JP2000248147A - Propylene resin composition, and molded article and container made from the composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition excellent in transparency and rigidity while retaining high impact resistance even at low temperature, for example, at 0 deg.C or lower, by adding a nucleating agent to a propylene resin which satisfies specified conditions based on measurements by the temperature-rise fractionation method. SOLUTION: The propylene resin used is a propylene/ethylene block copolymer comprising mainly a propylene homopolymer and a propylene/ethylene copolymer and has specified physical property values. The amount of its component eluted at 30 deg.C or lower, measured by the temperature-rise fractionation method, is 10-30 wt.% of the total elution amount and the ethylene content of the component is 10-25 wt.%. The amount of its component eluted in a temperature range from 40 to 85 deg.C, measured by the temperature-rise fractionation method, is 13-75 wt.% of the total elution amount. The intrinsic viscosity [η]1 of the component eluted at 103 deg.C or higher and the intrinsic viscosity [η]2 of the component eluted at 30 deg.C or lower, obtained by the temperature-rise fractionation method, satisfy the relation of the formula: 4/3.[η]1>[η]2.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a propylene-based resin composition and a molded article and a container obtained by molding the resin composition. The present invention relates to a novel propylene-based resin composition having excellent transparency and rigidity, and a molded article and a container obtained by molding the resin composition.

[0002]

2. Description of the Related Art Polypropylene resin is a resin having excellent rigidity and transparency, and is used for various purposes. However, on the other hand, it has a drawback of low impact resistance, especially at low temperatures (below zero degrees Celsius). There is. For this reason, for example, there is a problem that the container is broken or torn when dropped, for example, immediately after being taken out of the refrigerator or in a severe winter.

Conventionally, as a polypropylene resin having improved impact resistance, a random polypropylene obtained by copolymerizing propylene and ethylene, or a block polypropylene has been known. The former has excellent impact resistance and transparency at room temperature, but has a problem in that rigidity is reduced and impact resistance at low temperatures is not sufficiently improved. The latter has a drawback that transparency is reduced, although rigidity and low-temperature impact resistance are excellent. In addition, attempts have been made to improve these drawbacks by blending other resins with polypropylene resin. However, in this method, the quality is not stable due to poor dispersibility at the time of kneading. However, there is a problem that the cost is increased because other resins are used, and a polypropylene resin having a high balance of rigidity, low-temperature impact resistance and transparency has not yet been obtained. On the other hand, recently, a technique of highly balancing transparency, rigidity and low-temperature impact resistance using a polypropylene resin alone, particularly a block polypropylene copolymer, has been disclosed in JP-A-9-3294 and JP-A-8-27.
No. 238 publication. However, in the former, the cost of using a nucleating agent is increased, and the balance between transparency and low-temperature impact resistance is low. In the latter, the balance between rigidity and transparency is insufficient.

[0004]

DISCLOSURE OF THE INVENTION The present invention has been made from the above viewpoint, and is a polypropylene-based resin which is excellent in transparency and rigidity while maintaining high impact resistance even at a low temperature, for example, below zero degrees Celsius. It is an object of the present invention to provide a composition, and a molded article and a container obtained by molding the resin composition.

[0005]

Means for Solving the Problems The present inventors have conducted intensive studies to achieve the above object, and as a result, have found that a resin composition obtained by adding a nucleating agent to a specific propylene-based resin, A resin composition obtained by adding a nucleating agent to a propylene-based resin having a specific relationship between a component amount and an ethylene content and an intrinsic viscosity eluted in a specific temperature range by a temperature separation method,
The inventors have also found that low-temperature impact resistance, transparency and rigidity are excellent, and based on this, the present invention has been completed.

That is, the present invention provides the following propylene-based
Resin composition, molded article obtained by molding the resin composition, and
And containers. 1. Nucleating agent (B) to the following propylene resin (A)
A propylene-based resin composition added. Propylene resin (A): Mainly propylene homopolymerization
Comprising propylene and propylene-ethylene copolymer
-An ethylene block copolymer, comprising the following (1) to
Satisfies the requirements of (3). (1) Elution is performed at 30 ° C or less as measured by the temperature rising fractionation method.
The amount of the component is 10 to 30% by weight of the total eluted amount,
Has an ethylene content of 10 to 25% by weight. (2) Temperature of 40 ° C. to 85 ° C. measured by a temperature rising fractionation method
The amount of components eluted in the range is 13-75% by weight of the total eluted amount
Yes (3) Elution at 103 ° C or higher obtained by the temperature rising fractionation method
Intrinsic viscosity of the component [η] ₁And obtained by elevated temperature fractionation
Intrinsic viscosity [η] of components eluted below 30 ° C_TwoThe relationship
Satisfies the following formula (1)

[0007]

(Equation 2)

[0008] 2. 2. The propylene-based resin composition according to the above item 1, wherein the component of the propylene-based resin (A) eluted at a temperature of 103 ° C. or lower as measured by a temperature raising fractionation method is 45 to 85% by weight of the total eluted amount. 3. [Η] _{1 of the} propylene-based resin (A) is 0.7 to 6
3. The propylene resin composition according to the above 1 or 2, which is in deciliters / g. 4. The propylene-based resin composition according to any one of claims 1 to 3, wherein the nucleating agent (B) is any of the following or a crystal nucleating agent. Crystal nucleating agent mainly composed of rosin metal salt Sorbitol-based crystal nucleating agent (a) alkali metal carboxylate, alkali metal β-
At least one diketonate or an alkali metal β-ketoacetate; and (b) the following general formula (1):

[0009]

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 a metal atom or a hydrogen atom of Group 3 or 4 of the Periodic Table, and X represents H when M represents a metal atom of Group 3 of the Periodic Table.
O-, when M represents a metal atom of Group 4 of the periodic table, it represents O = or (HO) _2- ; when M represents a hydrogen atom, X does not exist; 4. A nucleating agent comprising at least one combination of cyclic organic phosphate compounds represented by the formula (1) when a hydrogen atom is represented and 2 in other cases). The above 1 to 10 wherein the nucleating agent (B) is added in an amount of 0.001 to 5 parts by weight based on 100 parts by weight of the propylene resin (A).
5. The propylene-based resin composition according to any one of 4. 6. A molded article obtained by molding the propylene-based resin composition according to any one of the above 1 to 5. 7. A container obtained by blow molding the propylene-based resin composition according to any one of the above 1 to 5.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The propylene resin of the present invention will be described below.
Composition [1], molded article of the present invention and container [2]
explain in detail. [1] Propylene-based resin composition The propylene-based resin composition of the present invention comprises the following propylene
Resin composition obtained by adding nucleating agent (B) to base resin (A)
It is. Propylene resin (A): Mainly propylene homopolymerization
Comprising propylene and propylene-ethylene copolymer
-An ethylene block copolymer, comprising the following (1) to
Satisfies the requirements of (3). (1) Elution is performed at 30 ° C or less as measured by the temperature rising fractionation method.
The amount of the component is 10 to 30% by weight of the total eluted amount,
Has an ethylene content of 10 to 25% by weight. (2) Temperature of 40 ° C. to 85 ° C. measured by a temperature rising fractionation method
The amount of components eluted in the range is 13-75% by weight of the total eluted amount
Yes (3) Elution at 103 ° C or higher obtained by the temperature rising fractionation method
Intrinsic viscosity of the component [η] ₁And obtained by elevated temperature fractionation
Intrinsic viscosity [η] of components eluted below 30 ° C_TwoThe relationship
Satisfies the following formula (1)

[0012]

(Equation 3)

The above-mentioned propylene-ethylene block copolymer is a so-called block copolymer in which propylene is polymerized in the presence of an olefin polymerization catalyst, and ethylene and propylene are introduced and copolymerized without deactivating polymerization active sites. It is a polymer obtained by polymerization and mainly comprises a propylene homopolymer and a propylene-ethylene copolymer, and may contain a small amount of an ethylene homopolymer. The component (A) in the present invention includes the components (1) to (3) described above.
If the above relationship is satisfied, it is not always necessary to perform block copolymerization, and a material obtained by powder blending or the like may be used. The propylene-based resin composition of the present invention is a resin composition obtained by adding a nucleating agent (B) to a propylene-ethylene block copolymer (A) satisfying the above relationships (1) to (3), Excellent impact resistance, transparency and rigidity.

However, when the component (A) does not satisfy the above (1), that is, when the amount of the component eluted at 30 ° C. or less as measured by the temperature rising fractionation method is less than 10% by weight of the total eluted amount, the low-temperature impact resistance If it exceeds 30% by weight, the rigidity is reduced. In addition, 30 measured by a temperature rising fractionation method.
If the ethylene content of the components eluted at a temperature of not more than 10 ° C. is less than 10% by weight, the low-temperature impact resistance decreases, and if it exceeds 25% by weight, the rigidity decreases. The components eluted at 30 ° C. or lower as measured by the temperature rising fractionation method are mainly ethylene-propylene copolymers in which the main components are amorphous. When the component (A) does not satisfy the above (2), that is, when the amount of the component eluted in the temperature range of 40 ° C. to 85 ° C. measured by the temperature rising fractionation method is less than 13% by weight of the total eluted amount, the low-temperature impact strength If it exceeds 75% by weight, the rigidity is reduced. In addition, the component eluted in the temperature range of 40 ° C. to 85 ° C. measured by the temperature rising fractionation method is a main component of a crystalline ethylene-propylene copolymer. When the component (A) does not satisfy the above (3), that is, at 103 ° C. obtained by a temperature rising fractionation method.
If the relationship between the intrinsic viscosity [η] _{1 of} the component eluted as described above and the intrinsic viscosity [η] ₂ of the component eluted at 30 ° C. or lower obtained by the temperature raising fractionation method does not satisfy the above-mentioned formula (1), the transparency is lowered. Invite.

Further, in the present invention, the component (A) is
(4) to (6) are satisfied when the temperature is low, for example, zero Celsius
And high transparency, while maintaining high impact resistance
It is also preferable because of its excellent rigidity. (4) Elution at 30 ° C. or less as measured by the temperature rising fractionation method
The amount of the component is 10 to 30% by weight of the total eluted amount,
Has an ethylene content of 10 to 19% by weight. (5) Temperature of 40 ° C. to 85 ° C. measured by a temperature rising fractionation method
The amount of components eluted in the range is 13 to 70% by weight of the total eluted amount.
Yes (6) Elution at 103 ° C or higher obtained by the temperature rising fractionation method
Intrinsic viscosity of the component [η] ₁And obtained by elevated temperature fractionation
Intrinsic viscosity [η] of components eluted below 30 ° C_TwoThe relationship
Satisfies the following equation (2)

[0016]

(Equation 4)

Further, in the present invention, regarding the component (A), in addition to the above (1) to (6), the more the component eluted at 103 ° C. or lower of the component (A) measured by the temperature-increased fractionation method, the more resistant. The balance between impact resistance, transparency and rigidity is excellent, and it is particularly preferable that the content is 50 to 85% by weight of the total dissolution amount.
~ 80 wt% is most preferred. If it is less than 50% by weight, the impact strength may be reduced. If it exceeds 85% by weight, the rigidity may decrease. Further, in the present invention, regarding the component (A), in addition to the above, the intrinsic viscosity [η] _{1 of} the component eluted at 103 ° C. or higher of the component (A) obtained by the temperature rising fractionation method is 0.7 to 6 deciliters. / G, particularly preferably 1.0 to 4.0 deciliter / g, and most preferably 1.5 to 3.5 deciliter / g. If [η] ₁ is out of the range of 0.7 to 6 deciliters / g, the transparency may decrease.

The method for measuring the resin properties of the component (A) in the present invention is as follows. (1) Method of Measuring Each Component Amount by Temperature Separation Method Each component amount is calculated according to the following method based on the result of measurement using a temperature separation apparatus. That is, at room temperature, a sample was prepared by adding polymer 5.x in 60 ml of paraxylene containing 0.03% by weight of BHT (antioxidant, Yoshitomi Pharmaceutical Co., Ltd.).
0 g is weighed and stirred at 130 to 140 ° C. for 2 hours to dissolve. The sample solution was placed in the column at 135 ° C for 60m.
After the injection, the polymer is slowly cooled to 30 ° C. at 10 ° C./h to crystallize the polymer on the surface of the filler. After cooling, add 20 parts of para-xylene.
The eluate in the 50 ml column was fractionated while flowing at ml / min, and the component precipitated in 10 times the amount of methanol was designated as A. Then, after elevating the temperature to 103 ° C. over 2 hours and 26 minutes and maintaining the temperature for 2 hours, the eluate in the column was fractionated over 50 minutes and the component precipitated in 10-fold amount of methanol was designated as B. Then from 103 ° C to 135
After elevating the temperature to 135 ° C over 20 minutes and maintaining the temperature for 1 hour, the eluate was fractionated over 50 minutes while flowing para-xylene at 20 ml / min. The component is designated as C. Further, a sample solution of the same concentration prepared separately was dissolved in the same manner, and 30
The temperature is raised from 40 ° C. to 40 ° C. over 20 minutes, and the dissolved components in the column are washed over 50 minutes while flowing para-xylene at 20 ml / min. Then, from 40 ° C to 85
After elevating the temperature to 1 ° C. for 1 hour and 30 minutes and maintaining the temperature for 2 hours, the eluate was fractionated over 50 minutes while flowing para-xylene at 20 ml / min, and the component precipitated in 10-fold amount of methanol was D. These A to D are 24h
After being air-dried, it is dried and collected for 10 hours by a nitrogen air dryer at 80 ° C., and the weight is measured. For A and D, the amount of ethylene is measured. The total output is represented by (A + B + C), and the amount of the component eluted at 103 ° C. or less based on the total output is (A + B) / (A + B + C).
The component amount eluted at 0 ° C or less is A / (A + B + C),
Further, the amount of the component eluted in the temperature range of 40 ° C. to 85 ° C. with respect to the total volume is calculated and calculated from D / (A + B + C). The column (GL Science) is 30mmφ × 25
0mm, filler is Celite (Jhon Manivil
e Celite 560) is used. The temperature is monitored at the center of the oven and controlled by a temperature controller. (2) Method for measuring ethylene content The ethylene content is measured by a ¹³ C-NMR method. That is, ¹³ C-NMR of a sample was measured, and 35 to 21 ppm [tetramethylsilane (TM
S) Chemical shift standard] First, the triad chain fraction (mol%) of ethylene (E) and propylene (P) is calculated from the following equation based on the seven peak intensities in the region.

F _EPE = [K (Tδδ) / T] × 100 f _PPE = [K (Tβδ) / T] × 100 f _EEE = [K (Sγδ) / 4T + K (Sδδ) / 2T]
× 100 f _PPP = [K (Tββ) / T] × 100 f _PEE = [K (Sβδ) / T] × 100 f _PEP = [K (Sββ) / T] × 100 where T = K (Tδδ) + K (Tβδ) + K (Sγ
δ) / 4 + K (Sδδ) / 2 + K (Tββ) + K (Sβ
δ) + K (Sββ) Here, for example, F _EPE indicates the EPtriad chain fraction (mol%), and K (Tδδ) indicates the integrated intensity of the peak attributed to the Tδδ carbon. Next, the ethylene unit content (% by weight) is calculated by the following equation using the above triad chain fraction.

Ethylene unit content (% by weight) = 28 ｛3
f_EEE+2 (f_PEE+ F_EPE) + F _PPE+ F_PEP｝ × 1
00 / [28 ｛3f_EEE+2 (f_PEE+ F_EPE) + F
_PPE+ F_PEP｝ +42 ｛3f_PPP+2 (f_PPE+
f_PEP) + F_EPE+_PEE｝] (3) Measurement method of intrinsic viscosity [η] The intrinsic viscosity [η] is determined by dissolving a sample in tetralin,
It is a value obtained by measuring in.

As a method for producing the component (A) in the present invention, as described above, after propylene is polymerized in the presence of an olefin polymerization catalyst, ethylene and propylene are further introduced without deactivating the polymerization active site. A method of copolymerizing (also referred to as block copolymerization) is exemplified. Further, it is not necessarily required to be a polymer obtained by block copolymerization, and a method of producing a homopolymer or a copolymer of ethylene and propylene by a powder blend may be used.

Examples of the olefin polymerization catalyst used for the block copolymerization include a Ziegler-Natta catalyst comprising a transition metal compound of Group 4 of the periodic table and an organoaluminum compound (JP-B-53-3356) and a magnesium compound. Highly active Ziegler-Natta catalyst comprising a catalyst component obtained by contacting a transition metal compound of Group 4 of the periodic table in the presence or absence of an electron donor with an organoaluminum compound (Japanese Patent Application Laid-Open No. Sho 53-43094) Gazette, JP 55
JP-A-135102, JP-A-55-135103, JP-A-56-18606, etc., or a catalyst called metallocene catalyst (JP-A-58-1930).
9 and JP-A-2-167307). In the present invention, from the viewpoint of increasing the rigidity as much as possible, it is desirable to select a catalyst that can increase the stereoregularity of the polypropylene as much as possible. For example, a catalyst system that gives isotactic polypropylene with a mesopentad fraction of 92% or more is preferable. .

As the transition metal compound belonging to Group 4 of the periodic table in the Ziegler-Natta catalyst, there may be mentioned transition metal halides. As the transition metal halogen compound, a halide of titanium or the like is preferable, and titanium trichloride or the like is particularly preferable. The titanium trichloride is obtained by reducing titanium tetrachloride by various methods; these are further subjected to ball mill treatment and / or solvent washing (for example, washing with an inert solvent and / or an inert solvent containing a polar compound) to activate the titanium trichloride. Titanium trichloride or titanium trichloride eutectic (for example, TiCl ₃ + () Al
Cl ₃ ) further co-ground with amines, ethers, esters, sulfur, halogen derivatives, organic or inorganic nitrogen compounds or phosphorus compounds; precipitated from liquefied titanium trichloride in the presence of ether compounds Obtained products include those obtained by the method described in JP-B-53-3356.

The transition metal compound used in the highly active Ziegler-Natta catalyst is preferably a titanium compound, and particularly preferably a halogen-containing titanium compound. As the halogen, a chlorine atom is preferable, and as the transition metal compound, titanium tetrachloride is particularly preferable. The transition metal compounds may be used alone or in combination of two or more.
As the magnesium compound used for the carrier of the highly active Ziegler-Natta catalyst, magnesium halide (eg, magnesium chloride), alkoxymagnesium (eg, diethoxymagnesium) and the like are preferable. The magnesium compounds may be used alone or in combination of two or more.
Regarding the electron donor of the highly active catalyst, as the electron donor as the third component used as an internal donor, alcohols, phenols, ketones, aldehydes, carboxylic acids, malonic acids, organic acids or inorganic acids Examples include oxygen-containing electron donors such as esters, monoethers, diethers, and ethers such as polyethers, and nitrogen-containing electron donors such as ammonia, amines, nitriles, and isocyanates. Among these, esters of aromatic dicarboxylic acids (such as di-n-butyl phthalate) and malonic esters (cyclopentylmalonic acid) in which the organic group of the ester portion is a linear, branched or cyclic aliphatic hydrocarbon Di-n-butyl and the like) are preferred. The electron donor as the internal donor may be used alone or in combination of two or more. On the other hand, as an electron donor used as an external donor, an organosilicon compound having an alkoxy group,
A nitrogen-containing compound, a phosphorus-containing compound, and an oxygen-containing compound can be used. Particularly, it is preferable to use an organosilicon compound having an alkoxy group.
Preferred are 2-trimethylpropylcyclopentyldimethoxysilane, 1,1-dimethoxy-2,6-dimethyl-1-silacyclohexane and the like. The electron donor as an external donor may be used alone or in combination of two or more.

The organoaluminum compound as another component of the catalyst includes a compound represented by the following formula: AlR _n X _3-n
X represents an alkyl group having 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms, X represents a halogen atom, and n is a value satisfying 0 <n ≦ 3. And the like. Specifically, for example, triethylaluminum, triisobutylaluminum, tri-n-propylaluminum, diethylaluminum monochloride, diethylaluminum monobromide,
Diethylaluminum monoiodide, diethylaluminum monoethoxide, diisobutylaluminum monoisobutoxide, diethylaluminum monohydride, diisobutylaluminum monohydride, ethylaluminum sesquichloride, ethylaluminum dichloride, etc., and one or more of these are mentioned. Can be used.

As the metallocene catalyst, JP-A-58-1983
19309, JP-A-61-130314,
JP-A-3-1630088, JP-A-4-30088
No. 7, JP-A-4-21694, JP-T-Hei 1-1-1
A transition metal compound having one or two ligands such as a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, and a substituted indenyl group as described in JP-A No. 502036 and the like; The transition metal compound is controlled geometrically, and is characterized in that the properties of active sites are uniform. Preferred transition metals in these transition metal compounds include zirconium, titanium, and hafnium.

Specific metallocene catalysts include cyclopentadienyl zirconium trichloride, pentamethylcyclopentadienyl zirconium trichloride,
Bis (cyclopentadienyl) zirconium dichloride, bis (pentamethylcyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) zirconium dialkyl, indenyl zirconium trichloride, bis (indenyl) zirconium dichloride, dimethylsilylene-bis ( (Indenyl) zirconium dichloride, (dimethylsilylene) (dimethylsilylene)-
Bis (indenyl) zirconium dichloride, (dimethylsilylene) -bis (2-methyl-4-phenylindenyl) zirconium dichloride, (dimethylsilylene)
-Bis (benzoindenyl) zirconium dichloride,
Ethylene-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, (tert-butylamide) (tetramethyl-η5-cyclopentadienyl)-
1,2-ethanediyl zirconium dichloride, (third
Tert-butylamido) dimethyl (tetramethyl-η5-cyclopentadienyl) silane zirconium dichloride, (methylamido) (tetramethyl-η5-cyclopentadienyl) -1,2-ethanediylzirconium dichloride and the like, and zirconium in these compounds Those substituted with hafnium or titanium can be given.

The co-catalysts used simultaneously include:
Those described in the above publications can be used. Preferred cocatalysts are linear or cyclic aluminoxanes (eg, methylaluminoxane), ionic compounds (eg, N, N-dimethylammonium tetrakis (pentafluorophenyl) borate, triethylammonium tetraphenylborate), Lewis acids (eg, triethylammonium). Examples thereof include boron compounds such as phenylboric acid and tris (pentafluorophenyl) boric acid, and alkylaluminums (for example, trialkylaluminums such as triethylaluminum and isobutylaluminum).

In the above-mentioned block copolymerization, the propylene homopolymer part (hereinafter also referred to as a homo part) is usually in the presence of the above-mentioned catalyst under the following polymerization conditions, that is, the polymerization temperature is usually 0 to 100 ° C., preferably Is 30 to 90 ° C., and the polymerization pressure is usually set in the range of 0.01 to 45 kg / cm ² G, preferably 0.05 to 40 kg / cm ² G.
It is usually sufficient that the polymerization time is in the range of 0.1 to 10 hours. In this polymerization, it is also effective to carry out preliminary polymerization of propylene at a relatively low temperature and a low pressure. The amount of prepolymerization is 1 to 100 per gram catalyst.
0% by weight, preferably 3 to 800% by weight. The monomer used for the prepolymerization includes α having 2 or more carbon atoms.
Olefins, preferably propylene. The conditions for the prepolymerization are a temperature of 1 to 80C, preferably 20 to 6C.
0 ° C., the pressure is atmospheric pressure to 10 kg / cm ² G, preferably 0.05 to 5 kg / cm ² G, the time is 1 minute to 24 hours,
Preferably, it is 5 minutes to 12 hours. In the preliminary polymerization, if necessary, hydrogen gas or the like may be introduced to adjust the molecular weight.

On the other hand, in the block copolymerization, a random copolymerized portion of propylene and ethylene (hereinafter, also referred to as a random portion) is formed by polymerizing the homopolymeric portion and then activating 1 or 2 so as not to deactivate the active site. It can be produced by copolymerizing propylene and ethylene by two-stage polymerization or two-stage polymerization or more using two or more polymerization tanks. That is, the homo part is produced (first-stage polymerization).
After that, it can be produced by further introducing ethylene and propylene into the polymerization tank and copolymerizing (second-stage polymerization). As described above, the method of producing through two polymerization processes is also referred to as two-stage polymerization or simply two-stage polymerization. In the present invention, the polymerization may be performed in a two-stage polymerization, or may be performed by a multi-stage polymerization performed through two or more polymerization processes. Alternatively, the homo part can be produced by transferring it to another polymerization tank without losing the catalytic activity and then introducing and copolymerizing ethylene and propylene. Alternatively, it can also be produced by introducing ethylene and propylene in a polymerization tank different from the polymerization tank of the homo part to carry out copolymerization. Further, in the polymerization of the random part, the polymerization may be carried out with or without the addition of a new stereoregular catalyst. In this case, the newly added stereoregular catalyst may be one subjected to the prepolymerization as described above.

In both cases of two-stage polymerization (or multi-stage polymerization) or copolymerization in a separate polymerization tank, the polymerization reaction should be carried out at the same polymerization temperature and pressure range as in the homo part. The molecular weight may be adjusted by introducing hydrogen gas or the like. In the present invention, as described above, with respect to the component (A), the amount of the component eluted in a temperature range of 40 ° C. to 85 ° C. measured by a temperature-raising fractionation method is 13 to 75% by weight of the total output. Is preferred.
For this reason, it is preferable to carry out copolymerization while reducing the proportion of ethylene during copolymerization, or it is preferable to reduce the proportion of ethylene during copolymerization and make the copolymerization time as long as possible. For example, when ethylene and propylene are copolymerized in a pressure-free state by batch polymerization using a catalyst system composed of titanium trichloride and an organoaluminum compound, the ethylene / propylene flow ratio is 0.01 / 1 to 0.25 / 1
(NLM / NLM), preferably 0.04 /
1 to 0.15 / 1 (NLM / NLM) is particularly preferred.
Alternatively, the ethylene / propylene flow ratio is 0.01 / 1 to
Under the conditions of 0.25 / 1 (NLM / NLM), the copolymerization time is preferably at least 1 time, more preferably at least 2.7 times, the time of the first stage propylene homopolymerization. In addition, when ethylene and propylene are copolymerized in a pressure-free state by batch polymerization using a supported high activity catalyst system, the ethylene / propylene flow ratio is 0.01 / 1 to 1
0.3 / 1 (NLM / NLM),
0.03 / 1 to 0.2 / 1 (NLM / NLM) is particularly preferred. Alternatively, if the ethylene / propylene flow ratio is 0.01
/ 1 to 0.3 / 1 (NLM / NLM), the copolymerization time is preferably at least 0.5 times the time of the first stage propylene homopolymerization, particularly preferably at least 1 time. preferable.

For the polymerization or copolymerization of the homo part and the random part, known polymerization methods can be applied. For example, slurry polymerization, solution polymerization, gas phase polymerization or monomer such as propylene or other α-olefin And liquid-phase polymerization using a medium as a medium. In the case of performing the slurry polymerization, a solvent used for polymerization using a general stereoregular catalyst may be used. For example, pentane, hexane, heptane, octane, nonane, decane,
Examples include inert hydrocarbon solvents such as dodecane and cyclohexane. Among them, hexane, heptane, octane and the like are preferably used. In the polymerization or copolymerization of the homo part and the random part, the molecular weight can be adjusted. Various techniques can be used to adjust the molecular weight, but it is usually sufficient to introduce a suitable amount of a molecular weight regulator used for stereoregular polymerization, such as hydrogen gas, into the reaction system.

After the polymerization, the unreacted monomer, solvent and the like are separated from the polymerization product thus obtained, and further subjected to a deashing step and a washing step as required, followed by a drying step. In the case where the homo part and the random part are polymerized in separate polymerization tanks, after performing the above-described treatment, the two are blended in a predetermined ratio, and kneaded using a Banbury mixer, a twin-screw kneader, or the like. May be used to produce the component (A).

As another method for producing the component (A),
A method in which a homopolymer or a copolymer of ethylene and propylene is powder-blended. Two or more homopolymers or copolymers may be blended in the powder blend. Examples of the blending method include a method of kneading using the above-described Banbury mixer, twin-screw kneader, or the like.

As a method for producing a homopolymer or a copolymer of ethylene and propylene, the homopolymerization method or the random polymerization method in the block copolymerization described above can be mentioned. In addition, in the copolymer of ethylene and propylene, it is preferable that the molecular weight distribution and / or the composition distribution is wide because the balance between the impact resistance, the transparency, and the rigidity is excellent, and the copolymer having a wide molecular weight distribution or the composition distribution is preferably used. It is desirable to use internal and external donors to provide. Among the above electron donors, 1,1, trimethylpropylcyclopentyldimethoxysilane and 1,1,
Preferred is 1-dimethoxy-2,6-dimethyl-1-silacyclohexane or di-n-butyl cyclopentylmalonate.

Next, the nucleating agent (B) in the present invention is not particularly limited as long as the nucleating agent (B) can be added to the propylene-based resin (A) to obtain the above-mentioned effects. Nucleator (B)
Examples of the nucleating agent include the following. Crystal nucleating agent mainly composed of rosin metal salt Sorbitol-based crystal nucleating agent (a) alkali metal carboxylate, alkali metal β-
At least one diketonate or an alkali metal β-ketoacetate; and (b) the following general formula (1):

[0037]

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 a metal atom or a hydrogen atom of Group 3 or 4 of the Periodic Table, and X represents H when M represents a metal atom of Group 3 of the Periodic Table.
O-, when M represents a metal atom of Group 4 of the periodic table, it represents O = or (HO) _2- ; when M represents a hydrogen atom, X does not exist; In the present invention, a nucleating agent comprising at least one combination of a cyclic organic phosphate compound represented by the following formula: The addition amount of B) is not particularly limited, but usually 0.001 to 5 parts by weight of nucleating agent (B) may be added to 100 parts by weight of propylene resin (A).

Examples of the crystal nucleating agent containing the rosin metal salt as a main component include a crystal nucleating agent disclosed in Japanese Patent Application Laid-Open No. 7-331081. The nucleating agent having a rosin metal salt as a main component in the present invention contains a rosin metal salt in an amount of 5 to 100% by weight, preferably 10 to 100% by weight. The metal salt of a rosin in the present invention refers to a reaction product of a rosin and a metal compound. Rosins include gum rosin, tall oil rosin,
Natural rosins such as wood rosin: variously modified rosins such as disproportionated rosin, hydrogenated rosin, dehydrogenated rosin, polymerized rosin, α, β-ethylenically unsaturated carboxylic acid modified rosin: purified products of the above natural rosin, modified rosin And the like. The unsaturated carboxylic acid used for preparing the α, β-ethylenically unsaturated carboxylic acid-modified rosin includes, for example, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid,
Acrylic acid, methacrylic acid and the like can be mentioned.
Among them, at least one rosin selected from the group consisting of a natural rosin, a modified rosin, a purified product of a natural rosin and a purified modified rosin is preferable. Here, rosins include pimaric acid, sandaracopimaric acid, parastolic acid, isopimaric acid, abietic acid, dehydroabietic acid, neoabietic acid, dihydropimalic acid,
It contains a plurality of resin acids selected from dihydroabietic acid, tetrahydroabietic acid and the like. The metal compound which reacts with the rosin to form a metal salt includes sodium, potassium, a metal element such as magnesium,
And a compound that forms a salt with the rosin. Specifically, the metal chloride, nitrate, acetate, sulfate,
Carbonates, oxides, hydroxides and the like.

In the present invention, the rosins are preferably at least one rosin selected from the group consisting of natural rosins, modified rosins and purified products thereof. Further, in the present invention, the metal salt of rosin,
It is preferable that at least one metal salt of a rosin selected from the group consisting of a sodium salt of the rosin, a potassium salt of the rosin, and a magnesium salt of the rosin. Further, the metal salt of the rosin is preferably a metal salt of at least one rosin selected from the group consisting of a metal salt of a hydrogenated rosin, a metal salt of a disproportionated rosin, and a metal salt of a dehydrogenated rosin. Among them, a metal salt of at least one rosin selected from the group consisting of a metal salt of dehydroabietic acid, a metal salt of dihydroabietic acid and a metal salt of dihydropimaric acid is preferable. In the present invention, 0.001 to 5 parts by weight, preferably 0.05 to 2 parts by weight of a crystal nucleating agent containing a metal salt of the rosin as a main component is added to 100 parts by weight of the propylene-based resin.

Specific examples thereof include Pine Crystal KM1600, Pine Crystal KM1500 and Pine Crystal KM1300 (trade name) manufactured by Arakawa Chemical Industries, Ltd. Examples of the sorbitol-based crystal nucleating agent include benzylidene sorbitols. The benzylidene sorbitol is a condensate of an aromatic aldehyde and a pentavalent or higher polyhydric alcohol. Here, as aromatic aldehydes, benzaldehyde,
A benzaldehyde-substituted product having 1 to 5 alkyl groups having 1 to 3 carbon atoms, a benzaldehyde-substituted product having 1 to 5 halogen atoms, and 1 alkoxy group having 1 to 3 carbon atoms
There may be mentioned substituted benzaldehydes having up to 5 substitutions and mixtures thereof in any proportion. Examples of the polyhydric alcohol include sugar alcohols such as sorbitol and xylit, and mixtures thereof at any ratio. As a condensate obtained by condensing these, that is, benzylidene sorbitols, the type and number of each aromatic substituent in benzaldehyde are different, or the position of the substituent is different from the ortho, meta and para positions. Asymmetric benzaldehydes which are isomers or symmetric benzaldehydes having the same aromatic substituents and mixtures thereof may be used. For example, the benzylidene group may be one monobenzylidene sorbitol, two dibenzylidene sorbitols, three tribenzylidene sorbitols or more benzylidene sorbitols. For example, asymmetric benzylidene sorbitols obtained by using a mixture of benzaldehyde and cumylaldehyde as a raw material as benzaldehydes may be used.

The polyhydric alcohol which is one of the raw materials is not limited to sugar alcohols such as sorbit and xylit and a mixture of any ratio thereof, but also includes sorbitol derivatives, xylit derivatives and any mixture of these derivatives. You. In the present invention, the sorbitols are preferably dibenzylidene sorbitols. Among them, the following general formula (2) disclosed in Japanese Patent No. 2631652 is preferred.

[0043]

Embedded image

(Wherein X ¹ and X ² each represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a halogen atom, and may be the same. M and n may be the same.) 0 to
An integer of 5, p represents 0 or 1. ) Are more preferred. Examples of the alkyl group having 1 to 3 carbon atoms in the general formula (1) include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. As the alkoxy group having 1 to 3 carbon atoms,
Examples include a methoxy group, an ethoxy group, an n-propoxy group, and an isopropoxy group. As the halogen atom, chlorine,
Fluorine, iodine and bromine.

Further, in the present invention, a specific stabilizer is added to a purified product obtained by washing the dibenzylidene sorbitol represented by the general formula (2) with a specific solvent. When used as a nucleating agent, thermal stability is improved, which is preferable. As the washing solvent for purifying the dibenzylidene sorbitols, specifically, in addition to an aliphatic lower alcohol having 1 to 3 carbon atoms, n-
One or more selected from the group consisting of saturated hydrocarbons having 6 to 12 carbon atoms such as hexane, alicyclic hydrocarbons such as cyclohexane, and aromatic hydrocarbons such as toluene;
A mixed solvent comprising an aliphatic lower alcohol such as methanol, ethanol and isopropanol and one or more selected from the group consisting of ketones exemplified by acetone, methyl ethyl ketone and methyl isobutyl ketone is exemplified.

Stabilizers added to the purified dibenzylidene sorbitols include alkaline compounds and / or
Or a radical inhibitor. Specific examples of the alkaline compound include inorganic hydroxides such as sodium hydroxide and potassium hydroxide, and citric acid, lactic acid, lactic acid dimer stearate, succinic acid, benzoic acid, stearic acid, hydroxystearic acid, oleic acid, and beheenoic acid. Illustrative fatty acids, sodium salts of organic acids such as ethylenediaminetetraacetic acid, alkali metal salts such as potassium, calcium,
And alkaline earth metal salts such as magnesium.

As the radical inhibitor, bisphenol A and butylhydroxyanisole (also known as BH
A), 2,6-di-tert-butylhydroquintoluene (also known as BHT), 2,6-di-tert-butyl-p-cresol, 2,6-di-tert-butyl-phenol,
4,4'-methylenebis (2,6-di-tert-butylphenol), 2,6-di-tert-butyl-α-dimethylamino-p-cresol, 2,6-di-tert-butyl-
p-ethylphenol, 2,4,6-tri-tert-butylphenol, tris (3,5-di-tert-butyl-4
-Hydroxybenzyl) isocyanurate, tris [β
-(3.5-tert-butyl-4-hydroxyphenyl)
Propionyl-oxyethyl] isocyanurate, 1,
3,5-trimethyl-2,4,6-tris (3.5-di-tert-butyl-4-hydroxybenzyl) benzene,
1,6-hexanediol-bis [3- (3,5-di-
tert-butyl-4-hydroxyphenyl) propionate], 6- (4-hydroxy-3,5-di-tert-butylanilino) -2,4-bisoctyl-thio-1,3,3.
5-triazine, tetrakis [methylene-3- (3,5
-Di-tert-butyl-4-hydroxyphenyl) propionate] methane (also known as Irganox 1010)
1), n-octadecyl-3- (3,5-ditert-butyl-4-hydroxyphenyl) propionate, N,
N'-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamamide, 3.5-di
Polymeric exemplified by tert-butyl-4-hydroxy-benzylphosphonate diethyl ester, 2,2-thio-diethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] and the like. Examples include phenol compounds such as hindered phenols and phosphorus compounds such as tris (nonylphenyl) phosphite.

The above-mentioned alkaline compounds or radical inhibitors are used alone or in combination of two or more.
The amount added to the purified dibenzylidene sorbitol is 50 to 1 in total of the alkaline compound and / or the radical inhibitor per 100 parts by weight of the purified product.
What is necessary is just to add 0.00000 ppm. Further, in the present invention, as disclosed in JP-A-8-239386, the dibenzylidene sorbitol represented by the above general formula (2) has a crystal structure as measured by an X-ray diffraction method. Are preferable, and among them, a hexagonal crystal and / or
Alternatively, it is particularly preferable that the crystal is a crystal other than a hexagonal crystal such as a cubic crystal. Among the hexagonal crystal and the cubic crystal, the hexagonal crystal is superior in the dispersing rate and dissolution rate in the molten polyolefin resin, and has excellent performance as a crystal nucleating agent. May be used. The proportion of the mixture is such that crystals other than hexagonal crystals such as cubic crystals are 19 parts by weight or less, preferably 0.05 to 19 parts by weight, particularly preferably 0.05 to 19 parts by weight, based on 1 part by weight of hexagonal crystals. 5.7 parts by weight. In the present invention,
Use of hexagonal crystals alone as described above, or to use in the form of a mixture of hexagonal crystals and crystals other than hexagonal crystals such as cubic crystals, as preferred dibenzylidene sorbitols, for example, the following Compounds. 1,3:
2,4-bis (O-3,4-dimethylbenzylidene)-
D-sorbitol, 1,3: 2,4-bis (Op-methylbenzylidene) -D-sorbitol, 1,3: 2
4-bis (Op-ethylbenzylidene) -D-sorbitol, 1,3- (O-dimethylbenzylidene) -2,
4- (O-benzylidene) -D-sorbitol, 1,3
-(O-benzylidene) -2,4- (O-dimethylbenzylidene) -D-sorbitol, 1,3: 2,4-bis (O-benzylidene) -D-sorbitol, 1,3:
2,4-bis (Op-chlorobenzylidene) -D-sorbitol, 1,3- (Op-chlorobenzylidene)
-2,4- (OP-methylbenzylidene) -D-sorbitol and 1,3- (Op-methylbenzylidene) -2,4- (Op-chlorobenzylidene) -D-
Sorbitol.

More specifically, Gelol MD and Gelol DX from Shin Nippon Rika (manufactured), Millard 3988, Milliken (manufactured), NC-6, Mitsui Chemicals (manufactured by NC) 6, EC-1 (manufactured by EC Chemical), EC- 1-55, EC-1-70, E
C-2, EC-4 and the like. In the present invention,
The sorbitol is usually used in an amount of 0.001 to 5 parts by weight, preferably 0.00 to 100 parts by weight of the propylene-based resin.
3 to 3 parts by weight, particularly preferably 0.05 to 1 part by weight is used.

Examples of the alkali metal constituting (a) the alkali metal carboxylate, the alkali metal β-diketonate or the alkali metal β-ketoacetate in the crystal nucleating agent include lithium, sodium and potassium. Examples of the carboxylic acid constituting the alkali metal carboxylate include, for example, acetic acid, propionic acid, acrylic acid, octylic acid, isooctylic acid, nonanoic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, and oleic acid. Acid, ricinoleic acid, 12
-Hydroxystearic acid, behenic acid, montanic acid, melicic acid, β-dodecylmercaptoacetic acid, β-dodecylmercaptopropionic acid, β-N-laurylaminopropionic acid, β-N-methyl-N-lauroylaminopropionic acid and the like Aliphatic monocarboxylic acids; malonic acid, succinic acid, adipic acid, maleic acid: aliphatic polycarboxylic acids such as azelaic acid, sebacic acid, dodecanediic acid, citric acid, butanetricarboxylic acid, butanetetracarboxylic acid; naphthenic acid, Cyclopentanecarboxylic acid, 2-methylcyclopentanecarboxylic acid, 2-methylcyclopentanecarbonic acid, cyclopentenecarboxylic acid, cyclohexanecarboxylic acid, 1-methylcyclohexanecarboxylic acid, 4-methylcyclohexanecarboxylic acid, 3,5-dimethylcyclohexane Cal Alicyclic mono- or polycarboxylic acids such as boric acid, 4-butylcyclohexanecarboxylic acid, 4-octylcyclohexanecarboxylic acid, cyclohexenecarboxylic acid, 4-cyclohexene and 1,2-dicarboxylic acid; benzoic acid, toluic acid, xylyl acid And aromatic mono- or polycarboxylic acids such as ethylbenzoic acid, 4-secondary butylbenzoic acid, salicylic acid, phthalic acid, trimellitic acid and pyromellitic acid. Examples of the β-diketone constituting the alkali metal β-diketonate include acetylacetone, pivaloylacetone, palmitoylacetone, benzoylacetone, pivaloylacetone, dibenzoylacetone, and the like. Examples of the β-ketoacetate constituting the alkali metal β-ketoacetate include, for example, octyl acetoacetate octyl acetoacetate, lauryl acetoacetate,
Ethyl stearylinospenzazoylacetate, lauryl benzoylacetate and the like. Examples of the β-ketoacetate constituting the alkali metal β-ketoacetate include, for example, ethyl acetoacetate, octyl acetoacetate, lauryl acetoacetate, stearyl acetoacetate, ethyl benzoylacetate, and benzoyllaurylacetate. .

The alkali or alkali metal β-ketoacetate of the component (a) is a salt of the above alkali metal with a carboxylic acid, β-diketone compound or β-ketoacetate, and is produced by a conventionally well-known method. can do. As the component (a) in the present invention, an aliphatic monocarboxylate of an alkali metal, particularly, an aliphatic carboxylate of lithium is preferable, and particularly, an aliphatic monocarboxylate having 8 to 2 carbon atoms.
An aliphatic monocarboxylate of 0 is preferred.

On the other hand, in the cyclic organic phosphate compound represented by the general formula (1) in the component (b), R ¹
Examples of the alkyl group having 1 to 4 carbon atoms represented by are methyl, ethyl, propyl isopropyl, butyl, niptibusisobutyl and the like. Examples of the alkyl group having 1 to 12 carbon atoms represented by R ² and R ³ include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, amyl, tertiary amyl, hexyl, heptyl, Octyl, isooctyl, second octyl, 2-ethylhexyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tertiary dodecyl and the like: as the cycloalkyl group, cyclobutyl, cyclohexyl, cyclopentyl, cycloheptyl and the like, as the aralkyl group, Benzyl, α, α-dimethylbenzyl, α-methylbenzyl and the like. Also, M
Examples of the metal atom of Group 3 or Group 4 of the periodic table represented by are aluminum, gallium, germanium, tin, titanium, zirconium and the like, and a compound in which M is aluminum is particularly preferable.

In the present invention, the proportion of the component (b) in the nucleating agent is 35 to 80% by weight, preferably 40 to 75% by weight. Specific examples of the crystal nucleating agent include ADK STAB NA-21 (Asahi Denka Co., Ltd.). In the present invention, usually 0.001 to 5 parts by weight of at least one kind of the component (a) and 0.001 to 5 parts by weight of at least one kind of the component (b) are added to 100 parts by weight of the propylene resin. Just fine.
Preferably, at least one kind of the component (a) is used.
-0.65 parts by weight and at least one of component (b), 0.01-0.8 parts by weight. Particularly preferably,
0.03 to 0.6 parts by weight of at least one of the components (a) and (b) based on 100 parts by weight of the propylene resin.
In this case, at least one of the components is added in an amount of 0.03 to 0.6 parts by weight.

In the present invention, among the above-mentioned various nucleating agents, sorbitols are preferable to nucleating agents mainly containing a metal salt of rosin, and (a) alkali metal carboxylate, alkali metal Most preferred is a crystal nucleating agent comprising at least one kind of β-diketonate or an alkali metal β-ketoacetate and (b) at least one kind of a cyclic organic phosphate compound represented by the following general formula (2).

In the present invention, various additives may be added, if necessary, in addition to the components (A) and (B). Additives include additives for surface functions such as antistatic agents and antifogging agents, antiblocking agents, antioxidants, weathering agents, heat stabilizers, neutralizing agents, lubricants, nucleating agents, coloring agents, inorganic Or an organic filler. These additives may be used alone or in a combination of two or more. For example, examples of the antioxidant include a phosphorus-based antioxidant, a phenol-based antioxidant, and a sulfur-based antioxidant. Specific examples of the phosphorus antioxidant include trisnonylphenyl phosphite, tris (2,
4-di-t-butylphenyl) phosphite, distearylpentaerythritol diphosphite, bis (2,
4-di-t-butylphenyl) pentaerythritol phosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol phosphite, 2,
2-methylenebis (4,6-di-t-butylphenyl)
Octyl phosphite, tetrakis (2,4-di-t-
Butylphenyl) -4,4-biphenylene-di-phosphonite, ADEKA STAB 1178 (Asahi Denka Co., Ltd.), Sumilizer TNP (Sumitomo Chemical Co., Ltd.), JP-135 (Johoku Chemical Co., Ltd.), ADK STAB 2112 (Asahi Denka Co., Ltd.) (Product)), JPP-2000 (Johoku Chemical (product)), We
stone618 (GE (manufactured)), ADK STAB PEP-
24G (Asahi Denka (product)), Adekastab PEP-36
(Asahi Denka (product)), ADK STAB HP-10 (Asahi Denka (product)), Sandstab P-EPQ (sand (product)), phosphite 168 (Ciba Geigy (product)), and the like.

As specific examples of the phenolic antioxidant,
2,6-di-t-butyl-4-methylphenol, n-
Octadecyl-3- (3 ', 5'-di-t-butyl-
4'-hydroxyphenyl) propionate, tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, tris (3,5-di-t-butyl-4-hydroxybenzyl) )
Isocyanurate, 4,4'-butylidenebis- (3-
Methyl-6-t-butylphenol), triethylene glycol-bis [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionate], 3,9-
Bis {2- [3- (3-t-butyl-4-hydroxy-
5-methylphenyl) propionyloxy] -1,1-
Dimethylethyl {-2,4,8,10-tetraoxaspiro [5,5] undecane, Sumilizer BHT (Sumitomo Chemical Co., Ltd.), Yoshinox BHT (Yoshitomi Pharmaceutical Co., Ltd.), Antage BHT (Kawaguchi Chemical Co., Ltd.) ), Irganox 1076 (Ciba-Geigy (manufactured)), Irganox 1010 (Ciba-Geigy (manufactured)), ADK STAB AO-60 (Asahi Denka (manufactured)), Sumilizer BP-
101 (Sumitomo Chemical Co., Ltd.), Tominox TT (Yoshitomi Pharmaceutical Co., Ltd.), TTHP (Toray Co., Ltd.), Irganox 3114 (Ciba Geigy Co., Ltd.), ADK STAB AO
-20 (Asahi Denka Co., Ltd.), ADK STAB AO-40 (Asahi Denka Co., Ltd.), Sumilizer BBM-S (Sumitomo Chemical Co., Ltd.), Yoshinox BB (Yoshitomi Pharmaceutical Co., Ltd.), Antage W-300 (Kawaguchi Chemical (manufactured)), Irganox 245 (Ciba-Geigy (manufactured)), Adekastab AO-
70 (Asahi Denka Co., Ltd.), Tominox 917 (Yoshitomi Pharmaceutical Co., Ltd.), ADK STAB AO-80 (Asahi Denka Co., Ltd.),
SUMILIZER GA-80 (Sumitomo Chemical Co., Ltd.) and the like.

Specific examples of the sulfur-based antioxidant include dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-
3,3'-thiodipropionate, pentaerythritol tetrakis (3-lauryl thiopropionate), Sumilizer TPL (Sumitomo Chemical Co., Ltd.), Yoshinox D
LTP (Yoshitomi Pharmaceutical (manufactured)), Antiox L (Nippon Yushi (manufactured)), Sumilizer TPM (Sumitomo Chemical (manufactured)),
Yoshinox DMTP (Yoshitomi Pharmaceutical Co., Ltd.), Antiox M (Nippon Oil & Fat Co., Ltd.), Sumilizer TPS (Sumitomo Chemical Co., Ltd.), Yoshinox DSTP (Yoshitomi Pharmaceutical Co., Ltd.), Antiox S (Nippon Yushi Co., Ltd.) ), ADK STAB AO-412S (Asahi Denka Co., Ltd.), SEENO
X 412S (Cipro Kasei Co., Ltd.), Sumilizer TD
P (Sumitomo Chemical Co., Ltd.) and the like.

When an antioxidant is used in the present invention, the antioxidant may be added to the component (A) in an amount of about 0.001 to 1 part by weight. This is preferable because yellowing and the like can be prevented. Specific examples of the use of the above antioxidants include: Example 1 Irganox 1010 1000 ppm PEP-Q 1000 ppm Example 2 Irganox 1076 1200 ppm PEP-Q 600 ppm Phosphite 168 800 ppm Example 3 Irganox 1010 400-1000 ppm Phosphite 168 750 to 1500 ppm. [2] Molded article and container The molded article of the present invention is a molded article obtained by molding the propylene-based resin composition. As a specific example of the molded body,
Containers, films, sheets, automotive interior materials, housing materials for call products, and the like. Also, as the molding method,
Examples include an injection molding method, a compression molding method, an injection compression molding method, a gas assist injection molding method, an extrusion molding method, and a blow molding method.

The molding conditions are not particularly limited as long as the temperature is such that the resin melts and flows.
It can be carried out at 0 ° C to 300 ° C and at a mold temperature of 60 ° C or less. When a film is formed as the molded article of the present invention, it can be performed by a general compression molding method, an extrusion molding method, a blow molding method, or the like. The film may or may not be stretched. When stretching, biaxial stretching is preferred. Conditions for biaxial stretching include the following conditions. Molding conditions during sheet molding Resin temperature 200-300 ° C, chill roll temperature 50 ° C or less Longitudinal stretching condition Stretching ratio 3-7 times, stretching temperature 130-160 ° C Lateral stretching condition Stretching ratio 6-12 times, stretching temperature 150-175 ° C The surface of the film may be treated, if necessary, to increase the surface energy or polarize the surface. For example, examples of the treatment method include a corona discharge treatment, a chromic acid treatment, a flame treatment, a hot air treatment, and an ozone or ultraviolet irradiation treatment. Examples of the method for making the surface uneven include a sand blast method and a solvent treatment method.

The container of the present invention is a container obtained by blow molding the propylene resin. Specific examples of containers include packaging containers for food, cosmetics,
Containers for household goods such as detergents and the like are included. The molding conditions of the blow molding are the same as the molding conditions of the above-mentioned molded body, and there is no particular limitation as long as the temperature is such that the resin melts and flows.
It can be carried out at a resin temperature of 160 ° C to 300 ° C and a mold temperature of 60 ° C or less.

[0061]

[Example 1]

Production of Propylene Resin by Block Copolymerization (1) Prepolymerization Using a 5 liter glass stirrer and a three-necked flask equipped with a thermometer, heptane dehydrated by molecular sieves (4A) and nitrogen bubbling was removed under nitrogen stream.
After adding 1 liter, at room temperature (23 ° C.), 142.3 g of diethyl aluminum chloride (DEAC; manufactured by Tosoh Akzo) and then 20.3 g of titanium trichloride (manufactured by Marubeni Solvay) were added with stirring. .

Next, with stirring, propylene
Continuously, and 0.8 times the amount of po per weight of titanium trichloride.
Performed to produce propylene. This is the reserve weight
A combined catalyst was used. (2) Production of propylene-ethylene block copolymer (Production of homo part)
With a molecular sieve in a pressure-resistant autoclave
Charge 6 liters of dehydrated n-heptane in a nitrogen stream
I do. Then, replace nitrogen with propylene gas at 80 ° C.
After that, 0.2kg / cm of hydrogen ^TwoGuided by G precision gauge
And propylene 8.0kg / cm^TwoUntil it becomes G
It was introduced with stirring.

The prepolymerized catalyst obtained in the above (1) was treated with trisalt
After loading 0.6g per weight of titanium oxide, 8.0kg
/ Cm^TwoContinuously introduce propylene so as to obtain G
At the same time, the polymerization temperature was kept at 80 ° C. 0.5 hour weight
After the combined reaction, the pressure was released to atmospheric pressure. (Manufacture of random part) Continue to etch inside the autoclave
Len / propylene flow rate ratio 0.07 / 1.0 (NLM / N
LM) and replace with 0.3 kg / cm of hydrogen^Two
After introducing G, ethylene / propylene was supplied at a flow rate ratio of 0.07.
/1.0 (NLM / NLM) continuously (pressure
Was in a free state) and copolymerized at 57 ° C. for 2 hours.
Where NLM is normal liters per m
inute). Then, depressurize to atmospheric pressure, n-
Polymerized powder containing heptane was washed with a 400 stainless steel powder.
After separation at 57 ° C. using a mesh wire mesh,
Washing with stirring for 30 minutes using 4 liters of heptane at
Polymerized powder using a 400 mesh stainless steel wire mesh
Was separated and dried to obtain a block copolymer. (3) Compounding and kneading An antioxidant as an additive to the obtained block copolymer
(Irganox 1010, manufactured by Nippon Ciba Geigy) 2
000 ppm, neutralizing agent (calcium stearate G, day
500 ppm of this fat and oil and nucleating agent (ADK STAB N
A-21, manufactured by Asahi Denka) 500 ppm, biaxial kneading
Using a machine (Laboplast Mill, manufactured by Toyo Seiki)
Propylene resin according to the measurement method described above.
Were evaluated. In addition, the following (a), (b), (c)
(Haze), impact resistance and rigidity depending on the measurement method
Was measured and molded by blow molding according to the method (d).
The container was subjected to a drop test and evaluated. Table 1 shows the obtained results.
Show. (A) Measurement of transparency; a flat plate having a thickness of 1 mm is melt-pressed
And measure haze according to JIS K7105
did. (B) Measurement of impact resistance; melt-pressing a flat plate with a thickness of 3 mm
5 ℃, -5 according to JIS K7110
The Izod impact strength at ℃ was measured. (C) Rigidity measurement; 1 mm thick flat plate is melt-pressed
JIS K7113 using the prepared and punched test pieces
The tensile modulus of elasticity was measured according to. (D) Drop test of container formed by blow molding JEB-7 manufactured by Japan Steel Works Ltd. was used as a blow molding machine.
Container with a 00ml flat mold (basis weight 45g ±
0.5 g). Tap water into the obtained container
Put it in front of the part, cover it and put it in a + 3 ° C thermostat.
For 24 hours. After that, remove from the thermostat and
Early, 10 times in the longitudinal direction of the container from a height of 120 cm,
It was dropped 10 times in the horizontal direction. Each time it falls, the container cracks
Was observed. Five containers were used. Table showing the results obtained
It is shown in FIG. [Example 2] In Example 1 (2), ethylene / pro
Example 1 except that the copolymerization time of pyrene was changed to 1.7 hours.
The same was done. Table 1 shows the obtained results. [Example 3] In Example 1 (2), ethylene / pro
Example 1 except that the copolymerization time of pyrene was changed to 1.5 hours.
The same was done. Table 1 shows the obtained results. [Example 4] Production of propylene-based resin by blending Ethylene / propylene copolymer obtained by the following method
Polymer (EP-1), ethylene / propylene copolymer
(EP-2) and Idemitsu Petrochemical Co., Ltd.
Ren homopolymer E105GM (trade name) in weight ratio
Blend at 20/50/30 respectively, and further with additives
Antioxidant (Irganox 1010, Nippon Cibaga)
2000 ppm, neutralizing agent (calcium stain)
Allate G, manufactured by NOF Corporation) 500ppm and nucleating agent
(ADK STAB NA-21, manufactured by Asahi Denka) 500 ppm
Addition, twin-screw kneader (Laboplast mill, manufactured by Toyo Seiki)
And pelletized. Evaluation as in Example 1
Table 1 shows the obtained results. (I) Production of ethylene / propylene copolymer (EP-1)
(1) Electron donor as the third component, ie, external donor
1,1, trimethylpropylcyclope used as
Methyldimethoxysilane [(Thexyl) (Cycl
opentyl) Si (OMe)_TwoSynthesis of 2,3-dimethyl in a 300 ml autoclave
Le-2-butene (750 ml, 0.60 mol)
And then add HSiCl_Three(240g, 1.8m
), 2,2'-azoisobutyronitrile (18 g,
0.11 mol) and stirred at 120 ° C. for 22 hours.
After that, remove the solution by decantation and decompress
Distillation (76 ° C., 6 mmHg), ThexylSiCl
_ThreeI got In a 1 liter three-necked flask, THF (500
Milliliter) and LiAlH_Four(67.8
g, 1.84 mol), and exotherm was observed.
Next, the above-mentioned TexylSiCl_Three(131.9 g,
(0.6 mol) in THF. After dropping, 65 ° C
And refluxed overnight. Then, excess LiAlH _Four 
Was hydrolyzed, and the organic layer was separated. It is concentrated and distilled (9
5 to 98 ° C.) to obtain TexylSiH_ThreeGet
Was.

Subsequently, ether (600 ml), ThexylSiH were placed in a 1-liter two-necked flask.
₃ (45.0 g, 0.39 mol), cooled to 0 ° C., CuCl ₂ (104.9 g, 0.78 mol), CuI
(1.56 g, 8.2 mmol) and the mixture was stirred at room temperature for 48 hours. The solution is filtered, the precipitate is concentrated,
Distillation (distillation at 134 to 142 ° C.)
₂ Cl was obtained. (34.3 g, 0.23 mol)
In a 00 ml two-necked flask, diethyl ether (50 ml), ThexylSiH ₂ Cl
(3.0 g, 19.9 mmol) and cyclopentyl MgBr / TH prepared separately while stirring.
F (30.O mmol) was added and stirring continued for 3 hours.
Hydrolyzing excess Cyclopentyl MgBr,
The organic layer was separated. It is concentrated and distilled under reduced pressure (80-15
(Distilled at 0 ° C., 1.0 mmHg), and (Thexyl)
(Cyclopentyl) SiH ₂ was obtained (1.93)
g, 10.3 mmol).

Subsequently, methanol (10 ml) and Na (23 mg,
1.0 mmol), and (Thexyl) (C
Yclopentyl) The SiH ₂ was added 1.8 g (9.8 mmol). After refluxing for 48 hours, concentration, distillation under reduced pressure (fraction at 125 ° C., 1.0 mmHg),
1) (Cyclopentyl) Si (OMe ₂ ) was obtained (1.75 g, 7.1 mmol). (2) Preparation of solid catalyst component In a three-necked flask equipped with a stirrer having an inner volume of 500 ml and purged with nitrogen, 16 g of diethoxymagnesium (0.1 g) was added.
4 mol), and 60 ml of dehydrated heptane was added. Heat to 40 ° C. and add 2.45 ml (22.5 mmol) of silicon tetrachloride. After stirring for 20 minutes, 12.7 mol of di-n-butyl phthalate was added.

The temperature of the solution was raised to 80 ° C., and 77 ml (0.70 mol) of titanium tetrachloride was added dropwise using a dropping funnel. When the internal temperature is 110 ° C, 24
The mixture was stirred for a time to perform a loading operation. Thereafter, washing was performed sufficiently using dehydrated heptane. In addition, titanium tetrachloride
2 ml (1.12 mol) was added and the internal temperature was 110 ° C
Then, the mixture was stirred for 24 hours to perform the second loading operation. After that, washing was performed sufficiently using dehydrated heptane to obtain a solid catalyst component. (3) Prepolymerization Using a 5-liter glass stirrer and a thermometer-equipped three-necked flask, molecular sieves (4A) and heptane dehydrated by nitrogen bubbling were mixed under nitrogen stream for 4 hours.
After adding 1 liter, at room temperature (23 ° C.), first, 26.8 mmol of triethylaluminum (TEA), then 2.5 mmol of 1,1,2-trimethylpropyl-cyclopentyldimethoxysilane obtained in (1), and further, The solid catalyst component obtained in (2) was added with stirring at 5.3 mmol per Ti atom (13.8 g-solid catalyst).

Next, propylene was continuously charged at room temperature with stirring, and the operation was performed so that 0.3 times the amount of polypropylene per solid catalyst weight was produced. This was used as a prepolymerization catalyst. (4) Synthesis of EP-1 6 liters of n-heptane well dehydrated with molecular sieves was charged into a 10-liter pressure-resistant autoclave, which had been thoroughly purged with nitrogen and dried in a nitrogen stream. Then 7.5 mmol of triethylaluminum (TEA) and (1)
After adding 0.5 mmol of 1,1,2-trimethylpropyl-cyclopentyldimethoxysilane obtained in the above, the prepolymerized catalyst obtained in the above (3) was converted to 0.0
5 moles were charged. Next, ethylene /
Propylene flow ratio 0.15 / 1.0 (NLM / NLM)
After introducing 0.5 kg / cm ² G of hydrogen, ethylene / propylene was mixed at a flow rate of 0.15 / 1.
0 (NLM / NLM) was introduced continuously (the pressure was in a free state), and polymerization was carried out at 57 ° C. for 2 hours. Thereafter, the pressure was released to atmospheric pressure, the polymerization powder containing n-heptane was evaporated to dryness by an evaporator, and further dried and pulverized to obtain an ethylene / propylene copolymer (EP-1). (II) Ethylene / propylene copolymer (EP-2) (1) Synthesis of 1,1-dimethoxy-2,6-dimethyl-1-silacyclohexane used as electron donor as third component, ie, external donor 100 To a milliliter three-necked flask were added 473.9 mg (19.5 mmol) of magnesium metal and 19.5 ml of diethyl ether, and a few drops of 1,2-dibromoethane, followed by 2 g of 2,6-dibromoheptane.
(7.8 mmol) was added dropwise over 50 minutes. The mixture was further distilled and aged for 8 hours, and the disappearance of the raw materials was confirmed. After returning to room temperature and dropping 1.19 g (7.8 mmol) of tetramethoxysilane, the mixture was distilled for 14 hours to confirm that the raw materials had disappeared. After adding 5 ml of methanol, the solution was filtered, dried, and further distilled and separated by column separation to give 1,1-dimethoxy-.
2,6-dimethyl-1-silacyclohexane 190 mg
Was obtained with a purity of 97.5%. The yield was 12.8%. (2) Synthesis of electron donor as the third component, that is, di-n-butyl cyclopentylmalonate used as an internal donor After replacing a 500 ml three-necked flask with a stirrer with a nitrogen gas in a nitrogen gas flow, , 7.2 g (0.3 mol) of sodium hydride and 250 ml of dehydrated tetrahydrofuran were added. Start stirring, 0 ° C
After cooling, 66 ml (0.3 mol) of di-n-butyl malonate was added dropwise over 30 minutes while maintaining the temperature. After completion of the dropwise addition, the temperature was raised to room temperature, and 32 ml of cyclopentyl bromide was added dropwise, followed by distillation for 4 hours. After cooling to room temperature, 10 g of sodium hydride and 32 ml of cyclopentyl bromide were added, and the mixture was further distilled for 4 hours. The obtained reaction solution was washed with 200 ml of water and distilled under reduced pressure to obtain 20 g of di-n-butyl cyclopentylmalonate. The yield was 12.8%. (3) Preparation of solid catalyst component After replacing a three-necked flask with an internal volume of 500 ml with a stirrer with nitrogen, 60 ml of dehydrated heptane and 4.0 g (35 mmol) of diethoxymagnesium were charged. After heating at 40 ° C for 20 minutes,
1.24 ml (4.4 mmol) of di-n-butyl cyclopentylmalonate obtained in (2) were added. This solution was heated to 90 ° C., and 116 ml (1.04 mol) of titanium tetrachloride was added thereto.
The mixture was stirred at 0 ° C. for 2 hours to carry out a loading operation. Thereafter, washing was sufficiently performed using dehydrated heptane. Further, 116 ml (1.04 mol) of titanium tetrachloride was added,
The mixture was stirred at 10 ° C. for 2 hours to perform a second loading operation.
Thereafter, the solid was sufficiently washed with dehydrated heptane to obtain a solid component. The titanium loading was 2.04% by weight. (4) Preliminary polymerization Using a 5-liter glass stirrer and a three-necked flask equipped with a thermometer, heptane dehydrated by molecular sieves (4A) and nitrogen bubbling was removed under nitrogen stream.
After charging 1 liter, at room temperature (23 ° C.), first, 26.8 mmol of triethylaluminum (TEA), and then 1,1-dimethoxy-2,6-dimethyl-1-silacyclohexane obtained in (1). 5 mmol, and 5.3 mmol (12.2 g-solid catalyst) per Ti atom of the solid catalyst component obtained in (2) were added with stirring.

Next, propylene was continuously charged at room temperature with stirring, and the operation was performed so that 0.3 times the amount of polypropylene per solid catalyst weight was produced. This was used as a prepolymerization catalyst. (5) Synthesis of EP-2 In a 10-liter pressure-resistant autoclave, which had been well purged with nitrogen, 6 liters of n-heptane sufficiently dehydrated with molecular sieves was charged in a nitrogen stream. Then 7.5 mmol of triethylaluminum (TEA) and (1)
After adding 0.5 mmol of 1,1-dimethoxy-2,6-dimethyl-1-silacyclohexane obtained in the above, the prepolymerized catalyst obtained in the above (3) was converted to 0.0 in terms of Ti atom.
5 moles were charged. Next, ethylene /
Propylene flow ratio 0.09 / 1.0 (NLM / NLM)
After introducing 0.8 kg / cm ² G of hydrogen, ethylene / propylene was mixed at a flow rate of 0.09 / 1.
0 (NLM / NLM) was introduced continuously (the pressure was in a free state), and polymerization was carried out at 57 ° C. for 2 hours. Thereafter, the pressure was released to atmospheric pressure, the polymer powder containing n-heptane was evaporated to dryness by an evaporator, and further dried and pulverized to obtain an ethylene / propylene copolymer (EP-2). Example 5 The procedure of Example 5 (5) was repeated except that the ethylene / propylene flow rate ratio was changed to 0.07 / 1.0.
3) was obtained. (EP-2) was changed to (EP-3), and the compounding ratio was further changed to (EP-1) / (EP-3) / (E105).
GM) = 5/55/40. Table 1 shows the obtained results. Example 6 In Example 1 (3), the nucleating agent NA-2 was used.
Gel all MD (Shin Nippon Rika) 1000 instead of 1
The same procedure was performed as in Example 1 except that ppm was used. Table 1 shows the obtained results. Example 7 In Example 1 (3), the nucleating agent NA-2 was used.
In the same manner as in Example 1 except that 6000 ppm of Pine Crystal KM1300 (manufactured by Arakawa Chemical Industries) was used instead of 1. Table 1 shows the obtained results. [Comparative Example 1] In Example 1 (3), the nucleating agent NA-2 was used.
Adekastab NA-11 (manufactured by Asahi Denka) 50 in place of 1
The procedure was performed in the same manner as in Example 1 except that 0 ppm was used. Table 2 shows the obtained results. [Comparative Example 2] The procedure of Example 1 (2) was repeated, except that the copolymerization time was changed to 1.3 hours.
Table 2 shows the obtained results. [Comparative Example 3] 500 ppm of nucleating agent (ADK STAB NA-21, manufactured by Asahi Denka) was added to polypropylene F744NP (trade name, random type, ethylene content 4%) manufactured by Idemitsu Petrochemical Co., Ltd. (Labo Plast Mill, manufactured by Toyo Seiki Co., Ltd.) and pelletized. Evaluation was performed in the same manner as in Example 1, and the obtained results are shown in Table 2. [Comparative Example 4] In Comparative Example 3, 1000 ppm of Gerol MD (manufactured by Shin Nippon Rika) was used instead of the nucleating agent NA-21.
Example 8 was carried out except that was used. Table 2 shows the obtained results. [Comparative Example 5] Production of propylene-based resin by blending Ethylene / propylene flow ratio 0.15 / 1.0 (NLM / N) in synthesis of (4) EP-1 in (I) of Example 4
LM) was changed to 0.1 / 1.0 (NLM / NLM), and an ethylene / propylene copolymer (EP-4) obtained in the same manner, polypropylene F744NP (trade name, manufactured by Idemitsu Petrochemical Co., Ltd.) Name, random type, ethylene content 4%) and polypropylene E105GM (trade name, homopolymer type) manufactured by Idemitsu Petrochemical Co., Ltd. are blended at a weight ratio of 20/50/30, respectively, and further oxidized as an additive. 2000 ppm of inhibitor (Irganox 1010, manufactured by Nippon Ciba Geigy), 500 ppm of neutralizing agent (calcium stearate G, manufactured by Nippon Oil & Fats), and 500 pp of nucleating agent (ADK STAB NA-21, manufactured by Asahi Denka)
m was added, and the mixture was melted and pelletized using a twin-screw kneader (Laboplast Mill, manufactured by Toyo Seiki). Evaluation was performed in the same manner as in Example 1, and the obtained results are shown in Table 2. [Comparative Example 6] The same procedure as in Comparative Example 5 was carried out except that 6000 ppm of Pine Crystal KM1300 (manufactured by Arakawa Chemical Industries) was used instead of nucleating agent NA-21. Table 2 shows the obtained results. [Comparative Example 7] In Example 1 (2), the hydrogen partial pressure during copolymerization of ethylene / propylene was changed to 0.08 kg / cm ² G.
The procedure was performed in the same manner as in Example 1 except that Table 2 shows the obtained results.

[0069]

[Table 1]

[0070]

[Table 2]

[0071]

The propylene-based resin composition of the present invention is a material having both transparency, rigidity and low-temperature impact resistance. The contents look good as a container,
In addition, it is possible to provide a container that does not crack or tear even if dropped, immediately after being taken out of the refrigerator or in the severe winter. Alternatively, it is formed into a film or sheet and is suitable as a packaging container for foods and the like.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08K 5/10 C08K 5/10 5/521 5/521 C08L 93/04 C08L 93/04 F term (reference) 4F071 AA15X AA20X AA71 AA75X AA88X AC09 AC10 AC15 AE22 AH04 AH05 BA01 BB05 BB06 BC01 BC04 4J002 AF022 BP021 EC056 EG026 EH026 EW046 FD202 FD206

Claims (7)

[Claims] 1. A nucleating agent for the following propylene resin (A)
A propylene-based resin composition to which (B) is added. Propylene resin (A): Mainly propylene homopolymerization
Comprising propylene and propylene-ethylene copolymer
-An ethylene block copolymer, comprising the following (1) to
Satisfies the requirements of (3). (1) Elution is performed at 30 ° C or less as measured by the temperature rising fractionation method.
The amount of the component is 10 to 30% by weight of the total eluted amount,
Has an ethylene content of 10 to 25% by weight. (2) Temperature of 40 ° C. to 85 ° C. measured by a temperature rising fractionation method
The amount of components eluted in the range is 13-75% by weight of the total eluted amount
Yes (3) Elution at 103 ° C or higher obtained by the temperature rising fractionation method
Intrinsic viscosity of the component [η] ₁And obtained by elevated temperature fractionation
Intrinsic viscosity [η] of components eluted below 30 ° C_TwoThe relationship
Satisfies the following equation (1). 2. The propylene resin composition according to claim 1, wherein the amount of the component eluted at a temperature of 103 ° C. or lower of the propylene resin (A) measured by a temperature-raising fractionation method is 45 to 85% by weight of the total eluted amount. 3. The propylene resin composition according to claim 1, wherein [η] _{1 of the} propylene resin (A) is 0.7 to 6 deciliter / g. 4. The propylene-based resin composition according to claim 1, wherein the nucleating agent (B) is any of the following or a crystal nucleating agent. Crystal nucleating agent mainly composed of rosin metal salt Sorbitol-based crystal nucleating agent (a) alkali metal carboxylate, alkali metal β-
At least one diketonate or an alkali metal β-ketoacetate; and (b) the following general formula (1): (Wherein, R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ² and R ³ represent a hydrogen atom and 1 to 4 carbon atoms, respectively)
And 12 alkyl groups, cycloalkyl groups, aryl groups or aralkyl groups. M represents a metal atom or a hydrogen atom of Group 3 or 4 of the Periodic Table; X represents HO— when M represents a metal atom of Group 3 of the Periodic Table;
Represents O = or (HO) ₂ -when represents a metal atom of Group 4 of the periodic table; X does not exist when M represents a hydrogen atom; and n represents a case where M represents a hydrogen atom. Indicates 1;
A nucleating agent comprising at least one combination of a cyclic organic phosphate compound represented by formula (2): 5. The propylene resin composition according to claim 1, wherein 0.001 to 5 parts by weight of the nucleating agent (B) is added to 100 parts by weight of the propylene resin (A). . 6. A molded product obtained by molding the propylene-based resin composition according to claim 1. 7. A container obtained by blow molding the propylene-based resin composition according to claim 1.