JPH111584A - Propylene polymer composition and film therefrom - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a well-balanced propylene polymer composition that retains high film stiffness and film impact properties, as attaining further improved heat-sealing properties, film therefrom and film for food packaging. SOLUTION: This propylene polymer composition is prepared by adding (A) >=10 ppm of a nucleating agent to (B) a propylene polymer that is a propylene homopolymer formed by using a metallocene catalyst, has isotactic pentad fraction (mmmm fraction) of 80-99%, molecular weight distribution (Mw/Mn) of <=3.5, and intrinsic viscosity [η] of 0.5-5.0 dl/g where the tensile elasticity in the MD direction (TM in MPa) and the heat-sealing temperature (HST in deg.C) satisfy the following formula: TM>=22×HST-1850 The film particularly the film for packaging food products comprising this propylene polymer composition are formed by the casting process.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a propylene polymer composition and a film comprising the same. More specifically, the present invention relates to a propylene-based polymer composition in which rigidity and heat-sealing properties are unprecedentedly highly balanced, and a film or a food packaging film comprising the same.

[0002]

2. Description of the Related Art Polypropylene is a general-purpose resin because it has tough physical properties with excellent heat resistance and is inexpensive.
It has been used in a wide variety of applications. However, in order to improve the productivity of the final molded product, further improvement in secondary workability is desired. In particular, in the field of films using polypropylene, it is desired to lower the heat sealing temperature. Further, in the field of other sheets and non-woven fabrics, lowering of the laminating temperature is similarly desired.

Conventionally, in order to improve heat sealability,
A method of copolymerizing a small amount of an α-olefin such as ethylene has been proposed, but a decrease in film stiffness due to a decrease in crystallinity, a deterioration in moldability thereby, and a deterioration in blocking properties have been caused. . In recent years, since polypropylene polymerized using a metallocene catalyst has a low melting point and a low stickiness component, these are blended with a polypropylene polymerized using a conventional catalyst (a Ziegler catalyst comprising a titanium compound and an aluminum compound), Methods for use as a film heat seal improver have been proposed (JP-A-2-173016, JP-A-5-15-1).
No. 12682, JP-A-5-112683).

[0004]

SUMMARY OF THE INVENTION Under such circumstances, the present invention provides a propylene-based polymer in which a film stiffness and a film impact characteristic are maintained at a high level while achieving a further improvement in heat sealability. An object of the present invention is to provide a composition and a film comprising the composition or a film for food packaging.

[0005]

Means for Solving the Problems As a result of intensive studies on the above problems, the present inventors have found that by adding a nucleating agent to a propylene polymer produced using a metallocene catalyst,
The inventors have found that a film having unprecedented characteristics can be provided with a completely unexpected effect, and have completed the present invention. That is, the present invention has the following gist. (1) (A) a propylene homopolymer having an isotactic pentad fraction (mmmm fraction) of 80 to 99;
%, A molecular weight distribution (Mw / Mn) of 3.5 or less, and a propylene polymer polymerized using a metallocene catalyst having an intrinsic viscosity [η] of 0.5 to 5.0 deciliter / g. (B) a propylene polymer composition in which a nucleating agent is added in an amount of 10 ppm or more. (2) (A) A propylene-based random copolymer composed of propylene, ethylene and / or an α-olefin having 4 to 20 carbon atoms, wherein the structural unit obtained from propylene is 80 to 100 mol%, and ethylene and / or Or a structural unit obtained from an α-olefin having 4 to 20 carbon atoms is 0 to
Propylene polymerized using a metallocene-based catalyst having a molar mass distribution (Mw / Mn) of 3.5 or less and an intrinsic viscosity [η] of 0.5 to 5.0 deciliter / g. A propylene-based polymer composition comprising (B) a nucleating agent in an amount of 10 ppm or more. (3) The propylene polymer resin composition according to the above (1) or (2), wherein the nucleating agent is an organic metal phosphate. (4) The propylene-based polymer resin composition according to the above (1) or (2), wherein the nucleating agent is talc. (5) The propylene polymer resin composition according to the above (1) or (2), wherein the nucleating agent is dibenzylidene sorbitol or a derivative thereof. (6) The propylene polymer resin composition according to the above (1) or (2), wherein the nucleating agent is an amide compound. (7) The tensile modulus in the MD (TM (MPa)) and the heat sealing temperature (HST (° C.)) are expressed by the following equation (II):
A propylene-based polymer composition characterized by satisfying the following. TM ≧ 22 × HST-1850 (II) (8) A film formed by casting the propylene-based polymer composition according to any one of the above (1) to (7). (9) A food packaging film obtained by casting the propylene polymer composition according to the above (3) or (4) by a cast molding method.

[0006]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described in detail below. [1] The first resin composition of the present invention is (A) a propylene homopolymer, having an isotactic pentad fraction (mmmm fraction) of 80 to 99% and a molecular weight distribution (Mw). / Mn) is 3.5 or less and the intrinsic viscosity [η]
Is a propylene polymer composition obtained by adding 10 ppm or more of a nucleating agent (B) to a propylene polymer polymerized using a metallocene catalyst having a concentration of 0.5 to 5.0 deciliters / g. As the component (A), a propylene homopolymer polymerized using a metallocene catalyst (a small amount (0.5
Mol% or less) (including propylene-based polymers preliminarily polymerized with an α-olefin), and an isotactic pentad fraction (mm) showing the stereoregularity of polypropylene.
mm fraction) is 80% to 99%, more preferably 85 to 99%.
97% and a molecular weight distribution (Mw / Mn) of 3.5
Or less, more preferably 3.0 or less, and an intrinsic viscosity [η] of 0.5 to 5.0 deciliter / g, more preferably 0.5 to 3 deciliter / g, and still more preferably 1 to 2.5 deciliter / g. Use what is deciliter / g.

The isotactic pentad fraction (mmmm fraction) in the present invention is defined as Cheng H.N., Ewen JA, Macr.
omol.cem., 1989,190,1350, based on the assignment of peaks in the ¹³ C-NMR spectrum, among the five propylene structural units, a meso structure (mmmm in which the sequence of five methyl groups is arranged in the same direction). Structure)).

The isotactic pentad fraction is
If it is less than 80%, the film rigidity may be insufficient, and if it exceeds 99%, the impact resistance of the film may be inferior, which is not preferable. Also, the molecular weight distribution (Mw / Mn)
If the value of (3) exceeds 3.5, the heat sealability may be reduced, or the blocking resistance may be reduced.

The propylene polymer of the component (A) used in the present invention is a transition metal compound belonging to Group 4 of the periodic table having a cyclopentadienyl ring and methylaluminoxane or a transition metal belonging to Group 4 of the periodic table. It can be produced by polymerizing in the presence of a metallocene-based catalyst comprising a compound which reacts with a compound to form an ionic complex and an organoaluminum compound.

The transition metal compound belonging to Group 4 of the Periodic Table having a cyclopentadienyl ring as a main catalyst includes a cycloalkadienyl group or a substituted product thereof, specifically, an indenyl group, a substituted indenyl group and a part thereof. Zirconium, titanium and hafnium compounds having a polydentate compound as a ligand in which at least two groups selected from the group consisting of hydrides are bonded via a lower alkylene group or a silylene group. That is, the transition metal compound is HHBrintzin
Ger et al, J. Organometal. Chem., 288, 63 (1985), ethylene-bis- (indenyl) zirconium dichloride, and ethylene-bis- (indenyl) zirconium dichloride, described in J. Am. Chem. Soc., 109, 6544 (1987).
Bis- (indenyl) hafnium dichloride, H. Yamaza
dimethylsilylbis (2,4-dimethylcyclopentadienyl) zirconium dichloride, dimethylsilylbis (2,4,5-trimethylcyclopentadienyl) zirconium dichloride described in ki et al, Chemistry Letters, 1853 (1989), or these. Is a stereorigid chiral compound of zirconium and hafnium compounds such as the complex of hafnium dichloride.

Specifically, ethylene bis (indenyl) zirconium dichloride, ethylene bis (4,
5,6,7-tetrahydro-1-indenyl) zirconium dichloride, ethylenebis (4-methyl-1-indenyl) zirconium dichloride, ethylenebis (5-
Methyl-1-indenyl) zirconium dichloride, ethylenebis (6-methyl-1-indenyl) zirconium dichloride, ethylenebis (7-methyl-1-indenyl) zirconium dichloride, ethylenebis (2,3
-Dimethyl-1-indenyl) zirconium dichloride, ethylenebis (4,7-dimethyl-1-indenyl) zirconium dichloride, ethylenebis (indenyl) hafnium dichloride, ethylenebis (4,5,
6,7-tetrahydro-1-indenyl) hafnium dichloride, ethylenebis (4-methyl-1-indenyl) hafnium dichloride, ethylenebis (5-methyl-1-indenyl) hafnium dichloride, ethylenebis (6-methyl-1- Indenyl) hafnium dichloride, ethylenebis (7-methyl-1-indenyl) hafnium dichloride, ethylenebis (2,3-dimethyl-)
1-indenyl) hafnium dichloride, ethylenebis (4,7-dimethyl-1-indenyl) hafnium dichloride, dimethylsilylenebis (indenyl) zirconium dichloride, dimethylsilylenebis (indenyl)
Hafnium dichloride, dimethylsilylenebis (4-methylindenyl) zirconium dichloride, dimethylsilylenebis (indenyl) hafnium dichloride, dimethylsilylenebis (2,4,5-trimethylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (2 4,5-trimethylcyclopentadienyl) hafnium dichloride, dimethylsilylenebis (2,4-dimethylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (2,4-dimethylcyclopentadienyl) hafnium dichloride, dimethylsilylenebis (3-methylcyclopentadienyl)
Zirconium dichloride, dimethylsilylenebis (3-
Methylcyclopentadienyl) hafnium dichloride,
Examples thereof include dimethylsilylenebis (2-methyl-4-phenylindenyl) zirconium dichloride and dimethylsilylenebis (benzoindenyl) zirconium dichloride.

Also, (dimethylsilylene) (dimethylsilylene) -bis (indenyl) zirconium dichloride, (ethylene) (ethylene) -bis (indenyl) zirconium dichloride, (ethylene) (ethylene) -bis (3-methylindenyl) Zirconium dichloride,
(Ethylene) (ethylene) -bis (4,7-dimethylindenyl) zirconium dichloride and the like, and those obtained by substituting zirconium in these compounds with hafnium or titanium.

Compounds which form an ionic complex by reacting with a transition metal compound belonging to Group 4 of the Periodic Table of the cocatalyst include triphenylcarbinium tetrakis (pentafluorophenyl) borate, N, N-dimethyl Anilinium tetrakis (pentafluorophenyl) borate,
Compounds containing a tetra (pentafluorophenyl) borate anion such as lithium tetrakis (pentafluorophenyl) borate, triphenylcarbinium tetrakis (pentafluorophenyl) aluminate, N,
Tetra (pentafluorophenyl) aluminate anion-containing compounds such as N-dimethylanilinium tetrakis (pentafluorophenyl) aluminate and lithium tetrakis (pentafluorophenyl) aluminate are preferably used.

Further, as the organoaluminum compound,
It has at least one Al-C bond in the molecule. Specific examples of such organoaluminum compounds include triethylaluminum, triisobutylaluminum, trialkylaluminum such as trihexylaluminum, diethylaluminum halide, dialkylaluminum halide such as diisobutylaluminum halide, a mixture of trialkylaluminum and dialkylaluminum halide, and tetraethylaluminum. Examples thereof include alkylalumoxanes such as dialumoxane and tetrabutylalumoxane. Among these organoaluminum compounds, trialkylaluminum, a mixture of trialkylaluminum and dialkylaluminum halide, and alkylalumoxane are preferable, and particularly, triethylaluminum, triisobutylaluminum, a mixture of triethylaluminum and diethylaluminum chloride and tetraethyldialumoxane are preferable. preferable. As the organic aluminum, triethylaluminum, triisobutylaluminum and the like are preferably used. These metallocene-based catalysts and / or cocatalysts may be supported and used, and examples of the carrier include organic compounds such as polystyrene and inorganic oxides such as silica and alumina. The polymerization method may be any of a bulk polymerization method, a solution polymerization method, a gas phase polymerization method, a suspension polymerization method, and the like, and may be any of a batch method and a continuous method.

Further, a small amount of α-olefin such as ethylene, propylene, 1-butene, 4-methyl-
Prepolymerization may be performed with 1-pentene or the like. The polymerization temperature is usually in the range of −50 to 250 ° C., preferably 0 to 150 ° C., the polymerization time is usually in the range of 1 to 10 hours, and the pressure is usually normal pressure to 300 kg / cm ² -G. Range.

As the nucleating agent of the component (B), any agent can be used as long as it can improve the progress rate of the crystal nucleation process. Generally, crystallization of polypropylene consists of two processes, a crystal nucleation process and a crystal growth process. In the crystal nucleation process, the temperature difference from the crystallization temperature and the orientation behavior of the molecular chains are determined. The rate of heterogeneous crystal nucleation due to the presence of a substance which influences the rate and particularly promotes the molecular chain orientation through the adsorption of the molecular chain and the like is remarkably increased.

Specific examples of the nucleating agent used in the present invention include:
Organic carboxylic acids or metal salts thereof, aromatic sulfonates or metal salts thereof, organic phosphoric acid compounds or metal salts thereof, dibenzylidene sorbitol or derivatives thereof, rosin acid partial metal salts, inorganic fine particles such as talc, imides, amides , Quinacridone quinones or mixtures thereof. Among them, inorganic fine particles such as organophosphate metal salts and talc represented by the following general formula (I) generate less odor and are suitable for foods.

[0018]

Embedded image

(Wherein R ¹ is a hydrogen atom or a carbon number of 1 to 4)
R ² and R ³ are each a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group,
It represents an aryl group or an aralkyl group. M represents any one of an alkali metal, an alkaline earth metal, aluminum and zinc. When M is an alkali metal, m represents 0, n represents 1, and when M is a divalent metal, n represents 1 or 2. , N is 1 when m is 1; when n is 2, m is 0; when M is aluminum, m is 1 and n is 2. Furthermore, a film formed using a resin containing inorganic fine particles such as talc has excellent slipping properties, thereby improving the secondary workability of bag making, printing, etc., and high-speed production of various automatic filling and packaging, laminators, etc. Suitable for all general-purpose packaging films in equipment.

A film formed using a resin containing dibenzylidene sorbitol or a derivative thereof is particularly suitable for packaging toys, stationery and the like because of its excellent transparency and large display effect. Specific examples of derivatives of dibenzylidene sorbitol include 1,3: 2,4-bis (o-
3,4-dimethylbenzylidene) sorbitol, 1,
3: 2,4-bis (o-2,4-dimethylbenzylidene) sorbitol, 1,3: 2,4-bis (o-4-ethylbenzylidene) sorbitol, 1,3: 2,4- Bis (o-4-chlorobenzylidene) sorbitol, 1,
3: 2,4-dibenzylidene sorbitol.

A film formed using a resin containing an amide compound is particularly excellent in rigidity and hardly causes problems such as winding wrinkles in high-speed bag-making, and is therefore suitable for all general-purpose packaging films in high-speed bag-making machines. . Specific examples of the amide compound include dianilide adipate and dianilide sperate.

The amount of these nucleating agents added to the propylene-based polymer is usually at least 10 ppm, preferably 5 ppm.
The range is from 0 to 3000 ppm. If it is less than 10 ppm, no improvement in heat sealability is observed, while 3000
Addition of more than ppm does not increase the desired effect. The film comprising the propylene-based polymer composition of the present invention, a commonly used antioxidant, neutralizing agent, slip agent,
An anti-blocking agent, an anti-fogging agent, an anti-static agent and the like can be added as required.

The film comprising the propylene polymer composition of the present invention is cast-molded by dry blending a propylene polymer, a nucleating agent, and various additives used as desired with a Henschel mixer. And film formation by a melt extrusion molding method such as inflation molding. Further, in advance, using a single-screw or twin-screw extruder, a Banbury mixer, or the like, a propylene polymer, a nucleating agent, and various additives used as desired are adjusted by kneading, and pelletized. Can be obtained by forming a film by the above-mentioned molding method.

In particular, a film formed by a T-die casting film forming method in which high-speed film forming is performed by a large film forming machine is preferable because rigidity, heat sealability and transparency are good.
The thickness of the film depends on the application, but is usually 5 to 500 μm
It is about. Further, the above-mentioned film can be suitably used not only for a single layer but also for a multilayer film by a co-extrusion film forming method, and can also be suitably used as a stretched and stretched film. Further, it can be suitably used for laminating sheets and nonwoven fabrics comprising the propylene-based polymer composition of the present invention.

[2] The second resin composition of the present invention comprises:
(A) propylene, ethylene and / or carbon number 4
A propylene random copolymer comprising α-olefins of from 20 to 20 in which the structural unit obtained from propylene is 80 to 100 mol%, ethylene and / or 4-2 carbon atoms.
0 to 20 mol% of the structural unit obtained from the α-olefin having a molecular weight distribution (Mw / Mn) of 3.5.
A propylene-based polymer obtained by adding a nucleating agent (B) in an amount of 10 ppm or more to a propylene-based polymer polymerized using a metallocene-based catalyst having an intrinsic viscosity [η] of 0.5 to 5.0 deciliter / g. It is a united composition.

The component (A) used in the resin composition of the present invention is a propylene-based random copolymer, which is obtained from ethylene and / or an α-olefin having 4 to 20 carbon atoms in the copolymer. It is necessary that the structural unit is contained in an amount of 0 to 20 mol%, more preferably 0 to 10 mol%. If the structural unit obtained from ethylene and / or an α-olefin having 4 to 20 carbon atoms in the propylene-based random copolymer is more than 20 mol%, the film rigidity may be reduced to be insufficient.

The propylene random copolymer has a molecular weight distribution (Mw / Mn) of 3.5 or less, more preferably 3.0 or less, still more preferably 2.5 or less. If (Mw / Mn) exceeds 3.5, a decrease in heat sealability and a decrease in blocking resistance may be observed. The intrinsic viscosity [η] is 0.5 to 5.0 deciliter / g, more preferably 0.5 to 3.0 deciliter / g, and still more preferably 1.0 to 2.5 deciliter / g.

The production of the propylene-based random copolymer is carried out using propylene and ethylene and / or C 4-20.
Of α-olefin. The amount ratio of each monomer in the reaction system does not need to be constant over time, and each monomer may be supplied at a constant mixing ratio, or the mixing ratio of the supplied monomers may be changed over time. Further, any of the monomers can be added in portions in consideration of the copolymerization reaction ratio. In addition, a gas with a constant monomer ratio is continuously introduced into the reaction system, and the excess gas is continuously discharged by a discharge valve, so that the ratio of each monomer in the reaction system is constant over time. It is also possible to keep Hydrogen may be used as a molecular weight regulator.

The propylene random copolymer of the component (A) used in the present invention may be a transition metal compound belonging to Group 4 of the periodic table having a cyclopentadienyl ring described in the above [1] and methylaluminoxane or It can be produced by polymerizing in the presence of a metallocene catalyst comprising a compound which reacts with a transition metal compound belonging to Group 4 of the periodic table to form an ionic complex and an organoaluminum compound.

Specific examples of the metallocene catalyst and the cocatalyst are the same as those described in the above [1], and they are used by supporting them on organic compounds such as polystyrene and inorganic oxides such as silica and alumina. Is also good. The polymerization method, preliminary polymerization, and polymerization conditions are the same as those described in the above [1]. The nucleating agent of the component (B) is the same as described in the above [1].

[3] The propylene polymer composition of the present invention has a MD elastic modulus (TM (MPa)) and a heat sealing temperature (HST (° C.)) satisfying the following relational expression (II). It is characterized by doing. TM ≧ 22 × HST-1850 (II) Preferably, the following relational expression (II) ′ is satisfied. TM ≧ 22 × HST-1800 (II) ′ More preferably, the following relational expression (II) ″ is satisfied. TM ≧ 22 × HST-1750 (II) ″ The above MD Tensile modulus (TM) in the direction is JIS K-
The cross head speed is 500 mm / min, and the measurement direction is M
The direction is D (take-up direction). Film thickness is 25μm
Is the representative value.

The above-mentioned heat sealing temperature (HST)
Is measured according to JIS K-1707. After sealing under the following fusion conditions, leave at room temperature for 24 hours,
Thereafter, at room temperature, the peeling rate was set to 200 mm / min, and the peeling strength was measured by a T-shaped peeling method.
The temperature at which the peel strength reaches 300 g / 15 mm is calculated from the peel strength curve, and this temperature is defined as the heat sealing temperature. The film thickness is 25 μm as a representative value.

Fusing conditions Sealing time: 2 seconds Sealing area: 15 × 10 mm Sealing pressure: 5.3 kg / cm ² Sealing temperature: Several points so that the heat sealing temperature can be interpolated. The temperature of the heat seal bar is calibrated with a surface thermometer.

The propylene polymer composition of the present invention is prepared by adding a nucleating agent to a propylene polymer produced using a metallocene catalyst as described in the above [1] or [2].
The film obtained by adding at least ppm is a film having a high level of rigidity and heat sealability balanced with each other.

[0035]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. First, a method for evaluating a propylene-based polymer and a method for evaluating a film will be described. (1) Measurement method of intrinsic viscosity [η] The intrinsic viscosity [η] (deciliter / g) was measured in decalin at 135 ° C.

(2) Mw / Mn Measuring Method Mw and Mw / Mn were measured using the following apparatus and conditions. GPC measuring device Column: ShodexUT806L manufactured by Showa Denko KK Infrared detector: IR detector for liquid chromatogram Infrared detection flow cell: KBr cell (optical path length 1 mm) Measurement conditions Solvent: o-dichlorobenzene Measurement temperature: 135 ° C. Flow rate: 1 0.0 ml / min Sample concentration: 2 mg / ml Injection volume: 200 μl Infrared absorption wavelength: 3.42 μm

(3) Ethylene content (% by weight) Determined by a ¹³ C-NMR apparatus. Analysis of the spectrum was performed by Kazuo Soga, Takeshi Shiono, Walter Kaminsky, Makr
omol.Chem., Rapid Commun., 8, 305 (1987), Alfonso Gra
ssi, Adolfo Zambelli, Luigi Resconi, Enrico Albizza
ti, Romano Mazzocchi, Macromolecules, 21,617 (1988)
Based on these reports, the ethylene content was determined.

¹³ C-NMR apparatus Apparatus: JNM-EX400 type NMR apparatus manufactured by JEOL Ltd. Sample concentration: 220 mg / NMR solvent 3 ml NMR solvent: 1,2,4-trichlorobenzene / deuterated benzene (90/10 vol%) Measurement temperature: 130 ° C. Pulse width: 45 ° Pulse repetition time: 10 seconds Integration frequency: 4000 times (4) Tensile modulus Measured by a tensile test according to JIS K7127NI. The measurement conditions are as follows: the crosshead speed is 500 mm / min, and the measurement direction is the machine direction (MD direction). (5) Film Impact (FI) The film impact indicates the impact breaking strength, and was measured using a 1-inch impact head with a film impact tester manufactured by Toyo Seiki.

(6) Isotactic pentad fraction The isotactic pentad fraction (mmmm fraction)
Cheng HN, Ewen JA, Macromol. Cem., 1989, 190, 1350, based on the assignment of peaks in the ¹³ C-NMR spectrum, among the five propylene structural units, the meso structure (the sequence of five methyl groups (Mmmm structure arranged in the same direction), and was determined by the following apparatus and conditions. Apparatus: JNM-EX400 type NMR apparatus manufactured by JEOL Ltd. Sample concentration: 220 mg / NMR solvent 3 ml NMR solvent: 1,2,4-trichlorobenzene / heavy benzene (90/10 vol%) Measurement temperature: 130 ° C. Pulse width: 45 ° pulse repetition time: 10 seconds Total number of times: 4000

Example 1 (1) Propylene polymerization 4 l of toluene and 8 mm of triisobutylaluminum were placed in a 10 l stainless steel autoclave.
ol, 20 μmol of tetrakispentafluorophenylborate dimethylanilinium salt, the temperature was raised to 40 ° C., 10 mmol of hydrogen was added, and the total pressure was 7.0 kg / c.
Propylene was introduced up to m ² -G. Here, (1,2 '
-Ethylene) (2,1′-ethylene) -bis (indenyl) hafnium dichloride (5 μmol) was added to initiate polymerization. Propylene was supplied by a pressure regulator so that the pressure became constant. Two hours later, the contents were taken out and dried under reduced pressure to obtain 820 g of a propylene polymer.
The isotactic pentad fraction (mmmm fraction) of this propylene polymer was 88%, [η] was 1.5 deciliters / g, and Mw / Mn was 1.9. (2) Blending and kneading The propylene polymer obtained above was added with I as an antioxidant
RG1010 (manufactured by Ciba Geigy) 750 ppm, IR
G168 (manufactured by Ciba-Geigy) 750 ppm, calcium stearate 500 ppm as a neutralizing agent, dimethylbenzylidene sorbitol (manufactured by Shin Nippon Rika:
100 ppm of Gerol MD, 1000 ppm of erucamide as a slipping agent, and 1800 ppm of a silica-based antiblocking agent as an antiblocking agent were added to a single screw extruder (TLC35-20 manufactured by Tsukada Juki Seisakusho, Ltd.).
(Mold) to obtain pellets. (3) Film molding Using a 20 mmφT die cast molding machine manufactured by Tsukada Juki Seisakusho, a film having a thickness of 25 μm was formed at a resin temperature (T die exit) of 191 ° C., a chill roll temperature (mirror roll) of 30 ° C.
A film was formed under a molding condition of a take-up speed of 5.8 m / min. The air gap was 5.5 cm using an air knife. After film formation, aging was performed at 40 ° C. for 24 hours. (4) Film evaluation Tensile modulus, film impact and heat sealing temperature were evaluated by the above-mentioned measuring methods. The results are shown in Table 1 and FIG.

Example 2 Gelol MD as a nucleating agent
(New Nippon Rika Co., Ltd.) was changed to 500 ppm.
It was the same as in Example 1. Comparative Example 1 The procedure of Example 1 was repeated except that no nucleating agent was added.

[Comparative Example 2] A propylene polymer obtained with a nonmetallocene catalyst (IDEMI, manufactured by Idemitsu Petrochemical Co., Ltd.)
TSU PP F704NP), and a film was formed and evaluated in the same manner as in Example 1 except that a nucleating agent was not added. The isotactic pentad fraction (mmmm fraction) of this propylene polymer was 90%, [η] =
1.7 deciliters / g and Mw / Mn were 4.2.

[Comparative Example 3] A propylene polymer obtained with a nonmetallocene catalyst (IDEMI, manufactured by Idemitsu Petrochemical Co., Ltd.)
A film was formed and evaluated in the same manner as in Example 1 except that TSU PP F704NP) was used, except that 500 ppm of Gelol MD (manufactured by Nippon Rika Co., Ltd.) was added as a nucleating agent. The propylene polymer had an isotactic pendat fraction (mmmm fraction) of 90%, [η].
= 1.7 deciliters / g and Mw / Mn = 4.2. In the propylene polymer obtained with this nonmetallocene catalyst, the heat sealing temperature was higher when the nucleating agent was added.

Example 3 (1) Propylene polymerization 4 liters of toluene and 8 mm of triisobutylaluminum were placed in a stainless steel autoclave having an internal volume of 10 liters.
ol, 20 μmol of tetrakispentafluorophenylborate dimethylanilinium salt, the temperature was raised to 50 ° C., and an ethylene / propylene mixed gas (gas composition ratio: ethylene / propylene = 7.0 kg / cm ² -G) at a total pressure of 7.0 kg / cm ² -G.
2/100). Here, 5 μmol of (1,2′-ethylene) (2,1′-ethylene) -bis (indenyl) hafnium dichloride was added to initiate polymerization.
Propylene was supplied by a pressure regulator so that the pressure became constant. Two hours later, the content was taken out and dried under reduced pressure to obtain 700 g of a propylene polymer. The ethylene content was 1.8% by weight, [η] was 1.8 deciliters / g, and Mw / Mn was 2.2. (2) Blending and kneading The propylene polymer obtained above was added with I as an antioxidant
RG1010 (manufactured by Ciba Geigy) 750 ppm, IR
G168 (manufactured by Ciba Geigy) 750 ppm, calcium stearate 500 ppm as a neutralizing agent, gelol MD (manufactured by Shin Nippon Rika) 500 ppm as a nucleating agent, erucamide amide 500 ppm as a slipping agent, and a silica-based antiblocking agent 230 as an antiblocking agent
0 ppm was added, and a single screw extruder (Tsukada Sikiki Seisakusho: T
LC35-20) to obtain pellets. (3) Film molding Using a 20 mmφT die cast molding machine manufactured by Tsukada Juki Seisakusho, a film having a thickness of 25 μm was formed at a resin temperature (T die exit) of 191 ° C., a chill roll temperature (mirror roll) of 30 ° C.
A film was formed under a molding condition of a take-up speed of 6.0 m / min. After film formation,
Aging was performed at 40 ° C. for 24 hours. (4) Film evaluation Tensile modulus, film impact and heat sealing temperature were evaluated by the above-mentioned measuring methods. The results are shown in Table 1 and FIG.

Example 4 A propylene polymer composition was obtained in the same manner as in Example 3 except that the ethylene / propylene mixed gas composition was reduced to 1/100. The ethylene content was 0.48% by weight, [η] was 1.9 deciliter / g, and Mw / Mn was 2.1.

Example 5 A propylene polymer composition was obtained in the same manner as in Example 3 except that the ethylene / propylene mixed gas composition was changed to 3/100. The ethylene content was 2.5% by weight, [η] was 1.6 deciliters / g, and Mw / Mn was 2.2.

Example 6 Talc MMR as nucleating agent
Except for using 2000 ppm (manufactured by Asada Flour Milling Co., Ltd.), blending and kneading, film forming, and film evaluation were performed in the same manner as in Example 3.

Example 7 The procedure of Example 3 was repeated except for using 250 ppm of sodium phosphate organic and NA-11 (manufactured by Asahi Denka Co., Ltd.) as a nucleating agent.

[Example 8] Organic aluminum phosphate as a nucleating agent, NA-21 (manufactured by Asahi Denka Co., Ltd.) 1500 ppm
The compounding and kneading, film forming, and film evaluation were performed in the same manner as in Example 3 except for using.

Example 9 Amide compound as a nucleating agent, Ngester NU-100 (manufactured by Shin Nippon Rika) 15
Except for using 00 ppm, compounding and kneading, film forming, and film evaluation were performed in the same manner as in Example 3.

[Comparative Example 4] Except that no nucleating agent was added,
It was the same as Example 3. [Comparative Example 5] The following propylene polymer obtained with a nonmetallocene catalyst was used, and the amount of the nucleating agent added was 1000 pp.
The procedure was the same as Example 3 except that m was used.

(Propylene polymerization) (1) Adjustment of solid catalyst component A reaction vessel equipped with a stirrer (internal volume: 500 L) was sufficiently replaced with nitrogen gas, and 97.7 kg of ethanol and 640 of iodine were added.
g and 6.4 kg of metallic magnesium were charged and reacted under reflux conditions with stirring until hydrogen gas was no longer generated from within the system to obtain a solid reaction product. The reaction solution containing the solid reaction product was dried under reduced pressure to obtain a target magnesium compound (solid product). 30 kg of the magnesium compound (not pulverized), 150 liters of purified heptane, 4.5 liters of silicon tetrachloride and di-n-phthalic acid were placed in a reactor (with an internal volume of 500 liters) equipped with a stirrer sufficiently purged with nitrogen gas. 5.4 liters of butyl were added. While maintaining the inside of the system at 90 ° C., 144 liters of titanium tetrachloride were added thereto with stirring and reacted at 110 ° C. for 2 hours. Then, a solid component was separated and washed with purified heptane at 80 ° C. Furthermore, after adding 228 liters of titanium tetrachloride and reacting at 110 ° C. for 2 hours, it was sufficiently washed with purified heptane to obtain a solid catalyst component.

(2) Polymerization Before starting the main polymerization, the following pretreatment is performed. Internal volume 5
Purified heptane 230 in a 100 liter reactor with stirrer
Then, 25 kg of the solid catalyst component, 1.0 mol / mol of triethylaluminum, and 1.8 mol / mol of dicyclopentylmethyldimethoxysilane with respect to Ti in the solid catalyst component were supplied. . Then, the propylene was supplied at a partial pressure of propylene of 0.3 kg / cm ^2.
G was introduced and reacted at 25 ° C. for 4 hours. After the completion of the reaction, the solid catalyst component was washed several times with purified heptane, further supplied with carbon dioxide, and stirred for 24 hours. After the above pretreatment, main polymerization is started. In a polymerization apparatus having a stirrer having an internal volume of 200 liters, the treated solid catalyst component was converted to 3 mmol / h in terms of Ti, triethylaluminum at 4 mmol / kg-PP, and cyclohexylmethyldimethoxysilane at 1 mmol / kg-PP. And reacted at a polymerization temperature of 80 ° C. and a total pressure of 28 kg / cm ² G. At this time, the ethylene supply amount was adjusted so as to have a predetermined ethylene content, and the hydrogen supply amount was adjusted so as to have a predetermined molecular weight. This propylene polymer has an ethylene structural unit of 5.9 mol% and a molecular weight distribution ( _Mw / _Mn ).
= 4.0, [η] = 1.7 deciliter / g.

Comparative Example 6 The same procedure as in Example 3 was carried out except that the propylene polymer shown in Comparative Example 5 obtained with a nonmetallocene catalyst was used and no nucleating agent was added.

[0055]

[Table 1]

[0056]

According to the present invention, it is possible to provide a propylene-based polymer and a film comprising the propylene-based polymer in which rigidity and heat sealability are balanced at a high level. This film can be expected to be used in place of a conventional film made of a propylene polymer, and also to expand its use by making use of preferable characteristics.

[Brief description of the drawings]

FIG. 1 shows the equation of relational formula (II) of the present invention.

──────────────────────────────────────────────────続 き Continued on front page (51) Int.Cl. ⁶ Identification code FI C08K 5/49 C08K 5/49

Claims (9)

[Claims] (A) A propylene homopolymer having an isotactic pentad fraction (mmmm fraction) of 80
-99% and a molecular weight distribution (Mw / Mn) of 3.
Propylene polymer obtained by adding (B) a nucleating agent of 10 ppm or more to a propylene polymer polymerized using a metallocene catalyst having an intrinsic viscosity [η] of 0.5 to 5.0 deciliters / g. Polymer composition. (A) propylene, ethylene and / or
Or a propylene-based random copolymer comprising an α-olefin having 4 to 20 carbon atoms, wherein the structural unit obtained from propylene is 80 to 100 mol%, and ethylene and / or an α-olefin having 4 to 20 carbon atoms is obtained. Is 0 to 20 mol%, and has a molecular weight distribution (Mw / M
n) is 3.5 or less, and the intrinsic viscosity [η] is 0.5 to
A propylene-based polymer polymerized using a metallocene-based catalyst of 5.0 deciliter / g was added with (B) a nucleating agent of 10%.
A propylene-based polymer composition added in at least ppm. 3. The propylene polymer resin composition according to claim 1, wherein the nucleating agent is a metal salt of an organic phosphate. 4. The propylene polymer resin composition according to claim 1, wherein the nucleating agent is talc. 5. The propylene polymer resin composition according to claim 1, wherein the nucleating agent is dibenzylidene sorbitol or a derivative thereof. 6. The propylene polymer resin composition according to claim 1, wherein the nucleating agent is an amide compound. 7. Tensile modulus in the MD (TM (MPa))
And a heat sealing temperature (HST (° C.)) satisfying the following relational expression (II): TM ≧ 22 × HST-1850 (II) 8. A film formed by casting the propylene-based polymer composition according to claim 1 by a cast molding method. 9. A food packaging film formed by casting the propylene polymer composition according to claim 3 or 4 by a cast molding method.