2'-methylene-bis (4-methyl-6-t-butylphenyl)
Phosphate, sodium-2,2'-methylene-bis (4-
Ethyl-6-t-butylphenyl) phosphate, sodium
(4,4'-dimethyl-5,6'-di-t-butyl-2,2'-biphenyl
Le) phosphate, calcium-bis [(4,4'-dimethyl
-6,6'-di-t-butyl-2,2'-biphenyl) phosphate
G], sodium-2,2'-ethylidene-bis (4-m-butyl-
6-t-butylphenyl) phosphate, sodium-2,
2'-methylene-bis (4,6-di-methylphenyl) phosph
, Sodium-2,2'-methylene-bis (4,6-di-ethyl
Ruphenyl) phosphate, potassium-2,2'-ethylide
N-bis (4,6-di-t-butylphenyl) phosphate,
Calcium-bis [2,2'-ethylidene-bis (4,6-di-t-butyl
Tylphenyl) phosphate], magnesium-bis
[2,2'-ethylidene-bis (4,6-di-t-butylphenyl)
Phosphate], barium-bis [2,2'-ethylidene-
Bis (4,6-di-t-butylphenyl) phosphate],
Aluminum-tris [2,2'-methylene-bis (4,6-di-t-
Butylfel) phosphate] and aluminum-
Tris [2,2'-ethylidene-bis (4,6-di-t-butyl
Nil) phosphate] and mixtures of two or more of these
Things can be exemplified. Especially sodium-2,2'-methyl
Len-bis (4,6-di-t-butylphenyl) phosphate
Is preferred.

[0186]

Embedded image

(Wherein R ⁴ is hydrogen or C 1-10)
M represents a metal atom having 1 to 3 valences, 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. Especially sodium
-Bis (4-t-butylphenyl) phosphate is preferred.

[0188]

Embedded image

(Wherein R ⁵ is hydrogen or C 1-10)
Represents a hydrocarbon group. ) Specifically, 1,3,2,4-dibenzylidene sorbitol, 1,3-benzylidene-2,4-p-methylbenzylidene sorbitol, 1,3-benzylidene-2,4-p-
Ethyl benzylidene sorbitol, 1,3-p-methyl benzylidene-2,4-benzylidene sorbitol, 1,3-p-ethyl benzylidene-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-
Chlorbenzylidene 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-
Chlorbenzylidene sorbitol, 1,3-p-ethylbenzylidene-2,4-p-chlorobenzylidene sorbitol and
Examples thereof include 1,3,2,4-di (p-chlorobenzylidene) sorbitol and a mixture of two or more of these. Particularly, 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-
Preferred are 2,4-p-methylbenzylidene sorbitol, 1,3,2,4-di (p-chlorobenzylidene) sorbitol and mixtures of two or more thereof.

Examples of other nucleating agents include metal salts of aromatic carboxylic acids and aliphatic carboxylic acids.
Examples thereof include aluminum benzoate, aluminum pt-butylbenzoate, sodium adipate, sodium thiophenecarboxylate, and sodium pyrrolecarboxylate.

In addition, inorganic compounds 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 to add 0.001 to 10 parts by weight, preferably 0.01 to 5 parts by weight, particularly preferably 0.1 to 3 parts by weight with respect to 00 parts by weight.

By adding the nucleating agent to the propylene polymer in the above amount, the propylene polymer having fine crystal particles and further improved crystallinity can be obtained without impairing the excellent properties inherent in the propylene polymer. can get.

A terpene resin containing no polar group,
The petroleum resin (B) terpene resins containing no polar group to be used in the present invention that does not contain a hydroxyl group, an aldehyde group, a carbonyl group, a carboxyl group, a sulfonic group (-SO ₃ Y, wherein Y is, H, N
a, Mg, etc.), a terpene resin having no polar group such as a polar group such as a halogen or a modified form thereof. That is, it is a hydrocarbon having a composition of (C ₅ H ₈ ) _n and a modified compound derived therefrom. The terpene resin is sometimes called a terpenoid.

Specific examples of the terpene resin include pinene,
Karen, Myrsen, Osimen, Limonene, Terpyrenone, Terpinene, Sabinen, Tricyclene, Bisabolene, Zingiberen, Santarem, Khanholene, Millen,
Examples include totalene.

The petroleum resin containing no polar group used in the present invention includes a hydroxyl group, a carboxyl group and a sulfone group (-
SO ₃ Y, where Y is H, Na, Mg, etc.),
It is a petroleum resin that does not have a polar group such as a halogen or a modified group thereof. That is, the resin is a cyclopentadiene-based resin using a petroleum unsaturated hydrocarbon directly as a raw material, or a resin using a higher olefinic hydrocarbon as a main raw material.

The petroleum resin having no polar group has a glass transition temperature (Tg) of 50 ° C. or higher, preferably 60 ° C. or higher, more preferably 60 to 100 ° C .;
The softening point measured according to E-28 is 100 ° C. or higher,
110 ° C. or higher, more preferably 110 to 150
° C, and the specific gravity measured in accordance with ASTM D-156 is 0.900 to 1.30, preferably 0.980 to 1.80.
1.20 and a weight average molecular weight (Mw) of 4 measured by gel permeation chromatography (GPC).
00 or more, preferably 500 or more, more preferably 50
Desirably, it is 0 to 2000. In the present invention, the GPC measurement was performed using TSKGEL G3 as a column.
000HXL and G4000HXL were used, the solvent was tetrahydrofuran, the measurement temperature was 40 ° C., and the weight average molecular weight was determined in terms of polystyrene.

In the present invention, as the petroleum resin containing no polar group, it is desirable to use a hydrogenated petroleum resin obtained by adding hydrogen to the above-mentioned petroleum resin and having a hydrogenation rate of 80% or more, preferably 95% or more. . As such a hydrogenated petroleum resin, a hydrogenated alicyclic petroleum resin is mentioned, and specifically, there is "ESCOLETS" (trade name: manufactured by Tonex Corporation).

Hydrogenated Petroleum Resin (D) As the hydrogenated petroleum resin (D) used in the present invention, conventionally known hydrogenated petroleum resins are widely used. Specifically, aromatic hydrocarbons are polymerized. And hydrides of terpene resins. Specifically, styrene, α-methylstyrene, vinyl toluene,
Hydrogenated resin obtained by polymerizing one kind of monomer selected from various aromatic unsaturated hydrocarbons such as vinyl xylene, propenyl benzene, indene, methyl indene and ethyl indene, and terpenes; Hydrogenated resins obtained by polymerizing two or more monomers selected from unsaturated hydrocarbons and terpenes can be used. Furthermore, a fraction (by boiling point of 20 to 300 ° C., preferably 1
(50-300 ° C.)) and hydrogenated resin obtained by polymerization.

The glass transition temperature (T
g) is 50 ° C or higher, preferably 60 ° C or higher, more preferably 60 to 100 ° C, and the softening point measured in accordance with ASTM E-28 is 100 ° C or higher, preferably 11 ° C or higher.
0 ° C. or higher, more preferably 110 to 150 ° C .;
The specific gravity measured according to STM D-156 is 0.9
00 to 1.30, preferably 0.980 to 1.20, and gel permeation chromatography (GP
C) a weight average molecular weight (Mw) of 400 or more,
Preferably 500 or more, more preferably 500 to 200
Desirably, it is 0.

Polypropylene Resin Composition The first polypropylene resin composition according to the present invention comprises the propylene polymer (A): 80 to 95% by weight, preferably 85 to 92% by weight, and the terpene containing no polar group. Resin and / or petroleum resin containing no polar group (B):
20 to 5% by weight, preferably 15 to 8% by weight.

The first polypropylene resin composition according to the present invention comprises, in addition to the propylene polymer and the terpene resin containing no polar group and / or the petroleum resin containing no polar group, other resins, for example, It may contain a polyolefin other than polypropylene, a terpene resin containing a polar group, or a petroleum resin containing a polar group. Such another resin is 2% based on a total of 100% by weight of the terpene resin containing no polar group and the petroleum resin containing no polar group.
It is desirably less than 0%, preferably less than 15% by weight. When a resin other than a terpene resin containing no polar group or a petroleum resin containing no polar group is blended in the propylene polymer at a ratio of 20% or more, the water vapor barrier property after film formation may be deteriorated.

The second polypropylene resin composition according to the present invention comprises the propylene polymer (A): 70 to 95% by weight, preferably 75 to 85% by weight, and the hydrogenated petroleum resin (D): 5 to 30%. % By weight, preferably 15 to 25% by weight
And is formed from

If the amount of the hydrogenated petroleum resin (D) is less than 5% by weight, the transparency and thermoformability of the sheet may be insufficient, and if it exceeds 30% by weight, the thermoformability may decrease. There is.

The first and second polypropylene resin compositions may contain a rubber component for improving impact strength, or may be a heat-resistant stabilizer, a weather-resistant stabilizer, an antistatic agent, a slip agent, and an anti-blocking agent. Agent, viscosity modifier,
Coloring inhibitors, antifogging agents, lubricants, dyes, pigments, natural oils, synthetic oils, waxes and the like can be compounded, and the mixing ratio is an appropriate amount.

In addition, silica, diatomaceous earth, alumina, titanium oxide, magnesium oxide, pumice powder, pumice balloon, aluminum hydroxide, magnesium hydroxide, basic carbonate are added to the polypropylene resin composition within a range not to impair the object of the present invention. Magnesium, dolomite, calcium sulfate, potassium titanate, barium sulfate, calcium sulfite, talc, clay, mica, asbestos, glass fiber, glass flake, glass beads, calcium silicate, montmorillonite, bentonite, graphite, aluminum powder, molybdenum sulfide, Boron fiber, silicon carbide fiber,
Fillers such as polyethylene fibers, polypropylene fibers, polyester fibers, and polyamide fibers may be blended.

The first polypropylene resin composition according to the present invention can be manufactured by using a known method, for example, the following method. (1) A method of mechanically blending a propylene polymer, a terpene resin containing no polar group and / or a petroleum resin containing no polar group, and other components to be added as desired with an extruder, a kneader or the like. .

(2) A propylene polymer, a terpene resin containing no polar group and / or a petroleum resin containing no polar group, and other components added as desired are mixed with a suitable good solvent (for example, hexane, heptane, decane). , Cyclohexane, benzene, toluene, and xylene) and then removing the solvent.

(3) A solution prepared by separately dissolving a propylene polymer, a terpene resin containing no polar group and / or a petroleum resin containing no polar group, and other components added as required in a suitable good solvent. A method of mixing after preparation, and then removing the solvent.

(4) A method in which the above methods (1) to (3) are combined. The second polypropylene resin composition according to the present invention can be manufactured by using a known method, and for example, can be manufactured by the same method as the first polypropylene resin composition.

The first polypropylene resin composition according to the present invention is used as a base material of a stretched film or a multilayer stretched film. The second polypropylene resin composition according to the present invention is used as a base material of a sheet or a multilayer sheet.

Next, a stretched polypropylene film made of the first polypropylene resin composition, a multi-layer stretched polypropylene film having a substrate layer made of the composition,
Further, a polypropylene sheet for PTP packaging comprising the second polypropylene resin composition and a polypropylene multilayer sheet for PTP packaging having a base material layer comprising the composition will be specifically described.

Stretched Polypropylene Film The stretched polypropylene film according to the present invention comprises the first
It is a biaxially stretched film formed from the polypropylene resin composition. The glass transition temperature (Tg) of the stretched polypropylene film is desirably in the range of 0 to 10 ° C.

In the present invention, the glass transition temperature (T
g) is measured as follows. That is, a scanning calorimeter DSC-II type (Perkin Elmer
Thermostat at a temperature of 40 ° C./min under nitrogen flow, and start the thermograph at 20 ° C. The temperature when the endothermic peak deviates from the baseline and the endothermic peak The value of the arithmetic mean with the temperature at the time of returning to the line was defined as the glass transition temperature (Tg).

The stretch ratio of the stretched polypropylene film is desirably in the range of 4 × 4 to 7 × 12 (length × width). The thickness of the stretched polypropylene film is not particularly limited, but is usually in the range of 10 to 100 μm, preferably 15 to 70 μm.

The stretched polypropylene film according to the present invention is produced, for example, as follows. First, a predetermined amount of the propylene polymer and the terpene resin containing no polar group and / or the petroleum resin containing no polar group are mixed, and then melt-extruded at a resin temperature of 220 to 280 ° C,
Cast on a cooling roll or in a water tank to obtain an unstretched raw material. At this time, the temperature of the cooling roll or the water tank was 20
It is desirably in the range of -80 ° C.

Next, the unstretched raw material is biaxially stretched and biaxially oriented to obtain a stretched polypropylene film of the present invention. The stretching ratio for biaxial stretching is 4
It is desirable to be in the range of × 4 to 7 × 12 (vertical × horizontal).

The biaxial stretching can be performed by a sequential or simultaneous tenter method, a sequential or simultaneous tubular method, or the like. In the present invention, the surface of the stretched polypropylene film may be further subjected to a corona discharge treatment in an atmosphere of air, carbon dioxide or nitrogen gas to increase the surface tension of the film to about 40 dyn / cm or more to improve the surface adhesion. .

The stretched polypropylene film according to the present invention
Has a water vapor transmission rate of 2.5 (g / m ^Two・ 24hr / 25μ
m) It has excellent water vapor barrier properties of
Excellent in properties, equivalent to or better than conventional K-OP film
The above shows the Young's modulus. In addition, chlorine gas is generated during incineration
do not do.

The multilayer stretched polypropylene film according to the present invention is a multilayer stretched film having a base layer formed from the first polypropylene resin composition and a surface layer composed of the propylene-based polymer (C). It is. The glass transition temperature (Tg) of the substrate layer of the multi-layer stretched polypropylene film is 0 to 1
It is desirable to be in the range of 0 ° C.

The thickness of the stretched polypropylene multilayer film is not particularly limited, but is usually in the range of 10 to 100 μm, preferably 15 to 70 μm.
Further, the layer configuration of the multi-layer stretched polypropylene film includes a base layer made of the first polypropylene resin composition,
A two-layer structure of a surface layer made of a propylene-based polymer (C) formed on one surface of the base material layer, or a base material layer made of the first polypropylene resin composition, and both surfaces of the base material layer It is desirable to have a three-layer structure with the formed surface layer made of the propylene-based polymer (C). In this multi-layer stretched polypropylene film, the thickness of the base layer made of the stretched polypropylene film is 80% or more, preferably 90%, of the total thickness of the multi-layer stretched polypropylene film.
% Is desirable.

The propylene polymer (C) forming the multi-layer stretched polypropylene film of the present invention is a homopolymer of propylene or a structural unit derived from propylene and ethylene and / or an olefin having 4 to 20 carbon atoms. Block copolymers or random copolymers comprising the structural units to be formed.

The propylene-based polymer (C) may contain propylene-derived structural units in a proportion of 50 mol% or more, preferably 60 mol% or more, more preferably 65 mol% or more. desirable.

Here, the olefin having 4 to 20 carbon atoms includes 1-butene, 1-pentene, 1-hexene, 4-methyl-1-
Pentene, 3-methyl-1-pentene, 1-octene, 3-methyl-1-butene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene,
Cyclopentene, cycloheptene, norbornene, 5-ethyl-2-norbornene, tetracyclododecene, 2-ethyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octa Hydronaphthalene and the like can be mentioned.

Further, this propylene polymer (C)
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, 1,7-octadiene, 1,9
-Structural units derived from diene compounds having 4 to 20 carbon atoms such as decadiene, isoprene, butadiene, ethylidene norbornene, vinylnorbornene and dicyclopentadiene may be contained in an amount of 2 mol% or less.

Such a propylene-based polymer (C) is
Pmmmm in ¹³ C-NMR spectrum of a boiling heptane-insoluble component, Pw, Sαγ, Sαδ ^+, the value of the pentad isotacticity [M _5] obtained by the above equation (3) from the absorption intensities of T.DELTA. ⁺ [Delta] ⁺ is 0.925 ７５0.975, preferably 0.930 or more and less than 0.970, and Pmmr in the ¹³ C-NMR spectrum of the boiling heptane-insoluble component.
m, Pmrmr, Pmrrr, Prrmr, Prmmr, Prrrr, Pw,
The value of the stereoregularity index [M ₃ ] obtained from the absorption intensity of Sαγ, Sαδ ⁺ and Tδ ⁺ δ ^{+ by} the above formula (4) is 0.0020 to 0.0050, preferably 0.0025.
It is desirably in the range of 0.0040 to 0.0040.

The propylene polymer (C) was heated at 135 ° C.
The intrinsic viscosity [η] measured in decalin is 0.01 to 1
It is desirably in the range of 0 dl / g, preferably 0.08 to 7 dl / g.

The propylene-based polymer (C) is a heat-resistant stabilizer, a weather-resistant stabilizer, an antistatic agent, a slip agent, an anti-blocking agent, a viscosity modifier, a coloring inhibitor, an anti-fogging agent, a lubricant, a dye, a pigment. , Natural oils, synthetic oils, waxes and the like can be compounded in appropriate amounts. Further, the above-mentioned fillers can be blended.

In the multilayer stretched polypropylene film according to the present invention, the layer comprising the propylene polymer (C) is provided on at least one surface of the unstretched raw fabric obtained in the step of producing the stretched polyethylene film. It is obtained by laminating so as to have a thickness of 20% or less with respect to the total thickness of the multilayer raw material, and biaxially stretching the unstretched multilayer raw material in the same manner as in the polyester stretched film.

As described above, by using the propylene-based polymer (C) as the surface layer of the multi-layer stretched polypropylene film, the chemical resistance of the film is improved, and the printability and the applicability of the adhesive are greatly improved. . Further, at the time of cast molding, since the adhesion between the cooling roll and the unstretched raw material is improved, the cooling effect is enhanced and the productivity is improved.

In the present invention, the surface of the multi-layer stretched polypropylene film is further subjected to a corona discharge treatment in an atmosphere of air, carbon dioxide gas or nitrogen gas to increase the surface tension of the film to about 40 dyn / cm or more to improve the surface adhesion. You may.

The multilayer stretched polypropylene film of the present invention has the properties of the stretched polypropylene film, as well as excellent chemical resistance, printability, and adhesive suitability. Recycling by re-extrusion is also possible.

PTP Packaging Polypropylene Sheet The PTP packaging polypropylene sheet according to the present invention is formed from the second polypropylene resin composition.

Although the thickness of the polypropylene sheet for PTP packaging is not particularly limited, it is usually 100 to 700.
It is about μm. The polypropylene sheet for PTP packaging according to the present invention is manufactured by sheeting the second polypropylene resin composition using a known machine such as a T-die.

The polypropylene sheet for PTP packaging according to the present invention has excellent steam barrier properties and excellent transparency as compared with a conventional sheet coated with PVDC. Normally, in PTP packaging, a resin sheet is thermoformed to form a plurality of recesses, tablets and the like are filled in these recesses, sealed with aluminum foil, and the sheet is perforated and slit, and the outer periphery is punched. Has been automated.

The polypropylene sheet for PTP packaging according to the present invention is excellent in moldability at the time of thermoforming, is excellent in thermal adhesion to aluminum foil, excellent in punching property, and has less uneven thickness.
P packaging can be manufactured at high speed.

The manufactured PTP package has transparency,
Excellent rigidity and water vapor barrier properties. Furthermore, no chlorine gas is generated during incineration. Polypropylene Multilayer Sheet for PTP Packaging The polypropylene multilayer sheet for PTP packaging according to the present invention is a multilayer sheet having a base layer formed from the second polypropylene resin composition and a surface layer formed from a synthetic resin. In such a PTP packaging polypropylene multilayer sheet, the synthetic resin forming the surface layer is preferably a synthetic resin containing no chlorine, and particularly preferably a propylene-based polymer (E) as described later.

Although the thickness of the polypropylene multilayer sheet for PTP packaging is not particularly limited, it is usually from 110 to 8
It is about 00 μm. Further, the layer configuration of the polypropylene multilayer sheet for PTP packaging includes a base layer made of the second polypropylene resin composition and a surface layer made of a propylene-based polymer (E) formed on one surface of the base layer. With 2
It is desirable to have a layer structure or a three-layer structure of a base layer made of the second polypropylene resin composition and a surface layer made of a propylene-based polymer (E) formed on both surfaces of the base layer. .

In the polypropylene multilayer sheet for PTP packaging according to the present invention, the ratio of the thickness of the base material layer is 50% or more, preferably 55% or more with respect to the total thickness of the sheet. The thickness T (μm) and the ratio H (%) of the thickness of the base layer to the total thickness T of the sheet are 3.4 ≦ log (T × H) ≦ 5.0, preferably 3.6 ≦ It is preferable that the relationship represented by log (T × H) ≦ 4.6 is satisfied.

When the ratio of the thickness of the base material layer is 50% or less with respect to the total thickness of the sheet, the moldability of the polypropylene multilayer sheet for PTP packaging may decrease. Also,
If the value of log (T × H) is less than 3.4, PT
If the polypropylene multilayer sheet for P packaging has insufficient water vapor barrier properties, and the value of log (T × H) exceeds 5.0, the thermoformability may decrease.

The propylene polymer (E) used in the present invention includes the propylene polymer (A) as described above.
Alternatively, a conventionally known propylene polymer is used. Specifically, the propylene polymer (A) as described above, a conventionally known propylene homopolymer, propylene, and ethylene and / or α having 4 or more carbon atoms. A random copolymer with -olefin, or a block copolymer of propylene with ethylene and / or an α-olefin having 4 or more carbon atoms.

In the random copolymer or the block copolymer, the structural unit derived from propylene is 90%.
Mol% or more, preferably 95 mol% or more, and the constitutional unit derived from a monomer selected from ethylene and an α-olefin having 4 or more carbon atoms is 10 mol% or less, preferably 5 mol% or less. It is desirable that it be contained.

Such a propylene-based polymer (E) is
Melt flow rate at 230 ° C. under a load of 2.16 kg is 0.1 to 500 g / 10 min, preferably 0.2 to 20 g
0 g / 10 min, with a density of 0.900 g / cm ³
As described above, the range is preferably 0.900 to 0.936 g / cm ³ .

The propylene polymer (E) used in the present invention may contain a component unit derived from the same diene compound as described above, as long as the properties are not impaired. The content of the diene component is usually 0 to 1 mol%, preferably 0 to 0.5 mol%.

The propylene polymer (E) may be blended with various stabilizers or fillers blended in the polypropylene resin composition. PTP according to the present invention
The polypropylene multilayer sheet for packaging is prepared by using a second polypropylene resin composition for forming a base layer and a resin for forming a surface layer such as the propylene polymer (E) using a known machine such as a T-die. It is manufactured by co-extrusion and sheeting.

The polypropylene multilayer sheet for PTP packaging according to the present invention has excellent steam barrier properties and excellent transparency as compared with the conventional sheet coated with PVDC.

The polypropylene multilayer sheet for PTP packaging according to the present invention is excellent in moldability during thermoforming, excellent in thermal adhesion to aluminum foil and punching properties, and can be used for high-speed PTP packaged products with less uneven thickness. Can be manufactured.

The manufactured PTP package has transparency,
Excellent rigidity and water vapor barrier properties. Moreover, no chlorine gas is generated during incineration. Furthermore, recycling by re-extrusion is possible.

[0248]

According to the first polypropylene resin composition of the present invention, a film having excellent water vapor barrier properties and transparency and having a high Young's modulus can be produced.

The stretched polypropylene film of the present invention comprises:
Excellent water vapor barrier properties and transparency, and high Young's modulus.
Moreover, no chlorine gas is generated during incineration. The multilayer stretched polypropylene film of the present invention has excellent water vapor barrier properties and transparency, has a high Young's modulus, and has excellent chemical resistance.
Moreover, no chlorine gas is generated during incineration. Furthermore, recycling by re-extrusion is possible.

The second polypropylene resin composition according to the present invention can form a sheet having excellent steam barrier properties and excellent rigidity and transparency. The polypropylene sheet for press-through pack packaging according to the present invention has excellent steam barrier properties, and is excellent in rigidity, transparency, and thermoformability. Moreover, no chlorine gas is generated during incineration.

The polypropylene sheet for press-through pack packaging and the polypropylene multilayer sheet for press-through pack packaging according to the present invention are excellent in steam barrier properties and excellent in rigidity, transparency and thermoformability. Moreover, no chlorine gas is generated during incineration. Furthermore, recycling by re-extrusion is possible.

[0252]

EXAMPLES Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples.

In this example, the melt flow rate and the density of the polymer were measured as follows. [Melt flow rate] Measured according to ASTM D-1238.

[Density] The density was measured according to ASTM D-1505. In this example, the physical properties of the film and the sheet were measured as described below.

[Moisture Permeability (Steam Barrier Property)] JIS Z
Measured under the conditions of 40 ° C. and 90% RH in accordance with −0208. [Young's modulus] It was measured in accordance with ASTM D-882.

Tensile speed: 50 mm / min Distance between chucks: 64.0 mm [Haze] Measured according to ASTM D-1003.

[Moldability] PTP packaging machine M2000
PTP packaging was performed using [manufactured by Kanae Co., Ltd.] to evaluate moldability.

[0258]

[Production example]

[Preparation of Solid Titanium Catalyst Component] A 4.5 m ³ reactor was charged with 240 kg of anhydrous magnesium chloride, 1100 liters of decane and 990 kg of 2-ethylhexyl alcohol, and heated at 130 ° C. to form a homogeneous solution. Was added to the mixture and stirred at 130 ° C. to dissolve phthalic anhydride. After cooling the thus obtained homogeneous solution to room temperature, the whole homogeneous solution was dripped into 6.7 m ^{3 of} titanium tetrachloride kept at −25 ° C. while stirring. Temperature after charging is about -20
° C. Next, the temperature of the mixture was raised to 1 over 4 hours.
The temperature was raised to 10 ° C., and when the temperature reached 110 ° C., 13 kg of diisobutyl phthalate (DIBP) was added.
Stirring was maintained at the same temperature for a period of time. After the completion of the reaction for 2 hours, a solid portion was collected by hot filtration, and this solid portion was resuspended in 7.3 m ³ of titanium tetrachloride, and then again at 110 ° C. for 2 hours.
A heating reaction was performed. After completion of the reaction, a solid portion was collected again by hot filtration, and sufficiently washed with decane and hexane at 110 ° C. until no free titanium compound was detected in the solution. Through the above operations, a solid titanium catalyst component (A) was obtained.

The composition of the obtained solid titanium catalyst component (A) was as follows: 2.2% by weight of titanium; 61% by weight of chlorine; 19% by weight of magnesium; and 12.7% by weight of DIBP.

[Preparation of Preliminary Polymerization Catalyst] In a 80-liter reactor equipped with a stirrer, under a nitrogen atmosphere, 40 liters of purified hexane, 3.0 mol of triethylaluminum, 3.0 mol of trimethylmethoxysilane and the above solid titanium catalyst component ( After adding 0.3 mol of A) in terms of titanium atom, 3-methyl-1-butene (3MB-1) was added at a temperature of 20 ° C.
1.5 kg was supplied to the reactor, and prepolymerization was performed for 2 hours. After completion of the reaction, the inside of the reactor was replaced with nitrogen, and a washing operation including removal of a supernatant and addition of purified hexane was performed three times to obtain a prepolymerized catalyst (B). This prepolymerized catalyst (B)
Was resuspended in purified hexane and stored.

[Polymerization] A reactor equipped with a stirrer having an internal volume of 1,000 liters was charged with 450 liters of purified n-hexane, and in a propylene atmosphere at 60 ° C., 500 mmol of triethylaluminum, 500 mmol of dicyclopentyldimethoxysilane, and a prepolymerization catalyst (B) was charged with 10 mmol of Ti in terms of titanium atoms. After introducing 250 liters of hydrogen and raising the temperature to 80 ° C., the temperature was maintained for 4 hours to carry out propylene polymerization. The pressure during the polymerization is 6 kg / c
m ² -G. After the polymerization was completed, the pressure was released, and the slurry containing the produced solid was centrifuged and dried with a drier to obtain 200 kg of a white powdery polymer.

The melt flow rate of this polymer was 2 g /
10 minutes, the value of the stereoregularity index [M ₅ ] of the boiling heptane-insoluble component was 0.986, and the value of the stereoregularity index [M ₃ ] of the boiling heptane-insoluble component was 0.0030. The crystallinity of the heptane-insoluble component is 78.5%, the content of the 3MB-1 polymer is 300 ppm,
The density was 0.919 g / cm ³ .

[0263]

[Comparative manufacturing example]

[Preparation of Preliminary Polymerization Catalyst] In a 80-liter reactor equipped with a stirrer, under a nitrogen atmosphere, 40 liters of purified hexane, 0.9 mol of triethylaluminum, and 0.3 mol of the solid titanium catalyst component (A) in terms of titanium atoms. After the addition, 1.66 kg of propylene was supplied to the reactor at a temperature of 20 ° C., and prepolymerization was performed for 2 hours. After the completion of the reaction, the inside of the reactor was replaced with nitrogen, and a washing operation including removal of a supernatant and addition of purified hexane was performed three times to obtain a prepolymerized catalyst (C).
I got This prepolymerized catalyst (C) was resuspended in purified hexane and stored.

[Polymerization] A reactor equipped with a stirrer having an internal volume of 1,000 liters was charged with 450 liters of purified n-hexane, and in a propylene atmosphere at 60 ° C., 500 mmol of triethylaluminum, 100 mmol of dicyclopentyldimethoxysilane, and prepolymerization were performed. The catalyst (C) was charged with 10 mmol Ti in terms of titanium atoms. After 100 liters of hydrogen was introduced and the temperature was raised to 80 ° C., the temperature was maintained for 3 hours to polymerize propylene. The pressure during the polymerization is 6 kg /
cm ² -G. After the completion of the polymerization, the pressure was released, and the slurry containing the produced solid was centrifuged and dried with a drier to obtain 230 kg of a white powdery polymer.

The melt flow rate of this polymer was 2 g /
10 minutes, the value of the stereoregularity index [M ₅ ] of the boiling heptane-insoluble component was 0.954, and the value of the stereoregularity index [M ₃ ] of the boiling heptane-insoluble component was 0.0036. The crystallinity of the component is 58.5%, 3M
The B-1 polymer content was 0 ppm and the density was 0.9.
It was 00 g / cm ³ .

[0266]

Example 1 Propylene polymer obtained in the above Production Example: 85 parts by weight Petroleum resin not containing a polar group: 15 parts by weight “ESCOLETS 5320 (trade name: manufactured by Tonex Corporation)” (hydrogenation rate: 98%, Tg: 70 ° C, softening point: 125 ° C, specific gravity: 1.10, Mw: 600) Irganox 1010: 1000 ppm (trade name: manufactured by Nippon Ciba Geigy Co., Ltd.) Calcium stearate: 100 ppm was mixed and melted at 250 ° C. The cast film was extruded, cooled on a cooling roll maintained at 60 ° C., and an unstretched raw material having a thickness of 900 μm was formed. Next, the unstretched raw material was stretched by a tenter method in a longitudinal direction of 4.5 times and a transverse direction of 8
The film was successively biaxially stretched twice to obtain a stretched polypropylene film having a thickness of 25 μm.

Table 1 shows the results of measuring the properties of the obtained stretched polypropylene film.

[0268]

Example 2 Propylene polymer obtained in the above Production Example: 85 parts by weight Petroleum resin not containing a polar group: 15 parts by weight “Escolets 5320 (trade name: manufactured by Tonex Corporation)” Irganox 1010: 1000 ppm (trade name: Nippon Ciba Geigy Co., Ltd.) Calcium stearate: 100 ppm Polypropylene “Hypol F309” is provided on both sides of a base material layer formed of a polypropylene resin composition.
(Product name: Mitsui Petrochemical Industry Co., Ltd.) ([M ₅ ] =
_{0.958, [M 3] = 0.0035} , melt flow rate; 2.0 g / 10 min, density; 0.912g / cm ³⁾
A co-extruded cast film having a surface layer of
Cool on a cooling roll maintained at 0 ° C.
A 0 μm unstretched multilayer raw material was formed. The thickness composition ratio of this unstretched multilayer raw material was 1/18/1 (surface layer / base material layer / surface layer). Next, this unstretched multilayer raw material was successively biaxially stretched in a longitudinal direction: 4.5 times and in a transverse direction: 8 times by a tenter method to obtain a 25 μm-thick polypropylene multilayer stretched film.

The properties of the obtained multilayer stretched polypropylene film were measured, and the results are shown in Table 1.

[0270]

Example 3 Propylene polymer obtained in the above Production Example: 85 parts by weight Petroleum resin not containing a polar group: 15 parts by weight “ESCORETS 5320 (trade name: manufactured by Tonex Corporation)” Irganox 1010: 1000 ppm (trade name: Nippon Ciba Geigy Co., Ltd.) Calcium stearate: 100 ppm was mixed and melted at 240 ° C., and a cylindrical film was extruded.
It was cooled with cooling water at 25 ° C. to form a 750 μm thick cylindrical unstretched raw material. Next, this tubular unstretched raw material was simultaneously biaxially stretched by a tubular method in a longitudinal direction: 6 times and in a transverse direction: 5 times to obtain a 25 μm thick polypropylene stretched film.

The properties of the obtained stretched polypropylene film were measured, and the results are shown in Table 1.

[0272]

Example 4 Example 1 except that the blending amounts of the propylene polymer and the petroleum resin containing no polar group were 95 parts by weight and the petroleum resin not containing a polar group was 5 parts by weight.
In the same manner as in the above, a 25 μm-thick stretched polypropylene film was obtained. Table 1 shows the results of measuring the properties of the obtained stretched polypropylene film.

[0273]

Example 5 The procedure of Example 1 was repeated except that the blending amounts of the propylene polymer and the petroleum resin containing no polar group were 90 parts by weight and the petroleum resin not containing a polar group was 10 parts by weight. Thus, a stretched polypropylene film having a thickness of 25 μm was obtained.

The properties of the obtained stretched polypropylene film were measured and the results are shown in Table 1.

[0275]

Example 6 The procedure of Example 1 was repeated except that the blending amounts of the propylene polymer and the petroleum resin containing no polar group were 80 parts by weight of the propylene polymer and 20 parts by weight of the petroleum resin containing no polar group. Thus, a stretched polypropylene film having a thickness of 25 μm was obtained.

Table 1 shows the results of measuring the properties of the obtained stretched polypropylene film.

[0277]

Example 7 As a petroleum resin containing no polar group, Escolets 5320 (trade name: manufactured by Tonex) was used instead of petroleum resin.
Escolets ECR356B (trade name: manufactured by Tonex Corporation) (hydrogenation rate: 98%, Tg: 84 ° C, softening point: 14)
(0 ° C., specific gravity: 1.10, Mw: 650) except that a stretched polypropylene film having a thickness of 25 μm was obtained in the same manner as in Example 1.

Table 1 shows the results of measuring the properties of the obtained stretched polypropylene film.

[0279]

Example 8 As a petroleum resin containing no polar group, Escolets 5320 (trade name: manufactured by Tonex) was used instead of petroleum resin.
Example except that Alcon P-115 (trade name: manufactured by Arakawa Chemical Industries, Ltd.) (hydrogenation rate: 99%, Tg: 68 ° C, softening point: 115 ° C, specific gravity: 0.999, Mw: 1600) was used. In the same manner as in Example 1, a stretched polypropylene film having a thickness of 25 μm was obtained.

The properties of the obtained stretched polypropylene film were measured, and the results are shown in Table 1.

[0281]

Example 9 As a petroleum resin containing no polar group, Escolets 5320 (trade name: manufactured by Tonex) was used instead of petroleum resin.
Example except that Alcon P-125 (trade name: manufactured by Arakawa Chemical Industries, Ltd.) (hydrogenation rate: 99%, Tg: 78 ° C, softening point: 125 ° C, specific gravity: 0.999, Mw: 1750) was used. In the same manner as in Example 1, a stretched polypropylene film having a thickness of 25 μm was obtained.

Table 1 shows the results of measuring the properties of the obtained stretched polypropylene film.

[0283]

Comparative Example 1 A stretched polypropylene film was obtained in the same manner as in Example 1 except that the polypropylene obtained in the above Comparative Production Example was used.

Table 1 shows the results of measuring each property of the obtained stretched polypropylene film.

[0285]

Comparative Example 2 A stretched polypropylene film was obtained in the same manner as in Example 1, except that no petroleum resin containing no polar group was used.

Table 1 shows the results of measuring the properties of the obtained stretched polypropylene film.

[0287]

[Reference Example 1] Polypropylene "HIPOL F309"
(Product name: Mitsui Petrochemical Industry Co., Ltd.) ([M ₅ ] =
0.958, [M ₃ ] = 0.0035) was melted at 250 ° C., the cast film was extruded, and cooled on a cooling roll maintained at 60 ° C. to form an unstretched raw material having a thickness of 900 μm. did. Next, the unstretched raw material was successively biaxially stretched by 4.5 times in the machine direction and 8 times in the transverse direction by a tenter method to obtain a 25 μm stretched polypropylene film. Furthermore, PVDC was coated on both sides of this polypropylene stretched film, and a coating layer of 0.5 μm was formed on each of the front and back sides to obtain a K-OP film.

The properties of the obtained K-OP film were measured, and the results are shown in Table 1.

[0289]

[Table 1]

The water vapor permeability of the stretched polypropylene film of the present invention is 1.9 to 2.6 g / m ² · 24 hr / 25 μm, which is 3.0 g / m ² · 24 hr / 25 μm which has been regarded as the limit for a polypropylene film. And has a water vapor barrier property equal to or higher than that of a K-OP film. On the other hand, the water vapor permeability of a stretched polypropylene film made of a conventional composition of polypropylene and a petroleum resin having no polar group is 3.8 g / m ² · 24 hr / 25 μm, and K-
It is about 1.5 times the moisture permeability of the OP film.

[0291]

[Reference Example 2] The propylene polymer obtained in the above Production Example: 80 parts by weight Hydrogenated petroleum resin: 20 parts by weight After “Escolets 5320 (trade name: manufactured by Tonex Corporation)” was mixed with a Henschel mixer, the mixture was mixed with a 65 mmφ. The mixture was extruded at 240 ° C. using an extruder to produce pellets formed from a polypropylene resin composition comprising a propylene polymer and a hydrogenated petroleum resin. This pellet was sheeted by T-die molding at a chill roll temperature of 40 ° C. and an extrusion temperature of 220 ° C. to obtain a width of 300 mm and a thickness of 30 mm.
A 0 μm PTP packaging polypropylene sheet was obtained.

Table 2 shows the results of measuring each property of the obtained polypropylene sheet for PTP packaging.

[0293]

Reference Example 3 A pellet formed from the polypropylene resin composition produced in Reference Example 2 and a propylene-based polymer “Hypole F401” (trade name: manufactured by Mitsui Petrochemical Industries, Ltd.) (melt flow rate: 2) 0.8 g / 10 min, density: 0.909 g / cm ³ )
T set at a chill roll temperature of 40 ° C and an extrusion temperature of 220 ° C
-Co-extrusion by die molding and sheeting were performed to obtain a three-layer PTP packaging multilayer sheet having a base layer made of a polypropylene resin composition and a surface layer made of a propylene-based polymer. This polypropylene multilayer sheet for PTP packaging has a width of 300 mm and a thickness of 300 μm.
20/260/20 μm (surface layer / substrate layer / surface layer).

Table 2 shows the results of measuring the properties of the obtained multilayer polypropylene sheet for PTP packaging.

[0295]

REFERENCE EXAMPLE 4 Width 3 was obtained in the same manner as in Reference Example 2 except that the blending amounts of the propylene polymer and the hydrogenated petroleum resin were 90 parts by weight for the propylene polymer and 10 parts by weight for the hydrogenated petroleum resin.
A PTP packaging polypropylene sheet having a thickness of 00 mm and a thickness of 300 μm was obtained.

Table 2 shows the results of measuring each property of the obtained polypropylene sheet for PTP packaging.

[0297]

[Reference Example 5] A width 3 was obtained in the same manner as in Reference Example 2 except that the blending amounts of the propylene polymer and the hydrogenated petroleum resin were 70 parts by weight of the propylene polymer and 30 parts by weight of the hydrogenated petroleum resin.
A PTP packaging polypropylene sheet having a thickness of 00 mm and a thickness of 300 μm was obtained.

Table 2 shows the results of measuring the properties of the obtained polypropylene sheet for PTP packaging.

[0299]

[Reference Example 6] Escolets 532 as hydrogenated petroleum resin
A polypropylene sheet for PTP packaging having a width of 300 mm and a thickness of 300 μm was obtained in the same manner as in Reference Example 2 except that Escolets ECR356B was used in place of 0 (trade name: manufactured by Tonex Corporation).

Table 2 shows the results of measuring the properties of the obtained polypropylene sheet for PTP packaging.

[0301]

[Reference Example 7] Escolets 532 as hydrogenated petroleum resin
0 (trade name: Tonex)
Except for using -115 (trade name: Arakawa Chemical Industry Co., Ltd.)
In the same manner as in Reference Example 2 , a polypropylene sheet for PTP packaging having a width of 300 mm and a thickness of 300 μm was obtained.

The physical properties of the obtained polypropylene sheet for PTP packaging were measured, and the results are shown in Table 2.

[0303]

[Reference Example 8] Escolets 532 as hydrogenated petroleum resin
0 (trade name: Tonex)
Except for using -125 (trade name: Arakawa Chemical Industries, Ltd.)
In the same manner as in Reference Example 2 , a polypropylene sheet for PTP packaging having a width of 300 mm and a thickness of 300 μm was obtained.

The properties of the obtained polypropylene sheet for PTP packaging were measured, and the results are shown in Table 2.

[0305]

[Comparative Example 1] Instead of the propylene polymer used in Reference Example 2, except for using propylene polymer obtained in Comparative Production Examples, to give the polypropylene sheet for PTP packaging in the same manner as in Reference Example 2 Was.

The physical properties of the obtained polypropylene sheet for PTP packaging were measured, and the results are shown in Table 2.

[0307]

Comparative Reference Example 2 A propylene polymer used in Reference Example 2 was used in the same manner as in Comparative Production Example, except that the propylene polymer was used.
The melt flow rate at 230 ° C. under a load of 2.16 kg is 2 g / 10 min, the value of the stereoregularity index [M ₅ ] of the boiling heptane insoluble component is 0.962, and the stereoregularity index of the boiling heptane insoluble component [M ₃ ] was 0.0024, and a polypropylene sheet for PTP packaging was obtained in the same manner as in Reference Example 2 except that polypropylene having a boiling heptane-insoluble component crystallinity of 60.5% was used.

The properties of the obtained polypropylene sheet for PTP packaging were measured, and the results are shown in Table 2.

[0309]

In Comparative Example 3 Reference Example 3, except that the layer structure of the multilayer sheet 80/140/80 [mu] m (surface layer / base layer / surface layer) is the same way PTP packaging polyps in Reference Example 3 <br / > to obtain a Ropi-les-down multi-layer sheet.

The physical properties of the obtained PTP packaging polypropylene multilayer sheet were measured, and the results are shown in Table 2.

[0311]

[Comparative Reference Example 4] Propylene polymer "Hypol F4"
01 "(trade name: manufactured by Mitsui Petrochemical Industry Co., Ltd.) was sheeted by T-die molding set at a chill roll temperature of 40 ° C. and an extrusion temperature of 220 ° C. to obtain a width of 300.
mm and a sheet having a thickness of 280 μm. A 10 μm-thick PVDC film was dry-laminated on both sides of this sheet to obtain a 300 μm-thick PVDC coated sheet.

[0312] Table 2 shows the results of measuring the properties of the obtained PVDC coated sheet.

[0313]

[Table 2]

──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Mamoru Kioka 6-1-2, Waki, Waki-cho, Kuga-gun, Yamaguchi Prefecture Examiner, Mitsui Petrochemical Industry Co., Ltd. Satoshi Morikawa (56) References JP-A-60- 90734 (JP, A) JP-A-2-84404 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08F 10/06 C08F 110/06 C08F 210/06 C08L 23/10- 23/16

Claims (4)

(57) [Claims] (A) The melt flow rate at 230 ° C. under a load of 2.16 kg is in the range of 0.1 to 500 g / 10 min, and the absorption intensities of Pmmmm and Pw in the ¹³ C-NMR spectrum of a boiling heptane-insoluble component. the value of the stereoregularity index determined by the following formula (1) [M _5] from the 0.970 to 0.
In the range of 995, Pmmrm in ¹³ C-NMR spectrum of a boiling heptane-insoluble component, Pmrmr, Pmrrr, Prmrr, Prmmr , Prrrr,
The value of the pentad tacticity [M _3] of the absorption intensity of Pw obtained by the following formula (2) is from 0.0020 to 0.0050
And the crystallinity of the boiling heptane-insoluble component is 60.
% Of a propylene polymer: 80 to 95% by weight; and (B) a polar group-free terpene resin and / or a polar group-free petroleum resin: 20 to 5% by weight. And a glass transition temperature (Tg) in the range of 0 to 10 ° C .; (Where [Pmmmm] is the absorption intensity derived from the methyl group of the third unit at the site where 5 units of propylene units are continuously bonded isotactically, and [Pw] is the absorption intensity derived from the methyl group of the propylene unit. (2) 2. The method according to claim 1, wherein the propylene polymer contains a polymer comprising a structural unit derived from a compound represented by the following formula (i) or (ii) at a ratio of 10 to 10000 ppm. Stretched polypropylene film; 3. [I] (A) the propylene polymer according to claim 1: 80 to 9;
5% by weight; (B) a terpene resin containing no polar group and / or a petroleum resin containing no polar group: 20 to 5% by weight, and a glass transition temperature (Tg). [II] from the absorption intensity of Pmmmm, Pw, Sαγ, Sαδ ⁺ , Tδ ⁺ δ ⁺ in the ¹³ C-NMR spectrum of the boiling heptane-insoluble component in the range of 0 to 10 ° C. the range value of 0.925 to 0.975 of pentad isotacticity [M _5] obtained by, Pmmrm in ¹³ C-NMR spectrum of a boiling heptane-insoluble component, Pmrmr, Pmrrr, Prmrr, Prmmr , Prrrr,
A propylene-based polymer having a stereoregularity index [M ₃ ] in the range of 0.0020 to 0.0050, which is obtained from the absorption intensities of Pw, Sαγ, Sαδ ⁺ , and Tδ ⁺ δ ^{+ by} the following formula (4): C), wherein the thickness of the base material layer is 80% of the total thickness of the film.
A multi-layer stretched polypropylene film characterized by the following: (Where [Pmmmm] and [Pw] are the same as those in the formula (1) according to claim 1, and [Sαγ] is a secondary carbon in the main chain and is closest to the secondary carbon. Of two tertiary carbons, one of which is at the α-position and the other is at the γ-position, which is the absorption intensity derived from the secondary carbon; [Sαδ ⁺ ]: secondary carbon in the main chain; The absorption intensity derived from a secondary carbon such that one of the two tertiary carbons closest to the secondary carbon is at the α-position and the other is at a position apart from the δ-position or the δ-position, [Tδ ⁺ δ ⁺ ]: a tertiary carbon in the main chain, one of two tertiary carbons closest to the tertiary carbon is located at the δ-position or a position away from the δ-position, and the other is This is the absorption intensity derived from the tertiary carbon located at the δ-position or at a position separated from the δ-position.) (Where [Pmmrm], [Pmrmr], [Pmrrr], [Prm
[rr], [Prmmr], [Prrrr] and [Pw] are the same as those in the formula (2) according to claim 1, and [Sαγ], [Sαδ ⁺ ] and [Tδ ⁺ δ ⁺ ] Same as (3). ). 4. A method according to claim 2, wherein said propylene polymer contains a polymer comprising a structural unit derived from the compound represented by formula (i) or (ii) according to claim 2 at a ratio of 10 to 10,000 ppm. Item 4. A multi-layer stretched polypropylene film according to item 3.