JP6095947B2 - Polypropylene resin composition for compression molding and molded product - Google Patents

Description

  The present invention relates to a polypropylene resin composition suitable for compression molding, and a molded product obtained by compression molding the polypropylene resin composition.

  Polypropylene resin compositions based on polypropylene are inexpensive and have excellent mechanical properties, so they are used in a variety of applications and are widely used in food containers such as beverage bottles and containers. It is used. As a method for molding a polypropylene resin composition, an injection molding method, a compression molding method, or the like is used. For example, in the case of a lid for a beverage bottle, it is molded mainly by a compression molding method.

  Polypropylene-based resin compositions used for beverage bottle lids are required to have high impact strength strength in order to prevent breakage due to dropping during transportation or use. In particular, low temperature impact strength suitable for chilled distribution is required. Also, high whitening resistance is required to prevent whitening when releasing after molding and whitening when tightening the lid. Heat resistance is required when filling a bottle with a beverage at high temperature. In order to prevent the lid from expanding due to the internal pressure after filling the beverage, high rigidity is required. Further, for ease of opening the lid at the time of opening (openability), slipperiness and breakage of the bridge are required. Furthermore, in order to improve the product appearance, it is also required that defects such as stringing do not occur during compression molding.

  On the other hand, conventionally molded products that require impact strength and heat resistance, such as food containers, contain block polypropylene (reaction blend type polypropylene resin) as a main component as described in Patent Document 1. A resin composition has been used. When heat resistance is not required, a molded product obtained by compression molding high-density polyethylene as described in Patent Document 2 has been used. Further, a propylene resin composition as described in Patent Document 3 is provided as a resin composition that is excellent in closing properties, cap-opening properties, and low-temperature impact resistance when used as a cap.

  However, the resin composition described in Patent Document 1 is insufficient in whitening resistance to be applied to a beverage bottle lid, and is said to be whitened when released after compression molding or when the lid is tightened. There was a problem. The resin composition described in Patent Document 2 is excellent in whitening resistance, but has insufficient heat resistance and rigidity, and further, it has been difficult to design for weight reduction. The resin composition described in Patent Document 3 has sufficient impact resistance, but has a problem in whitening resistance.

JP 7-3087 A JP 2002-249150 A JP 2005-314474 A Special table 2009-516767 Special table 2002-542347 WO2009 / 069483 WO2009 / 057747 JP-A-2005-306910 JP 2004-131537 A

  The present invention relates to a compression-molding polypropylene-based resin composition, and a molding resin excellent in the balance of whitening resistance, low-temperature impact strength, heat resistance, rigidity, openability, and product appearance obtained by a compression molding method, and the resin. It aims at providing the molded article obtained from the composition.

The present invention
[1] A compression-based polypropylene resin composition containing a propylene-based resin and a nucleating agent,
The propylene-based resin is at least one propylene-based polymer selected from a propylene homopolymer and a propylene / ethylene copolymer having an ethylene unit content of 0.5% by weight or less, and an ethylene unit content. A reactive blend resin with 68-80 wt% ethylene-propylene copolymer;
The ethylene / propylene copolymer content is 13 to 20% by weight based on the weight of the propylene-based resin;
The intrinsic viscosity of the propylene-based resin in 135 ° C. tetrahydronaphthalene which is soluble in xylene is 1.3 to 1.9 dl / g;
The propylene-based resin has a Mw / Mn insoluble in xylene of 7 to 15;
The content of the nucleating agent is 0.01 to 2 parts by weight with respect to 100 parts by weight of the propylene-based resin; and, according to JIS K 7210, the content measured at a temperature of 230 ° C. and a load of 2.16 kg. It is a polypropylene resin composition for compression molding, wherein the melt flow rate of the resin composition is 6 to 14 g / 10 min.

Furthermore, the present invention provides
[2] A solid catalyst in which the propylene-based resin contains an electron donor compound selected from magnesium, titanium, halogen, and a succinate-based compound as an essential component;
2. The resin composition according to 1 above, produced using a catalyst comprising an organoaluminum compound; and an external electron donor compound selected from silicon compounds.
[3] The resin composition according to the above 1 or 2, wherein the propylene resin additionally contains another polymer different from the polymer constituting the propylene resin.
[4] The resin composition as described in 3 above, wherein the content of the polymer additionally contained when the polypropylene resin composition is 100% by weight is 15% by weight or less.
[5] The resin composition as described in 3 or 4 above, wherein the additional polymer is a polymer containing an ethylene unit.
[6] The above 3 wherein the melt flow rate of the polymer additionally included is 0.15 to 0.45 g / 10 min measured under the conditions of a temperature of 190 ° C. and a load of 2.16 kg in accordance with JIS K 7210. The resin composition of any one of -5.
[7] A molded product obtained by compression molding the compression-molding polypropylene resin composition described in any one of 1 to 6 above.

  The compression molding polypropylene resin composition of the present invention (hereinafter sometimes simply referred to as “resin composition” in the present specification) contains a propylene-based resin and a nucleating agent. Here, the propylene-based resin is at least one propylene-based polymer that can be selected from a homopolymer of propylene or a propylene / ethylene copolymer having an ethylene unit content of 0.5% by weight or less, and ethylene. It is a reaction blend resin with an ethylene / propylene copolymer having a unit content of 68 to 80% by weight. The ethylene / propylene copolymer having an ethylene unit content of 68 to 80 wt% contained in the propylene resin is 13 to 20 wt%, preferably 14 to 19 wt% based on the weight of the propylene resin. .

  In the resin composition of the present invention, the intrinsic viscosity in the tetrahydronaphthalene at 135 ° C. of the xylene-soluble component of the propylene-based resin is 1.3 to 1.9 dl / g, particularly 1.3 to 1.8 dl / g. It is preferable that If the intrinsic viscosity is less than the lower limit of the above range, the low-temperature impact strength tends to decrease, the slipperiness and bridge breakage of the resin composition deteriorate, and the opening property when formed into a molded product such as a cap. There is also a tendency to decrease. On the other hand, when the intrinsic viscosity exceeds the upper limit of the above range, the whitening resistance tends to decrease.

The intrinsic viscosity of the propylene-based resin in the xylene solubles is a value that greatly depends on the viscosity of the ethylene / propylene copolymer contained in the propylene-based resin.
In the resin composition of the present invention, the Mw / Mn of the xylene-insoluble portion of the propylene-based resin is preferably 7 to 15, particularly 8 to 14. When the Mw / Mn is less than the lower limit of the above range, the unsealing property or rigidity when formed into a molded product tends to be lowered. On the other hand, if the Mw / Mn exceeds the upper limit of the above range, the production of the propylene-based resin itself becomes complicated, and the appearance of the resin composition also deteriorates.

  Here, in said Mw / Mn, Mw shows a weight average molecular weight, Mn shows a number average molecular weight, and Mw / Mn shows molecular weight distribution. Mw and Mn are values in terms of polystyrene measured by gel permeation chromatography (GPC).

  Mw / Mn of the xylene-insoluble component of the propylene resin is a propylene polymer contained in the propylene resin (that is, a propylene homopolymer or a propylene / ethylene copolymer having an ethylene unit content of 0.5% by weight or less). ) Mw / Mn. Therefore, the Mw / Mn of the propylene-based polymer can be evaluated from the Mw / Mn of the xylene-insoluble matter. Mw / Mn of the propylene-based polymer can be adjusted by polymerization conditions such as the type of catalyst used for polymerization, polymerization temperature, and hydrogen concentration.

The melt flow rate (MFR) of the resin composition of the present invention is 6 to 14 g / 10 minutes, preferably 6 to 13 g / 10 minutes. If the MFR is less than the lower limit of the above range, the compression moldability tends to decrease. On the other hand, when the MFR exceeds the upper limit of the above range, the low temperature impact strength tends to decrease. Further, stringing tends to occur at the time of molding and the product appearance tends to deteriorate.
Here, MFR is a value measured in accordance with JIS K 7210 under conditions of a temperature of 230 ° C. and a load of 2.16 kg.

(Production of propylene resin)
The propylene-based resin used in the present invention is at least one propylene-based heavy polymer selected from a propylene homopolymer and a propylene / ethylene copolymer having an ethylene unit content of 0.5% by weight or less in a polymerization reactor. It is a reaction blend type polypropylene obtained by polymerizing a polymer and then polymerizing an ethylene / propylene copolymer in a polymerization reactor in which the resulting propylene-based polymer is present. Here, the ethylene / propylene copolymer is a so-called “rubber component”, and has a high ethylene unit content of 68 to 80% by weight as described above.

  When a reaction blend type polypropylene resin is obtained by polymerizing an ethylene / propylene copolymer while the propylene polymer is present in the subsequent polymerization reactor, the productivity of the propylene resin is improved, and the rubber component ethylene -The dispersibility of the propylene copolymer in the resin is improved, and the physical property balance of the resin is improved.

  The propylene-based resin can be preferably produced by a multistage polymerization method. For example, the propylene polymer is polymerized in the first stage polymerization reactor, and the propylene polymer obtained here is supplied to the second stage polymerization reactor, and the second stage polymerization reactor is supplied. Thus, a propylene-based resin can be obtained by polymerizing the ethylene / propylene copolymer. In this method, the propylene-based polymer and the produced ethylene / propylene copolymer are mixed (reaction blend) in the second-stage polymerization reactor.

In the polymerization, hydrogen can be added as necessary to adjust the molecular weight, Mw / Mn, MFR of the propylene resin, and the like.
The multistage polymerization is not limited to the above method, and the propylene polymer may be polymerized in a plurality of polymerization reactors, or the ethylene / propylene copolymer may be polymerized in a plurality of polymerization reactors.

A catalyst is usually used for the production of the propylene-based resin. As a catalyst used for the polymerization reaction, a known olefin polymerization catalyst can be used. Among them, a Ziegler-Natta catalyst is preferable because a propylene-based resin exhibiting desired physical properties can be easily produced. More preferably, at least one kind having at least one titanium-halogen bond supported on magnesium chloride (MgCl ₂ ) as shown in paragraphs [0014] to [0022] of Patent Document 4, for example. Those containing a solid catalyst component, including a titanium compound and at least one electron donor compound (internal donor). As an internal donor, the diester compound of dicarboxylic acid is mentioned, for example. The Ziegler-Natta catalyst preferably further contains an organoaluminum compound as a cocatalyst, and in some cases, preferably contains an external electron donor compound. That is, the propylene-based resin contained in the resin composition of the present invention is typically a solid catalyst containing, as an essential component, an electron donor compound selected from magnesium, titanium, halogen, and a succinate compound; an organoaluminum compound And an external electron donor compound selected from silicon compounds.

  The titanium compound used for the preparation of the solid catalyst component used in the production of the resin composition of the present invention has the general formula:

(Ｒは炭化水素基、Ｘはハロゲン、０≦g≦４)で表される４価のチタン化合物が好適である。より具体的には、ＴiＣl₄、ＴiＢr₄、ＴiＩ₄などのテトラハロゲン化チタン；Ｔi(ＯＣＨ₃)Ｃl₃、Ｔi(ＯＣ₂Ｈ₅)Ｃl₃、Ｔi(Ｏ_n−Ｃ₄Ｈ₉)Ｃl₃、Ｔi(ＯＣ₂Ｈ₅)Ｂr₃、Ｔi(ＯisoＣ₄Ｈ₉)Ｂr₃などのトリハロゲン化アルコキシチタン;Ｔi(ＯＣＨ₃)₂Ｃl₂、Ｔi(ＯＣ₂Ｈ₅)₂Ｃl₂、Ｔi(Ｏ_n−Ｃ₄Ｈ₉)₂Ｃl₂、Ｔi(ＯＣ₂Ｈ₅)₂Ｂr₂などのジハロゲン化アルコキシチタン；Ｔi(ＯＣＨ₃)₃Ｃl、Ｔi(ＯＣ₂Ｈ₅)₃Ｃl、Ｔi(Ｏ_n−Ｃ₄Ｈ₉)₃Ｃl、Ｔi(ＯＣ₂Ｈ₅)₃Ｂrなどのモノハロゲン化トリアルコキシチタン；Ｔi(ＯＣＨ₃)₄、Ｔi(ＯＣ₂Ｈ₅)₄、Ｔi(Ｏ_n−Ｃ₄Ｈ₉)₄などのテトラアルコキシチタンなどが挙げられ、これらの中で好ましいものはハロゲン含有チタン化合物、とくにテトラハロゲン化チタンであり、とくに好ましいものは、四塩化チタンである。

A tetravalent titanium compound represented by (R is a hydrocarbon group, X is a halogen, and 0 ≦ g ≦ 4) is preferable. More specifically, titanium tetrahalides such as TiCl ₄ , TiBr ₄ , TiI ₄ ; Ti (OCH ₃ ) Cl ₃ , Ti (OC ₂ H ₅ ) Cl ₃ , Ti (O _n —C ₄ H ₉ ) Cl ₃ , Ti (OC ₂ H ₅ ) Br ₃ , Ti (OisoC ₄ H ₉ ) Br ₃ and other trihalogenated alkoxytitanium; Ti (OCH ₃ ) ₂ Cl ₂ , Ti (OC ₂ H ₅ ) ₂ Cl ₂ , Ti _{(O n -C 4 H 9)} 2 Cl 2, Ti (OC 2 H 5) 2 dihalogenated alkoxy titanium such as _{Br 2; Ti (OCH 3)} 3 Cl, Ti (OC 2 H 5) 3 Cl, Ti ( _{O n -C 4 H 9) 3} Cl, Ti (OC 2 H 5) monohalide trialkoxy titanium such as _{3 Br; Ti (OCH 3)} 4, Ti (OC 2 H 5) 4, Ti (O n - C ₄ H _{9) 4} such as tetraalkoxy titanium can be mentioned, such as, preferred are halogen-containing titanium compound among these, a particularly titanium tetrahalides, particularly preferred , It is titanium tetrachloride.

  Magnesium compounds used for the preparation of the solid catalyst component used in the production of the resin composition of the present invention include magnesium compounds having magnesium / carbon bonds or magnesium / hydrogen bonds, such as dimethylmagnesium, diethylmagnesium, dipropylmagnesium, dibutylmagnesium. , Diamyl magnesium, dihexyl magnesium, didecyl magnesium, ethyl magnesium chloride, propyl magnesium chloride, butyl magnesium chloride, hexyl magnesium chloride, amyl magnesium chloride, butyl ethoxy magnesium, ethyl butyl magnesium, butyl magnesium hydride and the like. These magnesium compounds can be used, for example, in the form of a complex compound with organic aluminum or the like, and may be in a liquid state or a solid state. Further suitable magnesium compounds include magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide, magnesium fluoride; methoxy magnesium chloride, ethoxy magnesium chloride, isopropoxy magnesium chloride, butoxy magnesium chloride, octoxy magnesium chloride, and the like. Alkoxymagnesium halides; aryloxymagnesium halides such as phenoxymagnesium chloride and methylphenoxymagnesium chloride; alkoxymagnesiums such as ethoxymagnesium, isopropoxymagnesium, butoxymagnesium, n-octoxymagnesium and 2-ethylhexoxymagnesium; Allyloxymagnesium such as sigmamagnesium and dimethylphenoxymagnesium; Lau Magnesium phosphate, such as carboxylic acid salts of magnesium such as magnesium stearate and the like.

  In the present invention, it is preferable to use a solid catalyst component containing a succinic diester compound as an internal donor from the viewpoint that it is easy to obtain a resin composition having an Mw / Mn of 7 or more in the xylene-insoluble portion of the propylene-based resin. The type of internal donor used greatly affects the Mw / Mn of the resulting polymer. When a succinic acid diester compound is used as an internal donor, for example, a propylene-based polymer having a large Mw / Mn can be obtained as compared with a case where a phthalic acid diester compound which is a typical internal donor compound is used.

  Examples of the succinic acid diester compound include those shown in paragraphs [0014] to [0019] of Patent Document 4. Specific examples include compounds having a succinic diester (succinate) structure represented by the following general formula (I).

（式中、Ｒ^１及びＲ^２は、それぞれ独立に、ヘテロ原子を含んでもよい炭素数１〜２０のアルキル基、アルケニル基、シクロアルキル基、アリール基、アリールアルキル基、またはアルキルアリール基であり；Ｒ^３〜Ｒ^６は、それぞれ独立に、ヘテロ原子を含んでもよい炭素数１〜２０のアルキル基、アルケニル基、シクロアルキル基、アリール基、アリールアルキル基もしくはアルキルアリール基、または水素原子であり、Ｒ^３とＲ^４とが互いに結合して環を形成してもよく、Ｒ^５とＲ^６とが互いに結合して環を形成してもよい。）
Ｒ_１及びＲ_２は、好ましくは、Ｃ_１〜Ｃ_８のアルキル、シクロアルキル、アリール、アリールアルキル、及びアルキルアリール基である。Ｒ^１及びＲ^２が第１級アルキル、特に分岐第１級アルキルから選択される化合物が特に好ましい。好適なＲ^１及びＲ^２基の例は、メチル、エチル、ｎ−プロピル、ｎ−ブチル、イソブチル、ネオペンチル、２−エチルヘキシルである。エチル、イソブチル、及びネオペンチルが特に好ましい。

Wherein R ¹ and R ² are each independently an alkyl group having 1 to 20 carbon atoms, an alkenyl group, a cycloalkyl group, an aryl group, an arylalkyl group, or an alkylaryl group that may contain a hetero atom. Each of R ^{3 to} R ⁶ is independently an alkyl group having 1 to 20 carbon atoms, an alkenyl group, a cycloalkyl group, an aryl group, an arylalkyl group or an alkylaryl group, or a hydrogen atom, which may contain a hetero atom; R ³ and R ⁴ may be bonded to each other to form a ring, or R ⁵ and R ⁶ may be bonded to each other to form a ring.)
R ₁ and R ₂ are preferably C ₁ -C ₈ alkyl, cycloalkyl, aryl, arylalkyl, and alkylaryl groups. Particularly preferred are compounds wherein R ¹ and R ² are selected from primary alkyls, especially branched primary alkyls. Examples of suitable R ¹ and R ² groups are methyl, ethyl, n-propyl, n-butyl, isobutyl, neopentyl, 2-ethylhexyl. Ethyl, isobutyl, and neopentyl are particularly preferred.

One preferred group of compounds represented by formula (I) are branched alkyl, cycloalkyl, aryl, arylalkyl, wherein R ^{3 to} R ⁵ are hydrogen and R ⁶ has 3 to 10 carbon atoms. And an alkylaryl group. Specific examples of suitable mono-substituted succinate compounds include diethyl-sec-butyl succinate, diethyl hexyl succinate, diethyl cyclopropyl succinate, diethyl norbornyl succinate, diethyl perihydrosuccinate, diethyl trimethylsilyls. Succinate, diethyl methoxy succinate, diethyl-p-methoxyphenyl succinate, diethyl-p-chlorophenyl succinate, diethyl phenyl succinate, diethyl cyclohexyl succinate, diethyl benzyl succinate, diethyl cyclohexyl methyls Succinate, diethyl-t-butyl succinate, diethyl isobutyl succinate, diethyl isopropyl succinate, diethyl neopentyl succinate, diethyl isopentyl succinate , Diethyl (1-trifluoromethylethyl) succinate, diethyl fluorenyl succinate, 1- (ethoxycarbodiisobutylphenyl) succinate, diisobutyl-sec-butyl succinate, diisobutyl texyl succinate, diisobutyl cyclopropyl succinate , Diisobutyl norbornyl succinate, diisobutyl perhydrosuccinate, diisobutyl trimethylsilyl succinate, diisobutyl methoxy succinate, diisobutyl-p-methoxyphenyl succinate, diisobutyl-p-chlorophenyl succinate, diisobutyl cyclohexyl succinate , Diisobutyl benzyl succinate, diisobutyl cyclohexyl methyl succinate, diisobutyl-t-butyl succinate, di Sobutyl isobutyl succinate, diisobutyl isopropyl succinate, diisobutyl neopentyl succinate, diisobutyl isopentyl succinate, diisobutyl (1-trifluoromethylethyl) succinate, diisobutyl fluorenyl succinate, dineopentyl-sec-butyl Succinate, dineopentyl texyl succinate, dineopentyl cyclopropyl succinate, dineopentyl norbornyl succinate, dineopentyl perhydrosuccinate, dineopentyl trimethylsilyl succinate, dineopentyl Methoxy succinate, dineopentyl-p-methoxyphenyl succinate, dineopentyl-p-chlorophenyl succinate, dineopentyl phenyl succinate, dineopenty Lucyclohexyl succinate, dineopentyl benzyl succinate, dineopentyl cyclohexyl methyl succinate, dineopentyl-t-butyl succinate, dineopentyl isobutyl succinate, dineopentyl isopropyl succinate, dineo Pentyl neopentyl succinate, dineopentyl isopentyl succinate, dineopentyl (1-trifluoromethylethyl) succinate, dineopentyl fluorenyl succinate.

Another preferred group of compounds within the scope of formula (I) are C ₁ -C ₂₀ linear, wherein at least two groups from R ^{3 to} R ⁶ are different from hydrogen and optionally contain heteroatoms. Or a branched alkyl, alkenyl, cycloalkyl, aryl, arylalkyl, or alkylaryl group. Particularly preferred are compounds in which two groups different from hydrogen are bonded to the same carbon atom. Specific examples of suitable disubstituted succinates include diethyl-2,2-dimethyl succinate, diethyl-2-ethyl-2-methyl succinate, diethyl-2-benzyl-2-isopropyl succinate, diethyl-2 -Cyclohexylmethyl-2-isobutyl succinate, diethyl-2-cyclopentyl-2-n-propyl succinate, diethyl-2-cyclopentyl-2-n-butyl succinate, diethyl-2,2-diisobutyl succinate Diethyl-2-cyclohexyl-2-ethylsuccinate, diethyl-2-isopropyl-2-methylsuccinate, diethyl-2-tetradecyl-2-ethylsuccinate, diethyl-2-isobutyl-2-ethyls Cuccinate, diethyl-2- (1-trifluoromethylethyl) -2-methyl Succinate, diethyl-2-isopentyl-2-isobutyl succinate, diethyl-2-phenyl-2-n-butyl succinate, diisobutyl-2,2-dimethyl succinate, diisobutyl-2-ethyl-2-methyl Succinate, diisobutyl-2-benzyl-2-isopropyl succinate, diisobutyl-2-cyclohexylmethyl-2-isobutyl succinate, diisobutyl-2-cyclopentyl-2-n-propyl succinate, diisobutyl-2- Cyclopentyl-2-n-butyl succinate, diisobutyl-2,2-diisobutyl succinate, diisobutyl-2-cyclohexyl-2-ethyl succinate, diisobutyl-2-isopropyl-2-methyl succinate, diisobutyl- 2-tetradecyl-2 Ethyl succinate, diisobutyl-2-isobutyl-2-ethyl succinate, diisobutyl-2- (1-trifluoromethylethyl) -2-methyl succinate, diisobutyl-2-isopentyl-2-isobutyl succinate Diisobutyl-2-phenyl-2-n-butyl succinate, diisobutyl-2,2-diisopropyl succinate, diisobutyl-2-phenyl-2-n-propyl succinate, dineopentyl-2,2-dimethyls Succinate, dineopentyl-2-ethyl-2-methyl succinate, dineopentyl-2-benzyl-2-isopropyl succinate, dineopentyl-2-cyclohexylmethyl-2-isobutyl succinate, dineopentyl-2-cyclopentyl-2 N-propyl succinate Dineopentyl-2-cyclopentyl-2-n-butyl succinate, dineopentyl-2,2-diisobutyl succinate, dineopentyl-2-cyclohexyl-2-ethyl succinate, dineopentyl-2-isopropyl-2-methyl succinate , Dineopentyl-2-tetradecyl-2-ethylsuccinate, dineopentyl-2-isobutyl-2-ethylsuccinate, dineopentyl-2- (1-trifluoromethylethyl) -2-methylsuccinate, dineopentyl- 2,2-diisopropyl succinate, dineopentyl-2-isopentyl-2-isobutyl succinate, dineopentyl-2-phenyl-2-n-butyl succinate.

Further particularly preferred are compounds in which at least two groups different from hydrogen, ie R ³ and R ⁵ , or R ⁴ and R ⁶ are bonded to different carbon atoms. Specific examples of suitable compounds are diethyl-2,3-bis (trimethylsilyl) succinate, diethyl-2,2-sec-butyl-3-methylsuccinate, diethyl-2- (3,3,3-trifluoro Propyl) -3-methylsuccinate, diethyl-2,3-bis (2-ethylbutyl) succinate, diethyl-2,3-diethyl-2-isopropylsuccinate, diethyl-2,3-diisopropyl-2-methyl Succinate, diethyl-2,3-dicyclohexyl-2-methylsuccinate, diethyl-2,3-dibenzylsuccinate, diethyl-2,3-diisopropylsuccinate, diethyl-2,3-bis ( (Cyclohexylmethyl) succinate, diethyl-2,3-di-t-butylsuccinate, diethyl-2,3-diisobu Rusuccinate, diethyl-2,3-dineopentyl succinate, diethyl-2,3-diisopentyl succinate, diethyl-2,3- (1-trifluoromethylethyl) succinate, diethyl-2,3- Tetradecyl succinate, diethyl-2,3-fluorenyl succinate, diethyl-2-isopropyl-3-isobutyl succinate, diethyl-2-tert-butyl-3-isopropyl succinate, diethyl-2- Isopropyl-3-cyclohexyl succinate, diethyl-2-isopentyl-3-cyclohexyl succinate, diethyl-2-tetradecyl-3-cyclohexylmethyl succinate, diethyl-2-cyclohexyl-3-cyclopentyl succinate, diethyl -2,2,3,3-tetramethylsk , Diethyl-2,2,3,3-tetraethylsuccinate, diethyl-2,2,3,3-tetrapropylsuccinate, diethyl-2,3-diethyl-2,3-diisopropylsuccinate, Diisobutyl-2,3-bis (trimethylsilyl) succinate, diisobutyl-2,2-sec-butyl-3-methylsuccinate, diisobutyl-2- (3,3,3-trifluoropropyl) -3-methylsuccinate , Diisobutyl-2,3-bis (2-ethylbutyl) succinate, diisobutyl-2,3-diethyl-2-isopropyl succinate, diisobutyl-2,3-diisopropyl-2-methyl succinate, diisobutyl-2, 3-dicyclohexyl-2-methyl succinate, diisobutyl-2,3-dibenzyl succinate, dii Butyl-2,3-diisopropyl succinate, diisobutyl-2,3-bis (cyclohexylmethyl) succinate, diisobutyl-2,3-di-t-butyl succinate, diisobutyl-2,3-diisobutyl succinate, Diisobutyl-2,3-dineopentyl succinate, diisobutyl-2,3-diisopentyl succinate, diisobutyl-2,3- (1-trifluoromethylethyl) succinate, diisobutyl-2,3-n- Propyl succinate, diisobutyl-2,3-tetradecyl succinate, diisobutyl-2,3-fluorenyl succinate, diisobutyl-2-isopropyl-3-isobutyl succinate, diisobutyl-2-tert-butyl- 3-isopropyl succinate, diisobutyl-2-iso Propyl-3-cyclohexyl succinate, diisobutyl-2-isopentyl-3-cyclohexyl succinate, diisobutyl-2-n-propyl-3- (cyclohexylmethyl) succinate, diisobutyl-2-tetradecyl-3-cyclohexylmethyl succinate , Diisobutyl-2,2,3,3-tetramethyl succinate, diisobutyl-2,2,3,3-tetraethyl succinate, diisobutyl-2,2,3,3-tetrapropyl succinate, diisobutyl -2,3-diethyl-2,3-diisopropyl succinate, diisobutyl-2-cyclohexyl-3-cyclopentyl succinate, dineopentyl-2,3-bis (trimethylsilyl) succinate, dineopentyl-2,2-sec-butyl -3-Methyls Xinate, dineopentyl-2- (3,3,3-trifluoropropyl) -3-methylsuccinate, dineopentyl-2,3-bis (2-ethylbutyl) succinate, dineopentyl-2,3-diethyl-2-isopropyl Succinate, dineopentyl-2,3-diisopropyl-2-methyl succinate, dineopentyl-2,3-dicyclohexyl-2-methyl succinate, dineopentyl-2,3-dibenzyl succinate, dineopentyl-2, 3-diisopropyl succinate, dineopentyl-2,3-bis (cyclohexylmethyl) succinate, dineopentyl-2,3-di-t-butyl succinate, dineopentyl-2,3-diisobutyl succinate, dineopentyl-2, 3-Dineopentyl succine Dineopentyl-2,3-diisopentyl succinate, dineopentyl-2,3- (1-trifluoromethylethyl) succinate, dineopentyl-2,3-dineopentyl succinate, dineopentyl-2,3-di Isopentyl succinate, dineopentyl-2,3-tetradecyl succinate, dineopentyl-2,3-fluorenyl succinate, dineopentyl-2-isopropyl-3-isobutyl succinate, dineopentyl-2-tert-butyl -3-isopropylsuccinate, dineopentyl-2-isopropyl-3-cyclohexyl succinate, dineopentyl-2-isopentyl-3-cyclohexyl succinate, dineopentyl-2-tetradecyl-3-cyclohexylmethyl succinate, di Opentyl-2-n-propyl-3- (cyclohexylmethyl) succinate, dineopentyl-2-cyclohexyl-3-cyclopentyl succinate, dineopentyl-2,2,3,3-tetraethylsuccinate, dineopentyl-2,2, 3,3-tetrapropyl succinate, dineopentyl-2,3-diethyl-2,3-diisopropyl succinate.

Among the compounds of formula I, compounds in which some of the groups R ^{3 to} R ⁶ are bonded together to form a ring can also be preferably used. Examples of such compounds include those listed in Patent Document 5, such as 1- (ethoxycarbonyl) -1- (ethoxyacetyl) -2,6-dimethylcyclohexane, 1- (ethoxycarbonyl) -1- (ethoxyacetyl). ) -2,5-dimethylcyclopentane, 1- (ethoxycarbonyl) -1- (ethoxyacetylmethyl) -2-methylcyclohexane, 1- (ethoxycarbonyl) -1- (ethoxy (cyclohexyl) acetyl) cyclohexane Can do. In addition, for example, a cyclic succinate compound as disclosed in Patent Document 6 can also be suitably used. As an example of another cyclic succinate compound, a compound disclosed in Patent Document 7 is also preferable. Also, among the compounds of formula I, when the groups R ^{3 to} R ⁶ contain heteroatoms, the heteroatoms may be group 15 atoms including nitrogen and phosphorus atoms or group 16 atoms including oxygen and sulfur atoms. preferable. Examples of the compound in which the groups R ^{3 to} R ⁶ include a Group 15 atom include compounds disclosed in Patent Document 8. On the other hand, examples of the compound in which the groups R ^{3 to} R ⁶ include a Group 16 atom include a compound disclosed in Patent Document 9.

  Examples of the halogen atom constituting the solid catalyst component used for the production of the propylene resin composition of the present invention include fluorine, chlorine, bromine, iodine or a mixture thereof, and chlorine is particularly preferable.

Examples of the organoaluminum compound used in the production of the propylene resin composition of the present invention include trialkylaluminum such as triethylaluminum and tributylaluminum, trialkenylaluminum such as triisoprenylaluminum, diethylaluminum ethoxide, and dibutylaluminum butoxide. In addition to alkylaluminum sesquialkoxides such as dialkylaluminum alkoxide, ethylaluminum sesquiethoxide, and butylaluminum sesquibutoxide, a portion having an average composition represented by a general formula such as R ¹ _2.5 Al (OR ² ) _0.5 Such as partially alkoxylated alkyl aluminum, diethyl aluminum chloride, dibutyl aluminum chloride, diethyl aluminum bromide Alkyl aluminum halogenides, ethyl aluminum sesquichloride, butyl aluminum sesquichloride, alkyl aluminum sesquihalides such as ethyl aluminum sesquibromide, alkyl aluminum dihalogenides such as ethyl aluminum dichloride, propyl aluminum dichloride, butyl aluminum dibromide, etc. Partially hydrogenated alkylaluminums such as alkyl aluminum dihydrides such as partially halogenated alkylaluminum, diethylaluminum hydride, dibutylaluminum hydride, ethylaluminum dihydride, propylaluminum dihydride , Ethyl aluminum ethoxy chloride, butyl aluminum butoxy Chloride, may be selected from partially alkoxylated and halogenated alkylaluminum such as ethyl aluminum ethoxy bromide.

  The electron donor compound used in the production of the propylene resin composition of the present invention is generally referred to as “external electron donor”. As such an electron donor compound, an organosilicon compound is preferably used. Preferred organosilicon compounds include, for example, trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diisopropyldimethoxysilane, t-butylmethyldimethoxysilane, t-butylmethyldiethoxysilane, and t-amylmethyldiethoxy. Silane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, diphenyldiethoxysilane, bis-o-tolyldimethoxysilane, bis-m-tolyldimethoxysilane, bis-p-tolyldimethoxysilane, bis-p-tolyldiethoxysilane, bis Ethylphenyldimethoxysilane, dicyclopentyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxy Lan, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, methyltrimethoxysilane, n-propyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, phenyltrimethoxysilane, γ-chloropropyltrimethoxy Silane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, t-butyltriethoxysilane, texyltrimethoxysilane, n-butyltriethoxysilane, iso-butyltriethoxysilane, phenyltriethoxysilane, γ -Aminopropyltriethoxysilane, chlorotriethoxysilane, ethyltriisopropoxysilane, vinyltributoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane 2-norbornanetrimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane, ethyl silicate, butyl silicate, trimethylphenoxysilane, methyltriallyloxysilane, vinyltris (β-methoxyethoxysilane) , Vinyltriacetoxysilane, dimethyltetraethoxydisiloxane, etc., among others, ethyltriethoxysilane, n-propyltriethoxysilane, t-butyltriethoxysilane, texyltrimethoxysilane, vinyltriethoxysilane, phenyltriethoxy Silane, vinyltributoxysilane, diphenyldimethoxysilane, diisopropyldimethoxysilane, dicyclopentyldimethoxysilane, cyclohexylmethyldimethoxysilane, phenylmethyl Dimethoxysilane, bis p-tolyldimethoxysilane, p-tolylmethyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, 2-nonebornanetriethoxysilane, 2-norbornanemethyldimethoxysilane, diphenyldiethoxysilane, ethyl silicate Etc. are preferable.

  As another method for obtaining a resin composition in which Mw / Mn of a propylene-based resin insoluble in xylene is 7 or more, polymerization of a propylene-based polymer is performed using two or more polymerization reactors. And a method of changing the hydrogen concentration during polymerization. When the hydrogen concentration in the polymerization reactor during polymerization is changed, the molecular weight of the resulting propylene polymer changes. For example, when two polymerization reactors are used as an example, the second stage polymerization reactor is made to have a higher hydrogen supply amount than the first stage polymerization reactor, thereby increasing the second stage polymerization reactor. The molecular weight of the polypropylene polymer produced in the polymerization reactor is small. Therefore, the greater the difference in hydrogen concentration between the plurality of polymerization reactors, the greater the Mw / Mn of the resulting propylene polymer, and the greater the Mw / Mn of the xylene-insoluble portion of the resin composition. This method is also preferable in that Mw / Mn of xylene-insoluble matter can be finely adjusted.

As yet another method for obtaining a resin composition in which the Mw / Mn of the xylene-insoluble component of the propylene-based resin is 7 or more, there is a method of using a polymerizer having a monomer concentration or a gradient of polymerization conditions. In such a polymerization vessel, for example, a monomer in which at least two polymerization regions are connected can be used, and the monomer can be polymerized by gas phase polymerization. Specifically, in the presence of a catalyst, a monomer is supplied and polymerized in a polymerization region including a riser, and a monomer is supplied and polymerized in a downcomer connected to the riser. The polymer product is recovered while circulating. This method comprises means for completely or partially preventing the gas mixture present in the riser from entering the downcomer. Also, a gas and / or liquid mixture having a different composition from the gas mixture present in the riser is introduced into the downcomer.
As the above polymerization method, for example, the method described in JP-T-2002-520426 can be applied.

  The ethylene unit content in the propylene polymer in the resin composition is preferably 0 to 0.5% by weight, particularly preferably 0 to 0.3% by weight. If the ethylene unit content in the propylene polymer exceeds the upper limit of the above range, the rigidity tends to decrease. When the ethylene unit content is 0% by weight, it means that the propylene polymer is a homopolymer of propylene, and when the ethylene unit content is more than 0% by weight, the propylene polymer is propylene. -Means an ethylene copolymer.

  The ethylene unit content in the ethylene / propylene copolymer is 68 to 80% by weight, and particularly preferably 70 to 78% by weight. If the ethylene unit content in the ethylene / propylene copolymer exceeds the upper limit of the above range, the low temperature impact strength of the resin composition tends to decrease, and if it is less than the lower limit of the above range, the resistance of the resin composition. There is a tendency for the whitening property to decrease.

The propylene-based resin in the resin composition of the present invention contains an ethylene / propylene copolymer that is a rubber component. The content of the ethylene / propylene copolymer is preferably 13 to 20% by weight, particularly preferably 14 to 19% by weight, when the resin composition is 100% by weight. When the content of the ethylene / propylene copolymer that is a rubber component exceeds the upper limit of the above range, the rigidity of the molded product obtained from the resin composition tends to decrease, and when it is less than the lower limit of the above range, There exists a tendency for the low-temperature impact strength of the molded article obtained from a resin composition to fall.
(Nucleating agent)
The nucleating agent promotes the formation of polypropylene crystal nuclei and improves the crystallinity of the resulting resin composition. By containing the nucleating agent, the rigidity of the molded product obtained from the resin composition is improved. Specific examples of the nucleating agent include sorbitol compounds, metal salts of carboxylic acids, aromatic phosphate ester compounds, silica, talc, mica and the like. In terms of low odor, an aromatic phosphate ester compound is preferable.

  Examples of the sorbitol compound include dibenzylidene sorbitol, 1,3,2,4-di- (methylbenzylidene) sorbitol, 1,3,2,4- (ethylbenzylidene) sorbitol, 1,3,2,4- (Methoxybenzylidene) sorbitol, 1,3,2,4- (ethoxybenzylidene) sorbitol, 1,2,3-trideoxy-4,6-5,7-bis-o-[(4-propylphenyl) methylene] nonitol Etc.

  Examples of the metal salt of carboxylic acid include sodium adipate, potassium adipate, aluminum adipate, sodium sebacate, potassium sebacate, aluminum sebacate, sodium benzoate, aluminum benzoate, and di-para-t-butylbenzoate. Examples thereof include aluminum oxide, titanium di-para-t-butylbenzoate, chromium di-para-t-butylbenzoate, and aluminum hydroxy-di-t-butylbenzoate.

  Examples of the aromatic phosphate compound include phosphoric acid-2,2′-methylenebis (4,6-di-tert-butylphenyl) sodium, aluminum-bis (4,4 ′, 6,6′-tetra). -Tert-butyl-2,2'-methylenediphenyl-phosphate) -hydroxide and the like. Moreover, a triaminobenzene derivative can be used as a nucleating agent.

  The content of the nucleating agent is preferably 0.01 to 2 parts by weight with respect to 100 parts by weight of the propylene-based resin. If the content of the nucleating agent is not less than the lower limit of the above range, the rigidity of the molded product obtained from the resin composition can be further increased, and if it is not more than the upper limit, the odor caused by the nucleating agent is suppressed. be able to. When using a triaminobenzene derivative as a nucleating agent, it is preferable to mix 0.01-0.02 weight part with respect to 100 weight part of propylene-type resin. When using talc as a nucleating agent, it is more preferable to mix 0.3-2 weight part with respect to 100 weight part of propylene-type resin. When using a nucleating agent other than the triaminobenzene derivative and talc, 0.1 to 0.4 parts by weight of the nucleating agent can be mixed with 100 parts by weight of the propylene-based resin. A nucleating agent can be used individually by 1 type, or can also combine 2 or more types.

(Other polymers)
If necessary, the resin composition of the present invention may additionally contain another polymer different from the polymer constituting the propylene-based resin as long as the effects of the present invention are not impaired. As other polymers, known thermoplastic resins or thermosetting resins can be used. Examples of the thermoplastic resin include ethylene or an α-olefin homopolymer having 4 to 10 carbon atoms, a copolymer of ethylene or an α-olefin having 3 to 10 carbon atoms (which may include a diene), a mixture thereof, Examples include nylon, polycarbonate, polyphenylene oxide, and petroleum resin. Specific examples of the ethylene or α-olefin homopolymer having 4 to 10 carbon atoms include high-density polyethylene, low-density polyethylene, poly-1-butene, poly-1-pentene, poly-1-hexene, and poly (3 -Methyl-1-pentene), poly (3-methyl-1-butene), poly (4-methyl-1-pentene), poly-1-hexene, poly-1-heptene, poly-1-octene, poly Examples include -1-decene, polystyrene, and combinations thereof. Examples of the ethylene-based random copolymer include an ethylene / propylene copolymer, an ethylene / propylene / diene copolymer, an ethylene / (1-) butene copolymer, an ethylene / (1-) pentene copolymer, an ethylene / ( Examples include 1-) hexene copolymer, ethylene / (1-) octene copolymer, ethylene / (1-) decene copolymer, and combinations thereof. Block copolymers include styrene / ethylene / butylene / styrene block copolymers, styrene / ethylene / propylene / styrene block copolymers, styrene / butadiene / styrene block copolymers, and styrene / isoprene / styrene block copolymers. , Ethylene / ethylene / butylene / ethylene block copolymers and combinations thereof. In the case of a mixture of two or more polymers, different types of polymers such as a random copolymer and a block copolymer may be combined. Among these, it is very preferable to use a polymer containing an ethylene unit. The other polymer additionally contained has a melt flow rate value of 0.15 to 0.45 g / 10 minutes measured under the conditions of a temperature of 190 ° C. and a load of 2.16 kg according to JIS K 7210. In this case, when the additionally contained polymer is a mixture of two or more kinds of polymers, the melt flow rate value of the mixture is in the above range. Moreover, content of the other polymer contained in addition is 0 to 15 weight% with respect to propylene-type resin, Preferably it is 1 to 15 weight%.

(Additive)
If necessary, the resin composition of the present invention may contain an additive as long as the effects of the present invention are not impaired. Examples of additives include antioxidants, hydrochloric acid absorbers, heat stabilizers, light stabilizers, UV absorbers, internal lubricants, external lubricants, antistatic agents, flame retardants, dispersants, copper damage inhibitors, and neutralization. Agents, plasticizers, foaming agents, anti-bubble agents, crosslinking agents, peroxides, pigments and the like. Examples of pigments include colored pigments (inorganic pigments such as titanium oxide, bengara, yellow lead, ultramarine, bitumen, and carbon black; organic pigments such as azo lake insoluble azo, condensed azo, anthraquinone, quinacridone, and phthalocyanine; aluminum flakes, glass flakes, etc. Flake pigments), extender pigments (kaolin, clay, calcium carbonate, barium sulfate, etc.), functional pigments (rust preventive pigments, fluorescent pigments, temperature pigments, photocatalyst pigments, lubricating pigments, etc.) and the like.

  The resin composition of the present invention comprises a propylene-based resin, a nucleating agent, and, if necessary, other polymers and additives, and then a single screw extruder, a twin screw extruder, a Banbury mixer, a kneader. It can be produced by melt kneading using a known kneader such as a roll mill.

(Molding)
The resin composition of the present invention is processed into a molded product by compression molding. The conditions for compression molding are not particularly limited, and may be the same as those conventionally used for molding a polypropylene resin composition. The shape and size of the target molded product and the type of compression molding machine to be used. It is appropriately selected depending on the scale.

  The polypropylene resin composition for compression molding of the present invention is suitable for compression molding, and the molded product obtained by compression molding the compression molding polypropylene resin composition has whitening resistance, low temperature impact strength, heat resistance. , Excellent balance of rigidity, openability and product appearance. The molded product of the present invention can be used for food containers, lids, containers, and the like, and can be suitably used particularly for beverage bottle lids.

The propylene-based resin composition of the present invention can be produced by appropriately combining conventional methods. The propylene resin constituting the propylene resin composition of the present invention can be preferably produced by a multistage polymerization method. For example, it can be produced by the following method:
First, an appropriate solid catalyst, an organoaluminum compound (for example, triethylaluminum), and an external donor (for example, a silane compound such as dicyclopentyldimethoxysilane) are contacted at a suitable ratio. At this time, the weight ratio (TEAL / DCPMS) of triethylaluminum (hereinafter sometimes referred to as “TEAL”) and dicyclopentyldimethoxysilane (hereinafter sometimes referred to as “DCPMS”) is preferably 0. .5 to 40, more preferably 1.0 to 20. The resulting solid catalyst system is then suspended in liquid propylene and prepolymerized. The obtained prepolymer is introduced into the first stage (previous stage) of a polymerization reactor arranged in series, and further propylene (and ethylene) is introduced to produce a propylene polymer (propylene homopolymer or propylene / ethylene). Copolymer). Here, when producing a propylene / ethylene copolymer, the concentration of ethylene introduced into the polymerization reactor is 0.01 to 0.12 mol%, preferably 0.02 to 0.10 mol%. The obtained propylene-based polymer is supplied to a second-stage (rear-stage) polymerization reactor, and ethylene and propylene are introduced therein to polymerize the ethylene / propylene copolymer. The ratio of the molar amount of ethylene introduced into the second stage polymerization reactor to the total molar amount of propylene and ethylene is 52 to 78%, preferably 54 to 76%. Thus, the reaction blend type propylene resin of the present invention can be obtained by the multistage polymerization method. Even without using a multistage polymerization reactor arranged in series, a plurality of polymerization reactors can be prepared and the polymerization reaction can be carried out sequentially. Moreover, you may perform the polymerization reaction of a 1st step and a 2nd step in multiple times, respectively. In each polymerization reaction step, hydrogen may be introduced for the purpose of adjusting the molecular weight, Mw / Mn, or MFR of the propylene-based resin.

  Subsequently, a suitable nucleating agent is kneaded into the obtained propylene-based resin. A known kneader such as a single screw extruder, a twin screw extruder, a Banbury mixer, a kneader, a roll mill, and the like, containing a propylene resin and a nucleating agent, and if necessary, other polymers and additives in an appropriate ratio. Can be used for melt kneading. The mixing ratio of the nucleating agent with respect to 100 parts by weight of the propylene-based resin is 0.01 to 2 parts by weight, preferably 0.1 to 1.5 parts by weight.

  Furthermore, you may add another suitable polymer to the obtained propylene-type resin by said polymerization reaction process and / or melt-kneading. The blending ratio of the other polymer to the propylene resin is preferably 15% by weight or less.

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to the examples.
[Example 1]
The solid catalyst used for polymerization was prepared by the method described in Example 1 of Patent Document 4 (Japanese translations of PCT publication No. 2009-516767). A specific manufacturing method is as follows: 250 mL of TiCl ₄ was introduced at 0 ° C. into a 500 mL four-necked round bottom flask purged with nitrogen. While stirring, 10.0 g of fine spherical MgCl ₂ .1.8C ₂ H ₅ OH (prepared according to the method described in Example 2 of USP 4,399,054 but operating at 3000 rpm instead of 10000 rpm) , And 9.1 mmol of diethyl 2,3- (diisopropyl) succinate. The temperature was raised to 100 ° C. and held for 120 minutes. Next, stirring was stopped, the solid product was allowed to settle, and the supernatant liquid was siphoned off. The following procedure was then repeated twice: 250 mL of fresh TiCl ₄ was added and the mixture was allowed to react at 120 ° C. for 60 minutes and the supernatant liquid was siphoned off. The solid was washed 6 times with anhydrous hexane (6 × 100 mL) at 60 ° C. Thus, a solid catalyst in which Ti and diethyl 2,3- (diisopropyl) succinate as an internal donor were supported on MgCl ₂ was obtained.

  The solid catalyst and triethylaluminum (TEAL) and dicyclopentyldimethoxysilane (DCPMS) are mixed in an amount such that the weight ratio of TEAL to the solid catalyst is 11 and the weight ratio of TEAL / DCPMS is 3 at 12 ° C. Contacted for 24 minutes. The resulting catalyst system was prepolymerized by holding it in liquid propylene in suspension for 5 minutes at 20 ° C.

  The obtained prepolymer was introduced into a previous polymerization reactor of a polymerization apparatus equipped with a two-stage polymerization reactor in series to polymerize a propylene polymer (propylene homopolymer). The obtained propylene homopolymer was supplied to the subsequent polymerization reactor, and the ethylene / propylene copolymer was polymerized in the subsequent polymerization reactor. At that time, the amount of hydrogen supplied to each polymerization reactor shown in Table 1 (molecular weight, used for the purpose of MFR adjustment), the amount of ethylene supplied to the subsequent polymerization reactor, the polymerization temperature, the polymerization pressure, the previous stage By adjusting the residence time in the latter stage, the propylene-based resin of Example 1 shown in the table was obtained.

To the resulting propylene resin, an aromatic phosphoric acid ester compound (ADEKA Corporation NA-18) and talc (Neoraito Kosan Co. Neotaruku UNI05) incorporated into the propylene resin as a nucleating agent, an extruder It was melt kneaded at 230 ° C. to obtain a resin composition. The nucleating agent was blended so that NA-18 was 0.2 parts by weight and talc was 1.0 parts by weight with respect to 100 parts by weight of the resin composition.

[Examples 2 to 7]
In Example 2, the propylene-based resin shown in the table was obtained in the same manner as in Example 1 except that the hydrogen concentrations in the polymerization reactors in the former stage and the latter stage were changed as shown in Table 1.
In Example 3, the propylene-based resin shown in the table was obtained in the same manner as in Example 1 except that the hydrogen concentrations in the polymerization reactors in the former stage and the latter stage were changed as shown in Table 1.
In Example 4, the hydrogen concentration of the former polymerization reactor was changed as shown in Table 1, and the residence time of the latter polymerization reactor was relatively increased as compared to the residence time of the former polymerization reactor. A propylene-based resin shown in the table was obtained in the same manner as in Example 1 except that.
Example 5 is a propylene-based resin shown in the table in the same manner as in Example 1 except that the hydrogen concentrations in the former and subsequent polymerization reactors and the ethylene concentration in the latter polymerization reactor were changed as shown in Table 1. Got.
In Example 6, while changing the hydrogen concentration of the former polymerization reactor as shown in Table 1, the residence time of the latter polymerization reactor was relatively increased as compared with the residence time of the former polymerization reactor. The propylene-based resin shown in the table was obtained in the same manner as in Example 1 except that it was obtained. After that, as an additional polymer, high molecular weight high density polyethylene (HDPE) (trade name: Novatec HB130R (manufactured by Nippon Polyethylene Co., Ltd.)) and hydrogenated styrene thermoplastic elastomer (styrene / ethylene / butylene / styrene block) Polymer, SEBS) (trade name: Tuftec H1062 (manufactured by Asahi Kasei Chemicals Corporation) was blended in an amount of 7% by weight and 3% by weight, respectively, with respect to the propylene resin.
In Example 7, an ethylene / 1-butene copolymer (EBR) (trade name: Engage HM7487 (manufactured by Dow Chemical Japan Co., Ltd.)) is added as an additional polymer to the propylene resin of Example 6, respectively. 10 weight% was mix | blended with respect to the propylene-type resin.
To the resulting propylene resin, an aromatic phosphoric acid ester compound as well as nucleating agent as in Example 1 (ADEKA Corporation NA-18) and talc (Neoraito Kosan Co. Neotaruku UNI05) in the propylene resin The mixture was melted and kneaded at 230 ° C. using an extruder to obtain a resin composition. The nucleating agent was blended so that NA-18 was 0.2 parts by weight and talc was 1.0 parts by weight with respect to 100 parts by weight of the resin composition.

[Comparative Examples 1-2]
Prepolymerization was carried out in substantially the same manner as in Example 1 using a phthalate-based solid catalyst. A method for producing a phthalate-based solid catalyst was prepared by a method described in European Patent No. 6749991. Specifically, 48 g of anhydrous magnesium chloride, 77 g of anhydrous ethyl alcohol and 830 mL of kerosene were introduced into a 2 liter autoclave equipped with a turbine stirrer and a drawing tube at room temperature under an inert gas. The contents of the autoclave were heated to 120 ° C. with stirring, thus producing an adduct between MgCl ₂ and the alcohol, which melted and remained dispersed in kerosene. A nitrogen pressure of 15 atmospheres is maintained in the autoclave. The autoclave drawing tube was externally heated to 120 ° C. by a heating jacket, and the heating jacket had an inner diameter of 1 mm and was 3 m from one end to the other end of the heating jacket. The dispersion was then flowed through the tube at a speed of about 7 m / sec. At the outlet of the tube, the dispersion was collected in a 5 liter flask under stirring (the flask was externally cooled with a jacket containing 2.5 liters of kerosene and maintained at an initial temperature of −40 ° C.). . The final temperature of the dispersion is 0 ° C. The spherical solid product constituting the dispersed phase of the dispersion was allowed to settle, then filtered and the solid was separated by washing with an aliquot of hexane and then drying. All these steps were performed in a nitrogen gas atmosphere. 130 g of MgCl ₂ .3C ₂ H ₅ OH adduct in the form of solid spherical particles with a maximum diameter of less than 50 μm were obtained. The solid adduct was dried under vacuum for 2 hours and 105 g after drying was complete. The solid product was heated to a temperature of about 60 ° C. in a stream of nitrogen to partially remove the alcohol from the adduct, thereby obtaining a MgCl ₂ .2.1C ₂ H ₅ OH adduct. This adduct is then used to prepare a solid catalyst component as follows. Into a 1 liter glass flask equipped with a condenser, a mechanical stirrer and a thermometer, 625 mL of TiCl ₄ and then 25 g of MgCl ₂ .2.1C ₂ H ₅ OH adduct were introduced with stirring at 0 ° C. in an anhydrous nitrogen atmosphere. did. The contents of the flask were heated to 100 ° C. in 1 hour. When the temperature reached 40 ° C., 9 mmol of diisobutyl phthalate were introduced into the flask. After maintaining the temperature at 100 ° C. for 2 hours, the contents were allowed to settle and then the liquid was siphoned off. 550 mL of TiCl ₄ was added and heated to 120 ° C. for 1 hour. The contents were then allowed to settle and the liquid was siphoned off. The solid residue was then washed 6 times with 200 cc of anhydrous hexane at 60 ° C. and 3 times at room temperature to obtain a solid catalyst component. The solid catalyst was contacted with TEAL and DCPMS in an amount such that the weight ratio of TEAL to the solid catalyst was 18 and the weight ratio of TEAL / DCPMS was 10 at room temperature for 5 minutes. The resulting catalyst system was prepolymerized by holding it in liquid propylene in suspension for 5 minutes at 20 ° C.
The obtained prepolymer was introduced into a polymerization reactor in the previous stage of a polymerization apparatus equipped with a two-stage polymerization reactor in series to polymerize the propylene homopolymer. The propylene polymer was supplied to a subsequent polymerization reactor, and the ethylene / propylene copolymer was polymerized in the subsequent polymerization reactor. At that time, ethylene supply amount and hydrogen supply amount to each polymerization reactor shown in Table 2 (molecular weight, used for the purpose of MFR adjustment), polymerization temperature, polymerization pressure, residence time in the first and second stages should be adjusted. The propylene-based resin shown in the table was obtained. In Comparative Examples 1 and 2, the ethylene concentration in the ethylene / propylene copolymer, the intrinsic viscosity of the xylene-soluble component, and the molecular weight distribution of the xylene-insoluble component did not satisfy the scope of the present invention.
To the resulting propylene resin, an aromatic phosphoric acid ester compound is further blended (ADEKA Corporation NA-18) and talc (Neoraito Kosan Co. Neotaruku UNI05) as nucleating agent, 230 ° C. using an extruder And kneaded to obtain a resin composition. The nucleating agent was blended so that NA-18 was 0.2 parts by weight and talc was 1.0 parts by weight with respect to 100 parts by weight of the resin composition.

[Comparative Examples 3 to 4]
Prepolymerization was performed in the same manner as in Example 1 using the same solid catalyst as in Example 1. A propylene polymer (propylene homopolymer) was polymerized by introducing it into a polymerization reactor in the previous stage of a polymerization apparatus equipped with a two-stage polymerization reactor in series. The obtained propylene homopolymer was supplied to the subsequent polymerization reactor, and the ethylene / propylene copolymer was polymerized in the subsequent polymerization reactor. At that time, ethylene supply amount and hydrogen supply amount to each polymerization reactor shown in Table 2 (molecular weight, used for the purpose of MFR adjustment), polymerization temperature, polymerization pressure, residence time in the first and second stages should be adjusted. The propylene-based resin shown in the table was obtained.
To the resulting propylene resin, an aromatic phosphoric acid ester compound is further blended (ADEKA Corporation NA-18) and talc (Neoraito Kosan Co. Neotaruku UNI05) as nucleating agent, 230 ° C. using an extruder And kneaded to obtain a resin composition. The nucleating agent was blended so that NA-18 was 0.2 parts by weight and talc was 1.0 parts by weight with respect to 100 parts by weight of the resin composition.
In Comparative Example 3, the hydrogen concentration in the preceding and subsequent polymerization reactors and the ethylene concentration in the subsequent polymerization reactor were changed as shown in Table 2 from Example 1, and the residence time of the subsequent polymerization reactor was changed. The retention time of the polymerization reactor in the previous stage is relatively increased, and the ethylene concentration in the ethylene / propylene copolymer, the ethylene / propylene copolymer content, and the MFR of the composition are within the scope of the present invention. The thing which does not enter was manufactured. In Comparative Example 4, the polymerization conditions (particularly the hydrogen concentration of the polymerization reactor in the latter stage) were changed as shown in Table 2 from Example 1, and the intrinsic viscosity of the xylene-soluble component of the propylene-based resin was within the scope of the present invention. The thing which does not enter was manufactured.

[Comparative Example 5]
Prepolymerization was performed in the same manner as in Example 1 using the same solid catalyst as in Example 1. A propylene polymer (propylene homopolymer) was polymerized by introducing it into a polymerization reactor in the previous stage of a polymerization apparatus equipped with a two-stage polymerization reactor in series. The obtained propylene homopolymer was supplied to the subsequent polymerization reactor, and the ethylene / propylene copolymer was polymerized in the subsequent polymerization reactor. At that time, by adjusting the ethylene supply amount and hydrogen supply amount to each polymerization reactor shown in Table 2 (molecular weight, used for the purpose of MFR adjustment), the polymerization temperature, the polymerization pressure, the residence time of the former stage and the latter stage, Propylene-based resins shown in the table were obtained.
Comparative Example 5 is a resin composition that does not contain a nucleating agent.

[Comparative Example 6]
Prepolymerization was performed in the same manner as in Example 1 using the same solid catalyst as in Example 1. A propylene polymer (propylene homopolymer) was polymerized by introducing it into a polymerization reactor in the previous stage of a polymerization apparatus equipped with a two-stage polymerization reactor in series. The obtained propylene homopolymer was supplied to the subsequent polymerization reactor, and the ethylene / propylene copolymer was polymerized in the subsequent polymerization reactor. At that time, the ethylene supply amount and hydrogen supply amount to each polymerization reactor shown in Table 2 (molecular weight, used for the purpose of MFR adjustment), the residence time of the subsequent polymerization reactor are set to the residence time of the previous polymerization reactor. By adjusting the ratio, polymerization temperature, and polymerization pressure, the propylene-based resin shown in the table was obtained.
In Comparative Example 6, in particular, the hydrogen concentration in the polymerization reactor in the previous stage was reduced as shown in Table 2 from Example 1, and a resin composition having an MFR not falling within the scope of the present invention was produced.

[Comparative Example 7]
Prepolymerization was performed in the same manner as in Example 1 using the same solid catalyst as in Example 1. Propylene-based polymer (propylene / ethylene copolymer) was polymerized by introducing 0.17 mol% of ethylene together with propylene into the polymerization reactor in the previous stage of the polymerization apparatus equipped with two stages of polymerization reactors in series. The obtained propylene / ethylene copolymer was supplied to a subsequent polymerization reactor, and the ethylene / propylene copolymer was polymerized in the subsequent polymerization reactor. At that time, a propylene-based resin shown in the table was obtained in the same manner as in Example 1 except that the hydrogen concentration in the subsequent polymerization reactor shown in Table 2 was changed.
To the resulting propylene resin, an aromatic phosphoric acid ester compound is further blended (ADEKA Corporation NA-18) and talc (Neoraito Kosan Co. Neotaruku UNI05) as nucleating agent, 230 ° C. using an extruder And kneaded to obtain a resin composition. The nucleating agent was blended so that NA-18 was 0.2 parts by weight and talc was 1.0 parts by weight with respect to 100 parts by weight of the resin composition.
The comparative example 7 manufactured what the ethylene concentration in a propylene-type polymer did not enter into the range of this invention.

[Comparative Examples 8-9]
Prepolymerization was performed in the same manner as in Example 1 using the same solid catalyst as in Example 1. A propylene polymer (propylene homopolymer) was polymerized by introducing it into a polymerization reactor in the previous stage of a polymerization apparatus equipped with a two-stage polymerization reactor in series. The obtained propylene homopolymer was supplied to the subsequent polymerization reactor, and the ethylene / propylene copolymer was polymerized in the subsequent polymerization reactor. At that time, by adjusting the ethylene supply amount and hydrogen supply amount (molecular weight, used for the purpose of MFR adjustment), polymerization temperature, and polymerization pressure to each polymerization reactor shown in Table 3, the propylene-based resin shown in the table was adjusted. Obtained.
To the resulting propylene resin, an aromatic phosphoric acid ester compound is further blended (ADEKA Corporation NA-18) and talc (Neoraito Kosan Co. Neotaruku UNI05) as nucleating agent, 230 ° C. using an extruder And kneaded to obtain a resin composition. The nucleating agent was blended so that NA-18 was 0.2 parts by weight and talc was 1.0 parts by weight with respect to 100 parts by weight of the resin composition.
In Comparative Examples 8 and 9, in particular, the ethylene concentration in the subsequent polymerization reactor was decreased and increased as shown in Table 1 to Example 3, and the ethylene concentration in the ethylene / propylene copolymer was reduced according to the present invention. Manufactured out of scope.

[Comparative Example 10]
Prepolymerization was performed in the same manner as in Example 1 using the same solid catalyst as in Example 1. A propylene polymer (propylene homopolymer) was polymerized by introducing it into a polymerization reactor in the previous stage of a polymerization apparatus equipped with a two-stage polymerization reactor in series. The obtained propylene homopolymer was supplied to the subsequent polymerization reactor, and the ethylene / propylene copolymer was polymerized in the subsequent polymerization reactor. At that time, by adjusting the ethylene supply amount and hydrogen supply amount (molecular weight, used for the purpose of MFR adjustment), polymerization temperature, and polymerization pressure to each polymerization reactor shown in Table 3, the propylene-based resin shown in the table was adjusted. Obtained.
In Comparative Example 10, in particular, the concentration of hydrogen in the polymerization reactor in the previous stage was increased as shown in Table 2 from Example 1, and a resin composition whose MFR was not within the scope of the present invention was produced.

[Comparative Examples 11 to 13]
In Comparative Example 11, first, the hydrogen concentration of the former polymerization reactor of Example 1 was changed as shown in Table 3, and the residence time of the latter polymerization reactor was changed with respect to the residence time of the former polymerization reactor. Increased to obtain a propylene-based resin. Further, as an additional polymer, ethylene / 1-butene copolymer (EBR, trade name: Engage ENG7380 (manufactured by Dow Chemical Japan Co., Ltd.)) was blended in an amount of 10% by weight with respect to the propylene resin.
In Comparative Example 12, first, the hydrogen concentration of the former polymerization reactor of Example 1 was changed as shown in Table 3, and the residence time of the latter polymerization reactor was changed with respect to the residence time of the former polymerization reactor. Increased to obtain a propylene-based resin. Further, as an additional polymer, ethylene / 1-octene copolymer (EOR, trade name: Engage ENG8445 (manufactured by Dow Chemical Japan Co., Ltd.)) was blended in an amount of 10% by weight with respect to the propylene resin.
In Comparative Example 13, first, the hydrogen concentration of the former polymerization reactor of Example 1 was changed as shown in Table 3, and the residence time of the latter polymerization reactor was changed with respect to the residence time of the former polymerization reactor. Increased to obtain a propylene-based resin. Further, as an additional polymer, 10% by weight of high density polyethylene (HDPE, trade name: Novatec HF313 (manufactured by Nippon Polyethylene Co., Ltd.)) was blended with respect to the propylene resin.
To the resulting propylene resin, an aromatic phosphoric acid ester compound is further blended (ADEKA Corporation NA-18) and talc (Neoraito Kosan Co. Neotaruku UNI05) as nucleating agent, 230 ° C. using an extruder And kneaded to obtain a resin composition. The nucleating agent was blended so that NA-18 was 0.2 parts by weight and talc was 1.0 parts by weight with respect to 100 parts by weight of the resin composition.
In addition, Comparative Examples 11-13 manufactured what the MFR in 190 degreeC of an additional polymer does not enter into the scope of the present invention.
The propylene-type resin composition manufactured in the Example and the comparative example and its performance are described in Tables 1-3.

プロピレン系重合体中またはエチレン・プロピレン共重合体中のエチレン濃度、プロピレン系樹脂のキシレン可溶分の極限粘度（以下、「ＸＳＩＶ」と称する。）、プロピレン系樹脂のキシレン不溶分の分子量分布Ｍｗ／Ｍｎ、プロピレン系樹脂組成物のＭＦＲ、追加の重合体のＭＦＲの測定方法を以下に示す。

Ethylene concentration in propylene-based polymer or ethylene-propylene copolymer, intrinsic viscosity of xylene-soluble component of propylene-based resin (hereinafter referred to as “XSIV”), molecular weight distribution Mw of propylene-based resin insoluble in xylene / Mn, MFR of propylene-based resin composition, and MFR of additional polymer are shown below.

Moreover, about each resin composition, impact resistance, rigidity, whitening resistance, and bridge breakage (bridge portion breaking elongation) were evaluated as follows. Each resin composition was evaluated using a sample molded by another molding method (injection molding or press molding), in which the evaluation results of the physical properties tend to be the same as the evaluation results in compression molding. It is.
[Ethylene concentration in polymer]
A sample dissolved in a mixed solvent of 1,2,4-trichlorobenzene / deuterated benzene was measured by ¹³ C-NMR method using JNM LA-400 ( ¹³ C resonance frequency 100 MHz) manufactured by JEOL Ltd. .
[Xylene insoluble matter]
2.5 g of the resin composition was placed in a flask containing 250 mL of o-xylene (solvent), and stirred for 30 minutes at 135 ° C. while purging with nitrogen using a hot plate and a reflux apparatus. Was completely dissolved and then cooled at 25 ° C. for 1 hour. The resulting solution was filtered using filter paper. At this time, acetone was added to the residue (mixture of xylene-insoluble component and solvent) remaining on the filter paper and filtered, and then the unfiltered component was evaporated to dryness in a vacuum drying oven set at 80 ° C. Insoluble matter was obtained.
[Xylene solubles]
100 mL of the filtrate after filtration when the xylene-insoluble matter was obtained was collected, transferred to an aluminum cup or the like, evaporated and dried at 140 ° C. while purging with nitrogen, and allowed to stand at room temperature for 30 minutes. A soluble content was obtained.
[XSIV]
Using the xylene solubles as a sample, the intrinsic viscosity was measured in 135 ° C. tetrahydronaphthalene using an Ubbelohde viscometer.
[Molecular weight distribution (Mw / Mn) of xylene insolubles of propylene resin]
Using the xylene-insoluble matter as a sample, the molecular weight distribution (Mw / Mn) was measured as follows.
PL GPC220 manufactured by Polymer Laboratories is used as an apparatus, 1,2,4-trichlorobenzene containing an antioxidant is used as a mobile phase, and UT-G (1) and UT-807 (1) manufactured by Showa Denko KK are used as columns. ), UT-806M (two) connected in series was used, and a differential refractometer was used as a detector. Moreover, the same solvent as the mobile phase was used as the solvent for the sample solution of the xylene-insoluble matter, and the sample for measurement was prepared by dissolving at a sample concentration of 1 mg / mL for 2 hours while shaking at a temperature of 150 ° C. 500 μL of the sample solution thus obtained was injected into the column and measured at a flow rate of 1.0 mL / min, a temperature of 145 ° C., and a data acquisition interval of 1 second. For column calibration, a polystyrene standard sample (shodex STANDARD, manufactured by Showa Denko KK) having a molecular weight of 580 to 7.45 million was used and approximated by a cubic equation. The Mark-Houkins coefficients are K = 1.21 × 10 ⁻⁴ and α = 0.707 for the polystyrene standard sample, and K = 1.37 × 10 ⁻⁴ and α = 0. 75 was used.
[MFR of resin composition]
The MFR of the resin composition was measured under the conditions of a temperature of 230 ° C. and a load of 2.16 kg according to JIS K 7210.
[MFR of additional polymer]
According to JIS K 7210, the measurement was performed at a temperature of 190 ° C. and a load of 2.16 kg.
[Shock resistance]
Each resin composition was injection-molded using a FANUC α100C as a molding machine at a molding temperature of 230 ° C. and a molding pressure of 50 MPa to produce a 130 × 130 × 2 mm plate-shaped molded product.
About this molded article, the surface impact strength (J) under the environment of 0 ° C. was measured with a surface impact strength measuring device (Hydroshot manufactured by Shimadzu Corporation), and the impact resistance was evaluated according to the following criteria.
◎: Impact absorption energy is 20J or more ○: Impact absorption energy is 10J or more ×: Impact absorption energy is less than 10J [Rigidity]
Based on JIS K6921-2, the flexural modulus of each resin composition was measured.
[Whitening resistance]
Each resin composition was injection-molded using a FANUC α100C as a molding machine at a molding temperature of 230 ° C. and a molding pressure of 50 MPa to produce a 130 × 130 × 2 mm plate-shaped molded product.
This molded product was visually observed for the presence or absence of whitening when an impact that does not destroy the molded product was applied using a hydroshot manufactured by Shimadzu Corporation, and the whitening resistance was evaluated according to the following criteria.
A: Whitening was not observed.
○: Slight whitening was observed.
X: Whitening was observed.
[Bridge elongation at break]
Each resin composition was subjected to press molding at a molding pressure of 100 MPa on a press machine cooled at 10 ° C. after melting the resin at a melting temperature of 230 ° C. using a 50-ton press molding machine manufactured by Shoji Co., Ltd. as a molding machine. A 110 × 25 × 2 mm plate-shaped molded article having four semi-cylindrical bridge portions with a diameter of 2 mm in the center was produced. After slitting with a knife so that only four bridge portions remain after 24 hours or more after molding, the breaking elongation (mm) of the bridge portion of this molded product is set to TENSILON UTM-III-500 manufactured by Toyo Baldwin Co., Ltd. Was measured at a tensile speed of 2 mm / min, and the breakage of the bridge was evaluated according to the following criteria.
◎: Bridge portion is small and good cut ○: Bridge portion is moderately stretched and cut is good ×: Bridge portion is large and badly cut

As shown in the above results, the molded products obtained by other molding methods that tend to be the same as the evaluation results in compression molding of the resin compositions of Examples 1 to 7 are impact resistance, rigidity, and whitening resistance. The balance between the property and the bridge breaking property was good.
On the other hand, Comparative Example 1 polymerized using a phthalate catalyst was inferior in whitening resistance and bridge breakage properties, and Comparative Example 2 was inferior in whitening resistance.
Comparative Example 3 having a high ethylene / propylene copolymer content and a low ethylene concentration in the ethylene / propylene copolymer had low rigidity and poor whitening resistance. Moreover, since the value of MFR is not suitable for compression molding, the evaluation of bridge breakage characteristics was not performed.
Comparative Example 4 having a low xylene-soluble XSIV content of the propylene-based resin was inferior in the bridging property.
The comparative example 5 which does not contain a nucleating agent was inferior to the bridge | braking property.
In Comparative Example 6 in which the MFR of the resin composition was low, the MFR value was not suitable for compression molding.
The comparative example 7 which contains ethylene concentration in a propylene-type polymer was inferior in the bridge | bridging property.
Comparative Example 8 having a low ethylene concentration in the ethylene / propylene copolymer was inferior in whitening resistance and bridge breakage characteristics.
Comparative Example 9 having a high ethylene concentration in the ethylene / propylene copolymer was inferior in bridging properties.
Comparative Example 10 having a high MFR of the resin composition was inferior in impact resistance, and the MFR was not suitable for compression molding.
Comparative Example 11 and Comparative Example 12 in which the MFR (190 ° C.) of the additional polymer was high were inferior in bridging properties. Further, Comparative Example 13 having a low MFR (190 ° C.) of the additional polymer was inferior in impact resistance and whitening resistance.

  The resin composition and molded product thereof of the present invention can be used for food container lids, containers, and the like, and in particular, can be suitably used for beverage bottle lids.

Claims (4)

A polypropylene resin composition for compression molding containing a propylene resin and a nucleating agent,
The propylene-based resin is at least one propylene-based polymer selected from a propylene homopolymer and a propylene / ethylene copolymer having an ethylene unit content of 0.5% by weight or less, and an ethylene unit content. A reactive blend resin with 68-80 wt% ethylene-propylene copolymer;
The ethylene / propylene copolymer content is 13 to 20% by weight based on the weight of the propylene-based resin;
The different additional polymers and polymer constituting the propylene resin, or does not contain, or contains in an amount of 1 to 5% by weight the polypropylene resin composition;
The intrinsic viscosity of the propylene-based resin in 135 ° C. tetrahydronaphthalene which is soluble in xylene is 1.3 to 1.9 dl / g;
The propylene-based resin has a Mw / Mn insoluble in xylene of 7 to 15;
The content of the nucleating agent is 0.01 to 2 parts by weight with respect to 100 parts by weight of the propylene resin;
When the additional polymer is included , the melt flow rate measured according to JIS K 7210 of the additional polymer under the conditions of a temperature of 190 ° C. and a load of 2.16 kg is 0.15 to 0.45 g / 10 min. And a polypropylene resin composition for compression molding, wherein the melt flow rate of the resin composition measured in accordance with JIS K 7210 at a temperature of 230 ° C. and a load of 2.16 kg is 6 to 14 g / 10 min. . A solid catalyst in which the propylene-based resin contains an electron donor compound selected from magnesium, titanium, halogen, and a succinate-based compound as an essential component;
The resin composition according to claim 1, wherein the resin composition is produced using a catalyst comprising an organoaluminum compound; and an external electron donor compound selected from silicon compounds.   The resin composition according to claim 1 or 2, wherein the additional polymer is a polymer containing an ethylene unit.   The molded article obtained by carrying out the compression molding of the polypropylene resin composition for compression molding of any one of Claims 1-3.