JP2013216772A - Polypropylene resin composition, and molding including the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polypropylene resin composition whose volatile organic compound component is reduced while maintaining rigidity, and to provide a molding including the same.SOLUTION: A polypropylene resin composition includes: a propylene polymer (component (β)) produced by using a specific catalyst for olefin polymerization; 0.01-0.5 pt.wt. of a specific compound (component (γ)) based on 100 pts.wt. of the component (β); and 0.01-0.5 pt.wt. of a specific compound (component (δ)) based on 100 pts.wt. of the component (β). A molding including the polypropylene resin composition is disclosed.

Description

  The present invention relates to a polypropylene resin composition in which volatile organic compound components are reduced while maintaining rigidity, and a molded body including the same.

  Polypropylene has a wide range of uses as a material with excellent rigidity and heat resistance, and is a molding material for various industrial parts such as automobile interior and exterior parts such as bumpers and instrument panels (dashboards), and home appliance parts such as TV cases. Has been used. In recent years, these products have been made thinner, more functional, and larger in size, and further enhancement of the performance of polypropylene as a material is required.

  For example, Patent Document 1 describes a polymerization catalyst capable of producing an olefin polymer obtained by combining a trivalent titanium compound-containing solid catalyst component, an organoaluminum compound, and a specific silicon compound. Patent Documents 2 and 3 describe a method for producing an α-olefin polymer in which an α-olefin is polymerized using an α-olefin polymerization catalyst obtained by contacting a specific triethoxysilicon compound. Has been.

  Patent Document 4 discloses a thermoplastic polymer composition containing trehalose and a thermoplastic polymer, a processing stabilizer for thermoplastic polymer containing trehalose as an active ingredient, and a processing stability of the thermoplastic polymer. Of trehalose is described.

  Patent Document 5 describes a polypropylene resin composition in which montmorillonite and an antioxidant are blended with a polypropylene resin containing an inorganic filler for the purpose of improving thermal degradation / thermal oxidation degradation and fogging.

  In Patent Document 6, ethylene and 4-acryloyloxy-2,2,6,6-tetramethylpiperidine are used for the resin composition for the purpose of suppressing VOC emission, improving weather resistance and preventing glass fogging. A polyolefin resin composition blended with a copolymer and a molded product thereof are described.

JP-A-2-163104 JP 2010-168545 A JP 2011-184538 A JP 2011-32460 A Japanese Patent Laid-Open No. 10-316809 JP 2006-290961 A

  In recent years, reduction of volatile organic compounds (abbreviated as VOC) has been demanded for resin materials to be used. Resin materials with low VOC are also used in interior materials of vehicles such as automobiles. The use of is desired.

  Also in the materials described in Patent Documents 1 to 6, reduction of volatile organic compound components is required. The objective of this invention is providing the polypropylene resin composition which reduced the volatile organic compound component, and a molded object containing the same, maintaining rigidity.

  As a result of intensive studies, the present inventors have found that the present invention can solve the above problems, and have completed the present invention.

（Ｉ）
（式中、Ｒ^ａ、Ｒ^ｂ、Ｒ^ｃ、Ｒ^ｄ、Ｒ^ｅおよびＲ^ｆはそれぞれ独立に、水素原子または炭素原子数１〜２０のハイドロカルビル基を表し、但し、Ｒ^ａ、Ｒ^ｂ、Ｒ^ｅおよびＲ^ｆの少なくとも１つは炭素原子数１〜２０のハイドロカルビル基である。Ｒ^ａおよびＲ^ｂ、Ｒ^ｃおよびＲ^ｄ、Ｒ^ｅおよびＲ^ｆは、それぞれ互いに結合して環を形成してもよい。形成される該環は、該環の骨格中に二重結合が含まれていてもよく、該環の骨格をなす炭素原子の数は５〜１０である。Ｒ^ａおよびＲ^ｂのいずれか１つと、Ｒ^ｃおよびＲ^ｄのいずれか１つとは互いに結合して環を形成していてもよく、Ｒ^ｃおよびＲ^ｄのいずれか１つとＲ^ｅおよびＲ^ｆのいずれか１つは互いに結合して環を形成していてもよい。形成される該環は、該環の骨格中に二重結合が含まれていてもよく、該環の骨格をなす炭素原子の数は５〜１０である。ｎは１〜４の数を表す。）

化合物（成分（γ））：下記の化合物群Ｓから選ばれる少なくとも１種の化合物。
化合物群Ｓ：一般式Ｃ_nＨ_n+2（ＯＨ）_nで表される化合物（式中、ｎは４以上の整数を表す。）、下記のアルコキシ化体、下記の式（２）で表される化合物、トレハロース、スクロース、ラクトース、マルトース、メレチトース、スタキオース、カードラン、グリコーゲン、グルコースおよびフルクトースからなる化合物群。
アルコキシ化体：下記の式（１）で表される化合物に含まれる水酸基の少なくとも１個が炭素数１〜１２のアルキル基でアルコキシ化された化合物であり、該式（２）で表される化合物は、分子内にアルデヒド基またはケトン基１個とｍ−１個の水酸基とを有する化合物である。
Ｃ_ｍＨ_２ｍＯ_ｍ （１）
（式（１）中、ｍは３以上の整数を表す。）

（２）
（式（２）中、ｐは２以上の整数を表す。）

（３）
（式（３）中、各Ｒ^ｓ１および各Ｒ^ｓ２は、それぞれ独立して、炭素数１〜８のアルキル基、炭素数６〜１２のアリール基または炭素数７〜１８のアラルキル基を表す。Ｒ^ｓ３は、水素原子または炭素数１〜３のアルキル基を表す。Ｒ^ｓ４は、水素原子またはメチル基を表す。）

（４）
（式（４）中、Ｒ^ｐ１、Ｒ^ｐ２、Ｒ^ｐ４およびＲ^ｐ５は、それぞれ独立して、水素原子、炭素数１〜８のアルキル基、炭素数５〜８のシクロアルキル基、炭素数６〜１２のアルキルシクロアルキル基、炭素数７〜１２のアラルキル基またはフェニル基を表し、Ｒ^ｐ３はそれぞれ独立して、水素原子または炭素数１〜８のアルキル基を表し、Ｘは単結合、硫黄原子または下記の式（４−１）

（４−１）
（式（４−１）中、Ｒ^ｐ６は水素原子、炭素数１〜８のアルキル基または炭素数５〜８のシクロアルキル基を示す。）で示される２価の基を表し、Ａは炭素数２〜８のアルキレン基または下記の式（４−２）

（４−２）
（式（４−２）中、Ｒ^ｐ７は単結合または炭素数１〜８のアルキレン基を表し、＊は酸素原子に結合する部位を表す。）で示される２価の基を表し、Ｙ、Ｚはいずれか一方がヒドロキシ基、炭素数１〜８のアルキル基、炭素数１〜８のアルコキシ基または炭素数７〜１２のアラルキルオキシ基を表し、他方が水素原子または炭素数１〜８のアルキル基を表す。） That is, the present invention relates to a propylene polymer (component (β)) produced using the following olefin polymerization catalyst and the following compound (component (γ)) with respect to 100 parts by weight of the component (β). 0.01 to 0.5 parts by weight and 100 parts by weight of the component (β) are selected from the group consisting of the compound represented by the following formula (3) and the compound represented by the formula (4) And a compound (component (δ)) in an amount of 0.01 to 0.5 parts by weight.
Olefin polymerization catalyst:
An olefin polymerization catalyst obtained by contacting the following components (A), (B) and (C).
(A) Solid catalyst component for olefin polymerization containing titanium atom, magnesium atom, and halogen atom (B) Organoaluminum compound (C) Lactone compound represented by formula (I)

(I)
(In the formula, R ^a , R ^b , R ^c , R ^d , R ^e and R ^f each independently represents a hydrogen atom or a hydrocarbyl group having 1 to 20 carbon atoms, provided that R ^a , R ^b , R ^e and R ^f are each a hydrocarbyl group having 1 to 20 carbon atoms, R ^a and R ^b , R ^c and R ^d , R ^e and R ^f are bonded to each other to form a ring. The ring formed may contain a double bond in the skeleton of the ring, and the number of carbon atoms forming the skeleton of the ring is 5 to 10. R ^a And R ^b and any one of R ^c and R ^d may be bonded to each other to form a ring, and any one of R ^c and R ^d and any of R ^e and R ^f Or one of them may be bonded to each other to form a ring. May be contained a double bond in the rating, the number of carbon atoms forming the ring backbone is 5 to 10 .n represents the number of 1-4.)

Compound (component (γ)): at least one compound selected from the following compound group S.
Compound group S: a compound represented by the general formula C _n H _{n + 2} (OH) _n (wherein _n represents an integer of 4 or more), the following alkoxy compound, and the following formula (2) A group of compounds consisting of a compound to be obtained, trehalose, sucrose, lactose, maltose, meletitose, stachyose, curdlan, glycogen, glucose and fructose.
Alkoxy compound: a compound in which at least one of the hydroxyl groups contained in the compound represented by the following formula (1) is alkoxylated with an alkyl group having 1 to 12 carbon atoms, and represented by the formula (2) The compound is a compound having one aldehyde group or ketone group and m-1 hydroxyl groups in the molecule.
C _m H _2m O _m (1)
(In formula (1), m represents an integer of 3 or more.)

(2)
(In formula (2), p represents an integer of 2 or more.)

(3)
(In Formula (3), each R ^s1 and each R ^s2 each independently represent an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 18 carbon atoms. R ^s3 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ^s4 represents a hydrogen atom or a methyl group.)

(4)
(In formula (4), R ^p1 , R ^p2 , R ^p4 and R ^p5 each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, or 6 carbon atoms. Represents an alkylcycloalkyl group having 12 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or a phenyl group, R ^p3 each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, X is a single bond, sulfur Atom or the following formula (4-1)

(4-1)
(In formula (4-1), R ^p6 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a cycloalkyl group having 5 to 8 carbon atoms), and A represents carbon. An alkylene group of 2 to 8 or the following formula (4-2)

(4-2)
(In formula (4-2), R ^p7 represents a single bond or an alkylene group having 1 to 8 carbon atoms, and * represents a site bonded to an oxygen atom.) Y, Z represents a hydroxy group, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms or an aralkyloxy group having 7 to 12 carbon atoms, and the other is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. Represents an alkyl group. )

  Moreover, this invention concerns on the molded object containing said polypropylene resin composition.

  ADVANTAGE OF THE INVENTION According to this invention, the polypropylene resin composition which reduced the volatile organic compound component can be obtained, maintaining rigidity.

（Ｉ）
（式中、Ｒ^ａ、Ｒ^ｂ、Ｒ^ｃ、Ｒ^ｄ、Ｒ^ｅおよびＲ^ｆはそれぞれ独立に、水素原子または炭素原子数１〜２０のハイドロカルビル基を表し、但し、Ｒ^ａ、Ｒ^ｂ、Ｒ^ｅおよびＲ^ｆの少なくとも１つは炭素原子数１〜２０のハイドロカルビル基である。Ｒ^ａおよびＲ^ｂ、Ｒ^ｃおよびＲ^ｄ、Ｒ^ｅおよびＲ^ｆは、それぞれ互いに結合して環を形成してもよい。形成される該環は、該環の骨格中に二重結合が含まれていてもよく、該環の骨格をなす炭素原子の数は５〜１０である。Ｒ^ａおよびＲ^ｂのいずれか１つと、Ｒ^ｃおよびＲ^ｄのいずれか１つとは互いに結合して環を形成していてもよく、Ｒ^ｃおよびＲ^ｄのいずれか１つとＲ^ｅおよびＲ^ｆのいずれか１つは互いに結合して環を形成していてもよい。形成される該環は、該環の骨格中に二重結合が含まれていてもよく、該環の骨格をなす炭素原子の数は５〜１０である。ｎは１〜４の数を表す。）

化合物（成分（γ））：下記の化合物群Ｓから選ばれる少なくとも１種の化合物。
化合物群Ｓ：一般式Ｃ_nＨ_n+2（ＯＨ）_nで表される化合物（式中、ｎは４以上の整数を表す。）、下記のアルコキシ化体、下記の式（２）で表される化合物、トレハロース、スクロース、ラクトース、マルトース、メレチトース、スタキオース、カードラン、グリコーゲン、グルコースおよびフルクトースからなる化合物群。
アルコキシ化体：下記の式（１）で表される化合物に含まれる水酸基の少なくとも１個が炭素数１〜１２のアルキル基でアルコキシ化された化合物であり、該式（２）で表される化合物は、分子内にアルデヒド基またはケトン基１個とｍ−１個の水酸基とを有する化合物である。
Ｃ_ｍＨ_２ｍＯ_ｍ （１）
（式（１）中、ｍは３以上の整数を表す。）

（２）
（式（２）中、ｐは２以上の整数を表す。）

（３）
（式（３）中、各Ｒ^ｓ１および各Ｒ^ｓ２は、それぞれ独立して、炭素数１〜８のアルキル基、炭素数６〜１２のアリール基または炭素数７〜１８のアラルキル基を表す。Ｒ^ｓ３は、水素原子または炭素数１〜３のアルキル基を表す。Ｒ^ｓ４は、水素原子またはメチル基を表す。）

（４）
（式（４）中、Ｒ^ｐ１、Ｒ^ｐ２、Ｒ^ｐ４およびＲ^ｐ５は、それぞれ独立して、水素原子、炭素数１〜８のアルキル基、炭素数５〜８のシクロアルキル基、炭素数６〜１２のアルキルシクロアルキル基、炭素数７〜１２のアラルキル基またはフェニル基を表し、Ｒ^ｐ３はそれぞれ独立して、水素原子または炭素数１〜８のアルキル基を表し、Ｘは単結合、硫黄原子または下記の式（４−１）

（４−１）
（式（４−１）中、Ｒ^ｐ６は水素原子、炭素数１〜８のアルキル基または炭素数５〜８のシクロアルキル基を示す。）で示される２価の基を表し、Ａは炭素数２〜８のアルキレン基または下記の式（４−２）

（４−２）
（式（４−２）中、Ｒ^ｐ７は単結合または炭素数１〜８のアルキレン基を表し、＊は酸素原子に結合する部位を表す。）で示される２価の基を表し、Ｙ、Ｚはいずれか一方がヒドロキシ基、炭素数１〜８のアルキル基、炭素数１〜８のアルコキシ基または炭素数７〜１２のアラルキルオキシ基を表し、他方が水素原子または炭素数１〜８のアルキル基を表す。） 1. Polypropylene Resin Composition The polypropylene resin composition of the present invention comprises a propylene polymer (hereinafter sometimes referred to as “component (β)”) produced using the following olefin polymerization catalyst, and the component ( β) 100 parts by weight of the following compound (hereinafter sometimes referred to as “component (γ)”) 0.01 to 0.5 parts by weight and 100 parts by weight of the component (β) In addition, a compound selected from the group consisting of a compound represented by the following formula (3) and a compound represented by formula (4) (hereinafter sometimes referred to as “component (δ)”): 01 to 0.5 parts by weight.
Olefin polymerization catalyst: Olefin polymerization catalyst obtained by contacting the following components (A), (B) and (C).
(A) Solid catalyst component for olefin polymerization containing titanium atom, magnesium atom, and halogen atom (B) Organoaluminum compound (C) Lactone compound represented by formula (I)

(I)
(In the formula, R ^a , R ^b , R ^c , R ^d , R ^e and R ^f each independently represents a hydrogen atom or a hydrocarbyl group having 1 to 20 carbon atoms, provided that R ^a , R ^b , R ^e and R ^f are each a hydrocarbyl group having 1 to 20 carbon atoms, R ^a and R ^b , R ^c and R ^d , R ^e and R ^f are bonded to each other to form a ring. The ring formed may contain a double bond in the skeleton of the ring, and the number of carbon atoms forming the skeleton of the ring is 5 to 10. R ^a And R ^b and any one of R ^c and R ^d may be bonded to each other to form a ring, and any one of R ^c and R ^d and any of R ^e and R ^f Or one of them may be bonded to each other to form a ring. May be contained a double bond in the rating, the number of carbon atoms forming the ring backbone is 5 to 10 .n represents the number of 1-4.)

Compound (component (γ)): at least one compound selected from the following compound group S.
Compound group S: a compound represented by the general formula C _n H _{n + 2} (OH) _n (wherein _n represents an integer of 4 or more), the following alkoxy compound, and the following formula (2) A group of compounds consisting of a compound to be obtained, trehalose, sucrose, lactose, maltose, meletitose, stachyose, curdlan, glycogen, glucose and fructose.
Alkoxy compound: a compound in which at least one of the hydroxyl groups contained in the compound represented by the following formula (1) is alkoxylated with an alkyl group having 1 to 12 carbon atoms, and represented by the formula (2) The compound is a compound having one aldehyde group or ketone group and m-1 hydroxyl groups in the molecule.
C _m H _2m O _m (1)
(In formula (1), m represents an integer of 3 or more.)

(2)
(In formula (2), p represents an integer of 2 or more.)

(3)
(In Formula (3), each R ^s1 and each R ^s2 each independently represent an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 18 carbon atoms. R ^s3 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ^s4 represents a hydrogen atom or a methyl group.)

(4)
(In formula (4), R ^p1 , R ^p2 , R ^p4 and R ^p5 each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, or 6 carbon atoms. Represents an alkylcycloalkyl group having 12 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or a phenyl group, R ^p3 each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, X is a single bond, sulfur Atom or the following formula (4-1)

(4-1)
(In formula (4-1), R ^p6 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a cycloalkyl group having 5 to 8 carbon atoms), and A represents carbon. An alkylene group of 2 to 8 or the following formula (4-2)

(4-2)
(In formula (4-2), R ^p7 represents a single bond or an alkylene group having 1 to 8 carbon atoms, and * represents a site bonded to an oxygen atom.) Y, Z represents a hydroxy group, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms or an aralkyloxy group having 7 to 12 carbon atoms, and the other is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. Represents an alkyl group. )

<Propylene polymer (component (β))>
The propylene polymer (component (β)) used in the present invention refers to a propylene homopolymer or a copolymer of propylene and another monomer. These may be used alone or in combination of two or more. Examples of the copolymer include a random copolymer, a block copolymer, a propylene homopolymer component, or a polymer component having a structural unit derived from propylene as a main structural unit (hereinafter referred to as “polymer component (β -1) ”) and a copolymer component of propylene and ethylene and / or α-olefin (hereinafter, sometimes referred to as“ polymer component (β-2) ”). Polymerized materials consisting of

The component (β) is described as an isotactic pentad fraction (hereinafter referred to as “[mmmm] fraction”) measured by ¹³ C-NMR, from the viewpoint of the balance between the tensile strength and impact resistance of the polypropylene resin composition. Is preferably 0.97 or more, and more preferably 0.98 or more. The isotactic pentad fraction referred to here is A.I. Isotactic linkage at the pentad unit in a crystalline polypropylene molecular chain as measured using the method published by Zambelli et al., Macromolecules, 1973, 6, 925-926, ie using ¹³ C-NMR. In other words, it is the fraction of propylene monomer units at the center of a chain in which five propylene monomer units are continuously meso-bonded. However, the assignment of the NMR absorption peak is based on Macromolecules, 1975, No. 8, pages 687 to 689, which was subsequently published. The theoretical upper limit of the [mmmm] fraction is 1.00. As the isotactic [mmmm] fraction is closer to 1.00, the component (A) is an index representing a highly crystalline polymer having a molecular structure exhibiting high stereoregularity.
In the case where the component (β) is a polymer material composed of the random copolymer or the polymer component (β-1) and the polymer component (β-2), a chain of propylene units in the copolymer. Use the value measured for.

  The melt flow rate (MFR) measured under a load of 2.16 kg at 230 ° C. of the component (β) is from the viewpoint of the balance between the tensile strength and impact resistance of the obtained molded product and the moldability of the resin composition. It is preferably 0.05 to 500 g / 10 minutes, more preferably 1 to 120 g / 10 minutes, further preferably 1 to 80 g / 10 minutes, and 5 to 50 g / 10 minutes. Particularly preferred.

Examples of the random copolymer include a random copolymer comprising a structural unit derived from propylene and a structural unit derived from ethylene; a structural unit derived from propylene and a structure derived from an α-olefin other than propylene. A random copolymer comprising units; a random copolymer comprising a structural unit derived from propylene, a structural unit derived from ethylene, and a structural unit derived from an α-olefin other than propylene.
The α-olefin other than propylene constituting the random copolymer is an α-olefin having 4 to 10 carbon atoms, such as 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene. 1-octene, 1-decene, etc., preferably 1-butene, 1-hexene or 1-octene.

Examples of the random copolymer composed of a structural unit derived from propylene and a structural unit derived from an α-olefin include, for example, propylene-1-butene random copolymer, propylene-1-hexene random copolymer, propylene- Examples thereof include 1-octene random and propylene-1-decene random copolymer.
Examples of the random copolymer comprising a structural unit derived from propylene, a structural unit derived from ethylene, and a structural unit derived from α-olefin include, for example, propylene-ethylene-1-butene copolymer, propylene-ethylene. Examples include -1-hexene copolymer, propylene-ethylene-1-octene, and propylene-ethylene-1-decene copolymer.

  The content of structural units derived from ethylene and / or α-olefin in the random copolymer is preferably 0.1 to 40% by weight, more preferably 0.1 to 30% by weight, More preferably, it is 2 to 15% by weight. The content of the structural unit derived from propylene is preferably 99.9 to 60% by weight, more preferably 99.9 to 70% by weight, and still more preferably 98 to 85% by weight. (However, the total weight of the random copolymer is 100% by weight.)

  The polymer component having a structural unit derived from propylene as the main structural unit in the polymer component (β-1) is, for example, at least one selected from the group consisting of ethylene and an α-olefin having 4 to 10 carbon atoms. Examples thereof include a propylene copolymer component composed of a structural unit derived from a kind of comonomer and a structural unit derived from propylene.

When the polymer component (β-1) is a polymer component having a structural unit derived from propylene as a main structural unit, at least one selected from the group consisting of ethylene and an α-olefin having 4 to 10 carbon atoms. The content of the structural unit derived from the seed comonomer is 0.01% by weight or more and less than 20% by weight (provided that the weight of the polymer component (β-1) is 100% by weight).
The α-olefin having 4 to 10 carbon atoms is preferably 1-butene, 1-hexene or 1-octene, more preferably 1-butene.

Examples of the polymer component having a structural unit derived from propylene as a main structural unit include, for example, a propylene-ethylene copolymer component, a propylene-1-butene copolymer component, a propylene-1-hexene copolymer component, and propylene. Examples include a -1-octene copolymer component, a propylene-ethylene-1-butene copolymer component, a propylene-ethylene-1-hexene copolymer component, and a propylene-ethylene-1-octene copolymer component.
The polymer component (β-1) is preferably a propylene homopolymer component, a propylene-ethylene copolymer component, a propylene-1-butene copolymer component or a propylene-ethylene-1-butene copolymer component. is there.

The polymer component (β-2) is preferably a structural unit derived from at least one comonomer selected from the group consisting of ethylene and an α-olefin having 4 to 10 carbon atoms, and a structural unit derived from propylene. Is a copolymer component.
The content of units derived from at least one comonomer selected from the group consisting of ethylene and an α-olefin having 4 to 10 carbon atoms contained in the polymer component (β-2) is preferably 20 to 80. % By weight, more preferably 20 to 60% by weight, still more preferably 30 to 60% by weight (provided that the weight of the polymer component (β-2) is 100% by weight).

  The α-olefin having 4 to 10 carbon atoms constituting the polymer component (β-2) is, for example, the same α as the α-olefin having 4 to 10 carbon atoms constituting the polymer component (β-1). -Olefins.

  Examples of the polymer component (β-2) include a propylene-ethylene copolymer component, a propylene-ethylene-1-butene copolymer component, a propylene-ethylene-1-hexene copolymer component, and propylene-ethylene-1. -Octene copolymer component, propylene-ethylene-1-decene copolymer component, propylene-1-butene copolymer component, propylene-1-hexene copolymer component, propylene-1-octene copolymer component, propylene -1-decene copolymer component and the like, preferably propylene-ethylene copolymer component, propylene-1-butene copolymer component or propylene-ethylene-1-butene copolymer component, more preferably. Is a propylene-ethylene copolymer component.

  The content of the polymer component (β-2) of the polymer material composed of the polymer component (β-1) and the polymer component (β-2) is preferably 1 to 50% by weight, and 1 to 40% by weight. %, More preferably 10 to 40% by weight, particularly preferably 10 to 30% by weight (provided that the weight of the propylene polymer (component (β)) is 100% by weight. To do).

  When the polymer component (β-1) of the propylene copolymer comprising the polymer component (β-1) and the polymer component (β-2) is a propylene homopolymer component, For example, (propylene)-(propylene-ethylene) copolymer, (propylene)-(propylene-ethylene-1-butene) copolymer, (propylene)-(propylene-ethylene-1-hexene) copolymer, (Propylene)-(propylene-ethylene-1-octene) copolymer, (propylene)-(propylene-1-butene) copolymer, (propylene)-(propylene-1-hexene) copolymer, (propylene)- (Propylene-1-octene) copolymer, (propylene)-(propylene-1-decene) copolymer and the like.

  In addition, the polymer component (β-1) of the polymer material composed of the polymer component (β-1) and the polymer component (β-2) has a structural unit derived from propylene as a main structural unit. In the case of, the propylene copolymer comprising the polymer component (β-1) and the polymer component (β-2) is, for example, a (propylene-ethylene)-(propylene-ethylene) copolymer, (propylene- (Ethylene)-(propylene-ethylene-1-butene) copolymer, (propylene-ethylene)-(propylene-ethylene-1-hexene) copolymer, (propylene-ethylene)-(propylene-ethylene-1-octene) Copolymer, (propylene-ethylene)-(propylene-ethylene-1-decene) copolymer, (propylene-ethylene)-(propylene-1-butene) copolymer, (propylene) -Ethylene)-(propylene-1-hexene) copolymer, (propylene-ethylene)-(propylene-1-octene) copolymer, (propylene-ethylene)-(propylene-1-decene) copolymer, (Propylene-1-butene)-(propylene-ethylene) copolymer, (propylene-1-butene)-(propylene-ethylene-1-butene) copolymer, (propylene-1-butene)-(propylene-ethylene) -1-hexene) copolymer, (propylene-1-butene)-(propylene-ethylene-1-octene) copolymer, (propylene-1-butene)-(propylene-ethylene-1-decene) copolymer , (Propylene-1-butene)-(propylene-1-butene) copolymer, (propylene-1-butene)-(propylene-1-hexene) copolymer , (Propylene-1-butene)-(propylene-1-octene) copolymer, (propylene-1-butene)-(propylene-1-decene) copolymer, (propylene-1-hexene)-(propylene) -1-hexene) copolymer, (propylene-1-hexene)-(propylene-1-octene) copolymer, (propylene-1-hexene)-(propylene-1-decene) copolymer, (propylene- 1-octene)-(propylene-1-octene) copolymer, (propylene-1-octene)-(propylene-1-decene) copolymer, and the like.

  The propylene copolymer composed of the polymer component (β-1) and the polymer component (β-2) is preferably a (propylene)-(propylene-ethylene) copolymer, (propylene)-(propylene-ethylene). -1-butene) copolymer, (propylene-ethylene)-(propylene-ethylene) copolymer, (propylene-ethylene)-(propylene-ethylene-1-butene) copolymer or (propylene-1-butene) -(Propylene-1-butene) copolymer, more preferably (propylene)-(propylene-ethylene) copolymer.

The intrinsic viscosity ([η] ₁ ) measured in 135 ° C. tetralin of the polymer component (β-1) is 0.1 to 5 dl / g, preferably 0.3 to 4 dl / g. More preferably, it is 0.5-3 dl / g.

The intrinsic viscosity ([η] ₂ ) measured in 135 ° C. tetralin of the polymer component (β-2) is 1 to 20 dl / g, preferably 1 to 10 dl / g, more preferably 2 ~ 7 dl / g.

The ratio of the intrinsic viscosity ([η] ₂ ) of the polymer component (β-2) to the intrinsic viscosity ([η] ₁ ) of the polymer component (β- ₁ ) is preferably 1 to 20, More preferably, it is 2-10, More preferably, it is 2-9.

The intrinsic viscosity (unit: dl / g) in the present invention is a value measured at a temperature of 135 ° C. using tetralin as a solvent by the following method.
Using a Ubbelohde viscometer, the reduced viscosity is measured at three points of concentrations of 0.1 dl / g, 0.2 dl / g and 0.5 dl / g. The intrinsic viscosity is a calculation method described in “Polymer Solution, Polymer Experiments 11” (published by Kyoritsu Shuppan Co., Ltd.), page 491. That is, the reduced viscosity is plotted against the concentration and the concentration is extrapolated to zero Obtained by extrapolation.

  When the propylene polymer (component (β)) is a polymerization material obtained by multi-stage polymerization of the polymer component (β-1) and the polymer component (β-2), a part of the polymer was extracted from the preceding polymerization tank. The intrinsic viscosity of the polymer component (β-1) or the polymer component (β-2) is obtained from the polymer powder, and the intrinsic viscosity of the remaining components is calculated using this intrinsic viscosity value and the content of each component. .

Moreover, the propylene copolymer which consists of a polymer component ((beta) -1) and a polymer component ((beta) -2), a polymer component ((beta) -1) is obtained at the superposition | polymerization process of a front | former stage, and a polymer component ((beta)) -2) is a copolymer produced by the method obtained in the subsequent step, the content of the polymer component (β-1) and the polymer component (β-2), the intrinsic viscosity ([η] _Total , [Η] ₁ , [η] ₂ ) are measured and calculated as follows. The intrinsic viscosity ([η] _Total ) indicates the intrinsic viscosity of the entire propylene polymer (component (β)).

The intrinsic viscosity ([η] ₁ ) of the polymer component (β-1) obtained in the preceding polymerization step, the final polymer (component (β-1) and component (β-2)) after the subsequent polymerization step. From the intrinsic viscosity ([η] _Total ) measured by the above method and the content of the polymer component (β-2) contained in the final polymer, the intrinsic viscosity [η] _{2 of the} polymer component (β-2) ₂ Is calculated from the following equation.
[Η] ₂ = ([η] _Total − [η] ₁ × F ₁ ) / F ₂
[Η] _Total : Intrinsic viscosity (dl / g) of the final polymer after the subsequent polymerization step
[Η] ₁ : Intrinsic viscosity of polymer powder extracted from the polymerization tank after the previous polymerization step (dl /
g)
F ₁ : Weight ratio of polymer component (β-1) to the entire propylene polymer (component (β)) F ₂ : Weight ratio of polymer component (β-2) to the entire propylene polymer (component (β)) F ₁ and F ₂ are determined from the material balance during polymerization.

Weight ratio (F ₂ ) of polymer component (β-2) to the entire propylene polymer (component (β)), and comonomer of the polymer component (β-2) in the propylene polymer (component (β)) The content of the unit derived from ((Cα ′) ₂ ) is based on the report of Kakugo et al. (Macromolecules 1982, 15, 1150-1152) from the ¹³ C-NMR spectrum of the propylene polymer (component (β)). You can ask.

In addition to the above, the weight ratio (F ₂ ) of the polymer component (β-2) to the entire propylene polymer (component (β)) is as follows: propylene homopolymer component and propylene polymer (component (β)) It is also possible to measure the amount of heat of crystal melting of each of them and calculate it using the following formula. The amount of heat of crystal melting can be measured by differential scanning thermal analysis (DSC).
F ₂ = 1− (ΔHf) _Total / (ΔHf)
(ΔHf) _Total : heat of fusion of the entire propylene polymer (β) (cal / g)
(ΔHf): heat of fusion of propylene homopolymer component (cal / g)

As a method for obtaining the content ((Cα ′) 2) of units derived from the comonomer of the polymer component (β-2) in the propylene polymer (component (β)), in addition to the above, by infrared absorption spectrum method The content ((Cα ′) Total) of units derived from the comonomer of the entire propylene polymer (β) is measured, and can be obtained by calculation using the following formula.
(Cα ′) ₂ = (Cα ′) _Total / F ₂
(Cα ′) _Total : Propylene polymer (component (β)) content of units derived from the entire comonomer (% by weight)
(Cα ′) ₂ : Content (% by weight) of units derived from the comonomer of the polymer component (β-2)

  The propylene polymer (component (β)) of the present invention is obtained by producing using a specific olefin polymerization catalyst.

  The catalyst for olefin polymerization used in the present invention is obtained by contacting the component (A), the component (B), the component (C) and optionally the component (D).

[Lactone compound (C)]
Examples of the hydrocarbyl group of R ^a , R ^b , R ^c , R ^d , R ^e and R ^{f in} the general formula (I) include an alkyl group, an aralkyl group, an aryl group, an alkenyl group, and the like. You may have an atom, a silyl group, etc. as a substituent.

^Examples of the alkyl group of R ^a , R ^b , R ^c , R ^d , R ^e and R ^{f in} the general formula (I) include a methyl group, an ethyl group, a n-propyl group, a n-butyl group, a n-pentyl group, linear alkyl groups such as n-hexyl, n-heptyl, and n-octyl; isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl Branched alkyl groups such as texyl group and 2-ethylhexyl group; cyclic alkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, and cyclooctyl group. A linear or branched alkyl group having 1 to 20 carbon atoms. Examples of the aralkyl group for R ^a , R ^b , R ^c , R ^d , R ^e and R ^f include a benzyl group and a phenethyl group, and an aralkyl group having 7 to 14 carbon atoms is preferable. Examples of the aryl group of R ^a , R ^b , R ^c , R ^d , R ^e and R ^f include a phenyl group, a tolyl group, a xylyl group, a mesityl group, and a 2,6-diisopropylphenyl group, preferably a carbon atom. It is an aryl group of formula 6-12. ^Examples of the alkenyl group for R ^a , R ^b , R ^c , R ^d , R ^e and R ^f include linear alkenyl groups such as vinyl group, allyl group, 3-butenyl group, and 5-hexenyl group; isobutenyl group, And branched alkenyl groups such as 5-methyl-3-pentenyl group; cyclic alkenyl groups such as 2-cyclohexenyl group and 3-cyclohexenyl group, preferably alkenyl groups having 2 to 10 carbon atoms It is.

R ¹ , R ^b , R ^c , R ^d , R ^e and R ^{f in} the general formula (I) are preferably an alkyl group having 1 to 10 carbon atoms as the hydrocarbyl group having 1 to 20 carbon atoms. More preferably a linear or branched alkyl group having 1 to 10 carbon atoms, particularly preferably a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n- A hexyl group, n-heptyl group, n-octyl group, isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isopentyl group, neopentyl group, tert-pentyl group, texyl group and 2-ethylhexyl group.

At least one, preferably two or three of R ^a , R ^b , R ^e and R ^{f in} the general formula (I) is ^a hydrocarbyl group. Preferably, both R ^a and R ^b are hydrocarbyl groups, or both R ^e and R ^f are hydrocarbyl groups.

R ^a and R ^b , R ^c and R ^d , R ^e and R ^f in the general formula (I) may be optionally combined to form a ring, for example, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring , A cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclononane ring, a cyclodecane ring, and a cyclododecane ring can be formed.
Any one of R ^a and R ^b in general formula (I) and any one of R ^c and R ^d may be bonded to each other to form a ring, and any one of R ^c and R ^d Any one of R ^e and R ^f may be bonded to each other to form a ring. The ring to be formed may contain a double bond in the skeleton of the ring, and the number of carbon atoms forming the skeleton of the ring is 5 to 10.
N in the general formula (I) represents a number of 1 to 4, preferably 1 to 3, more preferably 1.

Specific examples of the lactone compound represented by the general formula (I) include the following compounds.

In the above compound, methyl groups corresponding to R ^a , R ^b , R ^c , R ^d , R ^e and R ^f in the general formula (I) are substituted with ethyl, n-propyl, iso-propyl, n- Butyl group, iso-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, phenyl group, cyclopentyl group or cyclohexyl The compound replaced with the group can also be mentioned.

[Solid catalyst component (A)]
Although the manufacturing method of the solid catalyst component (A) used in this invention is not specifically limited, The manufacturing method given to (1) and (2) below can be illustrated.
[Production Method (1)]
A method of bringing a solid component (a) containing a titanium atom and a magnesium atom into contact with an electron donating compound (b).
[Production method (2)]
A method in which the titanium compound (c), the magnesium compound (d) and the electron donating compound (b) are brought into contact with each other.

[Production Method (1)]
Solid component containing titanium atom and magnesium atom (a)
The solid component (a) containing a titanium atom and a magnesium atom is not particularly limited, but a solid catalyst component precursor (a-1) containing a titanium atom, a magnesium atom and a hydrocarbyloxy group, magnesium titanate, Examples include aluminum magnesium titanate described in WO 2004/039747, preferably a solid catalyst component precursor (a-1).

  Examples of the hydrocarbyloxy group of the solid catalyst component precursor (a-1) include a hydrocarbyloxy group having 1 to 20 carbon atoms, preferably a methoxy group, an ethoxy group, and an n-propoxy group. , Isopropoxy group, n-butoxy group, isobutoxy group, pentoxy group, cyclopentoxy group, and cyclohexoxy group.

  The solid catalyst component precursor (a-1) may be synthesized by any preparation method. For example, a method of reducing the titanium compound (a-1b) with the organomagnesium compound (a-1c) in the presence of the silicon compound (a-1a) having a Si—O bond can be mentioned.

Examples of the silicon compound (a-1a) having a Si—O bond include compounds represented by the following formulas (i) to (iii).
Si (OR ⁷ ) _a R ⁸ _(4-a) (i)
_{^{R 3 (R 9 2 SiO)}} l SiR 10 3 ··· (ii)
(R ¹¹ ₂ SiO) _b (iii)
[Wherein R ^{7 to} R ¹¹ are each independently a hydrocarbyl group having 1 to 20 carbon atoms or a hydrogen atom, a is a number satisfying 0 <a ≦ 4, and l is a number from 1 to 1000. And b is a number from 2 to 1000]

As the hydrocarbyl group of R ^{7 to} R ¹¹ in the silicon compound (a-1a) having a Si—O bond represented by formulas (i) to (iii), a methyl group, an ethyl group, an n-propyl group, an isopropyl group, alkyl groups such as n-butyl, isobutyl, n-pentyl, isopentyl, hexyl, heptyl, octyl, decyl, and dodecyl; phenyl, cresyl, xylyl, and naphthyl Examples thereof include aryl groups such as: cycloalkyl groups such as cyclohexyl and cyclopentyl groups; alkenyl groups such as allyl groups; and aralkyl groups such as benzyl groups.

R ^{7 to} R ¹¹ in the silicon compound (a-1a) having an Si—O bond represented by the formulas (i) to (iii) are preferably an alkyl group having 2 to 18 carbon atoms or an alkyl group having 6 to 18 carbon atoms. An aryl group, particularly preferably a linear alkyl group having 2 to 18 carbon atoms.

  Specific examples of the silicon compound (a-1a) having a Si—O bond represented by formulas (i) to (iii) include tetramethoxysilane, dimethyldimethoxysilane, tetraethoxysilane, triethoxyethylsilane, and diethoxydiethylsilane. , Ethoxytriethylsilane, tetraisopropoxysilane, diisopropoxy-diisopropylsilane, tetrapropoxysilane, dipropoxydipropylsilane, tetrabutoxysilane, dibutoxydibutylsilane, dicyclopentoxydiethylsilane, diethoxydiphenylsilane, cyclohexyloxy Trimethylsilane, phenoxytrimethylsilane, tetraphenoxysilane, triethoxyphenylsilane, hexamethyldisilohexane, hexaethyldisilohexane, hexapropyldisiloxane Octaethyl trisiloxane, dimethyl polysiloxane, diphenyl polysiloxane, may be exemplified methyl hydrogen polysiloxane, and a phenyl hydro polysiloxane.

  Among the silicon compounds (a-1a) having a Si—O bond represented by formulas (i) to (iii), a in formula (i) is preferably a compound satisfying 1 ≦ a ≦ 4, more preferably, A is a tetraalkoxysilane in which 4 is 4, most preferably tetraethoxysilane.

［ただし、上式（ｉｖ）において、ｒは１〜２０の数を表し、Ｒ^１２は炭素原子数１〜２０のハイドロカルビル基を表す。Ｘ^１はハロゲン原子または炭素原子数１〜２０のハイドロカルビルオキシ基を表し、Ｘ^１は互いに同じであっても異なっていてもよい］ Examples of the titanium compound (a-1b) include compounds represented by the following formula (iv).

[However, in the above formula (iv), r represents a number of 1 to 20, and R ¹² represents a hydrocarbyl group having 1 to 20 carbon atoms. X ¹ represents a halogen atom or a hydrocarbyloxy group having 1 to 20 carbon atoms, and X ¹ may be the same or different.

R ¹² in the titanium compound (a-1b) represented by the formula (iv) is methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, n-pentyl group, isopentyl group, n- Alkyl groups such as hexyl, n-heptyl, n-octyl, n-decyl, and n-dodecyl; aryl groups such as phenyl, cresyl, xylyl, and naphthyl; cyclohexyl and Examples thereof include a cycloalkyl group such as a cyclopentyl group; an alkenyl group such as an allyl group; and an aralkyl group such as a benzyl group. R ¹² is preferably an alkyl group having 2 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms, particularly preferably a linear alkyl group having 2 to 18 carbon atoms.

Examples of the halogen atom for X ¹ in the above formula (iv) include a chlorine atom, a bromine atom and an iodine atom. Particularly preferred is a chlorine atom.
The hydrocarbyloxy group having 1 to 20 carbon atoms of X ¹ in the above formula (iv) is preferably an alkoxy group having 2 to 18 carbon atoms, more preferably an alkoxy group having 2 to 10 carbon atoms. And particularly preferably an alkoxy group having 2 to 6 carbon atoms.

  As the titanium compound (a-1b) represented by the above formula (iv), tetramethoxy titanium, tetraethoxy titanium, tetrapropoxy titanium, tetraisopropoxy titanium, tetrabutoxy titanium, tetraisobutoxy titanium, butoxy titanium trichloride, di Butoxytitanium dichloride, tributoxytitanium chloride, ditetraisopropylpolytitanate (mixture in the range n = 2-10), tetrabutylpolytitanate (mixture in the range r = 2-10), tetrahexylpolytitanate (r = 2) -10), tetraoctylpolytitanate (r = 2 to 10), and a tetraalkoxytitanium condensate obtained by reacting tetraalkoxytitanium with a small amount of water, and two or more thereof. The combination of can be illustrated

  The titanium compound (a-1b) represented by the above formula (iv) is preferably a titanium compound in which r is 1, 2 or 4, more preferably a titanium compound in which r is 1, particularly preferably. Tetra-n-alkoxytitanium, more preferably tetrabutoxytitanium.

The organomagnesium compound (a-1c) is an arbitrary compound having a magnesium atom-carbon atom bond. As the organomagnesium compound, compounds represented by the following formula (v) or (vi) can be exemplified, and from the viewpoint of obtaining a good form catalyst, the former Grignard compound represented by the formula (v) is preferable. Particularly preferred are ether solutions of Grignard compounds:
R ¹³ MgX ² (v)
R ¹⁴ R ¹⁵ Mg (vi)
[R ^{13 to} R ¹⁵ each independently represents a hydrocarbyl group having 1 to 20 carbon atoms, and X ² represents a halogen atom]

Examples of the hydrocarbyl group of R ^{13 to} R ¹⁵ in the formula (v) or (vi) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an n-pentyl group, and an isopentyl group. Groups, alkyl groups such as n-hexyl group, n-heptyl group, n-octyl group, n-decyl group, and n-dodecyl group; aryl groups such as phenyl group, cresyl group, xylyl group, and naphthyl group Cycloalkyl groups such as cyclohexyl and cyclopentyl groups; alkenyl groups such as allyl groups; and aralkyl groups such as benzyl groups.

Preferred R ^{13 to} R ¹⁵ in the formula (v) or (vi) are an alkyl group having 2 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms, and particularly preferably an alkyl having 2 to 18 carbon atoms. It is a group.

Examples of X ² in the formula (v) include a chlorine atom, a bromine atom and an iodine atom. Particularly preferred is a chlorine atom.

Examples of Grignard compounds represented by the above formula include methylmagnesium chloride, ethylmagnesium chloride, propylmagnesium chloride, isopropylmagnesium chloride, butylmagnesium chloride, isobutylmagnesium chloride, tert-butylmagnesium chloride, pentylmagnesium chloride, isopentylmagnesium. Chloride, cyclopentylmagnesium chloride, hexylmagnesium chloride, cyclohexylmagnesium chloride, octylmagnesium chloride, 2-ethylhexylmagnesium chloride, phenylmagnesium chloride, and benzylmagnesium chloride. Among them, ethylmagnesium chloride, propylmagnesium chloride, isopropylmagnesium chloride, butylmagnesium chloride, and isobutylmagnesium chloride are preferred, and butylmagnesium chloride is particularly preferred.
These Grignard compounds are preferably used as their ether solution. Examples of ethers are dialkyl ethers such as diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diisobutyl ether, ethyl butyl ether and diisopentyl ether, and cyclic ethers such as tetrahydrofuran. Among them, dialkyl ether is preferable, and dibutyl ether or diisobutyl ether is particularly preferable.

  During the reduction reaction of the titanium compound (a-1b) with the organomagnesium compound (a-1c) in the presence of the silicon compound (a-1a) having a Si—O bond, esters (a-1d) can be optionally added. You may coexist.

  Examples of the esters (a-1d) include aliphatic carboxylic acid esters, aromatic carboxylic acid esters, aliphatic dicarboxylic acid diesters, and aromatic dicarboxylic acid diesters. Specific examples include methyl acetate, ethyl acetate, and phenyl acetate. , Methyl propionate, ethyl propionate, ethyl butyrate, ethyl valerate, ethyl acrylate, methyl methacrylate, ethyl benzoate, butyl benzoate, methyl toluate, ethyl toluate, ethyl anisate, diethyl succinate, succinic acid Dibutyl, diethyl malonate, dibutyl malonate, dimethyl maleate, dibutyl maleate, diethyl itaconate, dibutyl itaconate, monoethyl phthalate, dimethyl phthalate, methyl ethyl phthalate, diethyl phthalate, dipropyl phthalate, diisopropyl phthalate , Dibutyl phthalate, diisobutyl phthalate, dipentyl phthalate, dihexyl phthalate, diheptyl phthalate, dioctyl phthalate, bis (2-ethylhexyl) phthalate, diisodecyl phthalate, dicyclohexyl phthalate, and diphenyl phthalate Can do. Among them, preferred are aromatic carboxylic acid esters such as ethyl benzoate; aromatic dicarboxylic acid diesters such as phthalic acid ester.

  As solvents in the reduction reaction, aliphatic hydrocarbons such as hexane, heptane, octane and decane; aromatic hydrocarbons such as toluene and xylene; alicyclic hydrocarbons such as cyclohexane, methylcyclohexane and decalin; diethyl ether, Dialkyl ethers such as dipropyl ether, diisopropyl ether, dibutyl ether, diisobutyl ether, ethyl butyl ether, and diisopentyl ether; cyclic ethers such as tetrahydrofuran; halogenated aromatics such as chlorobenzene and dichlorobenzene; Two or more types of combinations can be exemplified. Among them, preferred are aliphatic hydrocarbons, aromatic hydrocarbons or alicyclic hydrocarbons, more preferred are aliphatic hydrocarbons or alicyclic hydrocarbons, and even more preferred are aliphatic hydrocarbons. And particularly preferably hexane or heptane.

  In the reduction reaction, the silicon compound (a-1a) having an Si—O bond is used in an amount of usually 1 to 500 mol, preferably 1 to 500 mol of silicon atom per mol of total titanium atom in the titanium compound (a-1b) used. The amount is 1 to 300 mol, particularly preferably 3 to 100 mol.

In the reduction reaction, the amount of the organomagnesium compound (a-1c) used is usually 0. The sum of the titanium atoms and the silicon atoms is usually 0.1 per mol of total magnesium atoms in the organomagnesium compound (a-1c) used. The amount is 1 to 10 mol, preferably 0.2 to 5.0 mol, particularly preferably 0.5 to 2.0 mol.
The amount of the titanium compound (a-1b), the silicon compound (a-1a) having an Si—O bond and the organomagnesium compound (a-1c) used in the reduction reaction is also determined according to the solid catalyst component precursor (a-1) obtained. ) In 1) to 51 mol, preferably 2 to 31 mol, particularly preferably 4 to 26 mol per 1 mol of titanium atom in the precursor.

  In the reduction reaction, the amount of the esters (a-1d) used is generally 0.05 to 100 mol, preferably 0.1 to 60 mol, particularly preferably 0.2, per 1 mol of total titanium atoms in the titanium compound used. ~ 30 mol.

  In the reduction reaction, the temperature at which the organomagnesium compound (a-1c) is added to the solution containing the silicon compound (a-1a) having the Si—O bond, the titanium compound (a-1b) and the solvent is usually − It is 50-100 degreeC, Preferably it is -30-70 degreeC, Especially preferably, it is the range of -25-50 degreeC. The time when adding the organomagnesium compound (a-1c) is not particularly limited, and is usually about 30 minutes to 6 hours. From the viewpoint of obtaining a catalyst having a good form, the organomagnesium compound (a-1c) is preferably added continuously. In order to further advance the reaction, a reaction at 5 to 120 ° C. may be added.

Furthermore, a support material may be present during the reduction reaction, and the solid catalyst component precursor (a-1) may be supported on the support material. The support material is not particularly limited, and examples thereof include porous inorganic oxides such as SiO ₂ , Al ₂ O ₃ , MgO, TiO ₂ , and ZrO ₂ ; polystyrene, styrene-divinylbenzene copolymer, styrene- Ethylene glycol-methyl methacrylate copolymer, polymethyl acrylate, polyethyl acrylate, methyl acrylate-divinylbenzene copolymer, polymethyl methacrylate, methyl methacrylate-divinylbenzene copolymer, polyacrylonitrile, acrylonitrile -Organic porous polymers such as divinylbenzene copolymer, polyvinyl chloride, polyethylene, and polypropylene. Of these, an organic porous polymer is preferable, and a styrene-divinylbenzene copolymer is particularly preferable.

The support preferably has a pore volume at a pore radius of 20 to 200 nm of 0.3 cm ³ / g or more, more preferably 0, from the viewpoint of effectively immobilizing the solid catalyst component precursor (a-1). .4 cm ³ / g or more, and the pore volume in this range is 35% or more, more preferably 40% or more, with respect to the pore volume at a pore radius of 3.5 to 7500 nm. It is a carrier.

  When a silicon compound (a-1a) having a Si—O bond, a titanium compound (a-1b), an ester (a-1d), and an organomagnesium compound (a-1c) are added, an organomagnesium compound Since the reduction reaction of the titanium compound by proceeds, the titanium atom of the titanium compound is reduced from tetravalent to trivalent. In the present invention, it is preferable that substantially all tetravalent titanium atoms are reduced to trivalent. The obtained solid catalyst component precursor (a-1) contains a trivalent titanium atom, a magnesium atom and a hydrocarbyloxy group, and is generally amorphous or very weakly crystalline, preferably amorphous. It is a sex structure.

  The obtained solid catalyst component precursor (a-1) may be washed with a solvent. Examples of the solvent include aliphatic hydrocarbons such as pentane, hexane, heptane, octane and decane; aromatic hydrocarbons such as benzene, toluene, ethylbenzene and xylene; alicyclic hydrocarbons such as cyclohexane and cyclopentane; 1 2, halogenated hydrocarbons such as 2-dichloroethane and monochlorobenzene. Of these, aliphatic hydrocarbons or aromatic hydrocarbons are preferred, aromatic hydrocarbons are more preferred, and toluene or xylene is particularly preferred.

Electron donating compound (b)
The electron donating compound (b) is an organic compound containing an oxygen atom or a nitrogen atom, and examples thereof include alcohols, ketones, aldehydes, ethers, amines, amides and esters.

  Specific examples of the alcohols include aliphatic alcohols such as methanol, ethanol, propanol, and 2-ethylhexanol; aromatic alcohols such as phenol and cresol.

  Specific examples of ketones include aliphatic ketones such as acetone, methyl ethyl ketone, and methyl butyl ketone; aromatic ketones such as acetophenone and benzophenone.

  Specific examples of aldehydes include aliphatic aldehydes such as acetaldehyde, propionaldehyde, and octylaldehyde; aromatic aldehydes such as benzaldehyde.

  Specific examples of ethers include dialkyl ethers such as dimethyl ether, diethyl ether, dipropyl ether, dibutyl ether, dipentyl ether, and tert-butyl methyl ether; aromatic ethers such as diphenyl ether; 2-butyl-2 -Ethyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane 2,2-bis (cyclohexylmethyl) -1,3-dimethoxypropane, 2-cyclohexyl-2-isopropyl-1,3-dimethoxypropane, 2-isopropyl-2-sec-butyl-1,3-dimethoxypropane, 2,2-diphenyl Aliphatic diethers such as 1,3-dimethoxypropane, and 2-cyclopentyl-2-isopropyl-1,3-dimethoxypropane; 1,1-bis (methoxymethyl) indenyl, and 9,9-bis (methoxymethyl) ) Aromatic diethers such as fluorene.

  Specific examples of amines include alkylamines having 6 or more carbon atoms such as heptylamine, octylamine, nonylamine, laurylamine, 2-ethylhexylamine; piperidine, and 2,2,6,6-tetramethylpiperidine. Cyclic amines such as; aniline and aromatic amines such as pyridine; and aliphatic diamines such as N, N, N ′, N′-tetramethylethylenediamine.

  Specific examples of the amides include olefinic acid amides and stearic acid amides. Specific examples of nitriles include acetonitrile, benzonitrile, and tolunitrile. Specific examples of isocyanates include methyl isocyanate and ethyl isocyanate.

  Examples of the esters include aliphatic carboxylic acid esters, aromatic carboxylic acid esters, aliphatic dicarboxylic acid diesters, and aromatic dicarboxylic acid diesters and diol esters.

  As aliphatic carboxylic acid esters, specifically, aliphatic monocarboxylic acid esters such as methyl formate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, and ethyl butyrate;

  Ethyl 3-ethoxy-2-isopropylpropionate, ethyl 3-ethoxy-2-isobutylpropionate, ethyl 3-ethoxy-2-sec-butylpropionate, ethyl 3-ethoxy-2-tert-butylpropionate, 3- Ethyl ethoxy-2-tert-pentylpropionate, ethyl 3-ethoxy-2-cyclohexylpropionate, ethyl 3-ethoxy-2-cyclopentylpropionate, ethyl 3-methoxy-2-isopropylpropionate, 3-methoxy-2- Ethyl isobutylpropionate, ethyl 3-methoxy-2-tert-butylpropionate, ethyl 3-methoxy-2-tert-pentylpropionate, ethyl 3-methoxy-2-cyclohexylpropionate, 3-methoxy-2-cyclopentylpropion Ethyl, ethyl 3-methoxy-2-adamantylpropionate, methyl 3-ethoxy-2-isopropylpropionate, methyl 3-ethoxy-2-isobutylpropionate, methyl 3-ethoxy-2-tert-butylpropionate, 3- Methyl ethoxy-2-tert-pentylpropionate, methyl 3-ethoxy-2-cyclohexylpropionate, methyl 3-ethoxy-2-cyclopentylpropionate, methyl 3-ethoxy-2-adamantylpropionate, 3-methoxy-2- Methyl isopropylpropionate, methyl 3-methoxy-2-isobutylpropionate, methyl 3-methoxy-2-tert-butylpropionate, methyl 3-methoxy-2-tert-pentylpropionate, 3-methoxy-2-cyclohexylpro Methyl onate, methyl 3-methoxy-2-cyclopentylpropionate, methyl 3-methoxy-2-adamantylpropionate, ethyl 3-ethoxy-3-isopropyl-2-isobutylpropionate, 3-ethoxy-3-isobutyl-2 -Ethyl isobutylpropionate, 3-ethoxy-3-isobutyl-2-tert-butylpropionate, 3-ethoxy-2, ethyl 3-ditert-butylpropionate, 3-ethoxy-3-isobutyl-2-tert -Ethyl pentylpropionate, 3-ethoxy-3-tert-butyl-2-tert-pentylpropionate, 3-ethoxy-2, 3-di-tert-pentylpropionate, 3-ethoxy-3-isobutyl-2 -Ethyl cyclohexylpropionate, 3-ethoxy Cis-2, ethyl 3-dicyclohexylpropionate, ethyl 3-ethoxy-3-isobutyl-2-cyclopentylpropionate, 3-ethoxy-2, ethyl 3-dicyclopentylpropionate, 3-ethoxy-2,2-diisopropylpropionate Ethyl acetate, ethyl 3-ethoxy-2-isopropyl-2-isobutylpropionate, ethyl 3-ethoxy-2-isopropyl-2-tert-butylpropionate, 3-ethoxy-2-isopropyl-2-tert-pentylpropionic acid Ethyl, ethyl 3-ethoxy-2-isopropyl-2-cyclopentylpropionate, ethyl 3-ethoxy-2-isopropyl-2-cyclohexylpropionate, ethyl 3-ethoxy-2,2-diisobutylpropionate, 3-ethoxy-2 , 2-Diisobu Methyl lupropionate, ethyl 3-ethoxy-2-isobutyl-2-tert-butylpropionate, ethyl 3-ethoxy-2-isobutyl-2-tert-pentylpropionate, 3-ethoxy-2-isobutyl-2-cyclopentyl Ethyl propionate, ethyl 3-ethoxy-2-isobutyl-2-cyclohexylpropionate, ethyl 3-ethoxy-2,2-ditert-butylpropionate, methyl 3-ethoxy-2,2-ditert-butylpropionate , Ethyl 3-ethoxy-2-tert-butyl-2-methylpropionate, ethyl 3-ethoxy-2-tert-butyl-2-ethylpropionate, 3-ethoxy-2-tert-butyl-2-propylpropionic acid Ethyl, 3-ethoxy-2-tert-butyl-2-buty Like ethyl propionate, ethyl 3-ethoxy-2-tert-butyl-2-pentylpropionate, ethyl 3-ethoxy-2,2-dicyclohexylpropionate, and ethyl 3-ethoxy-2,2-dicyclopentylpropionate And an aliphatic carboxylic acid ester having an alkoxy group.

  Specific examples of aromatic carboxylic acid esters include ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, methyl p-toluate, and ethyl p-toluate. Benzoic acid esters; anisic acid esters such as methyl anisate and ethyl anisate.

  Specific examples of the aliphatic dicarboxylic acid diesters include dimethyl diisopropylmalonate, diethyl diisopropylmalonate, dipropylmalonate dipropyl, diisopropylmalonate diisopropyl, diisopropylmalonate dibutyl, diisopropylmalonate diisobutyl, diisopropylmalonate dineopentyl, diisobutylmalonic acid. Dimethyl, diethyl diisobutylmalonate, dipropyl diisobutylmalonate, diisopropyl diisobutylmalonate, dibutyl diisobutylmalonate, diisobutyldiisobutylmalonate, diisobutylmalonate dineopentyl, diisopentylmalonate dimethyl, diisopentylmalonate, isopropylisobutylmalonic acid Dimethyl, isopropyl isobutyl malonate, iso Malonic acid diester, such as Russia pills isopentyl dimethyl malonate, and isopropyl isopentyl diethyl malonate;

  Diethyl 2,3-diethyl succinate, diethyl 2,3-dipropyl succinate, diethyl 2,3-diisopropyl succinate, diethyl 2,3-dibutyl succinate, diethyl 2,3-diisobutyl succinate, 2,3- Diethyl tert-butyl succinate, dibutyl 2,3-diethyl succinate, dibutyl 2,3-dipropyl succinate, dibutyl 2,3-diisopropyl succinate, dibutyl 2,3-dibutyl succinate, 2,3-diisobutyl Succinic acid diesters such as dibutyl succinate and 2,3-di-tert-butyl dibutyl succinate;

  3-methylglutarate diisobutyl, 3-phenylglutarate diisobutyl, diethyl 3-ethylglutarate, diethyl 3-propylglutarate, diethyl 3-isopropylglutarate, diethyl 3-isobutylglutarate, diethyl 3-phenylglutarate, 3 -Diisobutyl ethyl glutarate, diisobutyl 3-isopropyl glutarate, diisobutyl 3-isobutyl glutarate, diethyl 3- (3,3,3-trifluoropropyl) glutarate, diethyl 3-cyclohexylmethyl glutarate, 3-tert-butyl Such as diethyl glutarate, diethyl 3,3-dimethylglutarate, diisobutyl 3,3-dimethylglutarate, diethyl 3-methyl-3-isobutylglutarate, and diethyl 3-methyl-3-tert-butylglutarate Una glutaric acid diester;

  1-cyclohexene-1,2-dicarboxylate diethyl, 1-cyclohexene-1,2-dicarboxylate dipropyl, 1-cyclohexene-1,2-dicarboxylate dibutyl, 1-cyclohexene-1,2-dicarboxylate di-isobutyl, Cyclohexene dicarboxylic acid diesters such as 1-cyclohexene-1,2-dicarboxylic acid dineopentyl and 1-cyclohexene-1,2-dicarboxylic acid bis (2,2-dimethylhexyl);

  Cyclohexane-1,2-dicarboxylate diethyl, cyclohexane-1,2-dicarboxylate dipropyl, cyclohexane-1,2-dicarboxylate dibutyl, cyclohexane-1,2-dicarboxylate di-isobutyl, cyclohexane-1,2-dicarboxylic acid Dineopentyl, bis (2,2-dimethylhexyl) cyclohexane-1,2-dicarboxylate, diethyl 3-methylcyclohexane-1,2-dicarboxylate, diethyl 4-methylcyclohexane-1,2-dicarboxylate, cyclohexane-1, 1-dicarboxylate diethyl, cyclohexane-1,1-dicarboxylate dipropyl, cyclohexane-1,1-dicarboxylate dibutyl, cyclohexane-1,1-dicarboxylate di-isobutyl, cyclohexane-1,1-dicarboxylate dineopenti Dicyclohexane such as bis (2,2-dimethylhexyl) cyclohexane-1,1-dicarboxylate, diethyl 3-methylcyclohexane-1,1-dicarboxylate, and diethyl 4-methylcyclohexane-1,1-dicarboxylate Acid diesters;

  Maleic acid diesters such as diethyl maleate and dibutyl maleate; adipic acid diesters such as dimethyl adipate, diethyl adipate, dipropyl adipate, diisopropyl adipate, dibutyl adipate, diisodecyl adipate, and dioctyl adipate ;

  Dimethyl dodecanedioate, diethyl dodecanedioate, dipropyl dodecanedioate, diisopropyl dodecanedioate, dibutyl dodecanedioate, diisobutyl dodecanedioate, dipentyl dodecanedioate, diisopentyl dodecanedioate, dihexyl dodecanedioate, diisohexyl dodecanedioate, Dodecanedioic acid diheptyl, dodecanedioic acid diisoheptyl, dodecanedioic acid dioctyl, dodecanedioic acid diisooctyl, dodecanedioic acid bis (2-ethylhexyl), α-methyldodecanedioic acid bis (2-ethylhexyl), α-ethyldodecanedioic acid bis (2-ethylhexyl), α-isopropyldodecanedioic acid bis (2-ethylhexyl), β-methyldodecanedioic acid bis (2-ethylhexyl), β-ethyldodecanedioic acid bis (2-ethylhexyl), β-isopropyldodecane Bis (2-ethylhexyl) diacid, bis (2-ethylhexyl) γ-methyldodecanedioic acid, bis (2-ethylhexyl) γ-ethyldodecanedioic acid, bis (2-ethylhexyl) γ-isopropyldodecanedioic acid, α, dodecanedioic acid diesters such as bis (2-ethylhexyl) β-dimethyldodecanedioic acid, bis (2-ethylhexyl) α, β-diethyldodecanedioic acid, bis (2-ethylhexyl) α, β-diisopropyldodecanedioic acid;

  Diethyl 2,5-dioxahexanedioate, diethyl 2,5-dioxa-3-methylhexanedioate, diethyl 2,5-dioxa-3-methylhexanedioate, 2,5-dioxa-3-ethylhexanediethyl Diethyl 2,2,5-dioxa-3-ethylhexanedioate, diethyl 2,5-dioxa-3-propylhexanedioate, diethyl 2,5-dioxa-3-isopropylhexanedioate, 2,5-dioxa Diethyl-3-cyclohexylhexanedioate, diethyl 2,5-dioxa-3-tert-butylhexanedioate, diethyl 2,5-dioxa-3-hexylhexanedioate, 2,5-dioxa-3-phenylhexane Diethyl diacid, 2,5-dioxa-3-benzyl hexane diacid diethyl, 2,5-dioxa-3,4-dimethylhexane diacid 2,2,5-dioxa-3,4-di Diethyl ethylhexanedioate, diethyl 2,5-dioxa-3,4-dipropylhexanedioate, diethyl 2,5-dioxa-3,4-diisopropylhexanedioate, 2,5-dioxa-3,4-dicyclohexyl Diethyl hexanedioate, 2,5-dioxa-3,4-di (tert-butyl) diethyl hexanedioate, 2,5-dioxa-3,4-dihexyl diethyl hexanedioate, 2,5-dioxa-3 Diethyl 2,4-diphenylhexanedioate, diethyl 2,5-dioxa-3,4-dibenzylhexanedioate, dibutyl 2,5-dioxahexanedioate, dibutyl 2,5-dioxa-3-methylhexanedioate Dicarbonates such as 2,5-dioxahexanedioic acid di (2-ethylhexyl);

  Specific examples of aromatic dicarboxylic acid diesters include dimethyl phthalate, diethyl phthalate, dipropyl phthalate, diisopropyl phthalate, dibutyl phthalate, diisobutyl phthalate, ethyl methyl phthalate, methyl isopropyl phthalate, and ethyl propyl phthalate , Ethylbutyl phthalate, ethyl isobutyl phthalate, dipentyl phthalate, diisopentyl phthalate, dineopentyl phthalate, dihexyl phthalate, dihebutyl phthalate, dioctyl phthalate, bis (2,2-dimethylhexyl) phthalate, bis (phthalate) 2-ethylhexyl), dinonyl phthalate, diisodecyl phthalate, bis (2,2-dimethylheptyl) phthalate, butyl isohexyl phthalate, butyl phthalate (2-ethylhexyl), pentylhexyl phthalate Pentyl isohexyl phthalate, isopentyl heptyl phthalate, pentyl phthalate (2-ethylhexyl), pentyl isononyl phthalate, isopentyl decyl phthalate, pentyl undecyl phthalate, isopentyl isohexyl phthalate, hexyl phthalate (2,2-dimethylhexyl), hexyl isononyl phthalate, hexyl decyl phthalate, heptyl phthalate (2-ethylhexyl), heptyl isonyl phthalate, heptyl decyl phthalate, (2-ethylhexyl) isononyl phthalate, 4- Dineopentyl methylphthalate, dineopentyl 4-ethylphthalate, dineopentyl 4,5-dimethylphthalate, dineopentyl 4,5-diethylphthalate, diethyl 4-chlorophthalate, dibutyl 4-chlorophthalate, 4-chloro Dineopentyl phthalate, diisobutyl 4-chlorophthalate, diisohexyl 4-chlorophthalate, diisooctyl 4-chlorophthalate, diethyl 4-bromophthalate, dibutyl 4-bromophthalate, dineopentyl 4-bromophthalate, diisobutyl 4-bromophthalate, 4-bromophthalic acid Phthalic acid diesters such as diisohexyl, diisooctyl 4-bromophthalate, diethyl 4,5-dichlorophthalate, dibutyl 4,5-dichlorophthalate, diisohexyl 4,5-dichlorophthalate, and diisooctyl 4,5-dichlorophthalate Can be mentioned.

  Specific examples of the diol ester include 1,2-propylene-glycol dibenzoate, 1,2-propylene-glycol di (p-chlorobenzoate), 1,2-propylene-glycol di (m-chlorobenzoate), 1,2-propylene-glycol di (o-bromobenzoate), 1,2-propylene-glycol di (p-methylbenzoate), 1,2-propylene-glycol monobenzoate monocinnamate, 1,2-propylene-glycol Dicinnamate, 2-methyl-1,2-propylene-glycol dibenzoate, 1,3-propylene-glycol dibenzoate, 2-methyl-1,3-propylene-glycol dibenzoate, 2,2-dimethyl-1, 3-propylene-glycol dibenzoate, (R) 1-phenyl-1,3-propylene-glycol dibenzoate, (S) -1-phenyl-1,3-propylene-glycol dibenzoate, 1,3-diphenyl-1,3-propylene-glycol dipropionate, 2 -Methyl-1,3-diphenyl-1,3-propylene-glycol dipropionate, 2,2-dimethyl-1,3-diphenyl-1,3-propylene-glycol dibenzoate, 2-ethyl-1,3- Di (tert-butyl) -1,3-propylene-glycol dibenzoate, 2-butyl-2-ethyl-1,3-propylene-glycol dibenzoate, 2,2-diethyl-1,3-propylene-glycol dibenzoate 2-dimethoxymethyl-1,3-propylene-glycol dibenzoate, 2-methyl- -Propyl-1,3-propylene-glycol dibenzoate, 2-isopentyl-2-isopropyl-1,3-propylene-glycol dibenzoate, 2-ethyl-2-methyl-1,3-propylene-glycol dibenzoate, 2 -Amino-1-phenyl-1,3-propylene-glycol dibenzoate, 2,2-dimethyl-1,3-propylene-glycol dibenzoate, 1,2-butylene-glycol dibenzoate, 2-methyl-1,2 -Butylene-glycol dibenzoate, 2,3-dimethyl-1,2-butylene-glycol dibenzoate, 2,3,3-trimethyl-1,2-butylene-glycol dibenzoate, 2,3-butylene-glycol dibenzoate 2-methyl-2,3-butylene-glycol diben Zoate, 2,3-dimethyl-2,3-butylene-glycol dibenzoate, 2-methyl-1-phenyl-1,3-butylene-glycol dibenzoate, 2-methyl-2- (2-furyl) -1, 3-butylene-glycol dibenzoate, 1,4-butylene-glycol dibenzoate, 2,3-diisopropyl-1,4-butylene-glycol dibenzoate, 4,4,4-trifluoro-1- (2-naphthyl) -1,3-butylene-glycol dibenzoate, 2,3-pentanediol dibenzoate, 2-methyl-2,3-pentanediol dibenzoate, 2,3-dimethyl-2,3-pentanediol dibenzoate, 2, 4,4-trimethyl-2,3-pentanediol dibenzoate, 2,3,4,4-tetramethyl- , 3-pentanediol dibenzoate, 3-ethyl-2,3-pentanediol dibenzoate, 3-ethyl-2-methyl-2,3-pentanediol dibenzoate, 3-ethyl-2,4-dimethyl-2, 3-pentanediol dibenzoate, 2,4-pentanediol dibenzoate, 3-methyl-2,4-pentanediol dibenzoate, 3,3-dimethyl-2,4-pentanediol dibenzoate, (2S, 4S)- (+)-2,4-pentanediol dibenzoate, (2R, 4R)-(+)-2,4-pentanediol dibenzoate, 2-methyl-1,3-pentanediol monobenzoate monocinnamate, 2, 2-dimethyl-1,3-pentanediol dibenzoate, 2-ethyl-1,3-pentanediol Dibenzoate, 2-ethyl-1,3-pentanediol dibenzoate, 1,3-pentanediol di (p-chlorobenzoate), 3-methyl-1-trifluoromethyl-2,4-pentanediol dibenzoate, 2 , 4-pentanediol di (p-fluoromethylbenzoate), 3-butyl-3-methyl-2,4-pentanediol dibenzoate, 2,2-dimethyl-1,5-pentanediol dibenzoate, 1,5- Diphenyl-1,5-pentanediol dibenzoate, 2,3-hexanediol dibenzoate, 2-methyl-2,3-hexanediol dibenzoate, 2,3-dimethyl-2,3-hexanediol dibenzoate, 2, 3,4-trimethyl-2,3-hexanediol dibenzoate, 2,3,4 , 4, -tetramethyl-2,3-hexanediol dibenzoate, 3-ethyl-2,3-hexanediol dibenzoate, 4-ethyl-2,3-hexanediol dibenzoate, 3-ethyl-2-methyl- 2,3-hexanediol dibenzoate, 3,4-diethyl-2,3-hexanediol dibenzoate, 4-ethyl-3-propyl-2,3-hexanediol dibenzoate, 3-ethyl-2,4-dimethyl -2,3-hexanediol dibenzoate, 2,5-dimethyl-3-propyl-2,3-hexanediol dibenzoate, 2,4,4-trimethyl-3-propyl-2,3-hexanediol dibenzoate, 3,4-diethyl-2-methyl-2,3-hexanediol dibenzoate, 2-ethyl-1,3-he Sundiol dibenzoate, 2,2,4,6,6-pentamethyl-3,5-hexanediol dibenzoate, 2,5-hexanediol dibenzoate, 2,5-dimethyl-2,5-hexanediol dibenzoate, 2,5-dimethyl-hex-3-yne-2,5-diol dibenzoate, hexa-3-yne-2,5-diol dibenzoate, 3,4-dibutyl-1,6-hexanediol dibenzoate, 1 , 6-Hexanediol dibenzoate, hepta-6-ene-2,4-diol dibenzoate, 2-methyl-hept-6-ene-2,4-diol dibenzoate, 3,5-diethyl-hepta-6 Ene-2,4-diol dibenzoate, 3,5-heptanediol dibenzoate, 3-ethyl-3,5-heptane All dibenzoate, 2,3-dimethyl-3,5-heptanediol dibenzoate, 3-ethyl-2-methyl-3,5-heptanediol dibenzoate, 2-methyl-3-propyl-3,5-heptanediol Dibenzoate, hepta-6-ene-2,4-diol dipivalate, 3,6-dimethyl-2,4-heptanediol dibenzoate, 2,2,6,6-tetramethyl-3,5-heptanediol Dibenzoate, 2,6-dimethyl-2,6-heptanediol dibenzoate, 4-ethyl-3,5-octanediol dibenzoate, 4,4-diethyl-3,5-octanediol dibenzoate, 4-ethyl- 4-methyl-3,5-octanediol dibenzoate, 3-phenyl-3,5-octanediol dibenzoe 5-ethyl-2-methyl-3,5-octanediol dibenzoate, 5-propyl-4,6-nonanediol dibenzoate, 5,5-dibutyl-4,6-nonanediol dibenzoate, 4- Ethyl-5-methyl-4,6-nonanediol dibenzoate, 5-phenyl-4,6-nonanediol dibenzoate, 4,6-nonanediol dibenzoate, 1,1-cyclohexanedimethanol dibenzoate, 1,2 Cyclohexanediol dibenzoate, 1,4-bis (benzoyloxymethyl) cyclohexane, 1,1-bis (propionyloxymethyl) -3-cyclohexene, 9,9-bis (benzoyloxymethyl) fluorene, 9,9-bis (Cinnamoyloxymethyl) fluorene, 9- (benzoyloxy) Chill) -9- (propionyloxymethyl) fluorene, and the like.

  The electron donating compound (b) is preferably an ether or an ester, more preferably an aliphatic diether, an aromatic diether, an aliphatic carboxylic acid ester, an aromatic carboxylic acid ester, an aliphatic dicarboxylic acid diester, And an aromatic dicarboxylic acid diester, more preferably an aliphatic diether, an aliphatic carboxylic acid ester having an alkoxy group, a benzoic acid ester, an anisic acid ester, a malonic acid diester, a succinic acid diester, a cyclohexene dicarboxylic acid diester, and a cyclohexanedicarboxylic acid. Acid diesters, phthalic acid diesters, and dodecanedioic acid diesters, particularly preferably aliphatic diethers, aliphatic carboxylic acid esters having an alkoxy group, malonic acid diesters, succinic acid diesters, cyclohexanes Cyclohexanedicarboxylic acid diesters, phthalic acid diesters, and dodecanedioic acid diester and carbonate, most preferably, aliphatic carboxylic acid esters having aliphatic diether, an alkoxy group, a phthalic acid diester.

  In addition, said electron donating compound (b) can also be used in combination of 2 or more type.

Production conditions of production method (1) In production method (1), the amount of electron-donating compound (b) used is usually 0.01 to 100 mmol, preferably 0.03 to 50 ml, per 1 g of solid component (a). Especially preferably, it is 0.05-30 ml.

  In the production method (1), the temperature at which the solid component (a) and the electron donating compound (b) are contacted is not particularly limited, and is usually −50 to 200 ° C., preferably 0 to 170 ° C., more preferably. Is in the range of 50 to 150 ° C, particularly preferably in the range of 50 to 120 ° C.

  In the production method (1), the time for contacting the solid component (a) and the electron donating compound (b) is not particularly limited, and is usually 10 minutes to 12 hours, preferably 30 to 10 hours, particularly preferably. Is in the range of 1 to 8 hours.

The solid component (a) and the electron donating compound (b) may optionally be further contacted with a metal halide compound (e) represented by the following formulas (vii) and (viii).
M ¹ R ¹⁶ _cd X ³ _d (vii)
M ¹ (OR ¹⁶ ) _cd X ³ _d (viii)
[Wherein M ¹ represents a Group 4, 13 or 14 atom, R ¹⁶ represents a hydrocarbyl group or hydrocarbyloxy group having 1 to 20 carbon atoms, and X ³ represents a halogen atom. , C represents the valence of M ¹ . d represents a number satisfying 0 <d ≦ c. ]

Examples of the group 4 element of M ¹ in the above formulas (vii) and (viii) include titanium, zirconium and hafnium. Among these, titanium is preferable. Examples of the group 13 element of M ¹ include boron, aluminum, gallium, indium, and thallium. Among these, boron or aluminum is preferable, and aluminum is more preferable. Examples of the Group 14 element of M ¹ include silicon, germanium, tin, and lead. Among these, silicon, germanium or tin is preferable, and silicon is more preferable.

As the hydrocarbyl group of R ^{16 in} the above formulas (vii) and (viii), methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, n-pentyl group, isopentyl group, Linear or branched alkyl groups such as hexyl, heptyl, octyl, decyl, and dodecyl; cyclic alkyl groups such as cyclohexyl and cyclopentyl; phenyl, cresyl, xylyl, and naphthyl And aryl groups such as groups.

As the hydrocarbyloxy group of R ^{16 in} the above formulas (vii) and (viii), methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, n-pentyloxy group, isoamyloxy group Linear, branched alkoxy groups such as hexyloxy group, heptyloxy group, octyloxy group, decyloxy group, and dodecyloxy group; cyclic alkoxy groups such as cyclohexyloxy group and cyclopentyloxy group; phenoxy group, xyloxy group And aryloxy groups such as naphthoxy groups.

R ¹⁶ in the above formulas (vii) and (viii) is preferably an alkyl group or alkoxy group having 2 to 18 carbon atoms; or an aryl group or aryloxy group having 6 to 18 carbon atoms.

X ³ in the above formulas (vii) and (viii) includes a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, preferably a chlorine atom or a bromine atom.

C in the above formula (vii) and (viii) is the valence of ^{M 1,} c when ^{M 1} is a Group 4 element is 4, p when the Group 13 element is 3, Group 14 C is 4 when it is an element.

In the above formulas (vii) and (viii), a represents a number satisfying 0 <d ≦ c, and when M ¹ is a Group 4 element or a Group 14 element, a represents a number satisfying 0 <d ≦ 4. In the case of a Group 13 element, b represents a number satisfying 0 <d ≦ 3. In the case where M ¹ is a Group 4 element or a Group 14 element, preferable d is 3 or 4, more preferably 4. Preferred d when M ¹ is a Group 13 element is 3.

  The titanium halide compound of the metal halide compound (e) represented by the above formulas (vii) and (viii) is preferably a titanium tetrahalide compound such as titanium tetrachloride, titanium tetrabromide and titanium tetraiodide. Or a trihalogenated alkoxytitanium compound such as methoxytitanium trichloride, ethoxytitanium trichloride, toxitanium trichloride, phenoxytitanium trichloride, and ethoxytitanium tribromide, more preferably a tetrahalogenated titanium compound; Particularly preferred is titanium tetrachloride.

  The group 13 element chlorinated compound or the group 14 element chlorinated compound of the metal halide compound (e) represented by the above formulas (vii) and (viii) is preferably ethylaluminum dichloride, ethylaluminum sesquioxide. Chloride, diethylaluminum chloride, trichloroaluminum, tetrachlorosilane, phenyltrichlorosilane, methyltrichlorosilane, ethyltrichlorosilane, normalpropyltrichlorosilane, or paratolyltrichlorosilane, more preferably a chlorinated compound of Group 14 element Particularly preferred are tetrachlorosilane and phenyltrichlorosilane.

  The amount of the metal halide compound (e) represented by the above formulas (vii) and (viii) is usually 0.1 to 1000 mmol, preferably 0.3 to 500 mmol, particularly preferably 0. 5-300 mmol. The metal halide compound (e) is used at once or divided into arbitrary plural times.

  The contact method in the manufacturing method (1) of the catalyst component is not particularly limited. Examples of the method include known methods such as a slurry method and a mechanical pulverization method (for example, a method using a ball mill). The mechanical pulverization method is preferably performed in the presence of the above-described diluent in order to suppress the fine powder content of the obtained solid catalyst component and the spread of its particle size distribution.

  The time for contacting the solid catalyst component precursor (a-1), the electron donating compound (b) and the optional metal halide compound (e) is not particularly limited, and is usually 10 minutes to 12 hours, Preferably it is 30 to 10 hours, and particularly preferably in the range of 1 to 8 hours.

  The method for bringing the solid catalyst component precursor (a-1), the electron donating compound (b) and the optional metal halide compound (e) into contact with each other is not particularly limited. Examples of the method include known methods such as a slurry method and a mechanical pulverization method (for example, a method using a ball mill). The mechanical pulverization method is preferably performed in the presence of the above-mentioned diluent in order to suppress the fine powder content of the obtained solid catalyst component (A) and the spread of its particle size distribution.

  The slurry concentration in the slurry method is usually 0.05 to 0.7 g solid / ml solvent, particularly preferably 0.1 to 0.5 g solid / ml solvent. The temperature of the contact is usually 30 to 150 ° C, preferably 45 to 135 ° C, particularly preferably 60 to 120 ° C. The contact time is not particularly limited, and usually about 30 minutes to 6 hours is preferable.

  In the production method (1) of the solid catalyst component (A), the organic acid chloride (f) can be optionally added. Specific examples of the organic acid chloride (f) include aromatic dicarboxylic acid dichlorides such as phthalic acid dichloride and terephthalic acid dichloride; aromatic carboxylic acids such as benzoic acid chloride, toluic acid chloride, and anisic acid chloride. Chloride; aliphatic dicarboxylic acid dichlorides such as succinic acid dichloride, malonic acid dichloride, maleic acid dichloride, itaconic acid dichloride, adipic acid dichloride, and dodecanedioic acid dichloride; acetyl chloride, propionic acid chloride, butyric acid chloride, valeric acid chloride, And aliphatic carboxylic acid chlorides such as acrylic acid chloride, methacrylic acid chloride, and 3-ethoxy-2-tert-butylpropionic acid chloride, preferably Aromatic dicarboxylic acid dichloride, and an aliphatic carboxylic acid chloride, more preferably a dichloride phthalic acid.

  In the production method (1) of the solid catalyst component (A), the amount of the organic acid chloride (f) used is usually 0.01 to 10,000 ml, preferably 1 to 10 ml, preferably 1 g of the solid catalyst component precursor (a-1) used. It is 0.03-5000 ml, Most preferably, it is 0.05-3000 ml.

[Production method (2)]
Titanium compound (c)
The compound is not particularly limited as long as it is a compound containing a titanium atom. Specific examples of the titanium compound (c) include titanium tetrachlorides such as titanium tetrachloride, titanium tetrabromide, and titanium tetraiodide; tetramethoxy Tetraalkoxy titanium such as titanium, tetraethoxy titanium, tetrapropoxy titanium, tetraisopropoxy titanium, tetrabutoxy titanium, tetraisobutoxy titanium, and tetracyclohexyloxy titanium; tetraaryloxy titanium such as tetraphenoxy titanium; methoxy titanium tri Alkoxytitanium trichlorides such as chloride, ethoxytitanium trichloride, propoxytitanium trichloride, butoxytitanium trichloride, and ethoxytitanium tribromide; dimethoxytitanium dichloride, diethoxytitanium dichloride Dihalogenated dialkoxytitanium such as lolide, diisopropoxytitanium dichloride, dipropoxytitanium dichloride, and diethoxytitanium dibromide; trimethoxytitanium chloride, triethoxytitanium chloride, triisopropoxytitanium chloride, tripropoxytitanium chloride, and And monohalogenated trialkoxytitanium such as tributoxytitanium chloride. The titanium compound (c) is preferably titanium tetrahalide or alkoxytitanium trichloride, more preferably titanium tetrahalide, and still more preferably titanium tetrachloride. These titanium compounds (c) may be used alone or in combination of two or more.

Magnesium compound (d)
Although there will be no restriction | limiting in particular if it is a compound containing a magnesium atom, The compound represented by the following formula (ix) or (x) can be illustrated.
MgR ¹⁷ _e X ⁴ _2-e (ix)
Mg (OR ¹⁷ ) _c X ⁴ _2-e (x)
(In the formula, e is a number satisfying 0 ≦ e ≦ 2; R ¹⁷ represents a hydrocarbyl group having 1 to 20 carbon atoms. X ⁴ represents a halogen atom.)

Examples of R ¹⁷ include an alkyl group, an aralkyl group, an aryl group, and an alkenyl group. These have a halogen atom, a hydrocarbyloxy group, a nitro group, a sulfonyl group, a silyl group, or the like as a substituent. Also good. Examples of the alkyl group for R ¹⁷ include linear groups such as methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, and n-octyl group. Alkyl group; branched alkyl group such as isopropyl group, isobutyl group, tert-butyl group, isopentyl group, neopentyl group and 2-ethylhexyl group; cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, And a cyclic alkyl group such as a cyclooctyl group, and a linear or branched alkyl group having 1 to 20 carbon atoms is preferable. Examples of the aralkyl group for R ¹⁷ include a benzyl group and a phenethyl group, and an aralkyl group having 7 to 20 carbon atoms is preferable. Examples of the aryl group for R ¹⁷ include a phenyl group, a naphthyl group, and a tolyl group, and an aryl group having 6 to 20 carbon atoms is preferable. Examples of the alkenyl group for R ¹² include linear alkenyl groups such as vinyl group, allyl group, 3-butenyl group, and 5-hexenyl group; branched groups such as isobutenyl group and 4-methyl-3-pentenyl group. Examples of the alkenyl group include cyclic alkenyl groups such as 2-cyclohexenyl group and 3-cyclohexenyl group, and linear and branched alkenyl groups having 2 to 20 carbon atoms are preferable. A plurality of R ¹⁷ may be the same or different.

Examples of the halogen atom for X ⁴ include a chlorine atom, a bromine atom, an iodine atom, and a fluorine atom, and a chlorine atom is preferable.

  Specific examples of the magnesium compound (d) represented by the above formulas (ix) and (x) include dimethylmagnesium, diethylmagnesium, diisopropylmagnesium, dibutylmagnesium, dihexylmagnesium, dioctylmagnesium, ethylbutylmagnesium, and butyloctylmagnesium. Dialkylmagnesium compounds such as: Dimethoxymagnesium, diethoxymagnesium, dipropoxymagnesium, dibutoxymagnesium, and dialkoxymagnesium compounds such as dioctoxymagnesium; methylmagnesium chloride, ethylmagnesium chloride, isopropylmagnesium chloride, isobutylmagnesium chloride , Tert-butylmagnesium chloride, isobutylmagnesium chloride Lid, benzyl magnesium chloride, methyl magnesium bromide, ethyl magnesium bromide, isopropyl magnesium bromide, isobutyl magnesium bromide, tert-butyl magnesium bromide, hexyl magnesium bromide, isobutyl magnesium bromide, benzyl magnesium bromide, methyl magnesium iodide, ethyl magnesium iodide, Alkylmagnesium halide compounds such as isopropylmagnesium iodide, isobutylmagnesium iodide, tert-butylmagnesium iodide, isobutylmagnesium iodide, benzylmagnesium iodide; methoxymagnesium chloride, ethoxymagnesium chloride, isopropoxymagnesium chloride, Alkoxy magnesium chloride, and alkoxy magnesium chloride compounds such as hexyloxy magnesium chloride; magnesium fluoride, may be mentioned halogenated magnesium compound such as magnesium chloride, magnesium bromide, and magnesium iodide.

  The magnesium compound (d) is preferably a magnesium halide compound (d-1) and a dialkoxymagnesium compound (d-2). The magnesium halide compound (d-1) is preferably magnesium chloride. The magnesium halide compound (d-2) is more preferably a dialkoxymagnesium having 1 to 20 carbon atoms, still more preferably a dialkoxymagnesium having 1 to 10 carbon atoms, particularly preferably dimethoxymagnesium, di- Ethoxymagnesium, dipropoxymagnesium, diisopropoxymagnesium and dibutoxymagnesium. These magnesium compounds can be used as solutions or solids dissolved in alcohols such as methanol, ethanol, and 2-ethylhexanol or in hydrocarbon solvents such as hexane, and contain alcohols, ethers, esters, etc. May be.

  As a manufacturing method of a dialkoxy magnesium compound (d-2), the method of contacting metal magnesium and alcohol in presence of a catalyst can be mentioned, for example. Alcohols include methanol, ethanol, propanol, butanol, and octanol. Catalysts include halogens such as iodine, chlorine, and bromine; magnesium iodides, and magnesium halides such as magnesium chloride, preferably iodine.

Further, the magnesium compound (d) may be supported on a carrier material. The support material is not particularly limited, and examples thereof include porous inorganic oxides such as SiO ₂ , Al ₂ O ₃ , MgO, TiO ₂ , and ZrO ₂ ; polystyrene, styrene-divinylbenzene copolymer, styrene- Ethylene glycol-methyl methacrylate copolymer, polymethyl acrylate, polyethyl acrylate, methyl acrylate-divinylbenzene copolymer, polymethyl methacrylate, methyl methacrylate-divinylbenzene copolymer, polyacrylonitrile, acrylonitrile -Organic porous polymers such as divinylbenzene copolymer, polyvinyl chloride, polyethylene, and polypropylene. Of these, porous inorganic oxides are preferable, and SiO ₂ is particularly preferable.

The carrier preferably has a pore volume at a pore radius of 20 to 200 nm of 0.3 cm ³ / g or more, more preferably 0.4 cm ³ / g from the viewpoint of effectively immobilizing the magnesium compound (d). The pore volume in the above range is 35% or more, more preferably 40% or more with respect to the pore volume at a pore radius of 3.5 to 7500 nm.

  In the production method (2) of the solid catalyst component (A), the organic acid chloride (f) can be optionally added.

Production conditions of production method (2) In production method (2) of solid catalyst component (A), the amount of titanium compound (c) used is usually 0 per 1 mol of total magnesium atoms in magnesium compound (d) used. 0.01 to 100 mol, preferably 0.03 to 50 mol, particularly preferably 0.05 to 30 mol. The titanium compound (c) is used at once or divided into arbitrary plural times.

  In the production method (2) of the solid catalyst component (A), the amount of the electron donating compound (b) used is usually 0.01 to 10,000 ml, preferably 0.03 to 1 g of the magnesium compound (d) used. 5000 ml, particularly preferably 0.05 to 3000 ml.

  In the production method (2) of the solid catalyst component (A), the amount of the organic acid chloride (f) used is usually 0.01 to 10,000 ml, preferably 0.03 to 5000 ml, per 1 g of the magnesium compound (d) used. Particularly preferred is 0.05 to 3000 ml.

  In the production method (2) of the solid catalyst component (A), the method of bringing the titanium compound (c), the magnesium compound (d) and the electron donating compound (b) into contact with each other is not particularly limited. Examples of the method include known methods such as a slurry method and a mechanical pulverization method (for example, a method using a ball mill).

  The slurry concentration in the slurry method is usually 0.05 to 0.7 g solid / ml solvent, particularly preferably 0.1 to 0.5 g solid / ml solvent. The temperature of the contact is usually 30 to 150 ° C, preferably 45 to 135 ° C, particularly preferably 60 to 120 ° C. The contact time is not particularly limited, and usually about 30 minutes to 6 hours is preferable.

  The mechanical pulverization method is preferably performed in the presence of a diluent in order to suppress the fine powder content of the obtained solid catalyst component (A) and the spread of its particle size distribution. As diluents, aliphatic hydrocarbyls such as pentane, hexane, heptane and octane; aromatic hydrocarbons such as benzene, toluene and xylene; alicyclic hydrocarbons such as cyclohexane and cyclopentane; Illustrative are halogenated hydrocarbons such as 2-dichloroethane and monochlorobenzene. Of these, aromatic hydrocarbons or halogenated hydrocarbons are particularly preferable.

  In the production method (2), the temperature at which the titanium compound (c) is contacted with the magnesium compound (d) and the electron donating compound (b) is not particularly limited, and is usually −50 to 200 ° C., preferably −20 to 20 ° C. It is 150 degreeC, More preferably, it is the range of -20-130 degreeC, Most preferably, it is the range of -20-120 degreeC.

  In the production method (2), the time for contacting the titanium compound (c), the magnesium compound (d) and the electron donating compound (b) is not particularly limited, and is usually 10 minutes to 12 hours, preferably 30 to 10 hours. The time is particularly preferably in the range of 1 hour to 8 hours, and may be divided into one time or a plurality of times at an arbitrary time.

  In the production method (2), the compound (g) represented by the following formula (xi) or (xii) may optionally be contacted.

M ² R ¹⁸ _fg X ⁵ _g (xi)
M ² (OR ¹⁸ ) _fg X ⁵ _g (xii)
Wherein M ² represents a Group 13 or Group 14 atom; R ¹⁸ represents a hydrocarbyl group having 1 to 20 carbon atoms; X ⁵ represents a halogen atom; f represents the valence of M ² And g represents a number satisfying 0 <g ≦ f.

Examples of the group 13 element of M ² in the above formulas (xi) and (xii) include boron, aluminum, gallium, indium, and thallium. Among these, boron or aluminum is preferable, and aluminum is more preferable. Examples of the group 14 element of M ² include silicon, germanium, tin, and lead. Among these, silicon, germanium or tin is preferable, and silicon is more preferable.

As R ¹⁸ in the above formulas (xi) and (xii), methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, isopentyl group, hexyl group, heptyl group, octyl group, decyl group, And linear or branched alkyl groups such as dodecyl group; cyclic alkyl groups such as cyclohexyl group and cyclopentyl group; and aryl groups such as phenyl group, cresyl group, xylyl group and naphthyl group. it can. Among these, an alkyl group having 2 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms is preferable.

X ⁵ in the above formulas (xi) and (xii) includes a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, preferably a chlorine atom or a bromine atom.

In the above formulas (xi) and (xii), f is the valence of M ² , f is 3 when it is a Group 13 element, and 4 is 4 when it is a Group 14 element.

In the above formula, g represents a number satisfying 0 <g ≦ f. When M ² is a Group 14 element, d represents a number satisfying 0 <d ≦ 4, and when M ² is a Group 13 element, g is 0 < This represents a number satisfying g ≦ 3. In the case where M ² is a Group 14 element, preferable g is 3 or 4, more preferably 4. A preferred g when M ² is a Group 13 element is 3.

  Among the compounds (g), the chloroaluminum compound or the chlorosilicon compound is preferably ethylaluminum dichloride, ethylaluminum sesquichloride, diethylaluminum chloride, trichloroaluminum, tetrachlorosilane, phenyltrichlorosilane, methyltrichlorosilane, ethyltrichlorosilane. Chlorosilane, normal propyltrichlorosilane, or paratolyltrichlorosilane, more preferably a chlorinated compound of Group 14 element, and particularly preferably tetrachlorosilane and phenyltrichlorosilane.

  In the catalyst component production method (2), the amount of the compound (g) used is usually 0.01 to 100 mol, preferably 0.03 to 50 mol, particularly preferably 0.05, per 1 mol of total magnesium atoms in the magnesium compound. ˜30 mol, the compound is used at once or divided into arbitrary multiple times.

  In the production method (2), the temperature at which the compound (g), the titanium compound (c), the magnesium compound (d) and the electron donating compound (b) are brought into contact is not particularly limited, and is usually −50 to 200 ° C., Preferably it is 0-170 degreeC, Most preferably, it is the range of 50-150 degreeC.

  In the production method (2), the time for contacting the compound (g), the titanium compound (c) with the magnesium compound (d) and the electron donating compound (b) is not particularly limited, and is usually 10 minutes to 12 hours, Preferably, it is 30 minutes to 10 hours.

[Organic aluminum compound (B)]
Examples of the organoaluminum compound (B) used in the present invention include the compounds described in US Pat. No. 6,903,041. Among them, preferred is trialkylaluminum, a mixture of trialkylaluminum and dialkylaluminum halide, or alkylalumoxane, and more preferred is triethylaluminum, triisobutylaluminum, a mixture of triethylaluminum and diethylaluminum chloride or tetraethyldichloride. Alumoxane.

[Alkoxysilicon compound (D)]
As the alkoxysilicon compound (D) optionally used in the present invention, a compound represented by the following formula (II) is preferable.
R ¹ mSi (OR ² ) _4-m (II)
(In the formula, R ¹ represents a hydrocarbyl group having 1 to 20 carbon atoms, a hydrogen atom or a heteroatom-containing substituent, R ² represents a hydrocarbyl group having 1 to 20 carbon atoms, and m represents 1 If .R ¹ representing the number of to 3 there are a plurality, R ¹ may be the same or different, when R ² are a plurality, R ² may be the same or different.)

Examples of the hydrocarbyl group of R ¹ in the above formula (II) include an alkyl group, an aralkyl group, an aryl group, and an alkenyl group. Examples of the alkyl group of R ¹ include a methyl group, an ethyl group, and an n-propyl group. , N-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, and n-octyl group, linear alkyl groups; isopropyl group, isobutyl group, tert-butyl group, isopentyl group, neopentyl group And a branched alkyl group such as 2-ethylhexyl group; and a cyclic alkyl group such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, and cyclooctyl group, preferably carbon These are linear, branched and cyclic alkyl groups having 1 to 20 atoms. Examples of the aralkyl group for R ¹ include a benzyl group and a phenethyl group, and an aralkyl group having 7 to 20 carbon atoms is preferable. Examples of the aryl group for R ¹ include a phenyl group, a tolyl group, and a xylyl group, and an aryl group having 6 to 20 carbon atoms is preferable. Examples of the alkenyl group for R ¹ include linear alkenyl groups such as vinyl group, allyl group, 3-butenyl group, and 5-hexenyl group; branched alkenyl groups such as isobutenyl group and 5-methyl-3-pentenyl group. A cyclic alkenyl group such as a 2-cyclohexenyl group and a 3-cyclohexenyl group, preferably an alkenyl group having 2 to 10 carbon atoms. R ¹ is preferably a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, more preferably a methyl group, an ethyl group, an n-propyl group, an n-butyl group or an n-pentyl group. N-hexyl group, n-heptyl group, n-octyl group, isopropyl group, isobutyl group, tert-butyl group, isopentyl group, neopentyl group, 2-ethylhexyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group , A cycloheptyl group, and a cyclooctyl group.

Examples of the hydrocarbyl group of R ² in the above formula (II) include an alkyl group, and include a methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n- Linear alkyl groups such as heptyl group and n-octyl group; branched alkyl groups such as isopropyl group, isobutyl group, tert-butyl group, isopentyl group, neopentyl group, and 2-ethylhexyl group; cyclopropyl group A cyclic alkyl group such as a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group, preferably a linear, branched and cyclic alkyl group having 1 to 20 carbon atoms. More preferably a straight-chain alkyl group having 1 to 5 carbon atoms, particularly preferably a methyl group or an ethyl group. The

Examples of the compound in which R ¹ in the above formula (II) is a heteroatom-containing substituent include compounds represented by the following formula (VI) or the following formula (VII).
Si (OR ¹⁹ ) ₃ (NR ²⁰ R ²¹ ) (VI)
Si (OR ¹⁹ ) ₃ (NR ²² ) (VII)
In the formula, R ¹⁹ is a hydrocarbyl group having 1 to 6 carbon atoms; R ²⁰ and R ²¹ are each independently a hydrogen atom or a hydrocarbyl group having 1 to 12 carbon atoms; NR ²² Is a cyclic amino group having 5 to 20 carbon atoms.
Examples of the hydrocarbyl group of R ^{19 in} the above formulas (VI) and (VII) include an alkyl group, and examples of the alkyl group of R ¹⁹ include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, linear alkyl groups such as n-pentyl group and n-hexyl group; branched alkyl groups such as isopropyl group, isobutyl group, tert-butyl group, isopentyl group, and neopentyl group; cyclopropyl group, cyclobutyl group , A cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, preferably a linear alkyl group having 1 to 6 carbon atoms. R ¹⁹ is particularly preferably a methyl group or an ethyl group.

Examples of the hydrocarbyl group of R ²⁰ and R ²¹ in the above formula (VI) include an alkyl group and an alkenyl group. Examples of the alkyl group of R ²⁰ and R ²¹ include a methyl group, an ethyl group, and an n-propyl group. Linear alkyl groups such as isopropyl, n-butyl, n-pentyl, and n-hexyl; branched alkyl such as isopropyl, isobutyl, tert-butyl, isopentyl, and neopentyl; Examples thereof include cyclic alkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, and cyclohexyl group, and a linear alkyl group having 1 to 6 carbon atoms is preferable. Examples of the alkenyl group for R ²⁰ and R ²¹ include linear alkenyl groups such as vinyl group, allyl group, 3-butenyl group, and 5-hexenyl group; isobutenyl group, and 5-methyl-3-pentenyl group Branched alkenyl group; cyclic alkenyl groups such as 2-cyclohexenyl group and 3-cyclohexenyl group are exemplified, and a linear alkenyl group having 2 to 6 carbon atoms is preferable. RR ²⁰ and R ²¹ are particularly preferably a methyl group and an ethyl group.

  Specific examples of the alkoxysilicon represented by the above formula (VI) include dimethylaminotrimethoxysilane, diethylaminotrimethoxysilane, dipropylaminotrimethoxysilane, dimethylaminotriethoxysilane, diethylaminotriethoxysilane, dipropylaminotri Examples include ethoxysilane, methylethylaminotriethoxysilane, methylpropylaminotriethoxysilane, tert-butylaminotriethoxysilane, diisopropylaminotriethoxysilane, and methylisopropylaminotriethoxysilane.

The cyclic amino group of NR ²² in the above formula (VII) includes a perhydroquinolino group, a perhydroisoquinolino group, a 1,2,3,4-tetrahydroquinolino group, a 1,2,3,4-tetrahydroiso group. A quinolino group and an octamethyleneimino group are mentioned.

  Specific examples of the alkoxysilicon represented by the above formula (VII) include perhydroquinolinotriethoxysilane, perhydroisoquinolinotriethoxysilane, 1,2,3,4-tetrahydroquinolinotriethoxysilane, Examples include 2,3,4-tetrahydroisoquinolinotriethoxysilane and octamethyleneiminotriethoxysilane.

It is preferable that the alkoxy silicon represented by the above formula (II) includes a compound represented by the following formula (III) or the following formula (IV).
R ³ R ⁴ Si (OCH ₃ ) ₂ (III)
(In the formula, R ³ and R ⁴ each independently represent a hydrocarbyl group having 1 to 20 carbon atoms, a hydrogen atom, or a heteroatom-containing substituent.)
R ⁵ _p Si (OC ₂ H ₅ ) _4-p (IV)
(In the formula, R ⁵ represents a hydrocarbyl group having 3 to 20 carbon atoms in which the carbon atom bonded to Si is a secondary carbon atom, and p represents a number of 1 to 3. When there are a plurality of R ^{5 s.} , R ² may be the same or different.)

Examples of the hydrocarbyl group of R ³ and R ⁴ in the above formula (III) include an alkyl group, an aralkyl group, an aryl group, and an alkenyl group. Examples of the alkyl group include linear alkyl groups such as methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, and n-octyl group; Branched alkyl groups such as isopropyl, isobutyl, tert-butyl, isopentyl, neopentyl, and 2-ethylhexyl; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclo Examples thereof include cyclic alkyl groups such as octyl group, and preferred are linear, branched and cyclic alkyl groups having 1 to 20 carbon atoms. Examples of the aralkyl group include a benzyl group and a phenethyl group, and an aralkyl group having 7 to 20 carbon atoms is preferable. Examples of the aryl group include a phenyl group, a tolyl group, and a xylyl group, and an aryl group having 6 to 20 carbon atoms is preferable. Examples of the alkenyl group include linear alkenyl groups such as vinyl group, allyl group, 3-butenyl group, and 5-hexenyl group; branched alkenyl groups such as isobutenyl group and 5-methyl-3-pentenyl group; 2 -Cyclohexenyl group and cyclic alkenyl groups such as 3-cyclohexenyl group can be mentioned, and an alkenyl group having 2 to 10 carbon atoms is preferred. R ³ and R ⁴ are preferably linear, branched and cyclic alkyl groups having 1 to 20 carbon atoms, more preferably methyl, ethyl, n-propyl, n-butyl, n -Pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isopropyl group, isobutyl group, tert-butyl group, isopentyl group, neopentyl group, 2-ethylhexyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group , A cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.
Examples of the hydrocarbyl group of R ⁵ in the above formula (IV) include an alkyl group, an aralkyl group, and an alkenyl group. Examples of the alkyl group include branched alkyl groups such as isopropyl group and sec-butyl group; and cyclic alkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, and cyclooctyl group. Preferred are branched and cyclic alkyl groups having 4 to 20 carbon atoms. Examples of the aralkyl group include an α-methylbenzyl group and an α-butylbenzyl group, and an aralkyl group having 8 to 20 carbon atoms is preferable. Examples of the alkenyl group include branched alkenyl groups such as 3-methyl-1-propenyl group and 4-methyl-1-butenyl group; cyclic alkenyl groups such as 2-cyclohexenyl group and 3-cyclohexenyl group. Preferably, it is an alkenyl group having 4 to 10 carbon atoms. R ⁵ is preferably a branched or cyclic alkyl group having 4 to 20 carbon atoms, more preferably a sec-butyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, or a cyclooctyl group. is there.

  Specific examples of the above formula (III) or the above formula (IV) include cyclohexylmethyldimethoxysilane, cyclohexylethyldimethoxysilane, diisopropyldimethoxysilane, tert-butylethyldimethoxysilane, tert-butylpropyldimethoxysilane, phenyltrimethoxysilane, Examples include diphenyldimethoxysilane, dicyclobutyldimethoxysilane, dicyclopentyldimethoxysilane, vinyltriethoxysilane, sec-butyltriethoxysilane, cyclohexyltriethoxysilane, and cyclopentyltriethoxysilane.

The alkoxysilicon compound (D) may be a mixture of a compound represented by the formula (III) or a compound represented by the formula (IV) and a compound represented by the following formula (V).
R ⁶ _q Si (OC ₂ H ₅ ) _4-q (V)
(In the formula, R ⁶ represents a hydrocarbyl group having 1 to 20 carbon atoms in which the carbon atom bonded to Si is a primary carbon, and q represents a number of 0 or 1.)

R ⁶ represents a hydrocarbyl group having 1 to 20 carbon atoms, preferably 1 to 7 carbon atoms, more preferably 1 to 3 carbon atoms in which the carbon atom bonded to Si is a primary carbon, and q is 0 or The number of 1 is represented. R ^{6 represents} a linear alkyl group such as a methyl group, an ethyl group, a normal propyl group or a normal butyl group; and a branched alkyl group such as an iso-butyl group, an iso-amyl group or an iso-hexyl group. It can be illustrated.

  Examples of the compound represented by the formula (V) include tetraethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, normal propyltriethoxysilane, normal butyltriethoxysilane, iso-butyltriethoxysilane, and normal amyltriethoxysilane. , Iso-amyltriethoxysilane, normal hexyltriethoxysilane, 2-methylpentyltriethoxysilane, 3-methylpentyltriethoxysilane, 4-methylpentyltriethoxysilane, normal heptyltriethoxysilane, and normal octyltriethoxysilane Can be exemplified. Among these, tetraethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, normal propyltriethoxysilane, and iso-butyltriethoxysilane are preferable, and tetraethoxysilane, methyltriethoxysilane, and ethyltriethoxysilane are more preferable. , Normal propyl triethoxysilane.

Preferred examples of the alkoxysilicon compound (D) include the following.
(1) an alkoxysilicon compound represented by formula (III) (2) an alkoxysilicon compound represented by formula (IV) (3) an alkoxysilicon compound represented by formula (III) or formula (IV), and a formula As the mixture (1) with the alkoxysilicon compound represented by (V), cyclohexylmethyldimethoxysilane, cyclohexylethyldimethoxysilane, diisopropyldimethoxysilane, tert-butylethyldimethoxysilane, tert-butylpropyldimethoxysilane, dicyclobutyl Dimethoxysilane, dicyclopentyldimethoxysilane, (2) as cyclohexyltriethoxysilane, cyclopentyltriethoxysilane, (3) as the alkoxysilicon compounds mentioned in (1) and (2) above, tetraethoxysilane, Triethoxysilane, ethyl triethoxysilane, or a mixture of normal propyl triethoxysilane, and the like.

[Method for preparing catalyst for olefin polymerization]
In the method for obtaining a catalyst for olefin polymerization by contacting the solid catalyst component (A), the organoaluminum compound (B), the lactone compound (C) and optionally the alkoxysilicon compound (D), a known method may be used. Yes, there are no particular restrictions.

The contact order of the solid catalyst component (A), the organoaluminum compound (B), the lactone compound (C) and the alkoxysilicon compound (D) is not particularly limited, but the following methods (1) to (4) ).
(1) A method in which the solid catalyst component (A), the organoaluminum compound (B), the lactone compound (C), and the alkoxysilicon compound (D) are contacted simultaneously.
(2) A method of contacting the solid catalyst component (A) after contacting the organoaluminum compound (B), the lactone compound (C) and the alkoxysilicon compound (D).
(3) A method of contacting the solid catalyst component (A) after contacting the mixed solution of the lactone compound (C) and the alkoxysilicon compound (D) with the organoaluminum compound (B).
(4) A method in which the lactone compound (C) and the alkoxysilicon compound (D) are contacted after contacting the solid catalyst component (A) and the organoaluminum compound (B).
The method (2) and the method (3) are preferable.

  The preparation of the olefin polymerization catalyst of the present invention is preferably carried out in an inert hydrocarbon, and more preferably in the presence of a solvent exemplified in the main polymerization or prepolymerization of olefins described later.

The method for forming the polymerization catalyst of the present invention may be preferably a method comprising the following steps:
(1) Prepolymerization catalyst component generation step:
In the presence of the solid catalyst component (A) and the organoaluminum compound (B), a small amount of olefin (same or different from the olefin used in the original polymerization (usually referred to as main polymerization)) is polymerized (produced). In order to adjust the molecular weight of the olefin polymer, a chain transfer agent such as hydrogen may be used.) A step of generating a catalyst component whose surface is covered with the polymer of the olefin (the polymerization is usually prepolymerization). Therefore, the catalyst component is usually referred to as a prepolymerized catalyst component).
(2) Production step of polymerization catalyst component for main polymerization:
A step of bringing the prepolymerization catalyst component into contact with the organoaluminum compound (B) optionally.

  The lactone compound (C) can be used in either or both of the above steps (1) and (2). Further, the alkoxysilicon compound (D) can also be used in any one or both of the above steps (1) and (2).

  The prepolymerization is preferably a slurry polymerization using an inert hydrocarbon such as propane, butane, isobutane, pentane, isopentane, hexane, heptane, octane, cyclohexane, benzene and toluene as a solvent.

  The amount of the organoaluminum compound (B) used in the step (1) is usually 0.5 to 700 mol, preferably 0.8 per mol of titanium atom in the solid catalyst component (A) used in the step (1). ˜500 mol, particularly preferably 1 to 200 mol.

  The amount of the prepolymerized olefin is usually 0.01 to 1000 g, preferably 0.05 to 500 g, particularly preferably 0.1 to 200 g, per 1 g of the solid catalyst component for olefin polymerization (A) used in the step (1). It is.

The slurry concentration of the solid catalyst component for olefin polymerization (A) in the slurry polymerization in the above step (1) is preferably 1 to 500 g-solid catalyst component for olefin polymerization / L-solvent, particularly preferably 3 to 300 g for olefin polymerization. Solid catalyst component / L-solvent.
The prepolymerization temperature is preferably -20 to 100 ° C, particularly preferably 0 to 80 ° C. The partial pressure of the olefin in the gas phase in the prepolymerization is preferably 0.01 to 2 MPa, particularly preferably 0.1 to 1 MPa. However, for olefins that are liquid at the prepolymerization pressure and temperature, Absent. The prepolymerization time is not particularly limited and is preferably 2 minutes to 15 hours.

The following methods (1) and (2) can be exemplified as methods for supplying the solid catalyst component (A), the organoaluminum compound (B) and the olefin to the polymerization tank in the prepolymerization:
(1) A method of supplying an olefin after supplying the solid catalyst component (A) and the organoaluminum compound (B); and (2) an organoaluminum compound (A) after supplying the solid catalyst component (A) and the olefin. B) Method of supplying.

The following methods (1) and (2) can be exemplified as methods for supplying olefin to the polymerization tank in the prepolymerization:
(1) A method of sequentially supplying olefins so that the pressure in the polymerization tank is maintained at a predetermined pressure;

  The amount of the lactone compound (C) used in the prepolymerization is usually 0.01 to 400 mol, preferably 0.02 to 200 mol, particularly preferably, relative to 1 mol of titanium atoms contained in the solid catalyst component (A). It is 0.03-100 mol, and is 0.003-5 mol normally with respect to 1 mol of organoaluminum compounds (B), Preferably it is 0.005-3 mol, Most preferably, it is 0.01-2 mol.

  The amount of the alkoxysilicon compound (D) used in the prepolymerization is usually 0.01 to 400 mol, preferably 0.02 to 200 mol, particularly preferably relative to 1 mol of titanium atom contained in the solid catalyst component (A). 0.03 to 100 mol, and usually 0.003 to 5 mol, preferably 0.005 to 3 mol, and particularly preferably 0.01 to 2 mol with respect to 1 mol of the organoaluminum compound (B).

Examples of the method of supplying the lactone compound (C) and the alkoxysilicon compound (D) to the polymerization tank in the prepolymerization include the following methods (1) to (6):
(1) A method of supplying the lactone compound (C) alone;
(2) A method of supplying the alkoxysilicon compound (D) alone;
(3) A method of supplying a mixture of a lactone compound (C) and an alkoxysilicon compound (D);
(4) A method of supplying a mixture of a lactone compound (C) and an organoaluminum compound (B);
(5) a method of supplying a mixture of an alkoxysilicon compound (D) and an organoaluminum compound (B); and (6) a mixture of a lactone compound (C), an alkoxysilicon compound (D) and an organoaluminum compound (B). How to supply.

  The usage-amount of the organoaluminum compound (B) at the time of this superposition | polymerization is 1-1000 mol normally with respect to 1 mol of titanium atoms in the solid catalyst component (A) for olefin polymerization, Most preferably, it is 5-600 mol.

  The amount of the lactone compound (C) used in the main polymerization is usually 0.1 to 2000 mol, preferably 0.3 to 1000 mol, particularly preferably 0.5, per 1 mol of titanium atoms contained in the solid catalyst component (A). The amount is usually from 0.001 to 5 mol, preferably from 0.005 to 3 mol, particularly preferably from 0.01 to 1 mol, per mol of the organoaluminum compound (B).

  The amount of the alkoxysilicon compound (D) used in the main polymerization is usually 0.1 to 2000 mol, preferably 0.3 to 1000 mol, particularly preferably 0.001 mol per 1 mol of titanium atoms contained in the solid catalyst component (A). It is 5-800 mol, and is 0.001-5 mol normally per 1 mol of organoaluminum compounds (B), Preferably it is 0.005-3 mol, Most preferably, it is 0.01-1 mol.

  When the alkoxysilicon compound (D) used in the prepolymerization or main polymerization is a mixture of the compound represented by the formula (III) or the formula (IV) and the formula (V), the formula (III) or the formula (IV The amount of the compound represented by the formula (V) is usually 0.01 to 10, preferably 0.05 to 7, and particularly preferably 0.1 to 5.0. (Molar ratio).

  The temperature of the main polymerization is usually -30 to 300 ° C, preferably 20 to 180 ° C. The polymerization pressure is not particularly limited, and is generally from atmospheric pressure to 10 MPa, preferably from about 200 kPa to 5 MPa in that it is industrial and economical. The polymerization is batch or continuous, and as a polymerization method, a slurry polymerization method or a solution polymerization method using an inert hydrocarbon such as propane, butane, isobutane, pentane, hexane, heptane and octane as a solvent, or a liquid at the polymerization temperature Examples thereof include a bulk polymerization method using an olefin as a medium and a gas phase polymerization method.

（２）
（式（２）中、ｐは２以上の整数を表す。） <Compound (component (γ))>
The component (γ) is at least one compound selected from the following compound group S.
Compound group S: a compound represented by the general formula C _n H _{n + 2} (OH) _n (wherein _n represents an integer of 4 or more), the following alkoxy compound, and the following formula (2) A group of compounds consisting of a compound to be obtained, trehalose, sucrose, lactose, maltose, meletitose, stachyose, curdlan, glycogen, glucose and fructose.
Alkoxy compound: a compound in which at least one of the hydroxyl groups contained in the compound represented by the following formula (1) is alkoxylated with an alkyl group having 1 to 12 carbon atoms, and represented by the formula (1) The compound is a compound having one aldehyde group or ketone group and m-1 hydroxyl groups in the molecule.

C _m H _2m O _m (1)
(In formula (1), m represents an integer of 3 or more.)

(2)
(In formula (2), p represents an integer of 2 or more.)

_{N in the} general formula of the compound represented by the general formula C _n H _{n + 2} (OH) _n (hereinafter sometimes referred to as “compound (S1)”) represents an integer of 4 or more. n is preferably an integer of 5 to 8, and more preferably 6.

  Examples of the compound (S1) include sugar alcohols having 4 or more carbon atoms. For example, n = 4 sugar alcohols such as erythritol, threitol; n = 5 sugar alcohols such as adonitol, arabinitol, xylitol; n = 6 sugar alcohols such as allitol, taritol, sorbitol, mannitol, iditol, galactitol; As sugar alcohols with n = 7, boregitol and perseitol; octitol can be mentioned as sugar alcohols with n = 8.

  Compound (S1) may be D-form or L-form, or a mixture of D-form and L-form. Further, it may be optically active or optically inactive.

  The compound (S1) is preferably a sugar alcohol having 6 carbon atoms.

The alkoxy compound used in the present invention means that at least one hydroxyl group contained in a compound represented by the following formula (1) (hereinafter sometimes referred to as “compound (S2)”) has 1 carbon atom. This compound is alkoxylated with ˜12 alkyl groups, and the compound (S2) is a compound having one aldehyde group or ketone group and m−1 hydroxyl groups in the molecule.
C _m H _2m O _m (1)

  M of a compound (S2) is an integer greater than or equal to 3, Preferably, it is 3-60, More preferably, it is 6 or 12.

  The compound (S2) has one aldehyde group or ketone group in the molecule. The compound (S2) has m-1 hydroxyl groups.

  The compound (S2) is preferably a monosaccharide, and specifically, for example, glycerose, erythrose, threose, ribose, lyxose, xylose, arabinose, aldohexose, allose, talose, gulose, glucose, altrose, mannose, galactose Monosaccharides having an aldehyde group such as idose and octose, such as ketotriose, dihydroxyacetone, ketotetorose, erythrulose, ketopentose, xylulose, ribulose, ketohexose, psicose, fructose, sorbose, tagatose, etc. can give.

The compound (S2) may be an optically active substance such as D-form or L-form, or an optically inactive substance such as DL-form.
As the compound (S2), among them, hexoses such as allose, talose, growth, glucose, altrose, mannose, galactose, idose, psicose, fructose, sorbose, tagatose are preferable, and glucose is particularly preferable.

The alkoxy compound is a compound in which at least one hydroxyl group contained in the compound (S2) is alkoxylated with an alkyl group. The alkoxy compound preferably has at least one hydroxyl group. Particularly preferably, it is an alkoxy compound in which one of the hydroxyl groups contained in the compound (S2) is alkoxylated and the other group remains a hydroxyl group.
Carbon number of the said alkyl group is 1-12, Preferably it is 1 or 2, More preferably, it is 1.

（１−１） Preferable alkoxylated compounds include, for example, compounds represented by the formula (1-1) (wherein R ⁴¹ represents an alkyl group having 1 to 12 carbon atoms, preferably 5 to 12 carbon atoms). Can give.

(1-1)

  Examples of the compound represented by the formula (1-1) include methyl α-D-glucopyranoside, methyl β-D-glucopyranoside, ethyl α-D-glucopyranoside, ethyl β-D-glucopyranoside, n-propyl α-D. -Glucopyranoside, n-propyl β-D-glucopyranoside, n-butyl α-D-glucopyranoside, n-butyl β-D-glucopyranoside, n-pentyl α-D-glucopyranoside, n-pentyl β-D-glucopyranoside, n- Hexyl α-D-glucopyranoside, n-hexyl β-D-glucopyranoside, n-heptyl α-D-glucopyranoside, n-heptyl β-D-glucopyranoside, n-octyl α-D-glucopyranoside, n-octyl β-D- Glucopyranoside, n-nonyl α-D-glucopyranoside, n-nonyl -D-glucopyranoside, n-decyl α-D-glucopyranoside, n-decyl β-D-glucopyranoside, n-undecyl α-D-glucopyranoside, n-undecyl β-D-glucopyranoside, n-dodecyl α-D-glucopyranoside, and n-dodecyl β-D-glucopyranoside.

As a method for producing an alkoxy compound, for example, New Experimental Chemistry Course 14 Synthesis and Reaction V of Organic Compounds (Maruzen Co., Ltd., issued on July 20, 1978) According to the description on page 2426, compound (S2) Examples thereof include a method in which hydrogen chloride gas is passed through an alkyl alcohol solution at −10 ° C. to room temperature, for example, a method in which a mixed solution of compound (S2), alkyl alcohol and hydrochloric acid is heated to reflux to perform alkoxylation.
In addition, methyl α-D-glucopyranoside, n-octyl β-D-glucopyranoside, and the like can be obtained from Tokyo Chemical Industry Co., Ltd.

（２） In the compound represented by the following formula (2) (hereinafter sometimes referred to as “compound (S3)”), in formula (2), p represents an integer of 2 or more, preferably 2 to 2. It represents an integer of 6, more preferably 5.

(2)

  Examples of the compound (S3) include 1,2,3-trihydroxycyclopropane, 1,2,3,4-tetrahydroxycyclopentane, 1,2,3,4,5-pentahydroxycyclopentane, , 2,3,4,5,6-hexahydroxycyclohexane, 1,2,3,4,5,6,7-heptahydroxycycloheptane, 1,2,3,4,5,6,7,8- And octahydroxycyclooctane.

Preferred examples include 1,2,3,4,5,6-hexahydroxycyclohexane such as myo-inositol, epi-inositol, allo-inositol, muco-inositol, neo-inositol, chiro-inositol, scyllo-inositol, etc. In particular, myo-inositol and scyllo-inositol represented by the following formula are preferred.

  The content of the component (γ) in the polypropylene resin composition of the present invention is 0.01 to 0.5 parts by weight, preferably 0.01 to 0.25, relative to 100 parts by weight of the component (β). Parts by weight.

  When the content of the component (γ) is less than 0.01 parts by weight with respect to 100 parts by weight of the component (β), a sufficient improvement effect for reducing the volatile organic compound component cannot be obtained, When the amount is more than 0.5 parts by weight, there may be a problem that the polypropylene resin composition is colored.

<Component (δ)>
The component (δ) is a compound selected from the group consisting of a compound represented by the following formula (3) and a compound represented by the formula (4).

（３）
（式（３）中、各Ｒ^ｓ１および各Ｒ^ｓ２は、それぞれ独立して、炭素数１〜８のアルキル基、炭素数６〜１２のアリール基または炭素数７〜１８のアラルキル基を表す。Ｒ^ｓ３は、水素原子または炭素数１〜３のアルキル基を表す。Ｒ^ｓ４は、水素原子またはメチル基を表す。）

(3)
(In Formula (3), each R ^s1 and each R ^s2 each independently represent an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 18 carbon atoms. R ^s3 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ^s4 represents a hydrogen atom or a methyl group.)

Each R ^s1 and each R ^{s2 in} Formula (3) each independently represent an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 18 carbon atoms. There are two R ^{s1 s,} but each R ^s1 may be the same as or different from each other, preferably the same. The same applies to each R ^s2 .

  The alkyl group having 1 to 8 carbon atoms may be either a chain or a ring, preferably a chain (straight or branched), more preferably a branched chain. Examples of the alkyl group having 1 to 8 carbon atoms include a linear alkyl group having 1 to 8 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, pentyl group (also referred to as amyl group)), Branched alkyl group having 3 to 8 carbon atoms (for example, isopropyl group, isobutyl group, sec-butyl group, t-butyl group, t-pentyl group, 2-ethylhexyl group), cyclic 3 to 8 carbon atoms (That is, a cycloalkyl group having 3 to 8 carbon atoms, such as a cyclopentyl group and a cyclohexyl group). Examples of the aryl group having 6 to 12 carbon atoms include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group. Examples of the aralkyl group having 7 to 18 carbon atoms include a benzyl group, a 1-phenylethyl group, a 2-phenylethyl group, and the like.

Each R ^s1 and each R ^s2 are each independently preferably a branched alkyl group having 3 to 8 carbon atoms, more preferably an alkyl group having 4 to 8 carbon atoms having a tertiary carbon atom. More preferably a t-butyl group or a t-pentyl group, and particularly preferably a t-pentyl group.

R ^s3 in formula (3) represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. The alkyl group having 1 to 3 carbon atoms may be linear or branched. Examples of the alkyl group having 1 to 3 carbon atoms include a methyl group, an ethyl group, a propyl group, and an isopropyl group. R ^s3 is preferably a hydrogen atom or a methyl group.

R ^s4 in formula (3) represents a hydrogen atom or a methyl group, preferably a hydrogen atom.

  Examples of the compound represented by the formula (3) include 2,4-di-t-butyl-6- [1- (3,5-di-t-butyl-2-hydroxyphenyl) ethyl] phenyl (meta ) Acrylate, 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl (meth) acrylate, 2,4-di-t-pentyl-6- [ 1- (3,5-di-t-pentyl-2-hydroxyphenyl) ethyl] phenyl (meth) acrylate, 2,4-di-t-butyl-6- (3,5-di-t-butyl-2 -Hydroxy-benzyl) phenyl (meth) acrylate, 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-ethylphenyl (meth) acrylate, or 2-t- Pentyl-6 (3-t-pentyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl (meth) acrylate and the like. Here, “(meth) acrylate” means “acrylate and methacrylate”.

  Among the compounds represented by formula (3), 2,4-di-t-pentyl-6- [1- (3,5-di-t-pentyl-2-hydroxyphenyl) ethyl] phenyl acrylate, And 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate. 2,4-di-t-pentyl-6- [1- (3,5-di-t-pentyl-2-hydroxyphenyl) ethyl] phenyl acrylate is Sumilizer (registered trademark) GS (F) (manufactured by Sumitomo Chemical Co., Ltd.) ), 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate is commercially available as Sumilizer (registered trademark) GM (manufactured by Sumitomo Chemical Co., Ltd.). Yes.

  The compound represented by formula (3) is a commercially available product, or is produced according to a known method (for example, the method described in JP 2010-168545 A or JP 58-84835 A). can do.

（４）
（式（４）中、Ｒ^ｐ１、Ｒ^ｐ２、Ｒ^ｐ４およびＲ^ｐ５は、それぞれ独立して、水素原子、炭素数１〜８のアルキル基、炭素数５〜８のシクロアルキル基、炭素数６〜１２のアルキルシクロアルキル基、炭素数７〜１２のアラルキル基またはフェニル基を表し、Ｒ^ｐ３はそれぞれ独立して、水素原子または炭素数１〜８のアルキル基を表し、Ｘは単結合、硫黄原子または下記の式（４−１）

（４−１）
（式（４−１）中、Ｒ^ｐ６は水素原子、炭素数１〜８のアルキル基または炭素数５〜８のシクロアルキル基を示す。）で示される２価の基を表し、Ａは炭素数２〜８のアルキレン基または下記の式（４−２）

（４−２）
（式（４−２）中、Ｒ^ｐ７は単結合または炭素数１〜８のアルキレン基を表し、＊は酸素原子に結合する部位を表す。）で示される２価の基を表し、Ｙ、Ｚはいずれか一方がヒドロキシ基、炭素数１〜８のアルキル基、炭素数１〜８のアルコキシ基または炭素数７〜１２のアラルキルオキシ基を表し、他方が水素原子または炭素数１〜８のアルキル基を表す。）

(4)
(In formula (4), R ^p1 , R ^p2 , R ^p4 and R ^p5 each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, or 6 carbon atoms. Represents an alkylcycloalkyl group having 12 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or a phenyl group, R ^p3 each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, X is a single bond, sulfur Atom or the following formula (4-1)

(4-1)
(In formula (4-1), R ^p6 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a cycloalkyl group having 5 to 8 carbon atoms), and A represents carbon. An alkylene group of 2 to 8 or the following formula (4-2)

(4-2)
(In formula (4-2), R ^p7 represents a single bond or an alkylene group having 1 to 8 carbon atoms, and * represents a site bonded to an oxygen atom.) Y, Z represents a hydroxy group, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms or an aralkyloxy group having 7 to 12 carbon atoms, and the other is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. Represents an alkyl group. )

In the formula (4), examples of the alkyl group having 1 to 8 carbon atoms represented by R ^p1 , R ^p2 , R ^p4 and R ^p5 include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, Examples include n-butyl group, i-butyl group, sec-butyl group, t-butyl group, t-pentyl group, i-octyl group, t-octyl group and 2-ethylhexyl group.

  Examples of the cycloalkyl group having 5 to 8 carbon atoms include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Examples of the alkylcycloalkyl group having 6 to 12 carbon atoms include 1-methylcyclopentyl group, 1-methylcyclohexyl group, and 1-methyl-4-i-propylcyclohexyl group. Examples of the aralkyl group having 7 to 12 carbon atoms include a benzyl group, an α-methylbenzyl group, and an α, α-dimethylbenzyl group.

R ^p1 , R ^p2 and R ^p4 are preferably each independently an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms or an alkylcycloalkyl group having 6 to 12 carbon atoms. R ^p1 and R ^p4 are more preferably each independently a t-alkyl group such as a t-butyl group, a t-pentyl group, or a t-octyl group, a cyclohexyl group, or a 1-methylcyclohexyl group. R ^p2 independently represents a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a sec-butyl group, a t-butyl group, a t-pentyl group, or the like. Is preferably an alkyl group having 1 to 5 carbon atoms, more preferably a methyl group, a t-butyl group or a t-pentyl group. R ^p5 is a C 1 -C group such as a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a sec-butyl group, a t-butyl group, or a t-pentyl group. 5 is preferably an alkyl group or a hydrogen atom, more preferably a methyl group or a hydrogen atom.

Examples of the alkyl group having 1 to 8 carbon atoms represented by R ^p3 include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t -Butyl group, t-pentyl group, i-octyl group, t-octyl group, 2-ethylhexyl group, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i- An alkyl group having 1 to 5 carbon atoms such as a butyl group, a sec-butyl group, a t-butyl group, or a t-pentyl group or a hydrogen atom is preferable, and a methyl group or a hydrogen atom is more preferable.

X represents a single bond, a sulfur atom or a divalent group represented by the formula (4-1). Examples of the alkyl group having 1 to 8 carbon atoms represented by R ^p6 in the formula (4-1) include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, and an i-butyl group. , Sec-butyl group, t-butyl group, t-pentyl group, i-octyl group, t-octyl group and 2-ethylhexyl group. Examples of the cycloalkyl group having 5 to 8 carbon atoms include a cyclopentyl group. , A cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. R ^p6 is preferably a C 1-5 alkyl group such as a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, or an i-butyl group, or a hydrogen atom. X is preferably a single bond or a divalent group represented by the formula (4-1), and more preferably a single bond.

A represents an alkylene group having 2 to 8 carbon atoms or a divalent group represented by the formula (4-2), and an alkylene group having 2 to 8 carbon atoms is preferred. Group, propylene group, butylene group, pentamethylene group, hexamethylene group, octamethylene group, 2,2-dimethyl-1,3-propylene group and the like, and propylene group is more preferable. The divalent group represented by the formula (4-2) is bonded to the oxygen atom and the benzene nucleus, but * indicates that it is bonded to the oxygen atom. Examples of the alkylene group having 1 to 8 carbon atoms represented by R ^p7 include a methylene group, an ethylene group, a propylene group, a butylene group, a pentamethylene group, a hexamethylene group, an octamethylene group, 2,2-dimethyl-1, A 3-propylene group etc. are mentioned. Such R ^p7 is preferably a single bond or an ethylene group.

  One of Y and Z represents a hydroxy group, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms or an aralkyloxy group having 7 to 12 carbon atoms, and the other is a hydrogen atom or carbon. The alkyl group of number 1-8 is shown. Here, examples of the alkyl group having 1 to 8 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, and t-butyl. Group, t-pentyl group, i-octyl group, t-octyl group and 2-ethylhexyl group. Examples of the alkoxy group having 1 to 8 carbon atoms include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, sec-butoxy group, t-butoxy group, t -Pentyloxy group, i-octyloxy group, t-octyloxy group, 2-ethylhexyloxy group may be mentioned. Examples of the aralkyloxy group having 7 to 12 carbon atoms include benzyloxy group, α-methylbenzyloxy group, α, α-dimethylbenzyloxy group.

Among the compounds represented by the formula (4), R ^p1 and R ^p4 are t-alkyl groups, cyclohexyl or 1-methylcyclohexyl groups, R ^p2 is an alkyl group having 1 to 5 carbon atoms, and R ^p5 Is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ^p3 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, X is a single bond, and A is an alkylene group having 2 to 8 carbon atoms. Preferably there is.

  Examples of the compound represented by the formula (4) include 6- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-t-. Butyl dibenz [d, f] [1,3,2] dioxaphosphine [commercially available from Sumitomo Chemical Co., Ltd. as “Sumilyzer (registered trademark) GP”. 2,10-dimethyl-4,8-di-t-butyl-6- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propoxy] -12H-dibenzo [d, g] [1,3,2] dioxaphosphocine, 2,4,8,10-tetra-t-butyl-6- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propoxy] dibenzo [D, f] [1,3,2] dioxaphosphine, 2,4,8,10-tetra-t-pentyl-6- [3- (3,5-di-t-butyl-4- Hydroxyphenyl) propoxy] -12-methyl-12H-dibenzo [d, g] [1,3,2] dioxaphosphocin, 2,10-dimethyl-4,8-di-t-butyl-6- [3 -(3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] -12H Dibenzo [d, g] [1,3,2] dioxaphosphocine, 2,4,8,10-tetra-t-pentyl-6- [3- (3,5-di-t-butyl-4- Hydroxyphenyl) propionyloxy] -12-methyl-12H-dibenzo [d, g] [1,3,2] dioxaphosphocin, 2,4,8,10-tetra-t-butyl-6- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] -dibenzo [d, f] [1,3,2] dioxaphosphine, 2,10-dimethyl-4,8-di -T-butyl-6- (3,5-di-t-butyl-4-hydroxybenzoyloxy) -12H-dibenzo [d, g] [1,3,2] dioxaphosphocin, 2,4,8 , 10-Tetra-t-butyl-6- (3,5-di-t-butyl-4- Roxybenzoyloxy] -12-methyl-12H-dibenzo [d, g] [1,3,2] dioxaphosphocin, 2,10-dimethyl-4,8-di-t-butyl-6- [3- (3-Methyl-4-hydroxy-5-t-butylphenyl) propoxy] -12H-dibenzo [d, g] [1,3,2] dioxaphosphocine, 2,4,8,10-tetra-t -Butyl-6- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propoxy] -12H-dibenzo [d, g] [1,3,2] dioxaphosphocine, 2,10 -Diethyl-4,8-di-t-butyl-6- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propoxy] -12H-dibenzo [d, g] [1,3 2] Dioxaphosphocin, 2,4,8,10-tetra-t-butyl Ru-6- [2,2-dimethyl-3- (3-t-butyl-4-hydroxy-5-methylphenyl) propoxy] -dibenzo [d, f] [1,3,2] dioxaphosphine 6- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-t-butyldibenz [d, f] [1, 3,2] Dioxaphosphepine is preferred.

  It can be produced by a compound represented by the formula (4) and a method described in, for example, JP-A-10-273494.

  When a compound selected from the group consisting of the compound represented by the above formula (3) and the compound represented by the formula (4) is used as the component (δ), another compound can be further combined.

  Another compound is preferably a compound represented by the following formula (5) (hereinafter sometimes referred to as “component (δ-2)”).

（５）
［式（５）中、各Ｒ^ｔ１および各Ｒ^ｔ２は、それぞれ独立して、水素原子または炭素数１〜６のアルキル基を表す。Ｌは、ヘテロ原子を含んでいてもよいｎ価の炭素数１〜２４のアルコール残基を表し、ｎは、１〜４の整数を表す。ここでアルコール残基とは、アルコールのヒドロキシ基から水素原子を除いた残りの基を表す。］

(5)
[In Formula (5), each R ^t1 and each R ^t2 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. L represents an n-valent alcohol residue having 1 to 24 carbon atoms which may contain a hetero atom, and n represents an integer of 1 to 4. Here, the alcohol residue represents the remaining group obtained by removing a hydrogen atom from the hydroxy group of the alcohol. ]

Each R ^t1 and each R ^{t2 in} Formula (5) each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. When n is 2 or more, each R ^t1 may be the same as or different from each other, and is preferably the same. The same applies to each R ^t2 . The alkyl group having 1 to 6 carbon atoms may be either a chain or a ring, and the chain may be either a straight chain or a branched chain. Examples of the alkyl group having 1 to 6 carbon atoms include straight chain alkyl groups having 1 to 6 carbon atoms (methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group), and branched chain carbon numbers. 3 to 6 alkyl groups (for example, isopropyl group, isobutyl group, t-butyl group, isopentyl group, t-pentyl group, t-hexyl group), cyclic alkyl groups having 3 to 6 carbon atoms (that is, 3 to 3 carbon atoms) 6 cycloalkyl groups such as cyclopentyl group and cyclohexyl group). Each R ^t1 and each R ^t2 are preferably each independently a linear alkyl group having 1 to 6 carbon atoms or a branched alkyl group having 3 to 6 carbon atoms, more preferably a methyl group or t-Butyl group. More preferably, each R ^t1 and each R ^t2 are all t-butyl groups.

  L in Formula (5) represents an n-valent alcohol residue having 1 to 24 carbon atoms which may contain a hetero atom, and n represents an integer of 1 to 4. Examples of the hetero atom include an oxygen atom, a sulfur atom, or a nitrogen atom, and these hetero atoms may be replaced with carbon atoms in the n-valent alcohol residue having 1 to 24 carbon atoms. That is, an n-valent C1-C24 alcohol residue is -O-, -S-, -NR- (wherein R is a hydrogen atom or other substituent (for example, an alkyl group having 1 to 6 carbon atoms). ), Etc.) may be included. As a hetero atom, an oxygen atom is preferable.

  The n-valent alcohol residue having 1 to 24 carbon atoms (n = 1 to 4) may be linear or cyclic, or a combination thereof. The chain may be linear or branched.

  Examples of the monovalent alcohol having 1 to 24 carbon atoms include methanol, ethanol, propanol, isopropanol, butanol, t-butanol, hexanol, octanol, decanol, dodecanol, tetradecanol, hexadecanol, and octadecanol. And the like.

  Examples of the divalent alcohol having 1 to 24 carbon atoms include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1, 6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, 1,14-tetradecanediol, 1,16-hexadecanediol, diethylene glycol, triethylene glycol, 3,9- Examples thereof include residues such as bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane.

  Examples of the trivalent alcohol residue having 1 to 24 carbon atoms include residues such as glycerol.

  Examples of the tetravalent alcohol having 1 to 24 carbon atoms include erythritol, pentaerythritol and the like.

  Examples of the component (δ-2) include 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid and 3- (3-tert-butyl-4-hydroxy-5-methylphenyl). Examples thereof include esters of propionic acid or 3- (3,5-dicyclohexyl-4-hydroxyphenyl) propionic acid and a monohydric or polyhydric alcohol. Examples of the monohydric or polyhydric alcohol include methanol, ethanol, octanol, octadecanol, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,9. -Nonanediol, neopentyl glycol, diethylene glycol, thioethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3- Thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2,2,2] octane, 3,9-bis (1,1- Dimethyl-2-hydroxy Ethyl) -2,4,8,10 such tetraoxaspiro [5.5] undecane and mixtures thereof.

  Preferred component (δ-2) is octadecyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate (commercially available as Irganox (registered trademark) 1076 (manufactured by BASF)), 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] Undecane (commercially available as “SUMILIZER (registered trademark) GA-80” (manufactured by Sumitomo Chemical Co., Ltd.)) and pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxy Phenyl) propionate] (commercially available as Irganox (registered trademark) 1010 "(manufactured by BASF)).

  A more preferred component (δ-2) is 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2. 4,8,10-tetraoxaspiro [5.5] undecane or pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate].

  A more preferred component (δ-2) is pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate].

  Component (δ-2) is a commercially available product or is produced according to a known method (for example, the method described in US Pat. No. 3,308,593, US Pat. No. 3,644,482 or JP-A-59-25826). can do.

  The content of the component (δ) in the polypropylene resin composition of the present invention is 0.01 to 0.5 parts by weight, preferably 0.01 to 0.25, relative to 100 parts by weight of the component (β). Parts by weight.

  When the content of the component (δ) is less than 0.01 parts by weight with respect to 100 parts by weight of the component (β), mechanical properties may deteriorate due to deterioration of the polypropylene resin composition.

  When the component (δ) is composed of two different compounds, the blending ratio of the other compound to one compound can be selected between 1: 1 and 10: 1 by weight ratio.

  The polypropylene resin composition according to the present invention is a resin or rubber other than the propylene polymer (component (β)), an additive other than the component (δ), if necessary, as long as the object of the present invention is not impaired, and An inorganic filler or the like may be added.

  Examples of the resin other than the propylene polymer (component (β)) include, for example, ethylene-α-olefin random copolymerization (hereinafter sometimes referred to as “component (ε)”), ABS (acrylonitrile / butadiene / styrene). Copolymer) resin, AAS (special acrylic rubber / acrylonitrile / styrene copolymer) resin, ACS (acrylonitrile / chlorinated polyethylene / styrene copolymer) resin, polychloroprene, chlorinated rubber, polyvinyl chloride, polyvinylidene chloride, fluorine resin , Polyacetal, polysulfone, polyetheretherketone, polyethersulfone and the like.

The component (ε) is preferably an ethylene-α-olefin random copolymer having a melt flow rate of 5 g / 10 min or less measured at 190 ° C. under a load of 2.16 kgf in accordance with JIS-K-7210. A polymer (hereinafter sometimes referred to as “component (ε-1)”) or an ethylene-α-olefin random copolymer (hereinafter referred to as “component (ε-1)” having a melt flow rate of 10 g / 10 min or more. -2) ").
The melt flow rate of the component (ε-1) is preferably 3 g / 10 min or less, and the melt flow rate of the component (ε-2) is preferably 12 g / 10 min or more.

Examples of the α-olefin used for the component (ε-1) and the component (ε-2) include the same α-olefin having 4 to 10 carbon atoms as the α-olefin used for the propylene polymer (component (β)). It is done. Specific examples include 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, α-olefins having a cyclic structure, and preferably 1-butene. , 1-hexene and 1-octene.
Specifically, as component (ε-1) and component (ε-2), ethylene-1-butene copolymer, ethylene-1-hexene copolymer, ethylene-1-octene copolymer, ethylene-1- Examples include decene copolymer, ethylene- (3-methyl-1-butene) copolymer, and a copolymer of ethylene and an α-olefin having a cyclic structure.

  The contents of α-olefins contained in the component (ε-1) and the component (ε-2) are each preferably 1 to 49% by weight, more preferably 5 to 49% by weight, and still more preferably 10 to 49% by weight (the weight of the component (ε-1) and the component (ε-2) is 100% by weight).

Further, from the viewpoint of improving the impact resistance of the molded product of the polypropylene resin composition, the density of the component (ε-1) and the component (ε-2) is 0.85 to 0.89 g / cm ³ , respectively, preferably 0. .85 to 0.88 g / cm ³ , more preferably 0.855 to 0.875 g / cm ³ .

The component (ε-1) and the component (ε-2) can be produced using a polymerization catalyst.
Examples of the polymerization catalyst include a homogeneous catalyst system represented by a metallocene catalyst, a Ziegler-Natta type catalyst system, and the like.
Examples of the homogeneous catalyst system include a catalyst system consisting of a transition metal compound of Group 4 of the periodic table having a cyclopentadienyl ring and an alkylaluminoxane, or a Group 4 transition metal compound of the periodic table having a cyclopentadienyl ring. A catalyst system composed of an organic aluminum compound and a compound that reacts with it to form an ionic complex, a transition metal compound of Group 4 of the periodic table having a cyclopentadienyl ring in inorganic particles such as silica and clay minerals, ionicity And a catalyst system in which a catalyst component such as an organoaluminum compound is supported and modified, and is prepared by prepolymerizing ethylene or α-olefin in the presence of the above catalyst system. A prepolymerization catalyst system may be mentioned.
Examples of the Ziegler-Natta type catalyst system include a catalyst system using a combination of a titanium-containing solid transition metal component and an organometallic component.

  Commercial components may be used as the component (ε-1) and the component (ε-2). For example, Dow Chemical Japan Co., Ltd. Engage (registered trademark), Mitsui Chemicals Co., Ltd. Toughmer (registered trademark), Prime Polymer Co., Ltd. Neozex (registered trademark), Ultozex (registered trademark), Sumitomo Chemical Co., Ltd. FX (registered trademark), Sumikasen (registered trademark), Esprene SPO (registered trademark), and the like.

  Examples of additives other than the component (δ) include an ultraviolet absorber, an antistatic agent, a lubricant, a nucleating agent, an adhesive, an antifogging agent, and an antiblocking agent.

  Examples of the inorganic filler include non-fibrous inorganic filler (hereinafter sometimes referred to as “component (ω-1)”), fibrous inorganic filler (hereinafter referred to as “component (ω-2)”). May be described.).

The component (ω-1) refers to an inorganic filler having a shape other than the fiber shape, such as powder, flakes, and granules. Specifically, talc, mica, calcium carbonate, barium sulfate, magnesium carbonate, clay, alumina, silica, calcium sulfate, silica sand, carbon black, titanium oxide, magnesium hydroxide, zeolite, molybdenum, diatomaceous earth, sericite Shirasu, calcium hydroxide, calcium sulfite, sodium sulfate, bentonite, graphite and the like. These may be used alone or in combination of two or more. Of these, talc is preferably used.
The component (ω-1) may be used without treatment, but improves the interfacial adhesion with the propylene polymer (component (β)) and is dispersed in the propylene polymer (component (β)). In order to improve the properties, the surface may be treated with a silane coupling agent, a titanium coupling agent, or a surfactant. Examples of the surfactant include higher fatty acids, higher fatty acid esters, higher fatty acid amides, higher fatty acid salts and the like.

  The average particle size of the component (ω-1) is preferably 10 μm or less, and more preferably 5 μm or less. Here, the “average particle size” in the present invention is 50% obtained from an integral distribution curve of a sieving method measured by suspending in a dispersion medium such as water or alcohol using a centrifugal sedimentation type particle size distribution measuring device. It means the equivalent particle diameter D50.

The component (ω-2) refers to an inorganic filler having a fiber shape. Specific examples include fibrous magnesium oxysulfate, potassium titanate fiber, magnesium hydroxide fiber, aluminum borate fiber, calcium silicate fiber, calcium carbonate fiber, carbon fiber, glass fiber, and metal fiber. These may be used alone or in combination of two or more. Among these, it is preferable to use fibrous magnesium oxysulfate and calcium silicate fiber, and it is more preferable to use fibrous magnesium oxysulfate.
The component (ω-2) may be used without treatment, but improves the interfacial adhesion with the propylene polymer (component (β)) and is dispersed in the propylene polymer (component (β)). In order to improve the properties, the surface may be treated with a silane coupling agent or a higher fatty acid metal salt. Examples of the higher fatty acid metal salt include calcium stearate, magnesium stearate, zinc stearate and the like.

  The average fiber length of the component (ω-2) measured by electron microscope observation is 3 μm or more, preferably 3 to 20 μm, more preferably 7 to 15 μm. Moreover, an aspect ratio is 10 or more, Preferably it is 10-30, More preferably, it is 12-25. And the average fiber diameter measured by electron microscope observation becomes like this. Preferably it is 0.2-1.5 micrometers, More preferably, it is 0.3-1.0 micrometer.

  The polypropylene resin composition according to the present invention comprises a propylene polymer (component (β)), a compound (component (γ)), a compound represented by the above formula (3), and a compound represented by the formula (4). Each component of a compound selected from the group (component (δ)) can be melt-kneaded and further molded to be used as a molded body.

  The melt kneading described above can be performed using a conventionally known method and apparatus. For example, selected from the group consisting of a propylene polymer (component (β)), a compound (component (γ)), a compound represented by the above formula (3), and a compound represented by the formula (4) A compound (component (δ)) is mixed with a mixing device such as a Henschel mixer, ribbon blender, tumble mixer, etc., and then melted and kneaded, or a fixed amount of propylene is used at a constant rate using a quantitative feeder. A homogeneous mixture is obtained by continuously feeding a polymer, an ethylene-α-olefin copolymer and various additives, and then the mixture is fed into a single-screw or twin-screw extruder, a Banbury mixer, And a melt kneading method using a roll type kneader.

  The melt kneading temperature is 180 ° C or higher, preferably 180 ° C to 300 ° C, more preferably 180 ° C to 250 ° C.

  The molded body obtained by molding the resin composition according to the present invention is preferably an injection molded body produced by an injection molding method. Examples of the injection molding method include a general injection molding method, an injection foam molding method, a supercritical injection foam molding method, an ultrahigh speed injection molding method, an injection compression molding method, a gas assist injection molding method, a sandwich molding method, and a sandwich foaming method. Examples thereof include molding methods and insert / outsert molding methods.

  By cooling after molding, a polypropylene resin molded body made of the polypropylene resin composition of the present invention is obtained. Polypropylene resin moldings obtained include containers, container caps, packaging materials, stationery, toys, household goods, furniture materials, textiles, agricultural films, automotive materials, household appliance materials, medical materials, or architecture. Material.

  The polypropylene resin molded body comprising the polypropylene resin composition of the present invention is a molded body with reduced volatile organic compound components, and is suitable for a member that coexists with a person in a sealed space. For example, as an automobile material, an automobile interior member or an automobile headlamp member is preferable. As a building material, an inner wall of a house or a member for wallpaper is preferable. As the furniture material, a chiffon or a storage container is preferable. As materials for home appliances, housing members such as displays for personal computers and televisions, OA equipment, air conditioners, washing machines, and air purifiers are preferable. As an agricultural film, a film for a house or a tunnel is preferable. The fibers are preferably clothing, carpet or sofa fibers.

  Hereinafter, although the present invention is explained using an example and a comparative example, the present invention is not limited to the following examples. In addition, the measured value of each item in detailed description of an invention and an Example and a comparative example was measured with the following method.

(1) Intrinsic viscosity ([η], unit: dl / g)
The reduced viscosity was measured at three points of concentrations of 0.1, 0.2, and 0.5 dl / g using an Ubbelohde viscometer. Intrinsic viscosity is calculated according to the calculation method described in Section 491 of “Polymer Solution, Polymer Experiments 11” (published by Kyoritsu Shuppan Co., Ltd., 1982). Obtained by extrapolation method. The reduced viscosity was measured at a temperature of 135 ° C. using tetralin as a solvent.

(2) Isotactic pentad fraction ([mmmm])
A sample was prepared by uniformly dissolving about 200 mg of polymer in 3 ml of orthodichlorobenzene in a 10 mmφ test tube, and the sample was measured by ¹³ C-NMR spectrum. The measurement conditions in the ¹³ C-NMR spectrum are shown below.
Measurement temperature: 135 ° C;
Pulse repetition time: 10 seconds;
Pulse width: 45 °;
Integration count: 2500 times;
From the measurement results, the isotactic pentad fraction was calculated according to the method described above.

(3) Fogging test A fogging test is performed under the following conditions, and the amount of volatile organic compound components volatilized from the propylene polymer and polypropylene resin is calculated by measuring the amount of decrease in the sample weight before and after the test. did.
Measuring device: Suga Tester Window screen fogging tester WF-2 type Heating condition: 120 ° C
Cooling conditions: 25 ° C
Time: 20 hours Sample amount: 5g

[Production Example 1]
A stainless steel autoclave with a stirrer with an internal volume of 3 liters was dried under reduced pressure, and then purged with argon and cooled. Thereafter, the autoclave was evacuated.
2.6 mmol of triethylaluminum (organoaluminum compound) and a mixture of cyclohexyltriethoxysilane and tetraethoxysilane (alkoxysilicon compound) (the amount of tetraethoxysilane used relative to cyclohexyltriethoxysilane is 0.25 (molar ratio)) 0.52 mmol, 0.26 mmol of the lactone compound described in Table 1, and 8.27 mg of the solid catalyst component (A-1) described in Example 1 (2) of JP-A No. 2004-182981 In this order, the mixture was supplied to a glass charger previously charged with heptane and contacted to obtain a mixture containing a polymerization catalyst.
The mixture was charged all at once into the autoclave. Next, 780 g of liquefied propylene (α-olefin) was supplied into the autoclave, and hydrogen corresponding to a partial pressure of 0.20 MPa was further added. Thereafter, the temperature of the autoclave was raised to 80 ° C. to initiate polymerization.
One hour after the start of the polymerization, unreacted propylene was purged out of the polymerization system to complete the polymerization, and the resulting polymer was dried under reduced pressure at 60 ° C. for 1 hour to obtain 287 g of a propylene polymer powder. Table 1 shows the measurement results of the intrinsic viscosity and isotactic pentad fraction of the obtained powder.

[Production Example 2]
A propylene polymer powder was obtained in the same manner as in Production Example 1 except that the amount of the solid catalyst component was changed to 9.55 milligrams and the amount of the lactone compound added was changed to 0.20 millimoles. Table 1 shows the measurement results of the intrinsic viscosity and isotactic pentad fraction of the obtained powder.

[Production Example 3]
The same procedure as in Production Example 1 was carried out except that the amount of the solid catalyst component was changed to 11.36 milligrams, and the addition amount was 0.26 mmol using the compounds shown in Table 1 as the alkoxysilicon compound. A coalesced powder was obtained. Table 1 shows the measurement results of the intrinsic viscosity and isotactic pentad fraction of the obtained powder.

[Production Example 4]
Propylene polymer powder was obtained in the same manner as in Production Example 1 except that the amount of the solid catalyst component was changed to 9.08 milligrams and no lactone compound was added. Table 1 shows the measurement results of the intrinsic viscosity and isotactic pentad fraction of the obtained powder.

[Production Example 5]
The amount of the solid catalyst component was changed to 6.70 milligrams, the lactone compound was not added, and the addition amount was 0.26 mmol using the compounds shown in Table 1 as the alkoxysilicon compound. Propylene polymer powder was obtained in the same manner as in Production Example 1. Table 1 shows the measurement results of the intrinsic viscosity and isotactic pentad fraction of the obtained powder.

[Example 1]
For 100 g of the propylene polymer polymer powder (component (β)) described in Production Example 1, trehalose (Tokyo Chemical Industry Co., Ltd., D-(+)-trehalose dihydrate) (component (γ) ) 0.05 g, 2,4-di-t-pentyl-6- [1- (3,5-di-t-pentyl-2-hydroxyphenyl) ethyl] phenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd .: 0.1 g of (Smilizer GS) (component (δ)) and pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate (manufactured by BASF: Irganox 1010) (component) (Δ-2)) was mixed with 0.05 g, and 2 using a 20 mm single screw extruder (VS20-14 type, manufactured by Tanabe Plastics Machinery Co., Ltd., with L / D = 12.6 full flight type screw). 0 was melt-kneaded and pelletized at ° C.. Table 2 shows the results of the fogging test of the pellets.

[Example 2]
Trehalose (manufactured by Tokyo Chemical Industry Co., Ltd., D-(+)-trehalose dihydrate) (component (γ)) is 0 with respect to 100 g of the polymer powder of the propylene polymer (β) described in Production Example 2. .05 g, 2,4-di-t-pentyl-6- [1- (3,5-di-t-pentyl-2-hydroxyphenyl) ethyl] phenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd .: Smither GS) 0.1 g of (component (δ)) was mixed and pelletized by the method described in Example 1. Table 2 shows the results of the fogging test of the pellets.

[Example 3]
Propylene polymer (β) pellets were obtained in the same manner as in Example 2 except that the propylene polymer (β) described in Production Example 3 was used. Table 2 shows the results of the fogging test of the pellets.

[Comparative Example 1]
Except having used the propylene polymer ((beta)) described in manufacture example 4, it carried out similarly to the method of Example 1, and obtained the pellet of the propylene polymer ((beta)). Table 2 shows the results of the fogging test of the pellets.

[Comparative Example 2]
Propylene polymer (β) pellets were obtained in the same manner as in Example 2 except that the propylene polymer (β) described in Production Example 4 was used. Table 2 shows the results of the fogging test of the pellets.

[Comparative Example 3]
Propylene polymer (β) pellets were obtained in the same manner as in Example 2 except that the propylene polymer (β) described in Production Example 5 was used. Table 2 shows the results of the fogging test of the pellets.

  In Examples 1, 2, and 3, which satisfy the requirements of the present invention, the isotactic pentad fraction is as high as 0.97 or more and the decrease in the sample weight by the fogging test is small, so that the rigidity is maintained. However, it turns out that there is little quantity of a volatile organic compound component. On the other hand, it can be seen that Comparative Examples 1, 2, and 3 that do not satisfy the requirements of the present invention have a large decrease in the sample weight due to the fogging test and a large amount of the volatile organic compound component.

Claims (9)

A propylene polymer (component (β)) produced using the following olefin polymerization catalyst;
0.01 to 0.5 parts by weight of the following compound (component (γ)) with respect to 100 parts by weight of the component (β),
Compound (component (δ)) 0.01 selected from the group consisting of the compound represented by the following formula (3) and the compound represented by formula (4) with respect to 100 parts by weight of the component (β) A polypropylene resin composition comprising -0.5 part by weight.

Olefin polymerization catalyst:
An olefin polymerization catalyst obtained by contacting the following components (A), (B) and (C).
(A) Solid catalyst component for olefin polymerization containing titanium atom, magnesium atom, and halogen atom (B) Organoaluminum compound (C) Lactone compound represented by formula (I)

(I)

(In the formula, R ^a , R ^b , R ^c , R ^d , R ^e and R ^f each independently represents a hydrogen atom or a hydrocarbyl group having 1 to 20 carbon atoms, provided that R ^a , R ^b , R ^e and R ^f are each a hydrocarbyl group having 1 to 20 carbon atoms, R ^a and R ^b , R ^c and R ^d , R ^e and R ^f are bonded to each other to form a ring. The ring formed may contain a double bond in the skeleton of the ring, and the number of carbon atoms forming the skeleton of the ring is 5 to 10. R ^a And R ^b and any one of R ^c and R ^d may be bonded to each other to form a ring, and any one of R ^c and R ^d and any of R ^e and R ^f Or one of them may be bonded to each other to form a ring. May be contained a double bond in the rating, the number of carbon atoms forming the ring backbone is 5 to 10 .n represents the number of 1-4.)

Compound (component (γ)): at least one compound selected from the following compound group S.
Compound group S: a compound represented by the general formula C _n H _{n + 2} (OH) _n (wherein _n represents an integer of 4 or more), the following alkoxy compound, and the following formula (2) A group of compounds consisting of a compound to be obtained, trehalose, sucrose, lactose, maltose, meletitose, stachyose, curdlan, glycogen, glucose and fructose.
Alkoxy compound: a compound in which at least one of the hydroxyl groups contained in the compound represented by the following formula (1) is alkoxylated with an alkyl group having 1 to 12 carbon atoms, and represented by the formula (2) The compound is a compound having one aldehyde group or ketone group and m-1 hydroxyl groups in the molecule.
C _m H _2m O _m (1)
(In formula (1), m represents an integer of 3 or more.)

(2)
(In formula (2), p represents an integer of 2 or more.)

(3)
(In Formula (3), each R ^s1 and each R ^s2 each independently represent an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 18 carbon atoms. R ^s3 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ^s4 represents a hydrogen atom or a methyl group.)

(4)
(In formula (4), R ^p1 , R ^p2 , R ^p4 and R ^p5 each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, or 6 carbon atoms. Represents an alkylcycloalkyl group having 12 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or a phenyl group, R ^p3 each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, X is a single bond, sulfur Atom or the following formula (4-1)

(4-1)
(In formula (4-1), R ^p6 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a cycloalkyl group having 5 to 8 carbon atoms), and A represents carbon. An alkylene group of 2 to 8 or the following formula (4-2)

(4-2)
(In formula (4-2), R ^p7 represents a single bond or an alkylene group having 1 to 8 carbon atoms, and * represents a site bonded to an oxygen atom.) Y, Z represents a hydroxy group, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms or an aralkyloxy group having 7 to 12 carbon atoms, and the other is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. Represents an alkyl group. ) A propylene polymer (component (β)) produced using the following olefin polymerization catalyst;
0.01 to 0.5 parts by weight of the following compound (component (γ)) with respect to 100 parts by weight of the component (β),
Compound (component (δ)) 0.01 selected from the group consisting of the compound represented by the following formula (3) and the compound represented by formula (4) with respect to 100 parts by weight of the component (β) A polypropylene resin composition comprising -0.5 part by weight.

Olefin polymerization catalyst:
An olefin polymerization catalyst obtained by contacting the following components (A), (B), (C) and (D).
(A) a solid catalyst component for olefin polymerization containing a titanium atom, a magnesium atom, and a halogen atom,
(B) Organoaluminum compound (C) Lactone compound represented by general formula (I) (D) Alkoxy silicon compound

(I)

(In the formula, R ^a , R ^b , R ^c , R ^d , R ^e and R ^f each independently represents a hydrogen atom or a hydrocarbyl group having 1 to 20 carbon atoms, provided that R ^a , R ^b , R ^e and R ^f are each a hydrocarbyl group having 1 to 20 carbon atoms, R ^a and R ^b , R ^c and R ^d , R ^e and R ^f are bonded to each other to form a ring. The ring formed may contain a double bond in the skeleton of the ring, and the number of carbon atoms forming the skeleton of the ring is 5 to 10. R ^a And R ^b and any one of R ^c and R ^d may be bonded to each other to form a ring, and any one of R ^c and R ^d and any of R ^e and R ^f Or one of them may be bonded to each other to form a ring. May be contained a double bond in the rating, the number of carbon atoms forming the ring backbone is 5 to 10 .n represents the number of 1-4.)

Compound (component (γ)): at least one compound selected from the following compound group S.
Compound group S: a compound represented by the general formula C _n H _{n + 2} (OH) _n (wherein _n represents an integer of 4 or more), the following alkoxy compound, and the following formula (2) A group of compounds consisting of a compound to be obtained, trehalose, sucrose, lactose, maltose, meletitose, stachyose, curdlan, glycogen, glucose and fructose.

Alkoxy compound: a compound in which at least one of the hydroxyl groups contained in the compound represented by the following formula (1) is alkoxylated with an alkyl group having 1 to 12 carbon atoms, and represented by the formula (2) The compound is a compound having one aldehyde group or ketone group and m-1 hydroxyl groups in the molecule.

C _m H _2m O _m (1)
(In formula (1), m represents an integer of 3 or more.)

(2)
(In formula (2), p represents an integer of 2 or more.)

(3)
(In Formula (3), each R ^s1 and each R ^s2 each independently represent an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 18 carbon atoms. R ^s3 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ^s4 represents a hydrogen atom or a methyl group.)

(4)
(In formula (4), R ^p1 , R ^p2 , R ^p4 and R ^p5 each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, or 6 carbon atoms. Represents an alkylcycloalkyl group having 12 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or a phenyl group, R ^p3 each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, X is a single bond, sulfur Atom or the following formula (4-1)

(4-1)
(In formula (4-1), R ^p6 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a cycloalkyl group having 5 to 8 carbon atoms), and A represents carbon. An alkylene group of 2 to 8 or the following formula (4-2)

(4-2)
(In formula (4-2), R ^p7 represents a single bond or an alkylene group having 1 to 8 carbon atoms, and * represents a site bonded to an oxygen atom.) Y, Z represents a hydroxy group, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms or an aralkyloxy group having 7 to 12 carbon atoms, and the other is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. Represents an alkyl group. )   The polypropylene resin composition according to claim 1 or 2, wherein the compound (component (γ)) is trehalose.   Component (δ) is 2,4-di-t-pentyl-6- [1- (3,5-di-t-pentyl-2-hydroxyphenyl) ethyl] phenyl acrylate, or 6- [3- ( 3-tert-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-tert-butyldibenz [d, f] [1,3,2] dioxaphosphine The polypropylene resin composition according to any one of claims 1 to 3.   The polypropylene resin composition in any one of Claims 1-4 whose n of general formula (I) is a number of 1-3. The polypropylene resin composition according to claim 2, wherein the alkoxysilicon compound (D) is a compound represented by the following formula (II).

R ¹ mSi (OR ² ) _4-m (II)

(In the formula, R ¹ represents a hydrocarbyl group having 1 to 20 carbon atoms, a hydrogen atom or a heteroatom-containing substituent, R ² represents a hydrocarbyl group having 1 to 20 carbon atoms, and m represents 1 If .R ¹ representing the number of to 3 there are a plurality, R ¹ may be the same or different, when R ² are a plurality, R ² may be the same or different.) The polypropylene resin composition according to claim 6, wherein the alkoxysilicon compound (D) comprises a compound represented by the following formula (III) or a compound represented by the following formula (IV).

R ³ R ⁴ Si (OCH ₃ ) ₂ (III)

(In the formula, R ³ and R ⁴ each independently represent a hydrocarbyl group having 1 to 20 carbon atoms, a hydrogen atom, or a heteroatom-containing substituent.)

R ⁵ _p Si (OC ₂ H ₅ ) _4-p (IV)

(In the formula, R ⁵ represents a hydrocarbyl group having 3 to 20 carbon atoms in which the carbon atom bonded to Si is a secondary carbon atom, and p represents a number of 1 to 3. When there are a plurality of R ^{5 s.} , R ² may be the same or different.) The alkoxysilicon compound (D) is a mixture of a compound represented by the formula (III) or a compound represented by the formula (IV) and a compound represented by the following formula (V): Polypropylene resin composition.

R ⁶ _q Si (OC ₂ H ₅ ) _4-q (V)

(In the formula, R ⁶ represents a hydrocarbyl group having 1 to 20 carbon atoms in which the carbon atom bonded to Si is a primary carbon, and q represents a number of 0 or 1.)   The molded object containing the polypropylene resin composition in any one of Claims 1-8.