JPH0812713A - Propylene resin for blow molding and blow molded article produced therefrom - Google Patents

Abstract

PURPOSE:To obtain a propylene resin which gives a blow molded article excellent in pinch-off characteristics by using a homopolymer and/or a copolymer having specified physical properties. CONSTITUTION:This resin comprises a propylene homopolymer and/or a propylene copolymer contg. 4mol% or lower olefin units other than propylene units and has a heat of fusion by differential scanning calorimetry(DSC) of 30-90J/g, a time for the max. heat absorption in isothermal crystallization at 120 deg.C determined by DSC of 0. 6-4min, a coefficient A indicating the rise of elongation viscosity from 1sec to 7sec and defined by the formula (wherein eta1 and eta2 are the elongation viscosity measured at 180 deg.C at a strain rate of 0.3sec<-1> at the time of 1sec and 7sec, respectively) of 0.3 or higher, and a melt index of 0.1-10g/10min.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a propylene resin for blow molding and a blow molded product using the same. More specifically, propylene homopolymers and copolymers capable of giving blow-molded products excellent in pinch-off characteristics, which were not possible with conventional polyolefin-based resins, and propylene-based resin compositions, and these were used. The present invention relates to a blow-molded article having excellent pinch-off characteristics.

[0002]

2. Description of the Related Art Conventionally, general-purpose polyolefin resins such as polyethylene and polypropylene have been molded into desired-shaped products by various molding methods such as extrusion molding, injection molding and blow molding. By the way, various bottles, tanks, ducts, etc. are made by blow molding,
And for such blow molding, polypropylene and high-density polyethylene have been conventionally used, but blow molded products obtained from these materials have excellent mechanical strength, but are inferior in pinch-off strength, It has drawbacks such as cracking and breaking from the pinch-off portion. As a method of improving such a defect, a method of controlling the shape of the pinch-off portion depending on the mold or molding conditions is used. However, depending on the product, these methods have not always been fully satisfactory. Therefore, it has been desired to improve the pinch-off characteristics of the blow-molded product by using a material.

[0003]

SUMMARY OF THE INVENTION Under the above circumstances, the present invention provides a blow molding propylene-based resin and a blow molding propylene-based resin which can provide a blow-molded article excellent in pinch-off characteristics, which is impossible with conventional polyolefin-based resins. It is an object of the present invention to develop a propylene-based resin composition and a blow-molded article using these, which is excellent in pinch-off characteristics.

[0004]

Means for Solving the Problems As a result of intensive studies for achieving the above-mentioned object, the present inventors have found that a propylene homopolymer having a specific property and / or a small amount of an olefin unit other than propylene can be obtained. A propylene-based resin comprising a copolymer containing, or a homopolymer of propylene having specific properties and / or a copolymer containing a small amount of an olefin unit other than propylene, and propylene containing an olefin unit other than propylene in a specific ratio. It has been found that the object can be achieved by a propylene resin composition containing a random copolymer at a predetermined ratio. The present invention has been completed based on such findings.

That is, the first aspect of the present invention is that (1) an endothermic amount ΔHw due to crystal melting measured by a differential scanning calorimeter (DSC) method is 30 to 90 J / g, and (2) a differential scanning calorific value. Time t _MAX showing the maximum endothermic amount at 120 ° C. isothermal crystallization determined by the DSC method is 0.6 to 4 min
(3) Temperature 180 ℃, strain rate 0.3sec
^{When the} extensional viscosities at 1 sec and 7 sec measured at ^-1 are η ₁ and η ₂ , respectively, the formula A = [log ₁₀ (η ₇ ) −log ₁₀ (η ₁ )] / [log ₁₀ (7) −log ₁₀ (1)], the coefficient A indicating the rise of extensional viscosity from 1 sec to 7 sec is 0.3 or more, and (4)
Blow-molding propylene comprising a propylene homopolymer characterized by a melt index (MI) of 0.1 to 10 g / 10 minutes and / or a copolymer containing 4 mol% or less of an olefin unit other than propylene. A resin is provided. The second aspect of the present invention is (a)
(1) An endothermic amount ΔHw due to crystal melting measured by a differential scanning calorimeter (DSC) method is 30 to 90 J / g,
(2) 12 determined by the differential scanning calorimeter (DSC) method
The time t _MAX showing the maximum endothermic amount at 0 ° C. isothermal crystallization is 0.
6 to 4 min, and (3) temperature 180 ° C., strain rate 0.3 sec ⁻¹ , time 1 sec and 7 sec
When the extensional viscosities at η ₁ and η ₂ are respectively expressed by the formula A = [log ₁₀ (η ₇ ) −log ₁₀ (η ₁ )] / [log ₁₀ (7) −log ₁₀ (1)] A homopolymer of propylene having a coefficient A showing a rise in elongational viscosity from 1 sec to 7 sec of 0.4 or more and / or 10 mol% to 95 wt% of a copolymer containing 4 mol% or less of an olefin unit other than propylene; (B)
A propylene random copolymer containing 10 to 70% by weight of an olefin unit other than propylene and 90 to 5% by weight, and having a melt index (MI) of 0.1 to 1
The propylene-based resin composition for blow molding is characterized in that the amount is 0 g / 10 minutes. Further, a third aspect of the present invention is to provide a blow molded product made of the propylene resin or the propylene resin composition.

The propylene-based resin of the first invention comprises a propylene homopolymer and / or a copolymer containing 4 mol% or less of an olefin unit other than propylene. The propylene homopolymer or copolymer is required to have the following properties. First, (1) it is necessary that the heat absorption amount ΔHw due to crystal melting measured by the differential scanning calorimeter (DSC) method is in the range of 30 to 90 J / g. If this ΔHw is out of the above range, the object of the present invention cannot be sufficiently achieved. Especially, ΔHw is 90 J / g
When it exceeds, the pinch-off portion tends to be brittlely broken and the strength of the pinch-off portion tends to be weakened. The preferable range of ΔHw is 40 to 80 J / g. This ΔHw
Is a value obtained by the following method using Perkin Elmer DSC-7. That is, about 10 mg of a sample is placed in a dedicated aluminum pan and sealed, and then heated at 220 ° C. for 3 minutes to completely melt the crystal of the polymer. Then, the temperature is lowered to 50 ° C. at a rate of 10 ° C./min to recrystallize. Then, after leaving at 50 ° C. for 3 minutes, the temperature is raised to 220 ° C. at a rate of 10 ° C./minute,
The exothermic curve at the time of temperature rise is measured. Next, 70 ℃ and 175 ℃
ΔHw is obtained by dividing the calorific value associated with the melting of the polymer, which is obtained from the area sandwiched between the baseline and the exothermic curve, by the weight of the sample with the straight line connecting the measurement points .

Next, (2) 120 determined by the DSC method
Time t showing the maximum endothermic amount at ℃ isothermal crystallization_MAXIs from 0.6
It must be in the range of 4 min. This t_MAXBut
If it is less than 0.6 min, the crystallization speed is too fast and pinch off.
Before the molecular chains are entangled in the part, it crystallizes
If the strength of the flap becomes weaker and if it exceeds 4 min,
The crystallization rate is slow and the molding cycle becomes long. Pinch off
From the viewpoint of strength of parts and molding cycle, preferable t_MAXof
The range is 0.7 to 3.6 min. This crystallization rate finger
The mark t_MAXIs a Perkin Elmer DSC-7
It is the value obtained by using the following method. That is, the sample
I put about 10 mg in a special aluminum pan and sealed it
Then, by heating at 220 ° C for 3 minutes, the polymer
The crystal is completely melted, the endothermic change over time is measured, and
Time t indicating large heat absorption _MAXTo determine. In addition, this place
In this case, the time when the temperature reaches 120 ° C. is set to time 0.

(3) Temperature 180 ° C., strain rate 0.3
When the extensional viscosities at 1 sec and 7 sec measured at sec ⁻¹ are respectively η ₁ and η ₂ , the formula A = [log ₁₀ (η ₇ ) −log ₁₀ (η ₁ )] / [log ₁₀ (7) − It is necessary that the coefficient A representing the rise of extensional viscosity from 1 sec to 7 sec represented by log ₁₀ (1)] is 0.3 or more. If this coefficient A is less than 0.3, during blow-up,
The pinch-off portion may be thinned and its strength may be weakened. The preferable range of the coefficient A is 0.4 to 1.0. The extensional viscosity is a value obtained by using an extensional rheometer manufactured by Iwamoto Seisakusho at a temperature of 180 ° C. and a strain rate of 0.3 sec ⁻¹ . Furthermore, (4) melt index (MI)
It should be in the range of 0.1 to 10 g / 10 minutes, preferably 0.1 to 5 g / 10 minutes. If the MI is less than 0.1 g / 10 minutes, the fluidity is low and the blow moldability is poor.
If it exceeds 0 g / 10 minutes, the drawdown is large and blow molding cannot be performed. This MI is JISK-72.
It is a value measured according to 10 under the conditions of a temperature of 230 ° C. and a load of 2,160 g.

The propylene-based resin in the first invention may be a propylene homopolymer as long as it satisfies the above conditions, and contains olefin units other than propylene in a proportion of 4 mol% or less. It may be a copolymer or a mixture thereof. further,
In this propylene homopolymer or copolymer, the intrinsic viscosity [η] measured in decalin at a temperature of 135 ° C.
Usually 0.5 to 10 deciliters / g, preferably 1.0 to 9.
It is in the range of 0 deciliter / g. This intrinsic viscosity [η]
Is less than 0.5 deciliter / g, mechanical properties are insufficient, and when it exceeds 10 deciliter / g, moldability is deteriorated.

On the other hand, in the propylene resin composition according to the second aspect of the invention, the component (a) is the component (1),
A propylene homopolymer satisfying the conditions (2) and (3) and / or a copolymer containing 4 mol% or less of an olefin unit other than propylene are used. The propylene homopolymer or copolymer, which is the component (a), is
If the conditions (2) and (3) are not satisfied, the object of the present invention cannot be sufficiently achieved for the same reason as above. In the propylene homopolymer or copolymer of the component (a), the intrinsic viscosity [η] measured in decalin at a temperature of 135 ° C. is usually 0.5 to 10 deciliter / g, preferably 1.0 to It is in the range of 9.0 deciliters / g. When the intrinsic viscosity [η] is less than 0.5 deciliter / g, the mechanical properties are insufficient, and when it exceeds 10 deciliter / g, the moldability deteriorates. Further, in the propylene resin composition, a propylene random copolymer containing 10 to 70% by weight of an olefin unit other than propylene is used as the component (b). This propylene-based random copolymer has an intrinsic viscosity [η] measured in decalin at a temperature of 135 ° C. of usually 0.5 to 10 deciliter / g, preferably 1.0 to 9.0 deciliter / g. is there. When the intrinsic viscosity [η] is less than 0.5 deciliter / g, the mechanical properties are insufficient, and when it exceeds 10 deciliter / g, the moldability deteriorates.

In the propylene resin composition of the second invention, the propylene homopolymer or copolymer as the component (a) is 10 to 95% by weight, preferably 30 to 95% by weight, and the component (b) is 90% propylene-based random copolymer
It is necessary to contain it in an amount of ˜5 wt%, preferably 70-5 wt%. If the content ratio of the component (a) and the component (b) deviates from the above range, the object of the present invention cannot be sufficiently achieved. This propylene-based resin composition needs to have a melt index (MI) of 0.1 to 10 g / 10 minutes, preferably 0.1 to 5 g / 10 minutes.
If the MI is less than 0.1 g / 10 minutes, the flowability is low and blow moldability is poor, and if it exceeds 10 g / 10 minutes,
Blow molding is not possible because of large drawdown. In addition,
This MI complies with JIS K-7210 and has a temperature of 23.
It is a value measured under the conditions of 0 ° C. and a load of 2,160 g.

The propylene-based resin of the first invention described above is, for example, (A) (a) a solid catalyst component composed of magnesium, titanium, a halogen atom and an electron donor, and (b) crystals used as necessary. Solid component composed of water-soluble polyolefin, (B) organoaluminum compound,
(C) General formula (I)

[0013]

Embedded image

[In the formula, R ¹ represents an alkyl group having 1 to 20 carbon atoms, R ² represents a hydrocarbon group having 1 to 10 carbon atoms, a hydroxyl group or a nitro group, m is an integer of 1 to 6, and n is 0 to 0. An integer of (6-m) is shown. ] In the presence of a catalyst system consisting of an alkoxy group-containing aromatic compound represented by and an (D) electron-donating compound optionally used, propylene is homopolymerized or copolymerized with other olefins. , Can be manufactured. On the other hand, the propylene-based resin composition of the second invention can be prepared, for example, by various polymerization methods such as a gas phase multi-step polymerization method and a slurry multi-step polymerization method, or a blending method. For example, when it is prepared by a polymerization method, propylene may be copolymerized with other olefins in the presence of the above catalyst system.

The solid component (A) is composed of a solid catalyst component consisting of magnesium, titanium, a halogen atom and an electron donor as the component (a), and a crystalline polyolefin as the component (b) which is optionally used. Has been done. The solid catalyst component of the component (a) is magnesium, titanium,
It has a halogen atom and an electron donor as essential components, and can be prepared by contacting a magnesium compound, a titanium compound and an electron donor. In this case, the halogen atom is included as a halide in the magnesium compound and / or the titanium compound.

Examples of the magnesium compound include:
Magnesium dihalide, such as magnesium chloride,
Magnesium oxide, magnesium hydroxide, hydrotalcite, carboxylates of magnesium, alkoxy magnesium such as diethoxy magnesium, allyloxy magnesium, alkoxy magnesium halide, allyloxy magnesium halide, alkyl magnesium such as ethyl butyl magnesium, alkyl magnesium halide, Alternatively, examples thereof include a reaction product of an organomagnesium compound with an electron donor, a halosilane, an alkoxysilane, a silanol, an aluminum compound, and the like. Among these, magnesium halide, alkoxymagnesium, alkylmagnesium, and alkylmagnesium halide are preferable. is there. These magnesium compounds may be used alone or in combination of two or more.

As the magnesium compound, a reaction product of metallic magnesium, halogen and alcohol can be used. The metallic magnesium used at this time is not particularly limited, and metallic magnesium having an arbitrary particle size, for example, granular, ribbon-like, powder-like or the like can be used. Further, the surface state of the magnesium metal is not particularly limited, but it is preferable that the surface of the surface is not coated with magnesium oxide. Further, although any alcohol can be used, it has 1 to 1 carbon atoms.
It is preferable to use a lower alcohol of 6, and ethanol is particularly preferable because it gives a solid catalyst component that remarkably improves the expression of catalytic performance. The purity and the water content of the alcohol are not limited, but when an alcohol having a high water content is used, magnesium hydroxide is formed on the surface of the metal magnesium, so the water content is 1% by weight or less, particularly 2000 ppm.
The following alcohols are preferably used, and the lower the water content, the more advantageous.

The kind of halogen and / or halogen-containing compound is not limited, and any compound containing a halogen atom in its molecule can be used. in this case,
The type of halogen atom is not particularly limited, but chlorine, bromine or iodine, particularly iodine is preferably used.
Among the halogen-containing compounds, halogen-containing metal compounds are particularly preferable. These states, shapes, particle sizes, etc. are not particularly limited and may be arbitrary, and for example, they can be used in the form of a solution in an alcohol solvent (eg ethanol). The amount of alcohol used is selected in the range of 2 to 100 mol, preferably 5 to 50 mol, per 1 mol of metallic magnesium. If the amount of alcohol is too large, it tends to be difficult to obtain a magnesium compound having a good morphology, and if it is too small, the reaction with metallic magnesium may not be carried out smoothly.

The halogen and / or the halogen-containing compound is usually used in an amount of 0.000 per mol of magnesium metal.
It is used in a proportion of 1 gram atom or more, preferably 0.0005 gram atom or more, and more preferably 0.001 gram atom or more. If it is less than 0.0001 gram atom, when the obtained magnesium compound is used without being crushed, the carried amount, activity, stereoregularity, morphology of the produced polymer and the like are lowered, and the crushing treatment becomes indispensable, which is not preferable. Further, by appropriately selecting the amount of halogen used, it is possible to arbitrarily control the particle size of the obtained magnesium compound.

The reaction itself of the magnesium metal, the alcohol, the halogen and / or the halogen-containing compound can be carried out by a known method. For example, metallic magnesium, alcohol, and halogen are usually refluxed under reflux for about 20 to 30 until generation of hydrogen gas is not observed.
This is a method of reacting for a time to obtain a desired magnesium compound. Specifically, for example, when iodine is used as the halogen, a method in which metallic magnesium and solid iodine are put into an alcohol and then heated and refluxed, and an alcohol solution of metallic magnesium and iodine is dropped into the alcohol. Examples include a method of post-heating and refluxing, a method of dropping an alcohol solution of iodine while heating an alcohol solution containing metallic magnesium, and the like. In either method, for example, under an inert gas atmosphere such as nitrogen gas or argon gas, an inert organic solvent (for example, n-) may be used.
It is preferable to use saturated hydrocarbon such as hexane). Regarding the addition of metal magnesium, alcohol, and halogen, it is not necessary to add all of them to the reaction tank from the beginning, and they may be added separately. A particularly preferred form is a method in which the alcohol is charged in its entirety from the beginning, and the magnesium metal is divided and charged several times.

In such a case, it is possible to prevent a temporary large amount of hydrogen gas from being generated, which is very desirable from the viewpoint of safety. Also, the size of the reaction tank can be reduced. Furthermore, it becomes possible to prevent the entrainment of alcohol or halogen caused by the temporary large generation of hydrogen gas. The number of times of division may be determined in consideration of the scale of the reaction tank, and usually 5 to 10 times is preferable considering the complexity of the operation. Further, it goes without saying that the reaction itself may be a batch type or a continuous type. Furthermore, as a modified method, a small amount of metallic magnesium is first added to the alcohol that has been entirely added from the beginning, the product produced by the reaction is separated and removed in another tank, and then a small amount of metallic magnesium is added again. It is also possible to repeat. When the magnesium compound thus obtained is used for the next preparation of the solid catalyst component, a dried one may be used, or a magnesium compound that has been filtered and washed with an inert solvent such as heptane may be used. In any case, the obtained magnesium compound can be used in the next step without pulverization or classification operation for adjusting the particle size distribution.

Examples of the titanium compound include
Tetramethoxy titanium, tetraethoxy titanium, tetra-n-propoxy titanium, tetraisopropoxy titanium, tetra-n-butoxy titanium, tetraisobutoxy titanium, tetracyclohexyloxy titanium, tetraphenoxy titanium and other tetraalkoxy titanium, titanium tetrachloride, Tetrahalogenated titanium such as titanium tetrabromide and titanium tetraiodide, methoxytitanium trichloride, ethoxytitanium trichloride, propoxytitanium trichloride, n-butoxytitanium trichloride, ethoxytitanium tribromide and other halogenated alkoxytitanium, dimethoxy Titanium dichloride, diethoxytitanium dichloride, dipropoxytitanium dichloride, di-n-butoxytitanium dichloride, diethoxytitanium Dihalogenated dialkoxy titanium, such as bromide, trimethoxy titanium chloride, triethoxy titanium chloride, tripropoxy titanium chloride, etc. monohalogenated trialkoxy titanium and tri -n- butoxy titanium chloride. Among these, titanium compounds having a high halogen content, particularly titanium tetrachloride, are preferable. These titanium compounds may be used alone or in combination of two or more.

Further, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and these halogen atoms are usually used as halides contained in magnesium compounds and / or titanium compounds. To be Further, as the electron donor, those exemplified later as the electron donating compound of the component (D) can be used. The (a) solid catalyst component can be prepared by a known method (JP-A-53-43094, JP-A-55).
-135102, JP-A-55-135103, JP-A-56-18606, JP-A-56-16
6205, JP-A-57-63309, JP-A-57-190004, and JP-A-57-30040.
No. 7, JP-A-58-47003).

The composition of the solid catalyst component (a) thus prepared usually has a magnesium / titanium atomic ratio of 2
-100, the halogen / titanium atomic ratio is 5-100, and the electron donor / titanium molar ratio is 0.1-10. The crystalline polyolefin of the component (b), which is optionally used in the preparation of the solid component (A), has, for example, 2 to 10 carbon atoms such as polyethylene, polypropylene, polybutene, and poly-4-methyl-1-pentene. Α-
Crystalline polyolefins obtained from olefins are mentioned. This crystalline polyolefin is (1) above (a)
A method of prepolymerizing an olefin in the presence of a combination of a solid catalyst component, an organoaluminum compound, and an electron-donating compound used as necessary (preliminary polymerization method), (2) crystalline polyethylene having uniform particle size (A) a method of dispersing the solid catalyst component (a), an organoaluminum compound optionally used and an electron donating compound (melting point 100 ° C. or higher) in a crystalline powder such as polypropylene or polypropylene (dispersion method), (3) It can be obtained by using a method combining the method (1) and the method (2).

In the prepolymerization method (1), the atomic ratio of aluminum / titanium is usually selected in the range of 0.1 to 100, preferably 0.5 to 5, and the molar ratio of electron donating compound / titanium. Is selected in the range of 0 to 50, preferably 0.1 to 2. Regarding the ratio of (a) solid catalyst component and (b) crystalline polyolefin in (A) solid component,
The weight ratio of component (b) to component (a) is usually 0.33.
To 200, preferably 0.1 to 50.

Next, as the organoaluminum compound used as the component (B), general formula (II) AlR ³ _p X _3-p (II) [wherein R ³ has 3 to 20 carbon atoms] An alkyl group or an aryl group having 6 to 20 carbon atoms, X is a halogen atom, and p is 1 to 3
Indicates the number of. ] Can be mentioned. For example, triisopropyl aluminum, triisobutyl aluminum, trialkyl aluminum such as trioctyl aluminum, diethyl aluminum monochloride, diisopropyl aluminum monochloride,
Dialkyl aluminum monohalides such as diisobutyl aluminum monochloride and dioctyl aluminum monochloride, alkyl aluminum sesquihalides such as ethyl aluminum sesquichloride, and the like can be preferably used. These aluminum compounds may be used alone or in combination of two or more.

In the catalyst system of the present invention, as the component (C), the general formula (I) is used.

[0028]

Embedded image

[Wherein R ¹ represents an alkyl group having 1 to 20 carbon atoms, R ² represents a hydrocarbon group having 1 to 10 carbon atoms, a hydroxyl group or a nitro group, m is an integer of 1 to 6, and n is 0. ~ (6-m)
Indicates an integer. ] An alkoxy group-containing aromatic compound represented by the following is used.

Specific examples of the alkoxy group-containing aromatic compound include m-methoxytoluene; o-methoxyphenol; m-methoxyphenol; 2-methoxy-4-.
Methylphenol; vinylanisole; p- (1-propenyl) anisole; p-allylanisole; 1,3-
Bis (p-methoxyphenyl) -1-pentene; 5-allyl-2-methoxyphenol; 4-hydroxy-3-
Methoxybenzyl alcohol; methoxybenzyl alcohol; nitroanisole; monoalkoxy compounds such as nitrophenetole; o-dimethoxybenzene; m-dimethoxybenzene; p-dimethoxybenzene; 3,4-
Dimethoxytoluene; 2,6-dimethoxyphenol;
Dialkoxy compounds such as 1-allyl-3,4-dimethoxybenzene, 1,3,5-trimethoxybenzene; 5
-Allyl-1,2,3-trimethoxybenzene; 5-allyl-1,2,4-trimethoxybenzene; 1,2,3
-Trimethoxy-5- (1-propenyl) benzene;
1,2,4-trimethoxy-5- (1-propenyl) benzene; 1,2,3-trimethoxybenzene; 1,2,
Examples thereof include trialkoxy compounds such as 4-trimethoxybenzene. Among these, dialkoxy compounds and trialkoxy compounds are preferable. These alkoxy group-containing aromatic compounds may be used alone or in combination of two or more.

Further, the catalyst may optionally contain (D)
An electron donating compound is used as a component. The electron donating compound is a compound containing oxygen, nitrogen, phosphorus, sulfur, silicon, and the like. Basically, a compound having a performance of improving regularity in propylene polymerization is considered. Examples of such electron-donating compounds include organosilicon compounds, esters, thioesters, amines, ketones, nitriles, phosphines, ethers, thioethers, acid anhydrides, acid halides, acid amides. Examples thereof include aldehydes, aldehydes, organic acids and azo compounds.

For example, diphenyldimethoxysilane, diphenyldiethoxysilane, dibenzylmethoxysilane, tetramethoxysilane, tetraethoxysilane, tetraphenoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriphenoxysilane, phenyltrimethoxysilane. , Phenyltriethoxysilane, benzyltrimethoxysilane, methyl tert-butyldimethoxysilane, di-tert-butyldiethoxysilane, di-tert-butyldimethoxysilane, isopropyl-tert-butyldimethoxysilane, methyl-tert-butyldiethoxysilane, methyl ( 3-ethylpentyl-3) dimethoxysilane, methyl sec-butyldimethoxysilane, (α, α
-Dimethylbenzyl) triethoxysilane, (2-cyclohexylpropyl-2) triethoxysilane, diisobutyldimethoxysilane, methyl (2-methylbutyl-
2) Diethoxysilane, (α, α-dimethylbenzyl)
Dimethoxysilane, (2-cyclohexylpropyl-
2) Trimethoxysilane, methylcyclohexyldimethoxysilane, dicyclopentyldimethoxysilane, methyl (2-methylbutyl-2) diethoxysilane, (3-
Ethylpentyl-3) triethoxysilane, tert-butyltrimethoxysilane, sec-butyltrimethoxysilane,
Tert-butyltriethoxysilane, (2-methylbutyl-
2) trimethoxysilane, (2-methylbutyl-2) triethoxysilane, isobutyl secondary butyldimethoxysilane, disecondary butyldimethoxysilane, isobutylcyclopentyldimethoxysilane, ethyl tertiary butyldimethoxysilane, propyl tertiary butyldimethoxysilane, Diisopropyldimethoxysilane, isobutyl (cyclopentylmethyl) dimethoxysilane, tert-butylcyclopentyldimethoxysilane, tert-butylcyclohexyldimethoxysilane, isobutylcyclohexyldimethoxysilane, methyl p-tolyldimethoxysilane, methyl o
-Tolyldimethoxysilane, di (p-tolyl) dimethoxysilane, di (o-tolyl) dimethoxysilane, dibenzyldimethoxysilane, bis (cyclohexylmethyl)
Organosilicon compounds such as dimethoxysilane, monomethylphthalate, monoethylphthalate, monopropylphthalate, monobutylphthalate, monoisobutylphthalate, monoamylphthalate, monoisoamylphthalate, monomethylterephthalate, monoethylterephthalate, monopropylterephthalate, monobutylterephthalate, Monoisobutyl terephthalate, dimethyl phthalate, diethyl phthalate, dipropyl phthalate, dibutyl phthalate, diisobutyl phthalate, diamyl phthalate, diisoamyl phthalate, methyl ethyl phthalate, methyl isobutyl phthalate, methyl propyl phthalate, ethyl butyl phthalate, ethyl isobutyl phthalate, ethyl propyl Phthalate, propyl isobutyl phthalate Rate, dimethyl terephthalate, diethyl terephthalate, dipropyl terephthalate, diisobutyl terephthalate, methyl ethyl terephthalate, methyl isobutyl terephthalate, methyl propyl terephthalate, ethyl butyl terephthalate,
Ethyl isobutyl terephthalate, ethyl propyl terephthalate, propyl isobutyl terephthalate, dimethyl isophthalate, diethyl isophthalate, dipropyl isophthalate, diisobutyl isophthalate, methyl ethyl isophthalate, methyl isobutyl isophthalate, methyl propyl isophthalate, ethyl butyl isophthalate, ethyl Aromatic dicarboxylic acid esters such as isobutyl isophthalate, ethyl propyl isophthalate, propyl isobutyl isophthalate, methyl formate, ethyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, butyric acid Methyl, ethyl butyrate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate,
Methyl methacrylate, ethyl crotonate, ethyl bivalate, dimethyl maleate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzoate Acid benzyl, methyl toluate, ethyl toluate, amyl toluate, ethyl ethyl benzoate, methyl anisate, ethyl anisate, ethyl ethoxybenzoate, ethyl p-butoxybenzoate, ethyl o-chlorobenzoate, ethyl naphthoate Such as monoester, γ-butyrolactone, δ-
Valerolactone, coumarin, phthalide, esters such as ethylene carbonate, organic acids such as benzoic acid and p-oxybenzoic acid, acid anhydrides such as succinic anhydride, benzoic acid anhydride and p-toluic acid anhydride, acetone, methyl ethyl ketone, Ketones such as methyl isobutyl ketone, acetophenone, benzophenone and benzoquinone, aldehydes such as acetaldehyde, propionaldehyde, octyl aldehyde, tolualdehyde, benzaldedo, naphthyl aldehyde, acetyl chloride, acetyl bromide, propionyl chloride, butyryl chloride, isobutyryl Chloride, 2-methylpropionyl chloride, valeryl chloride, isovaleryl chloride, hexanoyl chloride, methylhexanoyl chloride, 2-ethylhexanoyl chloride Octanoyl chloride, decanoyl chloride, undecanoyl chloride, hexadecanoyl chloride, octadecanoyl chloride, Heng Jill carbonyl chloride, di cyclohexane carbonyl chloride,
Malonyl dichloride, succinyl dichloride, pentanedioleyl dichloride, hexanedioleyl dichloride, dichlorohexanedicarbonyldichloride, benzoyl chloride, benzoyl bromide, methylbenzoyl chloride, phthaloyl chloride, isophthaloyl chloride, terephthaloyl chloride, benzene-1, 2,4-
Acid halides such as tricarbonyl trichloride,
Methyl ether, ethyl ether, isopropyl ether, n-butyl ether, isopropyl methyl ether, isopropyl ethyl ether, t-butyl ethyl ether, t-butyl-n-propyl ether, t-butyl-n-butyl ether, t-amyl methyl ether,
Ethers such as t-amyl ethyl ether, amyl ether, tetrahydrofuran, anisole, diphenyl ether, ethylene glycol butyl ether, acid amides such as acetic acid amide, benzoic acid amide, toluic acid amide, tributylamine, N, N′-dimethylpiperazine, Amine such as tribenzylamine, aniline, pyridine, pyrroline, tetramethylethylenediamine, nitriles such as acetonitrile, benzonitrile, tolunitrile, 2,2′-azobis (2-methylpropane), 2,2′-azobis (2 -Ethyl propane),
An azo compound in which a sterically hindering substituent is bonded to an azo bond such as 2,2′-azobis (2-methylpentane) is exemplified.

Of these, organosilicon compounds, esters, ketones, ethers, thioethers, acid anhydrides and acid halides are preferable, and particularly, organosilicon compounds such as methylcyclohexyldimethoxysilane and diphenyldimethoxysilane, Di-n-butyl phthalate,
Aromatic dicarboxylic acid diesters such as diisobutyl phthalate, alkyl esters of aromatic monocarboxylic acids such as benzoic acid, p-methoxybenzoic acid, p-ethoxybenzoic acid and toluic acid are preferable. These electron donating compounds may be used alone or in combination of two or more. Regarding the amount of each component used in the catalyst system, (A) the solid component is converted into titanium atoms and the reaction volume is 1
The amount is usually in the range of 0.0005 to 1 mol per liter. The (B) organoaluminum compound has an aluminum / titanium atom ratio of usually 1 to
An amount of 3,000, preferably 40 to 800, is used. If the amount deviates from the above range, the catalytic activity may be insufficient. Furthermore, the molar ratio of the (C) alkoxy group-containing aromatic compound to the titanium atom in the (A) solid component is usually 0.01 to 500, preferably 1 to 30.
It is used in a ratio such that it becomes 0. If this amount is less than 0.01, the physical properties of the produced polymer may be deteriorated.
If it exceeds, the catalytic activity may be insufficient.

In the present invention, the propylene-based resin of the first invention is produced by homopolymerizing propylene or copolymerizing propylene with other olefins in the presence of the above-mentioned catalyst system. You can Examples of other olefins used at this time include ethylene; butene-1; pentene 1: 4-methyl-1-pentene: hexene-1; heptene-1; octene-1; nonene-1; decene-1 [Alpha] -olefins can be mentioned. Of these, ethylene is preferred.
These other olefins may be used alone or in combination of two or more. Further, it is necessary to use these other olefins so that the content of the units derived from the olefins in the obtained propylene-based resin is 4 mol% or less. The polymerization method is not particularly limited, and slurry polymerization, gas phase polymerization, bulk polymerization, solution polymerization, suspension polymerization and the like can be used. Regarding the polymerization conditions when carrying out the polymerization by gas phase polymerization, the polymerization pressure is usually 10 to 45 kg / cm ² , preferably 20 to 3
0 kg / cm ² , and the polymerization temperature is appropriately selected in the range of usually 40 to 90 ° C, preferably 60 to 75 ° C. The molecular weight of the polymer can be adjusted by known means, for example, by adjusting the hydrogen concentration in the polymerization vessel or by melt-kneading in the presence of an organic peroxide. The polymerization time varies depending on the reaction temperature and the like and cannot be uniquely determined, but about 5 minutes to 10 hours is sufficient. In addition, the propylene-based resin of the first invention, as a polymerization method,
Although not particularly limited, it is preferable to use iodine as the halogen in the preparation of the solid catalyst component (A) and to use, for example, triisobutylaluminum having 3 or more carbon atoms as the organoaluminum compound of the component (B). Can be obtained. As a result, a novel polymer having a high molecular weight of the boiling n-heptane-soluble component can be obtained.

On the other hand, the propylene resin composition of the second invention can be obtained by multistage polymerization in the presence of the above-mentioned catalyst system. The polymerization order and the number of polymerization stages in the multi-stage polymerization can be arbitrarily selected. For example, the first polymerization (first-stage polymerization) can be a homopolymerization of propylene, and the ethylene-propylene copolymer or the ethylene-propylene-polyene copolymer can be performed after the second stage. Examples of the polyene that can be used include dicyclopentadiene and tricyclopentadiene. The polymerization method is not particularly limited, and slurry polymerization, gas phase polymerization, bulk polymerization, solution polymerization, suspension polymerization and the like can be used. When carrying out the polymerization by gas phase polymerization, the polymerization pressure is usually 10 to 4 for the homopolymerization stage of propylene.
5 kg / cm ² , preferably 20-30 kg / cm ² ,
The polymerization temperature is usually 40 to 90 ° C, preferably 60 to 75 ° C.
Is appropriately selected within the range. In the ethylene-propylene copolymerization stage and the ethylene-propylene-polyene copolymerization stage, the polymerization pressure is usually 5 to 30 kg / cm ² , preferably 10 to 20 kg / cm ² , and the polymerization temperature is usually 20.
To 90 ° C, preferably 40 to 60 ° C. At any stage, the molecular weight control of the polymer is
It can be carried out by a known means, for example, by adjusting the hydrogen concentration in the polymerization vessel. It can also be adjusted by melt-kneading in the presence of an organic peroxide. The polymerization time is appropriately selected from about 5 minutes to 10 hours.

In the production of the propylene-based resin of the first invention or the propylene-based resin composition of the second invention, each component constituting the catalyst system during polymerization, that is, (A)
~ (D) components may be mixed in a predetermined ratio and brought into contact with each other, and then olefin may be immediately introduced to initiate polymerization, or the mixture may be aged for about 0.2 to 3 hours after the contact, and then the olefin may be added. May be introduced. Furthermore, this catalyst component can be supplied by suspending it in an inert solvent or olefin. Post-treatment after the polymerization can be performed by a conventional method. That is, in the gas phase polymerization method, after the polymerization, a nitrogen stream or the like may be passed through the polymer powder discharged from the polymerization vessel in order to remove the olefin and the like contained therein. Also, if desired, it may be pelletized by an extruder,
At that time, a small amount of water, alcohol, or the like can be added to completely deactivate the catalyst. Further, in the bulk polymerization method, after the polymerization, the monomer may be completely separated from the polymer discharged from the polymerization vessel, and then pelletized.

The propylene-based resin of the first invention or the propylene-based resin composition of the second invention thus obtained is melt-kneaded in the presence of an organic peroxide to arbitrarily adjust the molecular weight. be able to. When performing melt kneading,
A propylene-based resin or a propylene-based resin composition and an organic peroxide are mixed, but the mixing method is not particularly limited, and for example, a method of mechanically mixing using a mixer such as a blender or a mixer, It is possible to use a method in which an organic peroxide is dissolved in an appropriate solvent, adhered to the resin or the resin composition, dried and then the solvent is removed to mix them. As the melt-kneading temperature, a temperature not lower than the melting temperature of the propylene-based resin or the propylene-based resin composition and not lower than the decomposition temperature of the organic peroxide is adopted. However, if the heating temperature is too high, the resin or the resin composition is thermally deteriorated. Generally, the melting temperature is selected in the range of 170 to 300 ° C, preferably 180 to 250 ° C.

The type of the organic peroxide is not particularly limited, and known ones such as ketone peroxides such as methyl ethyl ketone peroxide and methyl isobutyl ketone peroxide, isobutyl peroxide,
Diacyl peroxides such as acetyl peroxide,
Hydroperoxides such as diisopropylbenzene hydroperoxide, 2,5-dimethyl-2,5-di-
Dialkyl peroxides such as (t-butyl peroxide isopropyl) benzene, peroxide ketals such as 1,1-t-butyl peroxide cyclohexane, alkyl peroxides such as t-butyl peroxyacetate and t-butyl peroxybenzoate Esters, t
Examples include percarbonates such as -butyl peroxyisopropyl carbonate. The amount of these organic peroxides used varies depending on the melt index setting value of the propylene resin or propylene resin composition to be obtained, and cannot be determined unconditionally, but usually 100 parts by weight of the resin or resin composition is used. For 0.001-1.
It is selected in the range of 0 parts by weight, preferably 0.01 to 0.5 parts by weight. Melt index (MI) of propylene-based resin or propylene-based resin composition thus treated
Should be in the range of 0.1 to 10 g / 10 minutes. In the propylene resin composition of the second invention, a propylene homopolymer and an ethylene-propylene copolymer and / or a propylene-polyene copolymer are blended by a known method (for example, dry blending or kneading). It can be prepared by

In blow molding the propylene-based resin or propylene-based resin composition of the present invention, if desired, various additive components such as soft elastomer, modified polyolefin, various stabilizers, inorganic or organic fillers, and other heat-resistant materials are added. Stabilizers, weather resistance stabilizers, antistatic agents, chlorine scavengers, slip agents, anti-blocking agents, anti-fog agents, lubricants, organic flame retardants, dyes, pigments, natural oils, synthetic oils, waxes, etc. may be added. it can. Examples of the soft elastomer include a styrene copolymer elastomer, an α-olefin copolymer elastomer, an ethylene-unsaturated carboxylic acid-α, β-unsaturated carboxylic acid ester copolymer, and an acrylonitrile copolymer elastomer. .
Examples of the modified polyolefin include polyethylene, polypropylene, ethylene-α-olefin copolymer, ethylene-α-olefin-non-conjugated diene compound copolymer (eg EPDM), ethylene-aromatic monovinyl compound-conjugated diene compound copolymer Polyolefin such as rubber, acrylic acid, methacrylic acid, unsaturated carboxylic acid such as maleic acid, anhydride of unsaturated carboxylic acid such as maleic anhydride, methyl acrylate, ester of unsaturated carboxylic acid such as monomethyl maleate, Examples thereof include those chemically modified with amides of unsaturated carboxylic acids such as acrylic acid amide and maleic acid monoamide, and imides of unsaturated carboxylic acids such as maleimide and N-butylmaleimide. As the chemical modification method, for example, a method of reacting the polyolefin with a unsaturated carboxylic acid or a derivative thereof in a suitable solvent using a radical generator such as benzoyl peroxide can be used.

As the various stabilizers, for example, phenol-based stabilizers, organic phosphite-based stabilizers, thioether-based stabilizers, hindered amine-based stabilizers, higher fatty acid metal salts and the like can be used. As the phenolic stabilizer, conventionally known ones, for example, 2,6-di-t-
Butyl-4-methylphenol, 2,6-di-t-butyl-4-ethylphenol, 2,6-dicyclohexyl-4-methylphenol, 2,6-diisopropyl-4
-Ethylphenol, 2,6-di-t-amyl-4-methylphenol, 2,6-di-t-octyl-4-n-
Propylphenol, 2,6-dicyclohexyl-4-
n-octylphenol, 2-isopropyl-4-methyl-6-t-butylphenol, 2-t-butyl-2-
Ethyl-6-t-octylphenol, 2-isobutyl-4-ethyl-5-t-hexylphenol, 2-cyclohexyl-4-n-butyl-6-isopropylphenol, styrenated mixed cresol, dl-α-tocopherol, t -Butylhydroquinone, 2,2'-methylenebis (4-methyl-6-t-butylphenol), 4,
4'-butylidene bis (3-methyl-6-t-butylphenol), 4,4'-thiobis (3-methyl-6-t
-Butylphenol), 2,2'-thiobis (4-methyl-6-t-butylphenol), 4,4'-methylenebis (2,6-di-t-butylphenol), 2,2 '
-Methylenebis [6- (1-methylcyclohexyl)-
p-cresol], 2,2'-ethylidene bis (4,6
-Di-t-butylphenol), 2,2'-butylidenebis (2-t-butyl-4-methylphenol), 1,
1,3-tris (2-methyl-4-hydroxy-5-t
-Butylphenyl) butane, triethylene glycol-
Bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) Propionate], 2,2'-thiodiethylenebis [3- (3,5-di-t-butyl-4-
Hydroxyphenyl) propionate], N, N'-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamide), 3,5-di-t-butyl-4-hydroxybenzylphosphonate-diethyl ester 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-t-butylbenzyl) isocyanurate, 1,3,5-tris [(3,5-di-t-butyl-
4-Hydroxyphenyl) propionyloxyethyl]
Isocyanurate, Tris (4-t-butyl-2,6-
Dimethyl-3-hydroxybenzyl) isocyanurate, 2,4-bis (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,
3,5-triazine, tetrakis [methylene-3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate] methane, bis (3,5-di-t-butyl-4-hydroxybenzylphosphonate ethyl) calcium, bis (3,5-di-t-butyl-4-hydroxybenzylphosphonate ethyl) nickel, bis [ 3,3-
Bis (3-t-butyl-4-hydroxyphenyl) butyric acid] glycol ester, N, N'-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyl] hydrazine, 2 , 2'-Oxamide bis [ethyl-3- (3,5-di-t-butyl-4-
Hydroxyphenyl) propionate], bis [2-t
-Butyl-4-methyl-6- (3-t-butyl-5-methyl-2-hydroxybenzyl) phenyl] terephthalate, 1,3,5-trimethyl-2,4,6-tris (3,5-di -T-butyl-4-hydroxybenzyl)
Benzene, 3,9-bis [1,1-dimethyl-2- [β
-(3-t-Butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl] -2,4,8,1
0-Tetraoxaspiro [5,5] undecane, 2,2
-Bis [4- [2- (3,5-di-t-butyl-4-hydroxyhydrocinnamoyloxy)] ethoxyphenyl] propane and stearyl-β- (4-hydroxy-
Examples include β- (3,5-di-t-butyl-4-hydroxyphenyl) propionic acid alkyl ester such as 3,5-di-t-butylphenol) propionate. Among these, 2,6-di-t-butyl-4-methylphenol, stearyl-β- (4-hydroxy-
3,5-di-t-butylphenol) propionate,
2,2'-ethylidene bis (4,6-di-t-butylphenol) and tetrakis [methylene-3- (3,5-
Di-t-butyl-4-hydroxyphenyl) propionate] methane is preferred.

Examples of the organic phosphite stabilizer include, for example, trioctyl phosphite, trilauryl phosphite, tris tridecyl phosphite, tris isodecyl phosphite, phenyl diisooctyl phosphite, phenyl diisodecyl phosphite, Phenyldi (tridecyl) phosphite, diphenylisooctylphosphite, diphenylisodecylphosphite, diphenyltridecylphosphite, triphenylphosphite, tris (nonylphenyl) phosphite, tris (2,4-di-t-butylphenyl) ) Phosphite, tris (butoxyethyl) phosphite, tetratridecyl-4,4'-butylidene bis (3-methyl-6-t-butylphenol) -diphosphite, 4,
4'-isopropylidene-diphenol alkyl phosphite (where alkyl has about 12 to 15 carbon atoms),
4,4'-isopropylidene bis (2-t-butylphenol) ・ di (nonylphenyl) phosphite, tris (biphenyl) phosphite, tetra (tridecyl)-
1,1,3-tris (2-methyl-5-t-butyl-4
-Hydroxyphenyl) butanediphosphite, tris (3,5-di-t-butyl-4-hydroxyphenyl)
Phosphite, hydrogenated-4,4'-isopropylidene diphenol polyphosphite, bis (octylphenyl) bis [4,4'-butylidene bis (3-methyl-
6-t-Butylphenol)], 1,6-hexanediol diphosphite, hexatridecyl-1,1,3-
Tris (2-methyl-4-hydroxy-5-t-butylphenol) diphosphite, Tris [4,4'-isopropylidenebis (2-t-butylphenol)] phosphite, Tris (1,3-distearoyloxyisopropyl) Phosphite, 9,10-dihydro-9-phosphaphenanthrene-10-oxide, tetrakis (2,4-di-t-butylphenyl) -4,4'-biphenylene diphosphonite, distearyl pentaerythritol di Phosphite, di (nonylphenyl) pentaerythritol diphosphite, phenyl 4,4'-isopropylidene diphenol pentaerythritol diphosphite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite , Screw (2,
6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite and phenylbisphenol-A-pentaerythritol diphosphite. Among these, tris (2,4-di-t-butylphenyl) phosphite, tris (nonylphenyl) phosphite and tetrakis (2,4-di-t-butylphenyl) -4,4'-biphenylenediene Phosphite is preferable, and tris (2,4-di-t-butylphenyl) phosphite is particularly preferable.

Further, as the organic thioether stabilizer, it is preferable to use a polyhydric alcohol ester of dialkylthiodipropionate and alkylthiopropionic acid. The dialkylthiodipropionate used here is preferably a dialkylthiodipropionate having an alkyl group having 6 to 20 carbon atoms, and the polyhydric alcohol ester of alkylthiopropionic acid is an alkyl group having 4 to 20 carbon atoms. Polyhydric alcohol esters of alkylthiopropionic acids having groups are preferred. In this case, examples of the polyhydric alcohol that constitutes the polyhydric alcohol ester include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, and trishydroxyethyl isocyanurate.

Examples of such dialkylthiodipropionate include dilaurylthiodipropionate, dimyristylthiodipropionate and distearylthiodipropionate. On the other hand, as the polyhydric alcohol ester of alkylthiopropionic acid, for example, glycerin tributyl thiopropionate, glycerin trioctyl thiopropionate, glycerin trilauryl thiopropionate, glycerin tristearyl thiopropionate, trimethylolethane tributyl. Thiopropionate, trimethylolethane trioctyl thiopropionate, trimethylol ethane trilauryl thiopropionate, trimethylol ethane tristearyl thiopropionate, pentaerythritol tetrabutyl thiopropionate,
Pentaerythritol tetraoctyl thiopropionate, pentaerythritol tetralauryl thiopropionate, pentaerythritol tetrastearyl thiopropionate, etc. can be mentioned. Among these, dilauryl thiodipropionate, distearyl thiodipropionate, and pentaerythritol tetralauryl thiopropionate are preferable.

Examples of hindered amine stabilizers include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, dimethyl-1- (2-hydroxyethyl) -4-hydroxy-2, succinate. 2,6,6-Tetramethylpiperidine polycondensate, poly [6- (1,1,
3,3-Tetramethylbutyl) imino-1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [2,2 6,6-Tetramethyl-4-piperidyl) imino], tetrakis (2,2,6,6-tetramethyl-
4-piperidyl) -1,2,3,4-butane tetracarboxylate, 2,2,6,6-tetramethyl-4-piperidyl benzoate, bis- (1,2,6,6-pentamethyl-4-piperidyl ) -2- (3,5-di-t-
Butyl-4-hydroxybenzyl) -2-n-butylmalonate, bis- (N-methyl-2,2,6,6-tetramethyl-4-piperidyl) sebacate, 1,1'-
(1,2-ethanediyl) bis (3,3,5,5-tetramethylpiperazinone), (mixed 2,2,6,6
-Tetramethyl-4-piperidyl / tridecyl) -1,
2,3,4-butanetetracarboxylate, (mixed 1,2,2,6,6-pentamethyl-4-piperidyl / tridecyl) -1,2,3,4-butanetetracarboxylate, mixed [2 , 2,6,6-Tetramethyl-4-piperidyl / β, β, β ′, β′-Tetramethyl-3,9- [2,4,8,10-tetraoxaspiro (5,5) undecane] Diethyl] -1,2,3,4
-Butane tetracarboxylate, mixed [1,
2,2,6,6-pentamethyl-4-piperidyl / β,
β, β ', β'-tetramethyl-3,9- [2,4,
8,10-Tetraoxaspiro (5,5) undecane]
Diethyl] -1,2,3,4-butane tetracarboxylate, N, N'-bis (3-aminopropyl) ethylenediamine-2,4-bis [N-butyl-N- (1,
2,2,6,6-Pentamethyl-4-piperidyl) amino] -6-chloro-1,3,5-triazine condensate, poly [6-N-morpholyl-1,3,5-triazine-
2,4-diyl] [(2,2,6,6-tetramethyl-
4-piperidyl) imino] hexamethylene [(2,2,
6,6-Tetramethyl-4-piperidyl) imide],
N, N'-bis (2,2,6,6-tetramethyl-4-
Piperidyl) hexamethylenediamine and 1,2-dibromoethane condensate, [N- (2,2,6,6-tetramethyl-4-piperidyl) -2-methyl-2- (2,2
2,6,6-Tetramethyl-4-piperidyl) imino]
Examples include propionamide.

Among these hindered amine stabilizers, dimethyl succinate-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate, poly [6 -(1,1,3,3-
Tetramethylbutyl) imino-1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2
2,6,6-Tetramethyl-4-piperidyl) imino], tetrakis (2,2,6,6-tetramethyl-4)
-Piperidyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,6,6-pentamethyl-4)
-Piperidyl) -2- (3,5-di-t-butyl-4-
Hydroxybenzyl) -2-n-butylmalonate,
1,1 '-(1,2-ethanediyl) bis (3,3,
5,5-Tetramethylpiperazinone), (Mixed 2,2,6,6-tetramethyl-4-piperidyl / tridecyl) -1,2,3,4-butanetetracarboxylate, (Mixed 1, 2,2,6,6-Pentamethyl-4-piperidyl / tridecyl) -1,2,3,4-butane tetracarboxylate, mixed [2,2,2]
6,6-Tetramethyl-4-piperidyl / β, β,
β ', β'-tetramethyl-3,9- [2,4,8,1
0-Tetraoxaspiro (5,5) undecane] diethyl] -1,2,3,4-butanetetracarboxylate, mixed [1,2,2,6,6-pentamethyl-
4-piperidyl / β, β, β ′, β′-tetramethyl-
3,9- [2,4,8,10-Tetraoxaspiro (5,5) undecane] diethyl] -1,2,3,4-
Butane tetracarboxylate, N, N'-bis (3-
Aminopropyl) ethylenediamine-2,4-bis [N
-Butyl-N- (1,2,6,6-pentamethyl-4-
Piperidyl) amino] -6-chloro-1,3,5-triazine condensate, poly [6-N-morpholyl-1,3,5
-Triazine-2,4-diyl] [(2,2,6,6-
Tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imide], N, N'-bis (2,2,6,6-tetramethyl-4 -Piperidyl) hexamethylenediamine and 1,2-dibromoethane condensate, [N- (2,2,
6,6-Tetramethyl-4-piperidyl) -2-methyl-2- (2,2,6,6-tetramethyl-4-piperidyl) imino] propionamide is preferred.

Examples of the higher fatty acid metal salt include magnesium of higher fatty acids such as stearic acid, oleic acid, lauric acid, capric acid, arachidic acid, palmitic acid, behenic acid, 12-hydroxystearic acid, ricinoleic acid and montanic acid. Alkaline earth metal salts such as salts, calcium salts and barium salts, cadmium salts, zinc salts, lead salts and also alkali metal salts such as sodium salts, potassium salts and lithium salts are used. Specifically, magnesium stearate, magnesium laurate, magnesium palmitate, calcium stearate, calcium oleate, calcium laurate, barium stearate, barium oleate, barium laurate,
Barium arachidate, barium behenate, zinc stearate, zinc oleate, zinc laurate, lithium stearate, sodium stearate, sodium palmitate, sodium laurate, potassium stearate, potassium laurate, potassium 12-hydroxystearate. , Potassium montanate and the like.

Examples of the inorganic fillers include spherical fillers, plate fillers, fibrous fillers and inorganic flame retardants. Examples of the spherical filler include calcium carbonate, kaolin (aluminum silicate), silica, perlite, shirasu balloon, sericite, diatomaceous earth, calcium sulfite, calcined alumina, calcium silicate, and the like. Examples of the fibrous fillers such as mica and mica include needle-shaped fillers such as wollastonite, magnesium oxysulfate, potassium titanate fibers, fibrous fillers such as fibrous calcium carbonate, and glass. Examples include completely fibrous substances such as fibers. Examples of the inorganic flame retardant include hydrated aluminum, hydrated gypsum, zinc borate, barium borate, borax, kaolin, clay, calcium carbonate, alumite, basic magnesium carbonate, calcium hydroxide, and hydroxide. Examples include magnesium. On the other hand, examples of the organic filler include wood particles such as wood powder and cotton powder, fir shell powder, crosslinked rubber powder, plastic powder, and collagen powder.

The blow-molded article of the present invention can be obtained by blow-molding the propylene-based resin or the propylene-based resin composition containing various additives as desired. The blow molding method is not particularly limited, and a method conventionally used in blow molding of polypropylene or high-density polyethylene can be used.

[0049]

The present invention will be described in more detail by way of examples, which should not be construed as limiting the invention thereto. The pinch-off characteristic was evaluated as follows. (1) Sampling of pinch-off part and sample preparation Using a Cowtex V8 / S blow molding machine manufactured by Nippon Steel Co., Ltd., blow molding was performed at 220 ° C to prepare a bottle (average wall thickness 2 to 3 mm) shown in Fig. 1. The bottom of the sample was cut perpendicularly to the pinch-off (50 mm × 20 mm), and the padded part of the cut-out sample was cut and flattened to obtain a test piece (thickness: about 2 mm). (2) Evaluation method A tensile test was conducted under the conditions of a temperature of 23 ° C., a pulling speed of 50 mm / min, and a chuck-to-chuck distance of 30 mm using an INSTRON model 1125. At the pinch-off part, it is considered that it is difficult to maintain the performance of the product in the case of yielding (breaking) or a significant decrease in strength after yielding. Therefore, the yield energy (kgf · mm / mm ² )
The energy retention rate (%) was calculated by the following equation using the values up to the yield shown by the shaded area in FIG. Energy retention rate (%) = yield energy of pinch-off part / yield energy of general part x 100

Example 1 (1) Preparation of Magnesium Compound A glass reactor equipped with a stirrer and having an internal volume of about 6 liters was sufficiently replaced with nitrogen gas, and ethanol was added thereto in an amount of about 2,43.
0 g, 16 g of iodine and 160 g of metallic magnesium were charged, heated with stirring, and reacted under reflux conditions until hydrogen gas was not generated from the system, to obtain a solid reaction product. The reaction mixture containing this solid product was dried under reduced pressure to obtain a magnesium compound. (2) Preparation of solid catalyst component (A) In a glass reactor having an internal volume of 5 liters sufficiently replaced with nitrogen gas, 160 g of the magnesium compound (not crushed) obtained in (1) above and purified heptane 800
Charged milliliters, 24 milliliters of silicon tetrachloride and 23 milliliters of diethyl phthalate, and heated the system to 80 ° C.
The mixture was kept at 70 ° C., 770 ml of titanium tetrachloride was added with stirring, and the mixture was reacted at 110 ° C. for 2 hours. Then, the solid component was separated and washed with purified heptane at 90 ° C. Further, 1,220 ml of titanium tetrachloride was added, and the mixture was reacted at 110 ° C. for 2 hours and then thoroughly washed with purified heptane to obtain a solid catalyst component (A).

(3) Gas phase polymerization In a polymerization tank having an internal volume of 200 liters, 6.0 g / hour of the solid catalyst component (A) obtained in the above (2) and 0.2 mol / hour of triisobutylaluminum (TIBA). , 1-allyl-
3,4-dimethoxybenzene (ADMB) 0.012 mol / hour, methylcyclohexyldimethoxysilane (CH
MDMS) 0.0026 mol / hour, propylene 37 k /
It was supplied for an hour, polymerization was carried out at 70 ° C. and 28 k / cm ² G, and hydrogen was supplied in order to adjust the intrinsic viscosity of the polymer. The intrinsic viscosity [η] of the obtained polymer (13
(In decalin at 5 ° C) was 4.26 deciliter / g. The amount of polymer produced in the polymerization tank at this time was 30
It was kg / hour. The boiling n-heptane insoluble component amount (W) of this polymer was 62.5% by weight.

The boiling n-heptane-insoluble component [η] of the polymer was 5.21 deciliter / g, and the boiling n-heptane-soluble component [η] was 2.66 deciliter / g. After mixing 2,5-dimethyl-2,5-di- (tert-butylperoxy) -hexane with the obtained polypropylene powder and further adding an antioxidant, a heat stabilizer and a chlorine scavenger, 40 mmφ Extruded with an extruder to obtain pellets having a melt index (MI) of 0.5 g / 10 min. Using the pellets, a bottle shown in FIG. 1 was obtained with a blow extruder. The ΔHw, t _MAX and elongation viscosity ratio (coefficient A) of the obtained pellets were determined, and the pinch-off characteristics were evaluated using a bottle. The results are shown in Table 1.

Example 2 The polypropylene powder obtained in Example 1 was mixed with 2,5
-Dimethyl-2,5-di- (t-butylperoxy)-
Hexane was mixed, and then an antioxidant, a heat stabilizer and a chlorine scavenger were added and mixed, and then the mixture was extruded with a 40 mmφ extruder to obtain pellets having MI of 2.5 g / 10 min. Using these pellets, a bottle was obtained with a blow extruder. The ΔHw, t _MAX and elongation viscosity ratio (coefficient A) of the obtained pellets were determined, and the pinch-off characteristics were evaluated using a bottle. The results are shown in Table 1.

Example 3 The polypropylene powder obtained in Example 1 was mixed with 2,5
-Dimethyl-2,5-di- (t-butylperoxy)-
Hexane was mixed, and then an antioxidant, a heat stabilizer and a chlorine scavenger were added and mixed, and then the mixture was extruded with a 40 mmφ extruder to obtain pellets having MI of 7.0 g / 10 min. Using these pellets, a bottle was obtained with a blow extruder. The ΔHw, t _MAX and elongation viscosity ratio (coefficient A) of the obtained pellets were determined, and the pinch-off characteristics were evaluated using a bottle. The results are shown in Table 1.

Example 4 In Example 1, the amount of CHMDMS supplied was 0.0086.
Gas phase polymerization was conducted in the same manner as in Example 1 except that the mol / hour was used, and the intrinsic viscosity [η] (in decalin at 135 ° C.) was 4.
A polymer of 59 deciliter / g was obtained. The boiling n-heptane insoluble component amount (W) of this polymer was 80.7% by weight. The boiling n-heptane-insoluble component [η] of this polymer was 4.92 deciliter / g, and the boiling n-heptane-soluble component [η] was 2.27 deciliter / g. Antioxidant, heat stabilizer, chlorine scavenger was added to the obtained polypropylene powder and mixed, then 40 mmφ
Extruded with an extruder to obtain pellets having MI of 0.5 g / 10 min. Using these pellets, a bottle was obtained with a blow extruder. The ΔHw, t _MAX and elongation viscosity ratio (coefficient A) of the obtained pellets were determined, and the pinch-off characteristics were evaluated using a bottle. The results are shown in Table 1.

Comparative Example 1 Gas phase polymerization was carried out in the same manner as in Example 1 except that the supply amount of diphenyldimethoxysilane (DPDMS) was changed to 0.030 mol / hour instead of CHMDMS. Viscosity [η] (in Decalin at 135 ℃) is 5.4
A polymer of 2 deciliter / g was obtained. The boiling n-heptane-insoluble component amount (W) of this polymer was 93.4% by weight. After adding an antioxidant, a heat stabilizer and a chlorine scavenger to the obtained polypropylene powder and mixing them, 40
Extrusion was carried out with an mmφ extruder to obtain pellets having MI of 0.5 g / 10 min. Using these pellets, a bottle was obtained with a blow extruder. The ΔHw, t _MAX and elongation viscosity ratio (coefficient A) of the obtained pellets were determined, and the pinch-off characteristics were evaluated using a bottle. The results are shown in Table 1.

Comparative Example 2 In Example 1, no ADMB was supplied and DPDM was used.
Gas phase polymerization was conducted in the same manner as in Example 1 except that the amount of S supplied was changed to 0.057 mol / hour, and the intrinsic viscosity [η] (13
A polymer having a decalin content of 5 ° C. of 2.54 deciliter / g was obtained. The boiling n-heptane insoluble component amount (W) of this polymer was 98.0% by weight. An antioxidant, a heat stabilizer and a chlorine scavenger are added to the obtained polypropylene powder and mixed, and then extruded with a 40 mmφ extruder to obtain M
Pellets with an I of 0.5 g / 10 min were obtained. Using these pellets, a bottle was obtained with a blow extruder. The ΔHw, t _MAX and elongation viscosity ratio (coefficient A) of the obtained pellets were determined, and the pinch-off characteristics were evaluated using a bottle.
The results are shown in Table 1.

Comparative Example 3 In Example 1, no ADMB was supplied and DPDM was used.
Example 1 except that the amount of S supplied was 0.057 mol / hour.
The gas phase weight is determined in the same manner as, and the intrinsic viscosity [η] (135
A polymer with a decalin temperature of 1.43 deciliters / g was obtained. The boiling n-heptane-insoluble component amount (W) of this polymer was 96.0% by weight. An antioxidant, a heat stabilizer and a chlorine scavenger are added to the obtained polypropylene powder and mixed, and then extruded with a 40 mmφ extruder to obtain M
Pellets with an I of 11 g / 10 min were obtained. Using these pellets, a bottle was obtained with a blow extruder. The ΔHw, t _MAX and elongation viscosity ratio (coefficient A) of the obtained pellets were determined, and the pinch-off characteristics were evaluated using a bottle.
The results are shown in Table 1.

[0059]

[Table 1]

[0060]

[Table 2]

Example 5 (1) Preparation of magnesium compound A glass reactor equipped with a stirrer (internal volume of about 6 liters) was sufficiently replaced with nitrogen gas, and about 2,430 g of ethanol, 16 g of iodine and 160 g of magnesium metal were added. Then, the mixture was reacted under heating under reflux conditions with stirring until the generation of hydrogen gas disappeared from the system to obtain a solid reaction product.
The reaction mixture containing this solid product was dried under reduced pressure to obtain a magnesium compound. (2) Preparation of solid catalyst component (A) 160 g of magnesium compound (not crushed) obtained in (1) above, purified in a glass reactor (internal volume 5 liters) sufficiently replaced with nitrogen gas Heptane 800
Milliliter, 24 milliliters of silicon tetrachloride, and 23 milliliters of phthalic acid diester were added. 8 in the system
After maintaining at 0 ° C. and adding 770 ml of titanium tetrachloride with stirring and reacting at 110 ° C. for 2 hours, solid components were separated and washed with purified heptane at 90 ° C. Further, add 1,220 ml of titanium tetrachloride, and add 110 ° C.
After reacting for 2 hours, wash thoroughly with purified heptane,
A solid catalyst component (A) was obtained.

(3) Gas Phase Polymerization The solid catalyst component (A) obtained in the above (2) was added to 6.0 in a polymerization tank at the front stage of a continuous gas phase polymerization apparatus having an internal volume of 200 liters.
g / h, triisobutylaluminum (TIBA)
0.2 mol / hour, 1-allyl-3,4-dimethoxybenzene (ADMB) 0.012 mol / hour, methylcyclohexyldimethoxysilane (CHMDMS) 0.057
Mol / h, propylene is supplied at 37 k / h, 70
Polymerization was carried out at 28 ° C. and 28 k / cm ² G. The intrinsic viscosity [η] of the obtained polymer (135 ° C. in decalin) was 4.33 deciliter / g. The amount of polymer produced in the polymerization tank at this time was 30 kg / hour. The boiling n-heptane insoluble component amount (W) of this polymer was 90.2% by weight. Further, the sampling powder was pelletized, and ΔHw, t _MAX and elongation viscosity ratio (coefficient A) were obtained. The results are shown in Table 2.

Next, the above polymer (propylene homopolymer) was continuously transferred to the subsequent polymerization tank. In the latter polymerization tank, ethylene was 11 kg / hour and propylene was 6
It is supplied at a rate of kg / hour, polymerized at 50 ° C. and 15 kg / cm ² G, and the total intrinsic viscosity [η] (135 ° C. in decalin) is 4.77 deciliter / g and the ethylene unit content is
A polymer having a ratio of 4.4% by weight and a reaction ratio of 8.4% in the latter stage was obtained.
Table 3 shows the ethylene unit content of the propylene random copolymer produced in the latter stage and the amount of the random copolymer in all the polymers. 2,5-Dimethyl-2,5-di- (t-butylperoxy) -hexane is mixed with the obtained powder, and then an antioxidant, a heat stabilizer and a chlorine scavenger are added and mixed. After that, it was extruded with a 40 mmφ extruder to obtain pellets having MI of 0.4 g / 10 min. Using the above pellets, bottles were molded by a blow extruder and the pinch-off characteristics were evaluated. The results are shown in Table 4.

Example 6 A powder obtained in the same manner as in Example 5 except that the amount of ethylene fed to the subsequent polymerization tank was increased,
After mixing 2,5-dimethyl-2,5-di- (t-butylperoxy) -hexane and further adding and mixing an antioxidant, a heat stabilizer and a chlorine scavenger, 40 mmφ
Extruded with an extruder to obtain pellets having MI of 8.1 g / 10 min. Using the above pellets, bottles were molded by a blow extruder and the pinch-off characteristics were evaluated. The results are shown in Table 4.

Example 7 Example 5 was repeated except that the amount of CHMDMS supplied to the preceding polymerization tank was 0.0024 mol / hour and the amount of ethylene supplied to the latter polymerization tank was increased. Gas phase polymerization was carried out in the same manner as in. The intrinsic viscosity [η] of the polymer obtained by the first-stage polymerization was 4.27 deciliter / g, and the boiling n-heptane-insoluble component amount (W) was 60.0% by weight. Table 2 shows ΔHw, t _MAX and elongation viscosity ratio (coefficient A) of the propylene homopolymer obtained by the first-stage polymerization, and the ethylene unit content of the propylene-based random copolymer produced in the second-stage and the random The amount of copolymer in the total polymer is shown in Table 3. In the obtained powder,
After mixing 2,5-dimethyl-di-2,5- (t-butylperoxy) -hexane and further adding and mixing an antioxidant, a heat stabilizer and a chlorine scavenger, 40 mmφ
Extruded with an extruder to obtain pellets having MI of 0.5 g / 10 min. Using the above pellets, bottles were molded by a blow extruder and the pinch-off characteristics were evaluated. The results are shown in Table 4.

Example 8 2,5-Dimethyl-di-2,5- (t-butylperoxy) -hexane was mixed with the powder obtained in Example 7, which was further mixed with an antioxidant and a heat stabilizer. Agent and chlorine scavenger are added and mixed, then extruded with a 40 mmφ extruder,
Pellets with an MI of 5.0 g / 10 min were obtained. Using the above pellets, bottles were molded by a blow extruder and the pinch-off characteristics were evaluated. The results are shown in Table 4.

Comparative Example 4 Gas phase polymerization was carried out in the same manner as in Example 5 except that ADMB was not supplied to the preceding polymerization tank and the DPDMS supply rate was 0.057 mol / hour. . The intrinsic viscosity [η] of the polymer obtained by the first-stage polymerization was 2.54 deciliter / g, and the boiling n-heptane-insoluble component amount (W) was
Was 98.0% by weight. Table 2 shows ΔHw, t _MAX and elongation viscosity ratio (coefficient A) of the propylene homopolymer obtained by the first-stage polymerization, and the ethylene unit content of the propylene-based random copolymer produced in the second-stage and the random The amount of copolymer in the total polymer is shown in Table 3. An antioxidant, a heat stabilizer, and a chlorine scavenger are added to the obtained powder and mixed, and then extruded with a 40 mmφ extruder to give MI.
To give a pellet of 0.6 g / 10 min. Using the above pellets, bottles were molded by a blow extruder and the pinch-off characteristics were evaluated. The results are shown in Table 4.

Comparative Example 5 In Comparative Example 4, vapor phase polymerization was carried out in the same manner as in Example 5 except that hydrogen was supplied to the polymerization tanks at the front and rear stages. The intrinsic viscosity [η] of the polymer obtained by the previous polymerization is 1.43.
It was deciliter / g, and the boiling n-heptane insoluble component amount (W) was 96.0% by weight. Table 2 shows ΔHw, t _MAX and elongation viscosity ratio (coefficient A) of the propylene homopolymer obtained by the first-stage polymerization, and the ethylene unit content of the propylene-based random copolymer produced in the second-stage and the random The amount of copolymer in the total polymer is shown in Table 3. An antioxidant, a heat stabilizer and a chlorine scavenger were added to the obtained powder and mixed, and then extruded with a 40 mmφ extruder to obtain pellets having MI of 1.0 g / 10 min. Using the above pellets, bottles were molded by a blow extruder and the pinch-off characteristics were evaluated. The results are shown in Table 4.

[0069]

[Table 3]

[0070]

[Table 4]

[0071]

[Table 5]

[0072]

According to the present invention, it is possible to provide a blow-molded article having excellent pinch-off characteristics, which has been impossible with conventional polyolefin resins. Therefore, the propylene-based resin for blow molding and the propylene-based resin composition of the present invention are suitably used for blow molding of various bottles, tanks, ducts and the like.

[Brief description of drawings]

FIG. 1 is a detailed view of bottles obtained by blow molding in order to evaluate pinch-off characteristics in Examples and Comparative Examples.

FIG. 2 is an explanatory diagram of breakdown energy used to evaluate pinch-off characteristics in Examples and Comparative Examples.

[Explanation of symbols]

 1: Pinch off part 2: Parting line 3: Test piece part (pinch off part) 4: Test piece part (general part)

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Sueki Sugawara 1 Inezaki Kaigan, Ichihara City, Chiba Idemitsu Petrochemical Co., Ltd.

Claims (4)

[Claims] 1. A heat absorption amount ΔHw due to crystal melting measured by a differential scanning calorimeter (DSC) method is 30 to 90 J /.
g, (2) the time t _MAX showing the maximum endothermic amount at 120 ° C. isothermal crystallization determined by the differential scanning calorimeter (DSC) method is 0.6 to 4 min, (3) Temperature 1
Time measured at 80 ° C and strain rate of 0.3 sec ^-1 for 1 sec
When the extensional viscosities at _{7 and 7} sec are η ₁ and η ₂ , respectively, the formula A = [log ₁₀ (η ₇ ) −log ₁₀ (η ₁ )] / [log ₁₀ (7) −log ₁₀ (1)] The coefficient A indicating the rise of extensional viscosity from 1 sec to 7 sec is 0.3 or more, and (4)
Blow-molding propylene comprising a propylene homopolymer characterized by a melt index (MI) of 0.1 to 10 g / 10 minutes and / or a copolymer containing 4 mol% or less of an olefin unit other than propylene. Resin. 2. (a) (1) Differential scanning calorimeter (DS)
Endothermic amount ΔHw due to crystal melting measured by the method C) is 30 to
90 J / g, (2) Differential scanning calorimeter (DS
Maximum endotherm during isothermal crystallization at 120 ° C determined by method C)
Time t indicating quantity _MAXIs 0.6-4 min, and
(3) Temperature 180 ℃, strain rate 0.3sec^-1Measured by
Elongational viscosity at time 1 sec and 7 sec
₁, Η₂And then the formula A = [log_Ten(Η₇) −log_Ten(Η₁)] / [Log_Ten(7) -log_Ten(1)] Standing extensional viscosity from 1 sec to 7 sec
Propylene alone with a coefficient A indicating a rise of 0.4 or more
Polymer and / or less than 4 mol% of propylene
10-95% by weight of a copolymer containing fin units, (b)
Contains 10 to 70% by weight of olefin units other than propylene
90% to 5% by weight of the propylene random copolymer having
And has a melt index (MI) of 0.1 to 1
Blow molding professional characterized by 0 g / 10 minutes
Pyrene-based resin composition. 3. A blow molded product made of the propylene-based resin according to claim 1. 4. A blow molded product comprising the propylene resin composition according to claim 2.