α-olefin polymerization catalyst, method for producing the same, and method for producing polypropylene resin using the same

Abstract

To provide a polypropylene resin reduced in fish eye and the like.SOLUTION: A method for producing a polypropylene resin includes: (1) a process of producing an α-olefin polymerization catalyst by reacting (x) a solid catalyst including magnesium, titanium, halogen, and an inner electron donor compound as essential constituents, (y) an organic aluminum compound, and (z) an electron donor compound if necessary, by a (y) concentration of 0.8 to 4.0 mole / L in a hydrophobic hydrocarbon solvent; and (2) a process of producing a polypropylene resin comprising (A1) and (A2), and having characteristics of (i) and (ii) by polymerizing a corresponding monomer by using the catalyst. (A1) 30 to 85 wt% of a propylene homopolymer or a propylene copolymer. (A2) 15 to 70 wt% of an ethylene and 3-10C α-olefin copolymer having an ethylene content of 20 to 60 wt%. (i) MFR is 0.1 to 30 g / 10 min. (ii) XSIV is 5.5 to 9.0 dL / g.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to an α-olefin polymerization catalyst, a method for producing the same, and a method for producing a polypropylene-based resin using the same.

Background Art

[0002] Polypropylene-based resins are used in a wide range of fields. In particular, in a molded article composed of a composition containing a block copolymer having a high molecular weight of an elastomer component, there has been a problem that the appearance deteriorates due to the generation of gels or fish eyes. In order to reduce gels or fish eyes, Patent Document 1 proposes to carry out a continuous polymerization reaction of two or more stages. Further, Patent Document 2 proposes a heterophasic propylene polymer capable of reducing polymer aggregates.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0004] Unlike the methods described in the above patent documents, the inventors obtained the idea that the problem of gels or fish eyes might be solved by optimizing the catalyst. In view of such circumstances, an object of the present invention is to provide a polypropylene-based resin with reduced gels or fish eyes, and an α-olefin polymerization catalyst capable of producing the resin.

Means for Solving the Problems

[0005] The above problems are solved by the following invention. Aspect 1 (1) In a hydrophobic hydrocarbon solvent, (x) Magnesium, titanium, halogen, and a solid catalyst containing an internal electron donor compound as essential components, (y) An organoaluminum compound, (z) An electron donor compound as required, are reacted in a process where the reaction is carried out at a concentration of (y) organoaluminum of 0.8 to 4.0 mol / L to produce an α-olefin polymerization catalyst. (2) Using the catalyst, polymerize the corresponding monomer to produce a propylene-based resin consisting of the following (A1) and (A2) and having the characteristics of (i) and (ii): (A1) A propylene homopolymer or a propylene copolymer: 30 to 85% by weight (A2) A copolymer of ethylene and a C3 - C10 α-olefin with an ethylene content of 20 to 60% by weight: 15 to 70% by weight (i) The melt flow rate (at 230 °C, load 21.18 N) is 0.1 to 30 g / 10 min (ii) The intrinsic viscosity of the xylene-soluble fraction at room temperature in the propylene-based resin: 5.5 to 9.0 dL / g A method for producing a polypropylene-based resin comprising the above steps. Aspect 2 The production method according to Aspect 1, wherein the concentration of the component (y) is 1.0 to 4.0 mol / L. Aspect 3 The production method according to Aspect 1 or 2, wherein the component (y) is a trialkylaluminum. Aspect 4 The production method according to Aspect 3, wherein the component (y) is triethylaluminum. Aspect 5 The production method according to any one of Aspects 1 to 4, wherein the internal electron donor compound is selected from phthalate-based compounds or succinate-based compounds. Aspect 6 The production method according to any one of Aspects 1 to 5, wherein the component (z) contains Si and the Si / Al ratio in the catalyst is 0.005 to 1.0. Aspect 7 The propylene polymer has a fish-eye amount of 200 pieces / 0.1 m when formed into a film. 2 The production method according to any one of Aspects 1 to 6, wherein the amount is less than. Aspect 8 A polypropylene-based resin produced by the method according to any one of Aspects 1 to 7. Aspect 9 The polypropylene-based resin according to Aspect 8, wherein Component (A2) is an ethylene-α-olefin copolymer containing 20 to 35% by weight of ethylene-derived units. Aspect 10 A molded article obtained by molding a composition containing the polypropylene-based resin according to Aspect 8 or 9. Aspect 11 (x) A solid catalyst having magnesium, titanium, a halogen, and an internal electron donor compound as essential components (y) An organoaluminum compound (z) An electron donor compound as required A step of reacting in a hydrophobic hydrocarbon solvent, and the reaction is carried out at a concentration of (y) organoaluminum of 0.8 to 4.0 mol / L. The α-olefin polymerization catalyst produced by the method comprising this step.

Advantages of the Invention

[0006] It is possible to provide a polypropylene-based resin with reduced gel or fish-eye, and an α-olefin polymerization catalyst capable of producing the resin.

Modes for Carrying Out the Invention

[0007] In the present disclosure, "X to Y" includes X and Y which are the end values thereof. "X or Y" means either one or both of X and Y.

[0008] 1. Catalyst The α-olefin polymerization catalyst according to this embodiment is (x) A solid catalyst having magnesium, titanium, a halogen, and an internal electron donor compound as essential components, and (y) An organoaluminum compound, and (z) an electron donor compound, if necessary, and reacting in a hydrophobic hydrocarbon solvent, the reaction being carried out in a step where the concentration of the organoaluminum is 0.8 to 4.0 mol / L in (y).

[0009] The catalyst gives a polymer (preferably a polypropylene-based resin) with reduced gel or fish eyes. Although the mechanism is not limited, it is presumed that when the components are reacted in an environment where the component (y) is at a high concentration, the solid catalyst can be activated uniformly. The catalyst is suitable as a polymerization catalyst for α-olefins having 2 or 3 carbon atoms.

[0010] (1) Method for producing the catalyst The catalyst is produced by a method comprising a step of mixing components (x) to (z) in a hydrophobic hydrocarbon solvent. A hydrophobic hydrocarbon solvent is a liquid at 23 °C and atmospheric pressure and is a non-polar hydrocarbon. From the viewpoints of availability and handleability, etc., examples of the hydrocarbon include hexane or heptane, and heptane is particularly preferred. Usually, the term "solvent" is used as a medium for dissolving a certain component, but in the present disclosure, a medium having a function as a dispersion medium is also referred to as a solvent.

[0011] The mixing is carried out in an arbitrary atmosphere, but from the viewpoint of avoiding deterioration of the components, it is preferably carried out in an inert atmosphere. Examples of the atmosphere include a nitrogen atmosphere or an argon atmosphere. The temperature during mixing is not limited, but is preferably 0 to 40 °C from the viewpoints of promoting the reaction and avoiding deterioration of the components. The stirring time is also not limited, but in one embodiment, it is 0.05 to 0.5 hours. The scale during mixing is not limited, but in one embodiment, a reactor of 0.03 to 5 L can be used.

[0012] The order of charging each component into the reactor is not limited either. For example, all components can be charged into the reactor charged with a hydrophobic hydrocarbon solvent at once. Alternatively, an organoaluminum compound and an external electron donor compound can be charged into the reactor charged with a hydrophobic hydrocarbon solvent in this order, and finally a solid catalyst can be charged.

[0013] The concentration of component (y) in the mixture is 0.8 to 4.0 mol / L. When the concentration is less than the lower limit value, the catalytic activity is not sufficient. Also, when the concentration exceeds the upper limit value, the effect of reducing gel or fish eyes becomes insufficient. From such a viewpoint, the lower limit value of the concentration is preferably 1.0 mol / L or more.

[0014] The concentration of component (x) in the mixture is not limited, but is preferably 0.3 to 122 mg / mL. When the concentration is less than the lower limit value, a large amount of solvent is required in the system and the efficiency deteriorates. Also, when the concentration exceeds the upper limit value, stirring becomes poor and the reaction becomes non-uniform. From such a viewpoint, the lower limit value of the concentration is preferably 0.6 mg / mL or more, and the upper limit value thereof is 7 mg / mL or less.

[0015] The concentration of component (z) in the mixture is not limited, but is preferably 0.1 to 1.1 mol / L. When the concentration is less than the lower limit value, the stereoregularity becomes insufficient. Also, when the concentration exceeds the upper limit value, the activity decreases.

[0016] (2) Each component (2-1) Component (x): Solid catalyst Component (x) can be prepared by a known method, for example, by bringing a magnesium compound, a titanium compound, and an electron donor compound into mutual contact. As the titanium compound used for the preparation of component (x), a tetravalent titanium compound represented by the general formula: Ti(OR) g X 4-g is suitable. In the formula, R is a hydrocarbon group, X is a halogen, and 0 ≦ g ≦ 4. More specifically, as the titanium compound, TiCl 4 , TiBr 4 , TiI 4titanium tetrahalides such as; 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 trihalogenated alkoxytitaniums such as; 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 Br 2 dihalogenated alkoxytitaniums such as; 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 ) 3 Br monohalogenated trialkoxytitaniums such as; Ti(OCH 3 ) 4 、Ti(OC 2 H 5 ) 4 、Ti(O n -C 4 H 9 ) 4 tetraalkoxytitaniums etc. are mentioned. Among these, the preferred ones are halogen-containing titanium compounds, particularly titanium tetrahalides, and the particularly preferred one is titanium tetrachloride.

[0017] Examples of the magnesium compound used for the preparation of component (x) include magnesium compounds having a magnesium-carbon bond or a magnesium-hydrogen bond, such as dimethylmagnesium, diethylmagnesium, dipropylmagnesium, dibutylmagnesium, diamylmagnesium, dihexylmagnesium, didecylmagnesium, ethylmagnesium chloride, propylmagnesium chloride, butylmagnesium chloride, hexylmagnesium chloride, amylmagnesium chloride, butylethoxymagnesium, ethylbutylmagnesium, butylmagnesium hydride, etc. These magnesium compounds can be used, for example, in the form of a complex compound with an organoaluminum or the like, and may be in a liquid state or a solid state. Further preferred magnesium compounds include magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide, magnesium fluoride; alkoxymagnesium halides such as methoxymagnesium chloride, ethoxymagnesium chloride, isopropoxymagnesium chloride, butoxymagnesium chloride, octoxymagnesium chloride; aryloxymagnesium halides such as phenoxymagnesium chloride, methylphenoxymagnesium chloride; alkoxymagnesium such as ethoxymagnesium, isopropoxymagnesium, butoxymagnesium, n-octoxymagnesium, 2-ethylhexoxymagnesium; aryloxymagnesium such as phenoxymagnesium, dimethylphenoxymagnesium; magnesium carboxylates such as magnesium laurate, magnesium stearate, etc.

[0018] The electron donor compound used in the preparation of component (x) is generally referred to as an "internal electron donor compound". In the present invention, known compounds such as phthalate compounds, succinate compounds, diether compounds, diphenyldicarboxylic acid esters described in JP-A-2013-28704, cyclohexenedicarboxylic acid esters described in JP-A-2014-201602, dicycloalkyldicarboxylic acid esters described in JP-A-2013-28705, diol dibenzoates described in Patent No. 4959920, 1,2-phenylenedibenzoates described in WO 2010 / 078494, etc. can be used. Among them, phthalate compounds or succinate compounds are preferred.

[0019] Hereinafter, preferred internal electron donor compounds will be described. [Succinate Compounds] The succinate compounds used as the internal electron donor compound are diesters of succinic acid or diesters of substituted succinic acid. Preferred succinate compounds are represented by the following formula (1).

[0020] [Chemical Formula]

[0021] In the formula, the groups R 1 and R 2 are the same as or different from each other and are linear or branched alkyl, alkenyl, cycloalkyl, aryl, arylalkyl, or alkylaryl groups having C 1 to C 20 and may contain a heteroatom; the groups R 3 to R 6 are the same as or different from each other and are hydrogen or linear or branched alkyl, alkenyl, cycloalkyl, aryl, arylalkyl, or alkylaryl groups having C 1 to C 20 and may contain a heteroatom, and the groups R 3 to R 6 3 ~R 6may combine together to form a ring.

[0022] R 1 and R 2 are preferably C 1 ~C 8 alkyl, cycloalkyl, aryl, arylalkyl, and alkylaryl groups. R 1 and R 2 compounds selected from primary alkyls, especially branched primary alkyls, are particularly preferred. Suitable R 1 and R 2 group examples are C 1 ~C 8 alkyl groups, such as methyl, ethyl, n-propyl, n-butyl, isobutyl, neopentyl, 2-ethylhexyl. Ethyl, isobutyl, and neopentyl are particularly preferred.

[0023] One of the preferred groups of compounds represented by formula (1) is R 3 ~R 5 is hydrogen, R 6is a branched alkyl, cycloalkyl, aryl, arylalkyl, or alkylaryl group having 3 to 10 carbon atoms. Preferred specific examples of such monosubstituted succinate compounds are diethyl-sec-butyl succinate, diethyl texyl succinate, diethyl cyclopropyl succinate, diethyl norbornyl succinate, diethyl perhydro succinate, diethyl trimethylsilyl succinate, diethyl methoxy succinate, diethyl-p-methoxyphenyl succinate, diethyl-p-chlorophenyl succinate, diethyl phenyl succinate, diethyl cyclohexyl succinate, diethyl benzyl succinate, diethyl cyclohexylmethyl 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-ethoxycarbodiisobutyl phenyl succinate, diisobutyl-sec-butyl succinate, diisobutyl texyl succinate, diisobutyl cyclopropyl succinate, diisobutyl norbornyl succinate, diisobutyl perhydro succinate, diisobutyl trimethylsilyl succinate, diisobutyl methoxy succinate, diisobutyl-p-methoxyphenyl succinate, diisobutyl-p-chlorophenyl succinate, diisobutyl cyclohexyl succinate, diisobutyl benzyl succinate, diisobutyl cyclohexylmethyl succinate, diisobutyl-t-butyl succinate, diisobutyl 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 perhydro succinate, dineopentyl trimethylsilyl succinate, dineopentyl methoxy succinate,Neopentyl-p-methoxyphenyl succinate, neopentyl-p-chlorophenyl succinate, neopentyl phenyl succinate, neopentyl cyclohexyl succinate, neopentyl benzyl succinate, neopentyl cyclohexylmethyl succinate, neopentyl-t-butyl succinate, neopentyl isobutyl succinate, neopentyl isopropyl succinate, neopentyl neopentyl succinate, neopentyl isopentyl succinate, neopentyl(1-trifluoromethylethyl) succinate, neopentyl fluorenyl succinate.

[0024] Another preferred group of compounds within the scope of formula (1) is R 3 ~R 6 At least two groups from are different from hydrogen and optionally contain a heteroatom, C 1 ~C 20 Selected from linear or branched alkyl, alkenyl, cycloalkyl, aryl, arylalkyl, or alkylaryl groups. Compounds in which two groups different from hydrogen are bonded to the same carbon atom are particularly preferred. Specifically, R 3 and R 4 are groups different from hydrogen, and R 5 and R 6is a compound in which is a hydrogen atom. Preferred specific examples of such disubstituted succinate compounds are 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-butyl succinate, diethyl-2,2-diisobutyl succinate, diethyl-2-cyclohexyl-2-ethyl succinate, diethyl-2-isopropyl-2-methyl succinate, diethyl-2-tetradecyl-2-ethyl succinate, diethyl-2-isobutyl-2-ethyl succinate, diethyl-2-(1-trifluoromethyl ethyl)-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-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-trifluoromethyl ethyl)-2-methyl succinate, diisobutyl-2-isopentyl-2-isobutyl succinate, diisobutyl-2-phenyl-2-n-butyl succinate, dineopentyl-2,2-dimethyl succinate, dineopentyl-2-ethyl-2-methyl succinate, dineopentyl-2-benzyl-2-isopropyl succinate, dineopentyl-2-cyclohexylmethyl-2-isobutyl 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-ethyl succinate, dineopentyl-2-isobutyl-2-ethyl succinate, dineopentyl-2-(1-trifluoromethylethyl)-2-methyl succinate, dineopentyl-2-isopentyl-2-isobutyl succinate, dineopentyl-2-phenyl-2-n-butyl succinate.,

[0025] Furthermore, compounds in which at least two groups different from hydrogen are bonded to different carbon atoms are particularly preferred. Specifically, R 3 and R 5 are groups different from hydrogen. In this case, R 4 and R 6may be a hydrogen atom or a group different from hydrogen, but it is preferable that one of them is a hydrogen atom (trisubstituted succinate). Preferred specific examples of such compounds are diethyl-2,3-bis(trimethylsilyl)succinate, diethyl-2,2-sec-butyl-3-methylsuccinate, diethyl-2-(3,3,3-trifluoropropyl)-3-methylsuccinate, diethyl-2,3-bis(2-ethylbutyl)succinate, diethyl-2,3-diethyl-2-isopropylsuccinate, diethyl-2,3-diisopropyl-2-methylsuccinate, diethyl-2,3-dicyclohexyl-2-methyldiethyl-2,3-dibenzylsuccinate, diethyl-2,3-diisopropylsuccinate, diethyl-2,3-bis(cyclohexylmethyl)succinate, diethyl-2,3-di-t-butylsuccinate, diethyl-2,3-diisobutylsuccinate, diethyl-2,3-dineopentylsuccinate, diethyl-2,3-diisopentylsuccinate, diethyl-2,3-(1-trifluoromethylethyl)succinate, diethyl-2,3-tetradecylsuccinate, diethyl-2,3-fluorenylsuccinate, diethyl-2-isopropyl-3-isobutylsuccinate, diethyl-2-tert-butyl-3-isopropylsuccinate, diethyl-2-isopropyl-3-cyclohexylsuccinate, diethyl-2-isopentyl-3-cyclohexylsuccinate, diethyl-2-tetradecyl-3-cyclohexylmethylsuccinate, diethyl-2-cyclohexyl-3-cyclopentylsuccinate, diisobutyl-2,3-diethyl-2-isopropylsuccinate, diisobutyl-2,3-diisopropyl-2-methylsuccinate, diisobutyl-2,3-dicyclohexyl-2-methylsuccinate, diisobutyl-2,3-dibenzylsuccinate, diisobutyl-2,3-diisopropylsuccinate, diisobutyl-2,3-bis(cyclohexylmethyl)succinate, diisobutyl-2,3-di-t-butylsuccinate, diisobutyl-2,3-diisobutylsuccinate, diisobutyl-2,3-dineopentylsuccinate, diisobutyl-2,3-diisopentylsuccinate, diisobutyl-2,3-(1-Trifluoromethyl ethyl) 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-isopropyl-3-cyclohexyl succinate, diisobutyl-2-isopentyl-3-cyclohexyl succinate, diisobutyl-2-tetradecyl-3-cyclohexylmethyl succinate, diisobutyl-2-cyclohexyl-3-cyclopentyl succinate, dineopentyl-2,3-bis(trimethylsilyl) succinate, dineopentyl-2,2-sec-butyl-3-methyl succinate, dineopentyl-2-(3,3,3-trifluoropropyl)-3-methyl succinate, 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 succinate, dineopentyl-2,3-diisopentyl succinate, dineopentyl-2,3-(1-trifluoromethyl ethyl) succinate, dineopentyl-2,3-tetradecyl succinate, dineopentyl-2,3-fluorenyl succinate, dineopentyl-2-isopropyl-3-isobutyl succinate, dineopentyl-2-tert-butyl-3-isopropyl succinate, dineopentyl-2-isopropyl-3-cyclohexyl succinate, dineopentyl-2-isopentyl-3-cyclohexyl succinate, dineopentyl-2-tetradecyl-3-cyclohexylmethyl succinate, dineopentyl-2-cyclohexyl-3-cyclopentyl succinate.,

[0026] Among the compounds of formula (1), the group R 3 ~R 6 Compounds in which some of them are bonded together to form a ring can also be preferably used. Examples of such compounds include those listed in JP-T-2002-542347, for example, 1-(ethoxycarbonyl)-1-(ethoxyacetyl)-2,6-dimethylcyclohexane, 1-(ethoxycarbonyl)-1-(ethoxyacetyl)-2,5-dimethylcyclopentane, 1-(ethoxycarbonyl)-1-(ethoxymethylacetyl)-2-methylcyclohexane, 1-(ethoxycarbonyl)-1-(ethoxy(cyclohexyl)acetyl)cyclohexane. Other examples include cyclic succinate compounds such as diisobutyl 3,6-dimethylcyclohexane-1,2-dicarboxylate and diisobutyl cyclohexane-1,2-dicarboxylate as disclosed in WO 2009 / 069483. Examples of other cyclic succinate compounds also preferably include those disclosed in WO 2009 / 057747.

[0027] Among the compounds of formula (1), when the group R 3 ~R 6 contains a heteroatom, the heteroatom is preferably a Group 15 atom containing nitrogen and phosphorus atoms or a Group 16 atom containing oxygen and sulfur atoms. Examples of the compound in which the group R 3 ~R 6 contains a Group 15 atom include the compounds disclosed in JP-A-2005-306910. On the other hand, examples of the compound in which the group R 3 ~R 6 contains a Group 16 atom include the compounds disclosed in JP-A-2004-131537.

[0028] In addition, an internal electron donor compound that provides a molecular weight distribution equivalent to that of a succinate compound may also be used. Examples of such compounds include diphenyldicarboxylic acid esters described in JP-A-2013-28704, cyclohexenedicarboxylic acid esters described in JP-A-2014-201602, dicycloalkyldicarboxylic acid esters described in JP-A-2013-28705, diol dibenzoates described in Patent No. 4959920, and 1,2-phenylenedibenzoates described in International Publication No. 2010 / 078494.

[0029] [Phthalate compounds] Examples of phthalate compounds include monoethyl phthalate, dimethyl phthalate, methyl ethyl phthalate, monoisobutyl phthalate, mononormal butyl phthalate, diethyl phthalate, ethyl isobutyl phthalate, ethyl normal butyl phthalate, di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, di-n-heptyl phthalate, di-2-ethylhexyl phthalate, di-n-octyl phthalate, dineopentyl phthalate, didecyl phthalate, benzyl butyl phthalate, diphenyl phthalate, and the like. Among them, diisobutyl phthalate is particularly preferred.

[0030] [Diether compounds] Examples of the diether compounds include 2-(2-ethylhexyl)-1,3-dimethoxypropane, 2-isopropyl-1,3-dimethoxypropane, 2-butyl-1,3-dimethoxypropane, 2-sec-butyl-1,3-dimethoxypropane, 2-cyclohexyl-1,3-dimethoxypropane, 2-phenyl-1,3-dimethoxypropane, 2-tert-butyl-1,3-dimethoxypropane, 2-cumyl-1,3-dimethoxypropane, 2-(2-phenylethyl)-1,3-dimethoxypropane, 2-(2-cyclohexylethyl)-1,3-dimethoxypropane, 2-(p-chlorophenyl)-1,3-dimethoxypropane, 2-(diphenylmethyl)-1,3-dimethoxypropane, 2-(1-naphthyl)-1,3-dimethoxypropane, 2-(p-fluorophenyl)-1,3-dimethoxypropane, 2-(1-decahydronaphthyl)-1,3-dimethoxypropane, 2-(p-tert-butylphenyl)-1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, 2,2-diethyl-1,3-dimethoxypropane, 2,2-dipropyl-1,3-dimethoxypropane, 2,2-dibutyl-1,3-dimethoxypropane, 2,2-diethyl-1,3-diethoxypropane, 2,2-dicyclopentyl-1,3-dimethoxypropane, 2,2-dipropyl-1,3-diethoxypropane, 2,2-dibutyl-1,3-diethoxypropane, 2-methyl-2-ethyl-1,3-dimethoxypropane, 2-methyl-2-propyl-1,3-dimethoxypropane, 2-propyl-2-pentyl-1,3-diethoxypropane, 2-methyl-2-benzyl-1,3-dimethoxypropane, 2-methyl-2-phenyl-1,3-dimethoxypropane, 2-methyl-2-cyclohexyl-1,3-dimethoxypropane, 2-methyl-2-methylcyclohexyl-1,3-dimethoxypropane, 2,2-bis(p-chlorophenyl)-1,3-dimethoxypropane, 2,2-bis(2-phenylethyl)-1,3-dimethoxypropane, 2,2-bis(2-cyclohexylethyl)-1,3-dimethoxypropane, 2-methyl-2-isobutyl-1,3-dimethoxypropane, 2-methyl-2-(2-ethylhexyl)-1,3-dimethoxypropane, 2,1,3 - diethers such as 2 - bis(2 - ethylhexyl) - 1,3 - dimethoxypropane, 2,2 - bis(p - methylphenyl) - 1,3 - dimethoxypropane, 2 - methyl - 2 - isopropyl - 1,3 - dimethoxypropane, 2,2 - diisobutyl - 1,3 - dimethoxypropane, 2,2 - diphenyl - 1,3 - dimethoxypropane, 2,2 - dibenzyl - 1,3 - dimethoxypropane, 2 - isopropyl - 2 - cyclopentyl - 1,3 - dimethoxypropane, 2,2 - bis(cyclohexylmethyl) - 1,3 - dimethoxypropane, 2,2 - diisobutyl - 1,3 - diethoxypropane, 2,2 - diisobutyl - 1,3 - dibutoxypropane, 2 - isobutyl - 2 - isopropyl - 1,3 - dimethoxypropane, 2,2 - di - sec - butyl - 1,3 - dimethoxypropane, 2,2 - di - tert - butyl - 1,3 - dimethoxypropane, 2,2 - dineopentyl - 1,3 - dimethoxypropane, 2 - isopropyl - 2 - isopentyl - 1,3 - dimethoxypropane, 2 - phenyl - 2 - benzyl - 1,3 - dimethoxypropane, 2 - cyclohexyl - 2 - cyclohexylmethyl - 1,3 - dimethoxypropane, etc. are mentioned.,

[0031] Furthermore, as further specific examples of 1,3 - diether compounds, the following are mentioned. 1,1-Bis(methoxymethyl)cyclopentadiene; 1,1-bis(methoxymethyl)-2,3,4,5-tetramethylcyclopentadiene; 1,1-bis(methoxymethyl)-2,3,4,5-tetraphenylcyclopentadiene; 1,1-bis(methoxymethyl)-2,3,4,5-tetrafluorocyclopentadiene; 1,1-bis(methoxymethyl)-3,4-dicyclopentylcyclopentadiene; 1,1-bis(methoxymethyl)indene; 1,1-bis(methoxymethyl)-2,3-dimethylindene; 1,1-bis(methoxymethyl)-4,5,6,7-tetrahydroindene; 1,1-bis(methoxymethyl)-2,3,6,7-tetrafluoroindene; 1,1-bis(methoxymethyl)-4,7-dimethylindene; 1,1-bis(methoxymethyl)-3,6-dimethylindene; 1,1-bis(methoxymethyl)-4-phenylindene; 1,1-bis(methoxymethyl)-4-phenyl-2-methylindene; 1,1-bis(methoxymethyl)-4-cyclohexylindene; 1,1-bis(methoxymethyl)-7-(3,3,3-trifluoropropyl)indene; 1,1-bis(methoxymethyl)-7-trimethylsilylindene; 1,1-bis(methoxymethyl)-7-trifluoromethylindene; 1,1-bis(methoxymethyl)-4,7-dimethyl-4,5,6,7-tetrahydroindene; 1,1-bis(methoxymethyl)-7-methylindene; 1,1-bis(methoxymethyl)-7-cyclopentylindene; 1,1-bis(methoxymethyl)-7-isopropylindene; 1,1-bis(methoxymethyl)-7-cyclohexylindene; 1,1-bis(methoxymethyl)-7-tert-butylindene; 1,1-bis(methoxymethyl)-7-tert-butyl-2-methylindene; 1,1-bis(methoxymethyl)-7-phenylindene; 1,1-bis(methoxymethyl)-2-phenylindene; 1,1-bis(methoxymethyl)-1H-benzindene; 1,1-bis(methoxymethyl)-1H-2-methylbenzindene; 9,9-bis(methoxymethyl)fluorene; 9,9-bis(methoxymethyl)-2,3,6,7-tetramethylfluorene; 9,9-bis(methoxymethyl)-2,3,4,5,6,7-hexafluorofluorene;9,9-Bis(methoxymethyl)-2,3-benzofluorene; 9,9-bis(methoxymethyl)-2,3,6,7-dibenzofluorene; 9,9-bis(methoxymethyl)-2,7-diisopropylfluorene; 9,9-bis(methoxymethyl)-1,8-dichlorofluorene; 9,9-bis(methoxymethyl)-2,7-dicyclopentylfluorene; 9,9-bis(methoxymethyl)-1,8-difluorofluorene; 9,9-bis(methoxymethyl)-1,2,3,4-tetrahydrofluorene; 9,9-bis(methoxymethyl)-1,2,3,4,5,6,7,8-octahydrofluorene; 9,9-bis(methoxymethyl)-4-tert-butylfluorene.;

[0032] The electron donor compound used for the preparation of component (x) may be used alone or in combination of two or more kinds thereof.

[0033] (2) Component (y): Organoaluminum compound Examples of the organoaluminum compound of component (y) include the following. Trialkylaluminums such as triethylaluminum and tributylaluminum; Trialkenylaluminums such as triisoprenylaluminum; Dialkylaluminum alkoxides such as diethylaluminum ethoxide and dibutylaluminum butoxide; Alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide;

[0034] Partially halogenated alkylaluminums such as alkylaluminum dihalides such as ethylaluminum dichloride, propylaluminum dichloride, and butylaluminum dibromide; Dialkylaluminum hydrides such as diethylaluminum hydride and dibutylaluminum hydride; Partially hydrogenated alkylaluminums such as alkylaluminum dihydrides, such as ethylaluminum dihydride and propylaluminum dihydride; Partially alkoxylated and halogenated alkylaluminums such as ethylaluminum ethoxychloride, butylaluminum butoxychloride, and ethylaluminum ethoxybromide.

[0035] Among these, from the viewpoint of handleability and the like, trialkylaluminum is preferred, and triethylaluminum is more preferred.

[0036] (3) Component (z): Electron donor compound The electron donor compound of component (z) is generally referred to as an "external electron donor compound". As such a compound, a compound containing Si is preferred, and specifically, an organosilicon compound is preferred. Preferred organosilicon compounds are as follows. Trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diisopropyldimethoxysilane, t-butylmethyldimethoxysilane, t-butylmethyldiethoxysilane, t-amylmethyldiethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, diphenyldiethoxysilane, bis o-tolyldimethoxysilane, bis m-tolyldimethoxysilane, bis p-tolyldimethoxysilane, bis p-tolyldiethoxysilane, bis ethylphenyldimethoxysilane, dicyclopentyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, methyltrimethoxysilane, n-propyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, phenyltrimethoxysilane, γ-chloropropyltrimethoxysilane, 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, methyl(3,3,(3-Trifluoro-n-propyl)dimethoxysilane, cyclohexylethyldimethoxysilane, cyclopentyl-t-butoxydimethoxysilane, diisobutyldimethoxysilane, isobutylisopropyldimethoxysilane, n-propyltrimethoxysilane, di-n-propyldimethoxysilane, texyltrimethoxysilane, t-butylethyldimethoxysilane, t-butylpropyldimethoxysilane, t-butyl-t-butoxydimethoxysilane, isobutyltrimethoxysilane, cyclohexylisobutyldimethoxysilane, di-sec-butyldimethoxysilane, isobutylmethyldimethoxysilane, bis(dehydroisoquinolin-2-yl)dimethoxysilane, diethylaminotriethoxysilane, dicyclopentyl-bis(ethylamino)silane, tetraethoxysilane, tetramethoxysilane, isobutyltriethoxysilane.,

[0037] Among them, ethyltriethoxysilane, n-propyltriethoxysilane, n-propyltrimethoxysilane, t-butyltriethoxysilane, t-butylmethyldimethoxysilane, t-butylmethyldiethoxysilane, t-butylethyldimethoxysilane, t-butylpropyldimethoxysilane, t-butylt-butoxydimethoxysilane, t-butyltrimethoxysilane, i-butyltrimethoxysilane, isobutylmethyldimethoxysilane, i-butylsec-butyldimethoxysilane, ethyl(perhydroisoquinolin-2-yl)dimethoxysilane, bis(decahydroisoquinolin-2-yl)dimethoxysilane, tri(isopropenyloxy)phenylsilane, texyltrimethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane, phenyltrimethoxysilane, vinyltributoxysilane, diphenyldimethoxysilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane, i-butyl i-propyldimethoxysilane, cyclopentylt-butoxydimethoxysilane, dicyclopentyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexyl i-butyldimethoxysilane, cyclopentyl i-butyldimethoxysilane, cyclopentylisopropyldimethoxysilane, di-sec-butyldimethoxysilane, diethylaminotriethoxysilane, tetraethoxysilane, tetramethoxysilane, isobutyltriethoxysilane, phenylmethyldimethoxysilane, phenyltriethoxylane, bis p-tolyldimethoxysilane, p-tolylmethyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylethyldimethoxysilane, 2-norbornanetrie thoxysilane, 2-norbornanemethyldimethoxysilane, diphenyldiethoxysilane, methyl(3,3,3-trifluoropropyl)dimethoxysilane, ethyl silicate, etc. are preferable. The above component (z) may be used alone or in combination of two or more.

[0038] The Si / Al ratio in the catalyst is preferably from 0.005 to 1.0. When the ratio is less than the lower limit, the stereoregularity becomes insufficient and it is difficult to exhibit preferable physical properties. Further, when the ratio exceeds the upper limit, the activity decreases. From this viewpoint, the ratio is preferably from 0.01 to 0.5, more preferably from 0.02 to 0.3.

[0039] 2. Polypropylene-based resin The α-olefin polymer produced with the catalyst is preferably a polypropylene-based resin composed of component (A1) and component (A2).

[0040] (1) Component (A1) Component (A1) is a propylene homopolymer or a propylene copolymer, and is preferably a propylene (co)polymer containing 0 to 3% by weight of units derived from a comonomer selected from C2-C10-α-olefins (excluding C3-α-olefins). The comonomer selected from C2-C10-α-olefins naturally does not contain C3-α-olefins. When a comonomer is included, ethylene is preferable from the viewpoint of economy. When the amount of the units derived from the comonomer exceeds the upper limit, the rigidity of the multilayer sheet may decrease. From this viewpoint, it is preferable that component (A1) does not contain units derived from the comonomer, that is, it is a propylene homopolymer. Alternatively, when component (A1) contains units derived from the comonomer, the amount thereof is preferably more than 0% by weight and 0.5% by weight or less. The content of the units derived from the comonomer is 13 measured by the C-NMR method.

[0041] (2) Component (A2) Component (A2) is an ethylene-α-olefin copolymer containing 20 to 60% by weight of ethylene-derived units. When the content of ethylene-derived units is less than the lower limit or exceeds the upper limit, the cold impact resistance decreases. From this perspective, the content of ethylene-derived units is preferably 20 to 35% by weight. The α-olefin is not limited as long as it is other than ethylene, but is preferably a C3 to C10 α-olefin, more preferably propylene, 1-butene, 1-hexene, or 1-octene, still more preferably propylene or 1-butene, and even more preferably propylene.

[0042] (3) Ratio When the total of components (A1) and (A2) is 100% by weight, the weight ratio of components (A1) and (A2) is 30 to 85:15 to 70. When the content of component (A1) is large, the impact resistance of the polypropylene-based resin decreases, and when the content of component (A1) is small, the production of the polypropylene-based resin may become difficult.

[0043] (4) Physical properties (i) MFR The melt flow rate (MFR) of the polypropylene-based resin measured at 230°C under a load of 21.18 N is 0.1 to 30 g / 10 min. When the MFR exceeds the upper limit, extrusion molding becomes difficult, and when it is less than the lower limit, the production of the polypropylene-based resin becomes difficult. From this perspective, the lower limit of the MFR is preferably 0.3 g / 10 min or more, more preferably 0.5 g / 10 min or more, and the upper limit is preferably 20 g / 10 min or less, more preferably 15 g / 10 min or less. Therefore, the MFR is preferably 0.3 to 20 g / 10 min, more preferably 0.5 to 15 g / 10 min. The MFR is measured according to JIS K7210.

[0044] (ii) Intrinsic viscosity of xylene-soluble matter at room temperature (XSIV) The XSIV of the polypropylene resin is preferably 5.5 to 9.0 (dL / g). If the viscosity is excessively high, processing into a sheet becomes difficult, and if it is excessively low, the surface appearance of the molded product becomes poor. From this perspective, the upper limit value of the viscosity is more preferably 8.0 dl / g or less, and the lower limit value is more preferably 6.5 dl / g or more. Therefore, the XSIV is more preferably 6.5 to 8.0 dl / g. As described above, when the XSIV of the polypropylene resin is high, gels or fish eyes generally tend to increase. However, even if the XSIV of the polypropylene resin produced by the catalyst is within the above range, the generation of gels or fish eyes can be reduced.

[0045] XS can be obtained by known methods, but it is preferably obtained by the following method, for example. Put 2.5 g of the polypropylene resin into a flask containing 250 ml of o-xylene (solvent), and using a hot plate and a reflux apparatus, stir at 135 °C for 30 minutes while purging with nitrogen to completely dissolve it. Then, cool it (for example, at 25 °C for about 1 hour), and filter the obtained solution using filter paper to separate it into the filtrate and the residue on the filter paper. The portion obtained by removing the solvent from the filtrate is defined as the normal temperature xylene soluble fraction (XS). The solvent removal can be carried out, for example, by drying the filtrate at 140 °C under a nitrogen stream.

[0046] The intrinsic viscosity (IV) can be measured using a capillary viscometer, for example, a capillary automatic viscometer (SS-780-H1, manufactured by Shibayama Scientific Instruments Co., Ltd.) at 135 °C in tetrahydronaphthalene.

[0047] (iii) Fish eyes The amount of fish eyes in the propylene resin is preferably less than 200 pieces / 0.1 m 2 The amount of fish eyes is measured by making the propylene resin into a film. The amount of fish eyes is more preferably less than 100 pieces / 0.1 m 2 The lower limit value is not limited, but in one aspect, it is 5 pieces / 0.1 m 2 or more.

[0048] The fish-eye amount is preferably measured by the following method. Using a film defect detector (e.g., SCANTEC: Nagase Techno Engineering Co., Ltd.), under a certain threshold value, measure the number of fish-eyes (spherical defects with a diameter of 0.1 mm or more, with unmelted matter or gelified matter as the core) contained on the surface of the film. Then, evaluate this number as the number per 0.1 m 2 The threshold value is a value standardized so that the size and number of fish-eyes visually evaluated match the size and number of fish-eyes automatically detected by the film defect detector. For example, the threshold value can be set to -28. Classify and evaluate the size as follows. Large: Larger than 0.5 mm in diameter Medium: Larger than 0.2 mm in diameter and 0.5 mm in diameter or less Small: 0.2 mm in diameter or less

[0049] (5) Method for producing polypropylene-based resin The polypropylene-based resin is preferably produced through a step of polymerizing the corresponding monomer using the aforementioned catalyst. For example, the polypropylene-based resin is preferably produced through a sequential polymerization step of obtaining the component (A1) and then polymerizing the corresponding monomer in the presence of the (A1) to obtain the (A2).

[0050] As a method for producing the polymerization mixture, typically, a multi-stage polymerization method is used. For example, in the first-stage polymerization reactor of a polymerization apparatus equipped with two-stage polymerization reactors, propylene monomer and, if necessary, ethylene monomer are polymerized to obtain a propylene (co)polymer. Next, the obtained propylene (co)polymer is supplied to the second-stage polymerization reactor, and at the same time, an ethylene monomer and the α-olefin monomer are polymerized in the second-stage polymerization reactor to obtain a polypropylene-based resin. The polymerization conditions may be the same as known polymerization conditions. For example, as the polymerization conditions in the first stage, a slurry polymerization method in which propylene is in the liquid phase and has a high monomer density and productivity can be mentioned. As the polymerization conditions in the second stage, a gas-phase polymerization method that is generally easy to produce a copolymer with high solubility in propylene can be mentioned. The polymerization temperature is preferably 50 to 90°C, more preferably 60 to 90°C, and even more preferably 70 to 90°C. When the polymerization temperature is at or above the lower limit value of the above range, the productivity and the stereoregularity of the obtained polypropylene are more excellent.

[0051] When the polymerization pressure is carried out in the liquid phase, it is preferably 25 to 60 bar (2.5 to 6.0 MPa), more preferably 33 to 45 bar (3.3 to 4.5 MPa). When carried out in the gas phase, it is preferably 5 to 30 bar (0.5 to 3.0 MPa), more preferably 8 to 30 bar (0.8 to 3.0 MPa). The polymerization is usually carried out using a catalyst. During the polymerization, if necessary, hydrogen may be added for adjusting the molecular weight. By adjusting the molecular weight of component (A1) or component (A2), the MFR of the polypropylene-based resin can be adjusted. Before the polymerization in the first-stage polymerization reactor, prepolymerization of propylene may be carried out in order to form a polymer chain that serves as a basis for the subsequent main polymerization on the solid catalyst component. The prepolymerization is usually carried out at 40°C or lower, preferably 30°C or lower, and more preferably 20°C or lower.

[0052] For the polymerization, a polymerization reactor having a gradient of monomer concentration and polymerization conditions may be used. In such a polymerization reactor, for example, a reactor 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, the monomer is supplied and polymerized in a polymerization region composed of a riser pipe, and the monomer is supplied and polymerized in a downcomer pipe connected to the riser pipe. While circulating the riser pipe and the downcomer pipe, the polymer product is recovered. This method is provided with means for entirely or partially preventing the gas mixture present in the riser pipe from entering the downcomer pipe. Further, a gas or liquid mixture having a composition different from that of the gas mixture present in the riser pipe is introduced into the downcomer pipe. As the above polymerization method, for example, the method described in JP-T-2002-520426 can be applied.

[0053] 3. Molded article The polypropylene-based resin produced using the catalyst gives a molded article having an excellent appearance. Examples of the molded article include injection molded articles and extruded molded articles such as sheets. Since the polypropylene-based resin can reduce the generation of gels or fish eyes, the molded article has a good appearance. The temperature during molding may be 200 to 230 °C, which is a normal temperature. The sheet may be subjected to secondary molding (stretching, vacuum molding, etc.). For example, the stretching temperature may be 140 to 170 °C.

Examples

[0054] [Example 1] (1) Preparation of solid catalyst component (component (x)) According to the preparation method described in the examples of JP-A-2011-500907, a solid catalyst component was prepared. Specifically, the solid catalyst component was prepared as follows. Into a 500 mL four-necked round-bottom flask purged with nitrogen, 250 mL of TiCl 4 was introduced at 0 °C. While stirring, 10.0 g of finely spherical MgCl 2 ·1.8C 2 H 5 OH, and 9.1 mmol of diethyl-2,3-(diisopropyl) succinate were added. Finely spherical MgCl 2 ·1.8C2 H 5 OH was prepared according to the method described in Example 2 of U.S. Patent 4,399,054, except that it was produced by operating at 3000 rpm instead of 10000 rpm. Then, 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 was suctioned off. Next, the following operations were repeated twice. 250 mL of fresh TiCl 4 was added, and the mixture was reacted at 120 °C for 60 minutes, and the supernatant was suctioned off. The solid was washed 6 times with anhydrous hexane (6 × 100 mL) at 60 °C.

[0055] (2) Preparation of catalyst Ethylaluminum (TEAL) was taken as component (y), and dicyclopentyldimethoxysilane (DCPMS) was prepared as component (z). A 15 mL container was charged with 7.4 mL of heptane, 70 mg of component (x) prepared in (1) above, 6.7 mL of component (y), and 0.9 mL of component (z), and the reaction was carried out at 25 °C under a nitrogen atmosphere. The concentration of component (y) in the mixture (denoted as [TEAL] in the table) was 1.90 mol / L. The concentration of component (z) in the mixture was 0.1 mol / L.

[0056] (3) Polymerization The above solid catalyst, triethylaluminum (TEAL), and dicyclopentyldimethoxysilane (DCPMS) were brought into contact at room temperature for 5 minutes in such amounts that the weight ratio of TEAL to the solid catalyst was 0.005 and the weight ratio of TEAL / DCMPS was 28.6. The obtained catalyst system was prepolymerized by holding it in a suspended state in liquid propylene at 25°C for 5 minutes. The obtained prepolymer was introduced into a polymerization vessel as the first-stage (gas-liquid mixing) polymerization to obtain a propylene homopolymer (Component A1). After purging unreacted monomers from the obtained polymer, it was introduced into the polymerization vessel as the second-stage (gas) polymerization to polymerize a propylene-ethylene copolymer (Component A2). During the polymerization, the temperature and pressure were adjusted, and hydrogen was used as a molecular weight regulator. Regarding the polymerization temperature and the ratio of reactants, in the first stage, the polymerization temperature and hydrogen concentration were 75°C and 1.6 mol%, respectively. In the second stage, the polymerization temperature, hydrogen concentration, and C2 / (C2 + C3) were 80°C, 0 mol ppm, and 0.23 mol ratio, respectively. Also, the polymerization times of the first stage and the second stage were adjusted so that the ratio (Component A2) / (the polypropylene composition consisting of Component A1 and Component A2) (indicated as "BIPO" in the table) was 47% by weight. The MFR, BIPO, the amount of propylene in Component A2 (indicated as "Pc" in the table), and XSIV of the obtained polymer are shown in Table 1.

[0057] [Examples 2 to 9] A catalyst was prepared at the same TEAL concentration as in Example 1, and the polymerization conditions in the first stage and the second stage were appropriately adjusted to produce an ethylene-propylene copolymer as shown in Table 1.

[0058] [Example 10] A catalyst was prepared under the condition that the TEAL concentration was 0.96 mol / L, and an ethylene-propylene copolymer was produced in the same manner as in Example 1 except that the catalyst was used.

[0059] [Example 11] A catalyst was prepared under the condition that the TEAL concentration was 0.82 mol / L, and the propylene polymer shown in Table 1 was produced by using the catalyst and adjusting the polymerization conditions in the first stage and the second stage.

[0060] [Example 12] The catalyst was prepared under the condition that the TEAL concentration was 2.5 mol / L. Using this catalyst, the polymerization conditions in the first and second stages were adjusted to produce the propylene polymers shown in Table 1.

[0061] [Example 13] The catalyst was prepared under the condition that the TEAL concentration was 3.8 mol / L. Using this catalyst, the polymerization conditions in the first and second stages were adjusted to produce the propylene polymers shown in Table 1.

[0062] [Comparative Example 1] The catalyst was prepared under the condition that the TEAL concentration was 0.5 mol / L. Using this catalyst, the polymerization conditions in the first and second stages were adjusted to produce the propylene polymers shown in Table 1.

[0063] [Comparative Example 2] The catalyst was prepared under the condition that the TEAL concentration was 4.7 mol / L. Using this catalyst, the polymerization conditions in the first and second stages were adjusted to produce the propylene polymers shown in Table 1.

[0064]

Table 1

[0065] The properties shown in Table 1 were measured as follows. [Total ethylene amount of copolymer, ethylene-derived unit content of component (A1)] For the copolymer sample dissolved in the mixed solvent of 1,2,4-trichlorobenzene / deuterated benzene, using AVANCEIII HD400 ( 13 100 MHz C resonance frequency) manufactured by Bruker, under the conditions of measurement temperature 120 °C, flip angle 45 degrees, pulse interval 7 seconds, sample rotation speed 20 Hz, and integration times 5000 times 13 a C-NMR spectrum was obtained. Using the spectrum obtained above, the total ethylene content (wt%) of the copolymer sample was determined by the method described in the literature of Kakugo, Y. Naito, K. Mizunuma and T. Miyatake, Macromolecules, 15, 1150 - 1152 (1982).

[0066] [Ethylene-derived unit content in component (A2)] When calculating the ethylene-derived unit content (wt%) of component (a2), the calculation was performed in the same manner as for the total ethylene content, except that the integrated intensity T'ββ calculated by the following formula was used instead of the integrated intensity of Tββ determined when measuring the total ethylene content of the copolymer by the method described in the above literature. T'ββ = 0.98 × Sαγ × A / (1 - 0.98 × A) Here, A = Sαγ / (Sαγ + Sαδ), which is calculated from Sαγ and Sαδ described in the above literature. In the copolymer composed of component (A1) and component (A2), when component (A1) contains ethylene units, the ethylene-derived unit content in component (A2) can be determined by the following formula when the weight ratio component (A2) / [component (a1) + component (A2)] is clear from the polymerization conditions. Ethylene-derived unit content of component (A2) (unit: wt%) = [Total ethylene content of the copolymer - Ethylene-derived unit content of component (A1) × Content ratio of component (A1) in the copolymer] / (Content ratio of component (A2) in the copolymer)

[0067] [Weight ratio component (A2) / (component (A1) + component (A2))] It was determined by the following formula. Component (A2) / [component (A1) + component (A2)] (unit: wt%) = Total ethylene content of the copolymer / (Ethylene-derived unit content in component (A2) / 100)

[0068] [XSIV] The xylene-soluble fraction of the copolymer at room temperature was obtained by the following method, and the intrinsic viscosity (XSIV) of the xylene-soluble fraction at room temperature was measured. 2.5 g of the copolymer sample was placed in a flask containing 250 mL of o-xylene (solvent), and using a hot plate and a reflux apparatus, it was stirred at 135 °C for 30 minutes while purging with nitrogen until it was completely dissolved, and then cooled at 25 °C for 1 hour. The solution thus obtained was filtered using filter paper. 100 mL of the filtrate after filtration was collected, transferred to an aluminum cup or the like, and evaporated to dryness at 140 °C while purging with nitrogen, and left standing at room temperature for 30 minutes to obtain a normal temperature xylene-soluble component. The intrinsic viscosity was measured at 135 °C in tetralin using a capillary automatic viscometer (SS-780-H1, manufactured by Shibayama Scientific Instruments Co., Ltd.).

[0069] [MFR] For 5 g of the sample, it was measured according to JIS K6921-2 under the conditions of a temperature of 230 °C and a load of 2.16 kg.

[0070] [Fish eye] Using a film defect detector SCANTEC (Nagase Technopolis Corporation), the number of fish eyes (spherical defects with a diameter of 0.1 mm or more having unmelted matter or gelified matter as the core) contained on the surface of the film was counted, and it was evaluated as the number per 0.1 m. The threshold value was set to -28. The threshold value was a value standardized so that the size and number of fish eyes visually evaluated and the size and number of fish eyes automatically detected by the film defect detector would match. The size classification was as follows. 2 Large: Larger than a diameter of 0.5 mm Large: Larger than a diameter of 0.5 mm Medium: Larger than a diameter of 0.2 mmφ and 0.5 mmφ or less Small: 0.2 mmφ or less in diameter

Claims

1. (1) In a hydrophobic hydrocarbon solvent, (x) a solid catalyst comprising magnesium, titanium, a halogen, and an internal electron donor compound, (y) an organoaluminum compound, (z) an electron donor compound as required, are reacted in a step where the reaction is carried out at a concentration of (y) organoaluminum of 0.8 to 4.0 mol / L to produce an α-olefin polymerization catalyst. (2) A step of polymerizing a corresponding monomer using the catalyst to produce a propylene-based resin composed of the following (A1) and (A2) and having the characteristics of (i) and (ii): (A1) A propylene homopolymer or a propylene copolymer: 30 to 85% by weight (A2) A copolymer of ethylene and a C3-C10 α-olefin having an ethylene content of 20 to 60% by weight: 15 to 70% by weight (i) The melt flow rate (230 °C, load 21.18 N) is 0.1 to 30 g / 10 min (ii) The intrinsic viscosity of the xylene-soluble component at room temperature in the propylene-based resin: 5.5 to 9.0 dL / g A method for producing a polypropylene-based resin comprising the above.

2. The production method according to Claim 1, wherein the concentration of the component (y) is 1.0 to 4.0 mol / L.

3. The production method according to Claim 1 or 2, wherein the component (y) is a trialkylaluminum.

4. The production method according to Claim 3, wherein the component (y) is triethylaluminum.

5. The production method according to Claim 1 or 2, wherein the internal electron donor compound is selected from phthalate-based compounds or succinate-based compounds.

6. The production method according to Claim 1 or 2, wherein the component (z) contains Si and the Si / Al ratio in the catalyst is 0.005 to 1.

0.

7. The amount of fish eyes measured by forming the propylene polymer into a film is less than 200 pieces / 0.1 m ２ The production method according to claim 1 or 2, wherein the amount is less than 200 pieces / 0.1 m

8. A polypropylene-based resin produced by the method according to Claim 1 or 2.

9. The polypropylene-based resin according to Claim 8, wherein the component (A2) is an ethylene-α-olefin copolymer containing 20 to 35% by weight of ethylene-derived units.

10. A molded article formed by molding a composition containing the polypropylene-based resin according to Claim 8.

11. (x) A solid catalyst comprising magnesium, titanium, a halogen, and an internal electron donor compound as essential components (y) An organoaluminum compound (z) An electron donor compound as required A step of reacting in a hydrophobic hydrocarbon solvent, the reaction being carried out at a concentration of organoaluminum of 0.8 to 4.0 mol / L (y), and an α-olefin polymerization catalyst produced by a method comprising this step.

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