JP2000026673A - Polypropylene resin composition and film composed thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide polypropylene resin compositions capable of providing films excellent in rigidity, transparency, sliding properties, anti-block properties and resistance to whitening with time, and films composed thereof. SOLUTION: Polypropylene compositions comprise 99.5-99.99 pts.wt. polypropylene resin material containing 2-5 wt.% 40 deg.C extract by o- dichlorobenzene as the solvent having 50 wt.% propylene units whose number average molecular weight is 3,000-100,000 and further having a difference in amount between the 90 deg.C extract and the 40 deg.C extract of not more than 5 wt.% and a melt peak temperature by differential scanning calorimetry(DSC) of not lower than 150 deg.C; and 0.01-0.5 pt.wt. fatty acid amide, and films are molded with the used of these polypropylene resin compositions.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel polypropylene resin composition and a film comprising the same. More specifically, the present invention relates to a polypropylene resin composition capable of providing a polypropylene film having excellent transparency, rigidity, slipperiness, blocking resistance, and whitening resistance over time, and a film comprising the same.

[0002]

2. Description of the Related Art A polypropylene film widely used as a food packaging film or the like has hitherto been obtained by molding a polypropylene resin produced using a Ziegler catalyst comprising a titanium compound and organoaluminum.

In particular, in recent years, the development of catalysts and processes capable of obtaining highly active and highly ordered polypropylene resins has made it possible to efficiently obtain polypropylene films having excellent rigidity and transparency. However, problems have arisen in the processability of the film. That is, the polypropylene film obtained with such a highly active catalyst has a drawback that it is inferior in slipperiness and blocking resistance.

In order to solve this problem, conventionally, an appropriate amount of a so-called lubricant such as fatty acid amide has been added to cope with the problem. However, as rigidity and regularity are improved, even if a large amount of a lubricant is added, the lubricity is improved. The effect has tended to be poor. In addition, when the amount of the lubricant added is increased, especially after a high-temperature and high-humidity period such as in the summer, the added lubricant excessively bleeds and causes a whitening phenomenon to crystallize on the film surface, thereby significantly impairing the transparency. There was a problem.

On the other hand, when a polypropylene resin using a metallocene compound such as a metallocene compound such as zirconium or hafnium and a metallocene catalyst such as an alkylaminoxane or an ionic compound, which is being developed in recent years, a film having more excellent transparency can be obtained. For this reason, it has been found that the above tendency becomes more remarkable. Therefore, it has been desired to develop a film which is excellent in rigidity and transparency, has high slipperiness, blocking resistance, and the like, and hardly causes a whitening phenomenon.

[0006]

SUMMARY OF THE INVENTION The present invention has a high rigidity,
It is an object of the present invention to provide a polypropylene resin composition having transparency, slipperiness, and blocking resistance, and capable of providing a film having excellent whitening resistance with time, and a film comprising the same.

[0007]

Means for Solving the Problems As a result of intensive studies in view of such circumstances, the present inventors have found that the above problems can be solved by blending a fatty acid amide with a specific resin or resin mixture. The invention has been reached.

That is, the present invention provides a polypropylene resin composition comprising the following components (A) and (B). Component (A): a polypropylene resin material containing crystalline polypropylene as a main component and having the following physical properties (1) to (3):
99.5-99.99 parts by weight. (1) An extract at 40 ° C. using orthodichlorobenzene as a solvent contains 5 structural units derived from propylene.
0% by weight or more and the number average molecular weight is 3,000
A high-molecular compound having a molecular weight of up to 100,000, wherein the amount of the extract is 2 to 5% by weight based on the component (A). (2) An extract at 90 ° C. using orthodichlorobenzene as a solvent, and 4 extracts using orthodichlorobenzene as a solvent.
The difference in the extraction amount from the extract at 0 ° C. is 5% by weight or less based on the component (A). (3) The melting peak temperature by differential scanning calorimetry (DSC) is 150 ° C. or higher. Component (B): fatty acid amide: 0.01 to 0.5 part by weight.

The present invention also relates to an extract of the above-mentioned component (A) at 40 ° C. using ortho-dichlorobenzene as a solvent, which contains 50% by weight or more of a structural unit derived from propylene, and has a number-average molecular weight. Is 5,000-50,
The polypropylene resin composition is characterized by being an amorphous polypropylene having a molecular weight of 000.

In the present invention, the component (A) contains at least 50% by weight of crystalline polypropylene and a structural unit derived from propylene, and has a number average molecular weight of 5,
The present invention provides the above polypropylene resin composition, which is a mixture with an amorphous polypropylene having a molecular weight of 000 to 50,000.

Further, the present invention provides the polypropylene resin composition, wherein the crystalline polypropylene is produced by using a metallocene catalyst. The present invention also provides a film comprising any one of the above polypropylene resin compositions.

[0012]

Embodiments of the present invention will be described below. I. Polypropylene resin composition The polypropylene resin composition of the present invention comprises the following components (A) and (B).

(1) Component (A) The component (A) used in the present invention is a polypropylene resin material having all of the following physical properties (1) to (3).

(I) Physical properties of component (A) Physical property (1): The extract (hereinafter, referred to as “hereinafter”) obtained when component (A) is extracted at 40 ° C. using orthodichlorobenzene as a solvent.
The amount of “40 ° C. extract” is 2 to 5% by weight based on the total amount of the component (A). If the extraction amount is less than 2% by weight, sufficient lubricity cannot be obtained even if the component (B) is added. Alternatively, when a large amount of the component (B) is added to obtain slipperiness, the whitening resistance with time becomes poor. On the other hand, when the extraction amount is 5
If the content is more than 10% by weight, sufficient slip properties can be obtained by adding the component (B), but the blocking resistance and the rigidity become poor.

In the extract at 40 ° C., the constituent units derived from propylene (hereinafter referred to as “propylene units”) are at least 50% by weight, preferably 5% by weight, based on the whole extract.
5 to 100% by weight, and the number average molecular weight is 3,
000-100,000, preferably 5,000-5
000 high molecular compounds. When the content of the propylene unit is less than 50% by weight, the transparency becomes poor. When the number average molecular weight of the 40 ° C. extract is less than 3,000, the blocking resistance is poor, and the number average molecular weight is 10%.
If it exceeds 000, even if the component (B) is added, the slip property and the whitening resistance over time are not improved.

Particularly preferably, the 40 ° C. extract contains propylene units in an amount of 50% by weight or more, more preferably 60 to 99% by weight, based on the whole extract, and has a number average molecular weight of 5,000 to 50%. Amorphous polypropylene having a molecular weight of 6,000, more preferably 6,000 to 40,000. When the 40 ° C. extract is amorphous polypropylene having such specific physical properties, there is an advantage that the balance between slipperiness and blocking resistance is particularly excellent.

[0017] More preferably, the amorphous polypropylene has a DSC heat of fusion of 60 mj / mg or less, preferably 50 mj / mg or less. When the heat of fusion is within this range, a film having a better balance between slipperiness and blocking resistance can be obtained with a smaller amount.

Particularly preferred as the amorphous polypropylene is a copolymer of propylene and a comonomer selected from the group consisting of ethylene and other α-olefins, which contains 50% by weight of propylene units.
Specific examples of the comonomer of the amorphous polypropylene include ethylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-heptene, 4-methyl-pentene-1, and 4-methyl-hexene-1. , 4,4-dimethylpentene-1 and the like. The content of comonomer units is less than 50% by weight, preferably 1 to 40% by weight, more preferably 5% by weight, based on the whole amorphous polypropylene.
~ 35% by weight. Specific examples of such an amorphous polypropylene include a propylene-ethylene copolymer, a propylene-ethylene-butene copolymer, a propylene-butene copolymer, and the like.

Physical property (2): Extraction amount of the extract (hereinafter referred to as 90 ° C. extract) when the component (A) is extracted at 90 ° C. using orthodichlorobenzene as a solvent, and the amount of the 40 ° C. extract Is 5% by weight or less.

If the difference in the amount of extraction exceeds 5% by weight, blocking resistance and rigidity become poor. Particularly preferably,
The difference in the amount of extraction between the 90 ° C extract and the 40 ° C extract was 3% by weight.
The following is easy to obtain when using a crystalline polypropylene produced with a metallocene catalyst.

Physical Properties (3) The melting peak temperature of the component (A) by DSC must be 150 ° C. or higher.
When the melting peak temperature is lower than 150 ° C., the blocking resistance and the rigidity become poor. Particularly preferred DSC has a melting peak temperature of 153 ° C. or higher, and a film having excellent rigidity can be obtained.

The component (A) generally has an MFR (melt flow rate) of 1 to 20 g / 10 minutes, and particularly preferably 2 to 15 g / 10 minutes. The MFR in the present invention is JIS-K6758 (2
30 ° C., 2.16 kg load). If the MFR is larger than the above range, the film strength decreases and the film formation becomes unstable. On the other hand, when the MFR is smaller than the above range, the resin pressure increases, the extrudability decreases, and the moldability deteriorates.

(Ii) Production of Component (A) The polypropylene resin material of the present invention is mainly composed of crystalline polypropylene.
As long as (3) is satisfied, it may be composed of crystalline polypropylene alone, or may be a mixture obtained by blending the crystalline polypropylene with another specific polypropylene resin.

That is, the polypropylene resin material of the present invention needs to contain, for example, an extract at 40 ° C. shown in the above physical properties (1). A method may be used in which conditions for producing polypropylene as a by-product are selected and atactic polypropylene produced as a by-product is used, or a method in which amorphous polypropylene is separately added after the production of crystalline polypropylene may be used. Among these, the method of blending amorphous polypropylene with crystalline polypropylene,
It is preferable because a desired polypropylene resin material having the above physical properties (1) to (3) can be obtained more efficiently.

Here, the crystalline polypropylene as a main component may be a propylene homopolymer or a copolymer of propylene and another comonomer. In the case of a copolymer of propylene and another comonomer, a propylene unit is contained in an amount of 90% by weight or more, and a structural unit derived from the comonomer (hereinafter, referred to as “comonomer unit”)
Is preferably less than 10% by weight. If the propylene unit content is less than 90% by weight, heat resistance is poor, which is not preferred. In addition, the ratio of each structural unit is ¹³ C-NMR
Determined by spectral method.

In the case of the above copolymer, comonomer includes ethylene or other α-olefin. α
As the olefin, an α-olefin having 4 to 10 carbon atoms, specifically 1-butene, 1-pentene, 1-hexene, 1-octene, 1-heptene, 4-methyl-pentene-1, 4-methyl -Hexene-1,4,4-dimethylpentene-1 and the like. Comonomer is 1
It is not limited to the type, and a multi-component copolymer using two or more types such as a terpolymer is also included as a preferable one. Specific examples include a propylene-ethylene binary copolymer, a propylene-butene binary copolymer, a propylene-ethylene-butene ternary copolymer, and the like.

The MFR of the crystalline polypropylene is preferably 1 to 20 g / 10 min, particularly preferably 2 to 15 g / min.
10 minutes. If the MFR is larger than the above range, the film strength decreases and the film formation becomes unstable. Also,
If the MFR is smaller than the above range, the resin pressure increases, the extrudability decreases, and the moldability deteriorates.

As a method for producing the crystalline polypropylene used in the present invention, a Ziegler catalyst (Japanese Patent Laid-Open No.
4404, JP-A-3-234707, JP-A-5-287
019, JP-A-8-333414, and metallocene-based catalysts (JP-A-1-301704, JP-A-4-3008).
87, JP-A-5-65309).

When the propylene resin material of the present invention is obtained by blending the above-mentioned crystalline polypropylene with an amorphous polypropylene, the amorphous polypropylene to be used contains 50% by weight or more of propylene units, more preferably 60 to 9%.
A copolymer of propylene and ethylene or another α-olefin containing 9% by weight, having a number average molecular weight of 5,000 to 50,000, more preferably 6,000.
~ 40,000 is desirable. More preferably,
Its heat of fusion by DSC is 60 mj / mg or less, preferably 50 mj / mg or less.

Specific examples of the comonomer of the amorphous polypropylene include ethylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-heptene and 4-
Methyl-pentene-1, 4-methyl-hexene-1,
4,4-dimethylpentene-1 and the like can be mentioned. The content of the comonomer unit is less than 50% by weight, preferably 1 to 40% by weight, more preferably 5 to 35% by weight, based on the whole amorphous polypropylene.

Specific examples of the amorphous polypropylene include a propylene-ethylene copolymer, a propylene-ethylene-butene copolymer, a propylene-butene copolymer and the like. These amorphous polypropylenes may be produced from raw materials at the same time as the production of crystalline polypropylene, but in order to obtain stable quality, it is necessary to use amorphous polypropylene separately produced for the purpose. preferable. Some of them are commercially available, and can be appropriately selected from the corresponding commercially available products.

A preferred component (A) of the present invention is a mixture of a crystalline polypropylene produced by a Ziegler catalyst or a metallocene catalyst and an amorphous polypropylene having the above-mentioned specific properties. Among them, a mixture of a crystalline polypropylene produced by a metallocene catalyst and the above-mentioned amorphous polypropylene is particularly preferable because a desired polypropylene resin material can be obtained efficiently.

In the case of the mixture, the mixing ratio between the crystalline polypropylene and the amorphous polypropylene in the component (A) is as follows: crystalline polypropylene: amorphous polypropylene = 99 to 1:
It is preferred to be 95 to 5 (weight ratio).

(2) Component (B) As the fatty acid amide which is the component (B) used in the present invention, a fatty acid amide having 12 to 22 carbon atoms, particularly a fatty acid amide having an unsaturated bond having 18 to 22 carbon atoms, may be used. preferable. Specifically, oleamide, erucamide,
Stearic acid amide, behenic acid amide and the like.

(3) Polypropylene resin composition Component (A) in the polypropylene resin composition of the present invention
The mixing ratio of the component (B) to the crystalline polypropylene resin material of the component (A) is 99.5 to 99.99 parts by weight, and the fatty acid amide of the component (B) is 0.01 to 0.5. Parts by weight. If the ratio of the component (B) is less than 0.01 part by weight, the slipperiness is poor, and the mixing ratio of the component (B) is 0.5
When the amount is more than the weight part, the whitening resistance with time becomes poor.

In the present invention, in addition to these essential components (A) and (B), additives usually used for fine polypropylene materials, such as phenol-based, phosphorus-based or sulfur-based antioxidants, Agents, processing aids, antistatic agents, antiblocking agents, ultraviolet absorbers, neutralizing agents, antifogging agents, coloring agents, antibacterial agents, adhesives, etc., may also be added within a range that does not impair the effects of the present invention. it can.

The polypropylene resin composition of the present invention is produced by mixing these components (A), (B) and, if necessary, additives, followed by melt-kneading. Examples of the mixing method include a method of mixing using a known powder mixer, for example, a Henschel mixer, a ribbon blender, or the like.

After mixing in this manner, the mixture is melt-kneaded and pelletized to obtain a desired polypropylene resin composition. Examples of the kneading method include a method of melting and kneading using a single-screw or twin-screw extruder, a Brabender blast graph, a Banbury mixer, a kneader blender, or the like, and forming a pellet by a commonly used method.

Usually, prior to film formation, a resin composition is prepared by mixing all necessary components in a desired amount in advance, and the component (B) and other additives are used as the base component (A).
May be used in a larger amount than the target amount, and diluted at the time of film formation.

II. Film The film of the present invention comprises the above-mentioned polypropylene resin composition. The thickness of the film is not particularly limited and is appropriately selected depending on the purpose of use, but is preferably about 10 to 100 μm.

The film of the present invention can also be used as a multilayer film by laminating with other resin films having various functions within a range not to impair the effects of the present invention. For example, lamination of polyester such as nylon or polyethylene terephthalate, stretched polypropylene film or the like can improve functions such as mechanical strength, gas barrier property, and printing performance.

The method for producing the film includes air-cooled inflation molding, air-cooled two-stage cooling inflation molding, T-die film molding, and water-cooled inflation molding, and a film suitable for a packaging material can be obtained. As a method of forming a multilayer film, an extrusion lamination method, a heat lamination method, a dry lamination method,
Examples of the method include laminating the respective layers by a wet lamination method and the like, a co-extrusion lamination method, and the like.

The polypropylene film of the present invention obtained by the above method is a polypropylene film excellent in transparency, rigidity, slipperiness, blocking resistance, and whitening resistance with time, so that it can be used for various packaging films, especially for food packaging. Very useful as a film.

[0044]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples. The measurement of physical properties and evaluation of adhesion performance in the following Examples and Comparative Examples were performed by the following methods.

(1) Amount extracted with orthodichlorobenzene The amount extracted with orthodichlorobenzene was measured by a cross fractionation method. The measurement conditions are as follows. Apparatus: Mitsubishi Chemical Co., Ltd., CFC / T150A type Column: Showa Denko KK, AD80M / S ... 3 units Concentration: 40 mg / 19 ml Solvent: orthodichlorobenzene

(2) Number average molecular weight Measurement conditions are as follows. Apparatus: GPC / 150C type, manufactured by Waters Co., Ltd. Column: AD80M / S: 3 columns, manufactured by Showa Denko KK Concentration: 20 mg / 10 ml Solvent: orthodichlorobenzene

(3) Propylene Unit Content The propylene unit content was measured by ¹³ C-NMR spectrum analysis according to a standard method.

(4) Measurement of melting peak temperature by differential scanning calorimetry (DSC) Using a DSC manufactured by Seiko Co., Ltd., take a sample amount of 5.0 mg, hold at 200 ° C. for 5 minutes, and then 10 ° C./40° C.
The crystallization was performed at a temperature lowering speed of 10 minutes, and the melting peak temperature was further measured when melting was performed at a temperature increasing speed of 10 ° C./minute.

(5) MFR The MFR of the component (A) is JIS-K6758 (condition: 23
0 ° C., load 2.16 kgf) (unit:
g / 10 minutes).

(6) Transparency The haze was measured according to ASTM-D1003 (unit:%). (7) Rigidity Tensile modulus was measured in accordance with ISO-R1184 (unit: kg / cm ² ). (8) Slip property The dynamic friction coefficient was measured according to ASTM-D1894.

(9) Blocking resistance Two films were stacked so that the contact area was 10 cm ² , sandwiched between two glasses, and left under a load of 50 g / cm ² in an atmosphere of 40 ° C. for 72 hours. Thereafter, the maximum load when peeling was measured with a shopper type tester (unit: g).
/ 10 cm ² ).

(10) Temporal whitening resistance The haze difference between a film left standing at 50 ° C. for 7 days after film formation and a film left standing at 23 ° C. atmosphere for 24 hours after film formation was measured, and the whitening resistance over time was evaluated. (Unit:%)

[0053]

Example 1 (1) Synthesis of catalyst Example 1 of JP-A-3-234707 [Component (A)
Production of solid catalyst].

(2) Polymerization After sufficiently replacing propylene in the stirred autoclave having an internal volume of 200 liters, triethylaluminum 3
g, liquefied propylene 45 kg, and hydrogen 160 NL were introduced, and the internal temperature was maintained at 40 ° C. Next, 0.8 g of the solid catalyst prepared as described above was added. Thereafter, the temperature was raised to 75 ° C. to start polymerization, and the temperature was maintained for 1 hour.
Here, the reaction was stopped with ethanol, residual gas was purged, and the polymer was dried to obtain 20.3 kg of crystalline polypropylene (polymer A).

(3) Film Forming and Evaluation A commercially available atactic polypropylene (1) (APP (1) in the table) as amorphous polypropylene was added to 100 parts by weight of the obtained crystalline polypropylene (Polymer A). 2 parts by weight, 0.10 part by weight of 2,6-di-t-butyl-p-cresol as an antioxidant, 0.05 part by weight of calcium stearate as a catching agent for hydrochloric acid, 0.05 part by weight of synthetic silica, and erucic acid 0.06 parts by weight of the amide was mixed, mixed for 2 minutes with a super mixer, and then pelletized with a granulator. In addition, this atactic polypropylene (1)
Propylene content: 90% by weight, comonomer type: ethylene, number average molecular weight: 12,000, heat of fusion; 12 mj
/ Mg of amorphous polypropylene.

MFR of the obtained pellet-shaped resin composition
Was 7.2. Table 1 shows the physical properties of the obtained pellets. Next, a film having a thickness of 25 μm was obtained at 240 ° C. using an extruder having a T-die using the pellets. Table 1 shows the evaluation results of the physical properties of this film.

[0057]

Comparative Example 1 100 parts by weight of the crystalline polypropylene (Polymer A) of Example 1 was mixed with 2,6-di-t as an antioxidant.
-Butyl-p-cresol 0.10 part by weight, calcium stearate 0.05 part by weight as a hydrochloric acid catching agent, synthetic silica 0.05 part by weight, and further erucamide 0.0
An experiment was conducted in the same manner as in Example 1 by blending 6 parts by weight. The MFR of the obtained pellet-shaped resin composition was 7.1. Table 1 shows the physical property values of the pellets and the evaluation results of the film.

[0058]

Example 2 The atactic polypropylene (1) of Example 1 was replaced with the atactic polypropylene (2) (AP in the table).
The experiment was performed in the same manner as in Example 1 except that the mixing ratio was changed to 4 parts by weight instead of P (2)), and the mixing ratio was changed to 0.05 parts by weight by changing erucamide to oleic amide.
The atactic polypropylene (2) had a propylene content of 95% by weight, a comonomer type of ethylene,
Number average molecular weight; 6,000, heat of fusion; 30 mj / mg
Is an amorphous polypropylene. The MFR of the obtained pellet-shaped resin composition was 7.3. Table 1 shows the physical property values of the pellets and the evaluation results of the film.

[0059]

Example 3 (1) Synthesis of dimethylsilylenebis (2-methyl-4-phenyldihydroazulenyl) zirconium dichloride This was synthesized according to the method described in JP-A-62-207232. 2.22 g of 2-methylazulene was dissolved in 30 ml of hexane, and 15.6 ml (1.0 equivalent) of a solution of phenyllithium in cyclohexane-diethyl ether.
Was added portionwise at 0 ° C.

After the solution was stirred at room temperature for 1 hour,
After cooling to 8 ° C., 30 ml of tetrahydrofuran was added. 0.95 ml of dimethyldichlorosilane was added to this solution,
The temperature was raised to room temperature and further heated at 50 ° C. for 1.5 hours.
Thereafter, an aqueous solution of ammonium chloride was added, and the mixture was separated.
The organic phase was dried over magnesium sulfate, and the solvent was distilled off under reduced pressure.

The obtained crude product was subjected to silica gel column chromatography (hexane: dichloromethane = 5: 1).
Purification by dimethylbis [1- (2-methyl-4-
Phenyl-1,4-dihydroazulenyl)] silane
48 g were obtained.

The dimethyl bis [1- (2-
Methyl-4-phenyl-1,4-dihydroazulenyl)] silane (768 g) was dissolved in diethyl ether (15 ml), and normal butyllithium hexane solution (1.98 ml, 1.64 mol / L) was added dropwise at -78 ° C. And stirred at room temperature for 12 hours. After removing the solvent under reduced pressure, the obtained solid was washed with hexane and dried under reduced pressure.

To this is added toluene / diethyl ether (4
0: 1) 20 ml was added, 325 mg of zirconium tetrachloride was added at -60 ° C, the temperature was gradually raised, and the mixture was stirred at room temperature for 15 minutes. The obtained solution was concentrated under reduced pressure, and hexane was added to cause reprecipitation, whereby dimethylsilylenebis (2-methyl-
Diastereomeric mixture of 4-phenyldihydroazulenyl) zirconium dichloride (mixture of diastereomers A and B showing the following spectral data) 150 m
g was obtained.

[Spectral data] Diastereomer A: ¹ H-NMR (300 MHz, C
_{6 D 6) δ0.51 (s,} 6H, Si (CH 3) 2),
1.92 (s, 6H, CH ₃ ), 5.30 (br d,
2H), 5.75-5.95 (m, 6H), 6.13
(S, 2H), 6.68 (d, J = 14 Hz, 2H),
7.05-7.20 (m, 2H, arom), 7.56
(D, J = 7Hz, 4H)

Diastereomer B: ¹ H-NMR (30
0 MHz, C ₆ D ₆ ) δ 0.44 (s, 3H, Si (C
_{H 3)), 0.59 (s} , 3H, Si (CH 3)),
_{1.84 (s, 6H, CH 3} ), 5.38 (br d,
2H), 5.75-6.00 (m, 6H), 6.13
(S, 2H), 6.78 (d, J = 14 Hz, 2H),
7.00-7.20 (m, 2H, arom), 7.56
(D, J = 7Hz, 4H)

(2) Purification 887 mg of a diastereomer mixture of dimethylsilylenebis (2-methyl-4-phenyldihydroazulenyl) zirconium dichloride (a mixture of the above diastereomers A and B) was dissolved in 30 ml of methylene chloride. 1
It was introduced into a Pyrex glass reflector with a 00 W high pressure mercury lamp.

After the solution was irradiated with light (300 nm to 600 nm) under normal pressure for 30 minutes while stirring, methylene chloride was distilled off under reduced pressure. 7 ml of toluene was added to the obtained yellow solid, and the mixture was stirred and allowed to stand. When the yellow solid precipitated, the supernatant was removed.

Further, the same operation was performed with 4 ml of toluene and 2 m of toluene.
and 2 ml of hexane, and the resulting solid was dried under reduced pressure to give dimethylsilylenebis (2-methyl-4
437 mg of a single diastereomer of (-phenyldihydroazulenyl) zirconium dichloride (diastereomer A showing the above spectral data) were obtained.

(3) Production of methyl isobutylalumoxane It was synthesized according to the method described in Example 7 of JP-A-6-239914. That is, first, 1000 ml with a stirrer and a reflux condenser sufficiently purged with nitrogen
100 ml of dehydrated and deoxygenated toluene was introduced into the flask.

Then, 0.72 g (10 mmol) of trimethylaluminum and 1.96 g (10 mmol) of triisobutylaluminum were diluted in 50 ml of toluene in one of the two dropping funnels, and toluene in saturated water was added to the other. And a mixed aluminum solution and saturated water-containing toluene were fed at equimolar amounts of Al and H ₂ O over 3 hours at 30 ° C.

After the feed was completed, the temperature was raised to 50 ° C. and the reaction was performed for 2 hours. After completion of the reaction, the solvent was distilled off under reduced pressure to obtain 1.9 g of methylisobutylalumoxane as a white solid. The obtained white solid was diluted with toluene, and as a result of measuring ²⁷ Al-NMR, a chemical shift of 174 ppm and a half width of 58 were obtained.
The spectrum at 44 Hz was shown.

(4) Polymerization After sufficiently replacing the inside of a stirred autoclave having an internal volume of 200 liters with propylene, 60 liters of heptane sufficiently dehydrated and deoxygenated were introduced, and the internal temperature was maintained at 60 ° C. Next, 40 g of methyl isobutylalumoxane previously diluted in toluene was added, and 40 mg of dimethylsilylenebis (2-methyl-4-phenyldihydroazulenyl) zirconium dichloride diluted in toluene was further added.

Thereafter, the temperature was raised to 65 ° C., and hydrogen was added to 6.3N.
L and propylene were introduced up to 5 kg / cm ² · G to start polymerization, and the temperature was maintained for 3 hours. Here, after stopping the reaction with ethanol and purging the remaining gas,
The solvent was separated and dried. As a result, 12.6 kg of crystalline polypropylene (polymer B) was obtained.

(5) Film Forming and Evaluation 2 parts by weight of the atactic polypropylene (1) were added to 100 parts by weight of the crystalline polypropylene (polymer B) thus obtained using the metallocene catalyst, and oxidized. 2,6-di-tert-butyl-p-cresol 0.1 as an inhibitor.
The experiment was carried out in the same manner as in Example 1 except that 10 parts by weight, 0.10 part by weight of synthetic silica and 0.09 part by weight of erucamide were added. MF of the obtained pellet-shaped resin composition
R was 5.5. Table 1 shows the physical property values of the pellets and the evaluation results of the film.

[0075]

Example 4 An experiment was carried out in the same manner as in Example 3 except that atactic polypropylene (1) was replaced by 3 parts by weight and erucamide was replaced by 0.05 part by weight. The MFR of the obtained pellet-shaped resin composition was 6.2.
Table 1 shows the physical property values of the pellets and the evaluation results of the film.

[0076]

Comparative Example 2 100 parts by weight of the crystalline polypropylene (polymer B) of Example 3 was added with 2,6-di-t as an antioxidant.
An experiment was conducted in the same manner as in Example 3 except that 0.10 part by weight of -butyl-p-cresol, 0.10 part by weight of synthetic silica, and 0.09 part by weight of erucamide were added. The MFR of the obtained pellet-shaped resin composition was 5.3. Table 1 shows the physical property values of the pellets and the evaluation results of the film.

[0077]

Comparative Example 3 100 parts by weight of the crystalline polypropylene of Example 3 (polymer B), 5 parts by weight of atactic polypropylene (1), and a crystalline propylene-ethylene random copolymer (melting peak temperature: 133 ° C.) Was added, and the experiment was carried out in the same manner as in Example 3 except that erucamide was changed to 0.12 parts by weight. The MFR of the obtained pellet-shaped resin composition was 6.8. Table 1 shows the physical property values of the pellets and the evaluation results of the film.

[0078]

Example 5 The atactic polypropylene (1) of Example 3 was replaced with the atactic polypropylene (3) (AP in the table).
The experiment was carried out in the same manner as in Example 3 except that the blending ratio was changed to 25 parts by weight instead of P (3)). The atactic polypropylene (3) had a propylene content of 65% by weight, a comonomer type of butene-1, a number average molecular weight of 1
It is an amorphous polypropylene having a melting point of 0000 and a heat of fusion of 25 mj / mg. MF of the obtained pellet-shaped resin composition
R was 5.9. Table 1 shows the physical property values of the pellets and the evaluation results of the film.

[0079]

[Table 1]

[0080]

The polypropylene resin composition of the present invention has
With the above configuration, transparency, rigidity, slipperiness,
A polypropylene film having excellent blocking resistance and whitening resistance over time can be provided.

Continued on the front page F term (reference) 4F071 AA20 AA81 AA87 AB26 AC03A AC12 AE19A AF05Y AF11 AF14 AF28 AF30 AH04 BA01 BB06 BC01 4J002 BB121 BB142 BB152 EP016 GG02

Claims (5)

[Claims] 1. A polypropylene resin composition comprising the following components (A) and (B). Component (A): a polypropylene resin material containing crystalline polypropylene as a main component and having the following physical properties (1) to (3):
99.5-99.99 parts by weight. (1) An extract at 40 ° C. using orthodichlorobenzene as a solvent contains 5 structural units derived from propylene.
0% by weight or more and the number average molecular weight is 3,000
A high-molecular compound having a molecular weight of up to 100,000, wherein the amount of the extract is 2 to 5% by weight based on the component (A). (2) An extract at 90 ° C. using orthodichlorobenzene as a solvent, and 4 extracts using orthodichlorobenzene as a solvent.
The difference in the extraction amount from the extract at 0 ° C. is 5% by weight or less based on the component (A). (3) The melting peak temperature by differential scanning calorimetry (DSC) is 150 ° C. or higher. Component (B): fatty acid amide: 0.01 to 0.5 part by weight. 2. An extract of the component (A) at 40 ° C. using ortho-dichlorobenzene as a solvent contains 50% by weight or more of a structural unit derived from propylene and has a number average molecular weight of 5,000. 2. An amorphous polypropylene having a molecular weight of up to 50,000.
The polypropylene resin composition according to the above. 3. The composition according to claim 1, wherein said component (A) is composed of crystalline polypropylene and 50% by weight of a structural unit derived from propylene.
And a number average molecular weight of 5,000 to 50,
A mixture with amorphous polypropylene that is 000.
The polypropylene resin composition according to claim 1. 4. The polypropylene resin composition according to claim 3, wherein the crystalline polypropylene is produced using a metallocene catalyst. 5. A film comprising the polypropylene resin composition according to claim 1.