JP2013147602A - Polypropylene resin composition, and molded article comprising the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polypropylene resin composition which reduces the amount of a volatile organic compound component, and to provide a molded article comprising the same.SOLUTION: A polypropylene resin composition comprises propylene polymer (component (A)) produced with a specific olefin polymerization catalyst, a specific compound (component (B)) in an amount of 0.01-0.5 pt.wt. per 100 pts.wt. of the component (A), and a hydroxyphenyl group-having compound (component (C)) in an amount of 0.01-0.5 pt.wt. per 100 pts.wt. of the component (A).

Description

  The present invention relates to a polypropylene resin composition with reduced volatile organic compound components and a molded body containing 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 Documents 1 and 2 describe an olefin polymer produced using a solid catalyst component for olefin polymerization obtained by contacting a specific internal electron donor.

  Patent Document 3 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 process stability of the thermoplastic polymer. Of trehalose is described.

  Patent Document 4 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 5, 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 2011-246698 A JP 2011-246699 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 5, 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.

  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.

（１）
（式中、Ｒ^１は、炭素数１〜２０のハイドロカルビル基を表し、Ｒ^２、Ｒ^３、Ｒ^４およびＲ^５は、それぞれ独立して、水素原子、ハロゲン原子または炭素数１〜２０のハイドロカルビル基を表し、Ｒ^６は、ハロゲン原子または炭素数１〜２０のハイドロカルビルオキシ基を表す。）
化合物（成分（Ｂ））：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（３）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（２）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個の水酸基とを含有する化合物である。
Ｃ_ｍＨ_２ｍＯ_ｍ （２）
（式（２）中、ｍは３以上の整数を表す。）

（３）
（式（３）中、ｐは２以上の整数を表す。） That is, the present invention relates to a propylene polymer (component (A)) produced using the following olefin polymerization catalyst and 100 parts by weight of the component (A), and the following compound (component (B)). Polypropylene resin containing 0.01 to 0.5 parts by weight and 0.01 to 0.5 parts by weight of a compound having a hydroxyphenyl group (component (C)) with respect to 100 parts by weight of the component (A) It relates to the composition.
Olefin polymerization catalyst:
Obtained by contacting a solid catalyst component (component (a)) containing a titanium atom, a magnesium atom and a halogen atom, an organoaluminum compound (component (b)), and an external electron donor (component (c)),
The catalyst for olefin polymerization in which the said component (a) contains the compound (component (d)) represented by following formula (1).

(1)
(In the formula, R ¹ represents a hydrocarbyl group having 1 to 20 carbon atoms, and R ² , R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom, a halogen atom, or a C 1-20 carbon atom. And R ⁶ represents a halogen atom or a hydrocarbyloxy group having 1 to 20 carbon atoms.)
Compound (component (B)): 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 (3) 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 (2) is alkoxylated with an alkyl group having 1 to 12 carbon atoms, and represented by the formula (2) The compound is a compound containing one aldehyde group or ketone group and m-1 hydroxyl groups in the molecule.
C _m H _2m O _m (2)
(In formula (2), m represents an integer of 3 or more.)

(3)
(In formula (3), p represents an integer of 2 or more.)

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

  According to the present invention, a polypropylene resin composition with reduced volatile organic compound components can be obtained.

（１）
（式中、Ｒ^１は、炭素数１〜２０のハイドロカルビル基を表し、Ｒ^２、Ｒ^３、Ｒ^４およびＲ^５は、それぞれ独立して、水素原子、ハロゲン原子または炭素数１〜２０のハイドロカルビル基を表し、Ｒ^６は、ハロゲン原子または炭素数１〜２０のハイドロカルビルオキシ基を表す。）
化合物（成分（Ｂ））：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（３）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（２）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 （２）
（式（２）中、ｍは３以上の整数を表す。）

（３）
（式（３）中、ｐは２以上の整数を表す。） 1. Polypropylene resin composition The polypropylene resin composition of the present invention comprises a propylene polymer produced by using the following olefin polymerization catalyst (hereinafter sometimes referred to as “component (A)”) and the above-mentioned component ( A) 0.01 to 0.5 parts by weight of the following compound (hereinafter sometimes referred to as “component (B)”) with respect to 100 parts by weight, and 100 parts by weight of the component (A) And a compound having a hydroxyphenyl group (hereinafter sometimes referred to as “component (C)”) in an amount of 0.01 to 0.5 parts by weight.
Olefin polymerization catalyst:
A solid catalyst component containing a titanium atom, a magnesium atom and a halogen atom (hereinafter sometimes referred to as “component (a)”) and an organoaluminum compound (hereinafter referred to as “component (b)”). And an external electron donor (hereinafter sometimes referred to as “component (c)”), and the component (a) is represented by the following formula (1): (Hereinafter referred to as “component (d)”).

(1)
(In the formula, R ¹ represents a hydrocarbyl group having 1 to 20 carbon atoms, and R ² , R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom, a halogen atom, or a C 1-20 carbon atom. And R ⁶ represents a halogen atom or a hydrocarbyloxy group having 1 to 20 carbon atoms.)
Compound (component (B)): 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 (3) 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 (2) 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 (2)
(In formula (2), m represents an integer of 3 or more.)

(3)
(In formula (3), p represents an integer of 2 or more.)

<Propylene polymer (component (A))>
The propylene polymer (component (A)) 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 (I ) ”And a copolymer component of propylene and ethylene and / or α-olefin (hereinafter sometimes referred to as“ polymer component (II) ”). Materials and the like.

Component (A) 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 (A) is a polymer material composed of the random copolymer or the polymer component (I) and the polymer component (II), it is measured for the chain of propylene units in the copolymer. Use the value.

  The melt flow rate (MFR) measured under the load of component (A) at 230 ° C. and 2.16 kg is from the viewpoint of the balance between the tensile strength and impact resistance of the obtained molded product and the molding processability 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.)

  As a polymer component which makes the structural unit derived from propylene in polymer component (I) a main structural unit, at least 1 sort (s) selected from the group which consists of ethylene and a C4-C10 alpha olefin, for example Examples thereof include a propylene copolymer component composed of a structural unit derived from a comonomer and a structural unit derived from propylene.

When the polymer component (I) 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 comonomer is 0.01% by weight or more and less than 20% by weight (provided that the weight of the polymer component (I) 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 (I) 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.

The polymer component (II) 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. It 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 (II) is preferably 20 to 80% by weight More preferably, it is 20 to 60% by weight, and further preferably 30 to 60% by weight (provided that the weight of the polymer component (II) is 100% by weight).

  Examples of the α-olefin having 4 to 10 carbon atoms constituting the polymer component (II) include the same α-olefin as the α-olefin having 4 to 10 carbon atoms constituting the polymer component (I). It is done.

  Examples of the polymer component (II) 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 It is a propylene-ethylene copolymer component.

  The content of the polymer component (II) in the polymer material composed of the polymer component (I) and the polymer component (II) is preferably 1 to 50% by weight, more preferably 1 to 40% by weight. It is preferably 10 to 40% by weight, more preferably 10 to 30% by weight (provided that the weight of the propylene polymer (component (A)) is 100% by weight).

  When the polymer component (I) of the propylene copolymer comprising the polymer component (I) and the polymer component (II) is a propylene homopolymer component, examples of the propylene copolymer include (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 the case where the polymer component (I) of the polymer material composed of the polymer component (I) and the polymer component (II) is a polymer component having a structural unit derived from propylene as a main structural unit, the polymer component Examples of the propylene copolymer comprising (I) and the polymer component (II) include (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, (pro Len-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.

  As the propylene copolymer comprising polymer component (I) and polymer component (II), (propylene)-(propylene-ethylene) copolymer, (propylene)-(propylene-ethylene-1-butene) are preferable. ) 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] _I ) measured in 135 ° C. tetralin of the polymer component (I) is 0.1 to 5 dl / g, preferably 0.3 to 4 dl / g, more preferably Is 0.5-3 dl / g.

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

Further, the ratio of the intrinsic viscosity ([η] _II ) of the polymer component (II) to the intrinsic viscosity ([η] _I ) of the polymer component ( _I ) 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 g / dl. 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 (A)) is a polymer material obtained by multi-stage polymerization of the polymer component (I) and the polymer component (II), from a polymer powder partially extracted from the previous polymerization tank The intrinsic viscosity of the polymer component (I) or the polymer component (II) is determined, and the intrinsic viscosity of the remaining components is calculated using the intrinsic viscosity value and the content of each component.

In addition, a propylene copolymer composed of the polymer component (I) and the polymer component (II) is obtained in the polymerization step of the polymer component (I) in the former step, and the polymer component (II) in the latter step. In the case of a copolymer produced by the obtained method, the content of the polymer component (I) and the polymer component (II), the intrinsic viscosity ([η] _Total , [η] _I , [η] _II ) The procedure for measurement and calculation is as follows. The intrinsic viscosity ([η] _Total ) indicates the intrinsic viscosity of the entire propylene polymer (component (A)).

The intrinsic viscosity ([η] _I ) of the polymer component (I) obtained in the preceding polymerization step was measured by the above method of the final polymer (component (I) and component (II)) after the subsequent polymerization step. From the intrinsic viscosity ([η] _Total ) and the content of the polymer component (II) contained in the final polymer, the intrinsic viscosity [η] _II of the polymer component (II) is calculated from the following formula.
[Η] _II = ([η] _Total− [η] _I × F _I ) / F _II
[Η] _Total : Intrinsic viscosity (dl / g) of the final polymer after the subsequent polymerization step
[Η] _I : Intrinsic viscosity of polymer powder extracted from the polymerization tank after the pre-stage polymerization step (dl /
g)
F _I: weight ratio _{F II} of the propylene polymer (component (A)) polymer component to the total (I): the weight ratio of the propylene polymer (component (A)) polymer component to the whole (II) In addition, _{F I} , F _II is determined from the mass balance during polymerization.

Unit derived from the weight ratio (F _II ) of the polymer component (II) to the entire propylene polymer (component (A)) and the comonomer of the polymer component (II) in the propylene polymer (component (A)) Content ((Cα ′) _II ) can be determined from the 13C-NMR spectrum of the propylene polymer (component (A)) based on a report by Kakugo et al. (Macromolecules 1982, 15, 1150-1152).

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

As a method for obtaining the content ((Cα ′) II) of the unit derived from the comonomer of the polymer component (II) in the propylene polymer (component (A)), in addition to the above, propylene heavy weight can be obtained by infrared absorption spectroscopy. The content ((Cα ′) Total) of units derived from the comonomer of the entire coalesced (A) can be measured and obtained by calculation using the following formula.
(Cα ′) _II = (Cα ′) _Total / F _II
(Cα ′) _Total : Content of units derived from the comonomer of the entire propylene polymer (component (A)) (% by weight)
(Cα ′) _II : Content of units derived from the comonomer of the polymer component (II) (% by weight)

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

  The olefin polymerization catalyst used in the present invention is obtained by bringing the component (a), the component (b), and the component (c) into contact with each other, and the component (a) includes the component (d).

<Solid catalyst component (component (a))>
Component (a) may be any known solid catalyst component containing a titanium atom, a magnesium atom and a halogen atom. As the component (a), JP-B-46-34092, JP-B-47-41676, JP-B-55-23561, JP-B-57-24361, JP-B-52-39431, JP-B-52- 36786, JP-B-1-28049, JP-B-3-43283, JP-A-4-80044, JP-A-55-52309, JP-A-58-21405, JP-A-61 JP-A No. 181807, JP-A No. 63-142008, JP-A No. 5-339319, JP-A No. 54-148093, JP-A No. 4-227604, JP-A No. 6-2933, JP-A No. No. 64-6006, JP-A-6-179720, JP-B-7-116252, JP-A-8-134124, JP-A-9-31119 , JP-A 11-228628 discloses a solid catalyst component described in JP-A-11-80234 and JP-A No. 11-322833 can be exemplified.

As component (a), in addition to titanium atom, magnesium atom and halogen atom, component (d) is further included. Examples of the method for producing component (a) include the following methods (1) to (5).
(1) A method in which a magnesium halide compound, component (d), and a titanium compound are brought into contact with each other.
(2) A method in which the dialkoxymagnesium compound, the titanium halide compound, and the component (d) are brought into contact with each other.
(3) a solid component (hereinafter sometimes referred to as “component (x)”) containing a magnesium atom, a titanium atom and a hydrocarbon oxy group; and a halogenated compound (hereinafter referred to as “component (y)”) And a component (d) may be contacted.
Among these, the method (3) in which the component (x), the component (y), and the component (d) are contacted is preferable.

（６）
（式中、ｒは１〜２０の数を表し、Ｒ^１１は、炭素数１〜２０の炭化水素基を表す。Ｘ^１は、ハロゲン原子または炭素数１〜２０の炭化水素オキシ基を表し、全てのＸ^１は同一であっても異なっていてもよい。） <Solid component (component (x))>
The component (x) is preferably a solid substance containing at least 20% by weight or more of hydrocarbon oxy groups, more preferably a solid substance containing 25% by weight or more of hydrocarbon oxy groups. Specifically, it is obtained by reducing a titanium compound (f) represented by the following formula (6) with an organomagnesium compound (g) in the presence of a silicon compound (e) having a Si—O bond. A solid product is preferred. At this time, it is preferable to allow the ester compound (h) to coexist as an optional component because the polymerization activity and stereoregular polymerization ability are further improved.

(6)
(In the formula, r represents a number of 1 to 20, R ¹¹ represents a hydrocarbon group having 1 to 20 carbon atoms, X ¹ represents a halogen atom or a hydrocarbon oxy group having 1 to 20 carbon atoms, All X ¹ may be the same or different.)

Examples of the silicon compound (e) having a Si—O bond include those represented by the following general formula.
Si (OR ¹² ) _s R ¹³ _4-s
R ¹⁴ (R ¹⁵ ₂ SiO) _t SiR ¹⁶ ₃ , or
(R ¹⁷ ₂ SiO) _u
Here, R ¹² represents a hydrocarbon group having 1 to 20 carbon atoms, and R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ are each independently a hydrocarbon group or hydrogen atom having 1 to 20 carbon atoms. Represent. s represents a number satisfying 0 <s ≦ 4, t represents a number from 1 to 1000, and u represents a number from 2 to 1000.

Specific examples of the silicon compound (e) include tetramethoxysilane, dimethyldimethoxysilane, tetraethoxysilane, triethoxyethylsilane, diethoxydiethylsilane, ethoxytriethylsilane, tetraisopropoxysilane, diisopropoxy-diisopropylsilane, Tetrapropoxysilane, dipropoxydipropylsilane, tetrabutoxysilane, dibutoxydibutylsilane, dicyclopentoxydiethylsilane, diethoxydiphenylsilane, cyclohexyloxytrimethylsilane, phenoxytrimethylsilane, tetraphenoxysilane, triethoxyphenylsilane, hexa Methyldisilohexane, hexaethyldisilohexane, hexapropyldisiloxane, octaethyltrisiloxane, dimethylpolysiloxane Sun, diphenyl polysiloxane, may be exemplified methylhydropolysiloxane, phenyl hydropolysiloxane like.
Among these silicon compounds, preferred are alkoxysilane compounds represented by the general formula Si (OR ¹² ) _s R ¹³ _4-s , in which case t is preferably a number satisfying 1 ≦ s ≦ 4, Tetraalkoxysilane with s = 4 is preferred, and tetraethoxysilane is most preferred.

In the above formula (6), specific examples of R ¹¹ include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, amyl, isoamyl, hexyl, heptyl, octyl, decyl. Group, alkyl group such as dodecyl group, aryl group such as phenyl group, cresyl group, xylyl group, naphthyl group, cycloalkyl group such as cyclohexyl group, cyclopentyl group, allyl group such as propenyl group, aralkyl group such as benzyl group, etc. Is exemplified. Of these groups, an alkyl group having 2 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms is preferable. A linear alkyl group having 2 to 18 carbon atoms is particularly preferable.

Examples of the halogen atom for X ¹ include a chlorine atom, a bromine atom, and an iodine atom.
A chlorine atom is particularly preferable. Hydrocarbon oxy group having 1 to 20 carbon atoms in X ¹ is a hydrocarbon group having a hydrocarbon group of similar carbon number 1 to 20 and R ^11. X ¹ is particularly preferably an alkoxy group having a linear alkyl group having 2 to 18 carbon atoms.

  In the titanium compound represented by the above general formula (6), r represents a number of 1 to 20, preferably 1 ≦ r ≦ 5.

  Specific examples of the titanium compound (f) include tetramethoxy titanium, tetraethoxy titanium, tetra-n-propoxy titanium, tetra-iso-propoxy titanium, tetra-n-butoxy titanium, tetra-iso-butoxy titanium, n -Butoxytitanium trichloride, di-n-butoxytitanium dichloride, tri-n-butoxytitanium chloride, di-n-tetraisopropylpolytitanate (mixture in the range of r = 2-10), tetra-n-butylpolytitanate ( r = 2-10 mixture), tetra-n-hexylpolytitanate (r = 2-10 mixture), tetra-n-octylpolytitanate (r = 2-10 mixture). It is done. Moreover, the condensate of the tetraalkoxy titanium obtained by making a small amount of water react with tetraalkoxy titanium can also be mentioned.

  The titanium compound (f) is preferably a titanium compound in which r is 1, 2, or 4 in the titanium compound represented by the above formula (6). Particularly preferred is tetra-n-butoxytitanium, tetra-n-butyltitanium dimer or tetra-n-butyltitanium tetramer. The titanium compound (f) can also be used in a mixed state.

The organomagnesium compound (g) is any type of organomagnesium compound having a magnesium-carbon bond. In particular, a Grignard compound represented by the general formula R ¹⁸ MgX ² (wherein Mg represents a magnesium atom, R ¹⁸ represents a hydrocarbon group having 1 to 20 carbon atoms, and X ² represents a halogen atom) or a general formula R ¹⁹ Dihydrocarbyl magnesium represented by R ²⁰ Mg (wherein Mg represents a magnesium atom, and R ¹⁹ and R ²⁰ each represent a hydrocarbon group having 1 to 20 carbon atoms) is preferably used. Here, R ¹⁹ and R ²⁰ may be the same or different. Specific examples of R ^{18 to} R ²⁰ are methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, isoamyl group, hexyl group, octyl group and 2-ethylhexyl group, respectively. , A phenyl group, a benzyl group and the like, an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group, and an alkenyl group. In particular, the use of a Grignard compound represented by R ¹⁸ MgX ² in an ether solution is preferable from the viewpoint of catalyst performance.

  It is also possible to use a hydrocarbon-soluble complex of the above organic magnesium compound and an organic metal that solubilizes the organic magnesium compound in a hydrocarbon. Examples of organometallic compounds include Li, Be, B, Al or Zn compounds.

  As the ester compound (h), mono- or polyvalent carboxylic acid esters are used, and examples thereof include saturated aliphatic carboxylic acid esters, unsaturated aliphatic carboxylic acid esters, alicyclic carboxylic acid esters, and aromatic carboxylic acid esters. Mention may be made of esters. Specific examples include methyl acetate, ethyl acetate, phenyl acetate, methyl propionate, ethyl propionate, ethyl butyrate, ethyl valerate, ethyl acrylate, methyl methacrylate, ethyl benzoate, butyl benzoate, methyl toluate, toluyl Ethyl acetate, ethyl anisate, diethyl succinate, dibutyl succinate, diethyl malonate, dibutyl malonate, dimethyl maleate, dibutyl maleate, diethyl itaconate, dibutyl itaconate, monoethyl phthalate, dimethyl phthalate, methyl phthalate Ethyl, diethyl phthalate, di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, dipentyl phthalate, di-n-hexyl phthalate, diheptyl phthalate, di-phthalate n-octyl, phthalate Di (2-ethylhexyl), diisodecyl phthalate, dicyclohexyl phthalate, may be mentioned diphenyl phthalate.

  Among these ester compounds, unsaturated aliphatic carboxylic acid esters such as methacrylic acid esters and maleic acid esters or aromatic carboxylic acid esters such as phthalic acid esters are preferred, and dialkyl esters of phthalic acid are particularly preferred.

  Component (x) is obtained by reducing titanium compound (f) with organomagnesium compound (g) in the presence of silicon compound (e) or in the presence of silicon compound (e) and ester compound (h).

  The titanium compound (f), the silicon compound (e) and the ester compound (h) are preferably dissolved or diluted in an appropriate solvent. Such solvents include 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, dibutyl ether, di- Examples include ether compounds such as isoamyl ether and tetrahydrofuran.

  The reduction reaction temperature is preferably −50 to 70 ° C., more preferably −30 to 50 ° C., and still more preferably −25 to 35 ° C. The reaction time is preferably 30 minutes to 6 hours. Thereafter, a post reaction may be performed at a temperature of 20 to 120 ° C.

In the reduction reaction, a porous carrier such as an inorganic oxide or an organic polymer can be allowed to coexist, and the porous product can be impregnated with the porous product. The porous carrier used may be a known one. Porous inorganic oxides represented by SiO ₂ , Al ₂ O ₃ , MgO, TiO ₂ , ZrO _2, etc., or 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-divinylbenzene copolymer, polyvinyl chloride, Examples thereof include organic porous polymers such as polyethylene and polypropylene. Of these, an organic porous polymer is preferably used, and a styrene-divinylbenzene copolymer or an acrylonitrile-divinylbenzene copolymer is particularly preferable.

  The porous carrier preferably has a pore volume at a pore radius of 200 to 2000 mm of 0.3 cc / g or more, more preferably 0.4 cc / g or more. The pore volume at ˜75000 kg is preferably 35% or more, more preferably 40% or more. If the pore volume of the porous carrier is small, the catalyst component may not be effectively immobilized, which is not preferable. In addition, even when the pore volume of the porous carrier is 0.3 cc / g or more, the catalyst component cannot be effectively immobilized unless it is sufficiently present in the pore radius of 200 to 2000 mm. Is not preferable.

  The amount of silicon compound (e) used is the atomic ratio of silicon atoms to titanium atoms in the titanium compound (f), preferably Si / Ti = 1 to 500, more preferably 1 to 300, More preferably, it is 3-100. Furthermore, the amount of the organomagnesium compound (g) used is the atomic ratio of the sum of titanium atoms and silicon atoms and magnesium atoms, preferably (Ti + Si) /Mg=0.1-10, more preferably 0. .2 to 5.0, and more preferably 0.5 to 2.0. Further, in the component (x), the value of the molar ratio of Mg / Ti is preferably 1 to 51, more preferably 2 to 31, and still more preferably 4 to 26. You may determine the usage-amount of f), a silicon compound (e), and an organomagnesium compound (g). Moreover, the usage-amount of the ester compound (h) of an arbitrary component is the molar ratio of the ester compound with respect to the titanium atom of a titanium compound (f), Preferably, it is ester compound / Ti = 0.05-100, More preferably 0.1 to 60, and more preferably 0.2 to 30.

  The solid product obtained by the reduction reaction is usually subjected to solid-liquid separation and washed several times with an inert hydrocarbon solvent such as hexane, heptane, and toluene. The component (x) thus obtained contains a trivalent titanium atom, a magnesium atom and a hydrocarbyloxy group, and generally exhibits amorphous or extremely weak crystallinity. From the viewpoint of catalyst performance, an amorphous structure is particularly preferable.

<Halogenated Compound (Component (y))>
Component (y) is preferably a compound capable of substituting a halogen atom for the hydrocarbon oxy group in component (x). Among these, halogen compounds of Group 4 elements, halogen compounds of Group 13 elements, or halogen compounds of Group 14 elements are preferable.

As the halogen compound of the Group 4 element, the general formula M (OR ²¹ ) _v X ³ _4-v (wherein M represents a Group 4 element and R ²¹ represents a hydrocarbon group having 1 to 20 carbon atoms). X ³ represents a halogen atom, and v represents a number satisfying 0 ≦ v <4). Specific examples of M include titanium, zirconium, and hafnium, and titanium is particularly preferable. Specific examples of R ²¹ include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, amyl group, isoamyl group, tert-amyl group, hexyl group, heptyl group, octyl group. And an alkyl group such as a decyl group and a dodecyl group, an aryl group such as a phenyl group, a cresyl group, a xylyl group and a naphthyl group, an allyl group such as a propenyl group, and an aralkyl group such as a benzyl group. Among these, an alkyl group having 2 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms is preferable. A linear alkyl group having 2 to 18 carbon atoms is particularly preferable. It is also possible to use halogen compounds of Group 4 elements having two or more different OR ²¹ groups.

Examples of the halogen atom represented by X ³ include a chlorine atom, a bromine atom, and an iodine atom. Of these, a chlorine atom gives particularly favorable results.

In the halogen compound of the Group 4 element represented by the general formula M (OR ²¹ ) _v X ³ _4-v , b is a number satisfying 0 ≦ v <4, and preferably satisfies 0 ≦ b ≦ 2. More preferably, v = 0.

Specifically, titanium compounds represented by the general formula M (OR ²¹ ) _v X ³ _4-v include titanium tetrachlorides such as titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, methoxy titanium tri Trihalogenated alkoxy titanium such as chloride, ethoxy titanium trichloride, butoxy titanium trichloride, phenoxy titanium trichloride, ethoxy titanium tribromide, dimethoxy titanium dichloride, diethoxy titanium dichloride, dibutoxy titanium dichloride, diphenoxy titanium dichloride, diethoxy Examples thereof include dihalogenated dialkoxytitanium such as titanium dibromide, zirconium compounds corresponding to the respective compounds, and hafnium compounds. Titanium tetrachloride is preferred.

As a halogen compound of a Group 13 element or a Group 14 element, a general formula MR ²² _j-k X ⁴ _k (wherein M is a Group 13 or Group 14 atom, and R ²² is a carbon number of 1 to 20). In which X ⁴ is a halogen atom, j is a valence of M, and k is a number satisfying 0 <k ≦ j. Examples of Group 13 atoms include B, Al, Ga, In, and Tl. B or Al is preferable, and Al is more preferable. Examples of the Group 14 atom include C, Si, Ge, Sn, and Pb. Si, Ge, or Sn is preferable, and Si or Sn is more preferable.

j is the valence of M, for example, j = 4 when M is Si. c represents a number satisfying 0 <k ≦ j. When M is Si, k is preferably 3 or 4. Examples of the halogen atom represented by X ⁴ include F, Cl, Br, and I, and Cl is preferable.

Specific examples of R ²² include methyl group, ethyl group, normal propyl group, isopropyl group, normal butyl group, isobutyl group, amyl group, isoamyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group and the like. Examples include alkyl groups, phenyl groups, tolyl groups, cresyl groups, xylyl groups, naphthyl groups and other aryl groups, cyclohexyl groups, cyclopentyl groups and other cycloalkyl groups, propenyl groups and other alkenyl groups, and benzyl groups and other aralkyl groups. . Preferred R ²² is an alkyl group or an aryl group, and particularly preferred R ²² is a methyl group, an ethyl group, a normal propyl group, a phenyl group or a paratolyl group.

  Specific examples of Group 13 element halogen compounds include trichloroboron, methyldichloroboron, ethyldichloroboron, phenyldichloroboron, cyclohexyldichloroboron, dimethylchloroboron, methylethylchloroboron, trichloroaluminum, methyldichloroaluminum, ethyldichloro. Aluminum, phenyldichloroaluminum, cyclohexyldichloroaluminum, dimethylchloroaluminum, diethylchloroaluminum, methylethylchloroaluminum, ethylaluminum sesquichloride, gallium chloride, gallium dichloride, trichlorogallium, methyldichlorogallium, ethyldichlorogallium, phenyldichlorogallium, cyclohexyl Dichlorogallium, dimethylchlorogalli , Methyl ethyl chlorogallium, indium chloride, indium trichloride, methyl indium dichloride, phenyl indium dichloride, dimethyl indium chloride, thallium chloride, thallium trichloride, methyl thallium dichloride, phenyl thallium dichloride, dimethyl thallium chloride, etc. Also included are compounds in which chloro in the compound name is changed to fluoro, bromo, or iodo.

  Specific examples of halogen compounds of Group 14 elements include tetrachloromethane, trichloromethane, dichloromethane, monochloromethane, 1,1,1-trichloroethane, 1,1-dichloroethane, 1,2-dichloroethane, 1,1,2 , 2-tetrachloroethane, tetrachlorosilane, trichlorosilane, methyltrichlorosilane, ethyltrichlorosilane, normal propyltrichlorosilane, normal butyltrichlorosilane, phenyltrichlorosilane, benzyltrichlorosilane, paratolyltrichlorosilane, cyclohexyltrichlorosilane, dichlorosilane, Methyldichlorosilane, ethyldichlorosilane, dimethyldichlorosilane, diphenyldichlorosilane, methylethyldichlorosilane, monochlorosilane, trimethylchloro Silane, triphenylchlorosilane, tetrachlorogermane, trichlorogermane, methyltrichlorogermane, ethyltrichlorogermane, phenyltrichlorogermane, dichlorogermane, dimethyldichlorogermane, diethyldichlorogermane, diphenyldichlorogermane, monocrologermane, trimethylchlorogermane, triethylchlorogermane , Trinormalbutylchlorogermane, tetrachlorotin, methyltrichlorotin, normalbutyltrichlorotin, dimethyldichlorotin, dinormalbutyldichlorotin, diisobutyldichlorotin, diphenyldichlorotin, divinyldichlorotin, methyltrichlorotin, phenyltrichlorotin, Examples include dichlorolead, methylchlorolead, and phenylchlorolead. Oro, bromo or compound is changed to iodine, it is also included.

  As component (y), tetrachlorotitanium, methyldichloroaluminum, ethyldichloroaluminum, tetrachlorosilane, phenyltrichlorosilane, methyltrichlorosilane, ethyltrichlorosilane, normal propyltrichlorosilane, or tetrachlorotin is preferable from the viewpoint of polymerization activity. . As a component (y), only 1 type in the said compound may be used, and multiple types may be used.

（１）
（式中、Ｒ^１は、炭素数１〜２０のハイドロカルビル基を表し、Ｒ^２、Ｒ^３、Ｒ^４およびＲ^５は、それぞれ独立して、水素原子、ハロゲン原子または炭素数１〜２０のハイドロカルビル基を表し、Ｒ^６は、ハロゲン原子または炭素数１〜２０のハイドロカルビルオキシ基を表す。） <Component (d)>
The component (d) is a compound represented by the following formula (1). In the present invention, in preparation of the component (a), high stereoregular polymerization ability can be imparted by contact treatment with the component (d).

(1)
(In the formula, R ¹ represents a hydrocarbyl group having 1 to 20 carbon atoms, and R ² , R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom, a halogen atom, or a C 1-20 carbon atom. And R ⁶ represents a halogen atom or a hydrocarbyloxy group having 1 to 20 carbon atoms.)

It is preferable that at least one selected from R ² , R ³ , R ⁴ and R ⁵ in the formula (1) is a hydrocarbyl group having 1 to 20 carbon atoms.

Examples of the hydrocarbyl group of R ¹ in the formula (1) include an alkyl group, an aralkyl group, an aryl group, and an alkenyl group. Some or all of the hydrogen atoms contained in these groups are halogen atoms, hydrocarbyl groups, and the like. It may be substituted with a biloxy group, a nitro group, a sulfonyl group, a silyl group, or the like. Examples of the alkyl group for R ¹ 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 groups; branched alkyl groups such as iso-propyl group, iso-butyl group, tert-butyl group, iso-pentyl group, neopentyl group, and 2-ethylhexyl group; cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl And cyclic alkyl groups such as a cycloheptyl group and a cyclooctyl group, preferably a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, more preferably a linear or branched group. And an alkyl group having 1 to 20 carbon 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 ³ 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 groups such as iso-butenyl 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 20 carbon atoms.

R ¹ in Formula (1) is preferably an alkyl group having 1 to 20 carbon atoms, more preferably a linear or branched alkyl group having 1 to 20 carbon atoms, still more preferably a methyl group or an ethyl group. N-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, iso-propyl group, iso-butyl group, tert-butyl group, iso-pentyl group , Neopentyl group and 2-ethylhexyl group, particularly preferably methyl group and ethyl group.

As a halogen atom of R < ² > -R < ⁵ > in Formula (1), a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom is mentioned, Preferably it is a fluorine atom, a chlorine atom, or a bromine atom.

Examples of the hydrocarbyl group of R ^{2 to} R ⁵ in Formula (1) include an alkyl group, an aralkyl group, an aryl group, an alkenyl group, and the like, and some or all of the hydrogen atoms contained in these groups are halogen atoms. , A hydrocarbyloxy group, a nitro group, a sulfonyl group, a silyl group and the like may be substituted.
Examples of the alkyl group of R ^{2 to} R ⁵ include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, and an n-octyl group. Linear alkyl group; iso-propyl group, iso-butyl group, tert-butyl group, iso-pentyl group, neopentyl group, 2-ethylhexyl group, 1,1-dimethyl-2-methylpropyl group, 1,1- Branched alkyl groups such as dimethyl-2,2-dimethylpropyl group, 1,1-dimethyl-n-butyl group, 1,1-dimethyl-n-pentyl group, and 1,1-dimethyl-n-hexyl group Cyclic alkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, and cyclooctyl group; A straight, a branched or cyclic alkyl group. Examples of the aralkyl group of R ^{2 to} R ⁵ include a benzyl group and a phenethyl group, preferably an aralkyl group having 7 to 20 carbon atoms. Examples of the aryl group of R ^{2 to} R ⁵ 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 of R ^{2 to} R ⁵ include linear alkenyl groups such as vinyl group, allyl group, 3-butenyl group, and 5-hexenyl group; iso-butenyl group, and 5-methyl-3-pentenyl group Such a branched alkenyl group; cyclic alkenyl groups such as 2-cyclohexenyl group and 3-cyclohexenyl group are exemplified, and an alkenyl group having 2 to 10 carbon atoms is preferable.

R ⁴ in formula (1) is preferably an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, more preferably a branched or cyclic alkyl group having 3 to 20 carbon atoms or 6 to 6 carbon atoms. 20 aryl groups, more preferably iso-propyl group, iso-butyl group, tert-butyl group, iso-pentyl group, neopentyl group, 2-ethylhexyl group, 1,1-dimethyl-2-methylpropyl group, Such as 1,1-dimethyl-2,2-dimethylpropyl group, 1,1-dimethyl-n-butyl group, 1,1-dimethyl-n-pentyl group, and 1,1-dimethyl-n-hexyl group Branched alkyl group; cyclic such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, and cyclooctyl group Alkyl group: phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 2,6-dimethylphenyl group, 2,4,6-trimethylphenyl group, o-ethylphenyl group, m-ethylphenyl group An aryl group such as p-ethylphenyl group, 2,6-diethylphenyl group, 2,4,6-triethylphenyl group, m-normalpropylphenyl group, m-isopropylphenyl group, particularly preferably iso- Propyl group, iso-butyl group, tert-butyl group, iso-pentyl group, neopentyl group, 2-ethylhexyl group, 1,1-dimethyl-2-methylpropyl group, 1,1-dimethyl-2,2-dimethylpropyl Groups such as 1,1-dimethyl-n-butyl, 1,1-dimethyl-n-pentyl, and 1,1-dimethyl-n-hexyl Branched alkyl group; an aryl group such as phenyl group.

R ⁵ in Formula (1) is preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, more preferably a hydrogen atom, linear or branched having 1 to 20 carbon atoms. An alkyl group or an aryl group having 6 to 20 carbon atoms, and more preferably a hydrogen atom or a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n- Linear alkyl groups such as heptyl and n-octyl; iso-propyl, iso-butyl, tert-butyl, iso-pentyl, neopentyl, 2-ethylhexyl, 1,1-dimethyl 2-methylpropyl group, 1,1-dimethyl-2,2-dimethylpropyl group, 1,1-dimethyl-n-butyl group, 1,1-dimethyl-n-pentyl group And branched alkyl groups such as 1,1-dimethyl-n-hexyl group; phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 2,6-dimethylphenyl group, 2,4, 6-trimethylphenyl group, o-ethylphenyl group, m-ethylphenyl group, p-ethylphenyl group, 2,6-diethylphenyl group, 2,4,6-triethylphenyl group, 3-propylphenyl group, 3- An aryl group such as isopropylphenyl group, particularly preferably a hydrogen atom or a methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, and n A straight-chain alkyl group having 1 to 10 carbon atoms such as an octyl group, most preferably a hydrogen atom or a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pen A Le group.

R ² and R ³ in the formula (1) are preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom or a linear alkyl group having 1 to 10 carbon atoms, particularly preferably. Is a hydrogen atom or a methyl group, an ethyl group, an n-propyl group, an n-butyl group or an n-pentyl group, most preferably a hydrogen atom.

Examples of the halogen atom of R ⁶ in the formula (1) include a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, preferably a fluorine atom, a chlorine atom or a bromine atom, and more preferably a chlorine atom.

Examples of the hydrocarbyloxy group of R ⁶ in the formula (1) include an alkoxy group, an aralkyloxy group, an aryloxy group, an alkenyloxy group, etc., and some or all of the hydrogen atoms contained in these groups are halogen atoms, nitro It may be substituted with a group, a sulfonyl group, a silyl group or the like. Examples of the alkoxy group of R ⁶ include methoxy group, ethoxy group, n-propoxy group, n-butoxy group, n-pentoxy group, n-hexoxy group, n-heptoxy group, n-octoxy group, and n-decoxy group. Straight-chain alkoxy groups; branched alkoxy groups such as iso-propoxy, iso-butoxy, tert-butoxy, iso-pentoxy, neopentoxy, isoamyloxy, and 2-ethylhexyloxy; cyclopropyloxy Groups, cyclobutyloxy groups, cyclopentyloxy groups, cyclohexyloxy groups, cycloheptyloxy groups, cyclic alkoxy groups such as cyclooctyloxy groups, etc., preferably linear or branched alkoxy having 1 to 10 carbon atoms It is a group. Examples of the aralkyloxy group for R ⁶ include a benzyloxy group and a phenethyloxy group, and an aralkyloxy group having 7 to 10 carbon atoms is preferable. Examples of the aryloxy group for R ⁶ include a phenoxy group, a methylphenoxy group, and a mesityloxy group, and an aryloxy group having 6 to 10 carbon atoms is preferable. The alkenyloxy group of R ⁶ includes linear alkenyloxy groups such as vinyloxy group, allyloxy group, 3-butenyloxy group, and 5-hexenyloxy group; branched groups such as iso-butenyloxy group and 4-methyl-3-pentenyloxy group. A cyclic alkenyloxy group such as 2-cyclohexenyloxy group and a cyclic alkenyloxy group such as 3-cyclohexenyloxy, and a linear or branched alkenyloxy group having 2 to 10 carbon atoms is preferable.

Specific examples of the formula (1) include ethyl 3-ethoxy-2-iso-propylpropionate, ethyl 3-ethoxy-2-iso-butylpropionate, ethyl 3-ethoxy-2-tert-butylpropionate, 3 Ethyl-2-ethoxy-2-tert-amylpropionate, ethyl 3-ethoxy-2-cyclohexylpropionate, ethyl 3-ethoxy-2-cyclopentylpropionate, ethyl 3-ethoxy-2-adamantylpropionate, 3-ethoxy-2 -Ethyl phenylpropionate, ethyl 3-ethoxy-2- (2,3-dimethyl-2-butyl) propionate, ethyl 3-ethoxy-2- (2,3,3-trimethyl-2-butyl) propionate, Ethyl 3-ethoxy-2- (2-methyl-2-hexyl) propionate, 3-iso-butyl Ethyl 2-xiso-2-propyl-propionate, ethyl 3-iso-butoxy-2-iso-butylpropionate, ethyl 3-iso-butoxy-2-tert-butylpropionate, 3-iso-butoxy-2-tert -Ethyl amylpropionate, ethyl 3-iso-butoxy-2-cyclohexylpropionate, ethyl 3-iso-butoxy-2-cyclopentylpropionate, ethyl 3-iso-butoxy-2-adamantylpropionate, 3-iso-butoxy Ethyl 2-phenylpropionate, ethyl 3-methoxy-2-iso-propylpropionate, ethyl 3-methoxy-2-iso-butylpropionate, ethyl 3-methoxy-2-tert-butylpropionate, 3-methoxy -2-tert-amylpropio Ethyl acetate, ethyl 3-methoxy-2-cyclohexylpropionate, ethyl 3-methoxy-2-cyclopentylpropionate, ethyl 3-methoxy-2-adamantylpropionate, ethyl 3-methoxy-2-phenylpropionate, 3-methoxy Ethyl 2- (2,3-dimethyl-2-butyl) propionate, ethyl 3-methoxy-2- (2,3,3-trimethyl-2-butyl) propionate, 3-methoxy-2- (2- Methyl-2-hexyl) ethyl propionate, methyl 3-ethoxy-2-iso-propylpropionate, methyl 3-ethoxy-2-iso-butylpropionate, methyl 3-ethoxy-2-tert-butylpropionate, 3 -Ethoxy-2-tert-methyl amylpropionate, 3-ethoxy-2-cyclohexyl Methyl lupropionate, methyl 3-ethoxy-2-cyclopentylpropionate, methyl 3-ethoxy-2-adamantylpropionate, methyl 3-ethoxy-2-phenylpropionate, 3-ethoxy-2- (2,3-dimethyl) 2-butyl) methyl propionate, methyl 3-ethoxy-2- (2,3,3-trimethyl-2-butyl) propionate, methyl 3-ethoxy-2- (2-methyl-2-hexyl) propionate , Methyl 3-methoxy-2-iso-propylpropionate, methyl 3-methoxy-2-iso-butylpropionate, methyl 3-methoxy-2-tert-butylpropionate, 3-methoxy-2-tert-amylpropionate Methyl acid, methyl 3-methoxy-2-cyclohexylpropionate, 3-methoxy-2- Methyl clopentylpropionate, methyl 3-methoxy-2-adamantylpropionate, methyl 3-methoxy-2-phenylpropionate, methyl 3-methoxy-2- (2,3-dimethyl-2-butyl) propionate, 3 -Methyl-2-methoxy-2- (2,3,3-trimethyl-2-butyl) propionate, methyl 3-methoxy-2- (2-methyl-2-hexyl) propionate, 3-ethoxy-3-iso-propyl Ethyl 2-iso-butylpropionate, ethyl 3-ethoxy-3-iso-butyl-2-iso-butylpropionate, ethyl 3-ethoxy-3-iso-butyl-2-tert-butylpropionate, 3- Ethoxy-2,3-di-tert-butylpropionate, 3-ethoxy-3-iso-butyl-2-ter -Ethyl amylpropionate, 3-ethoxy-3-tert-butyl-2-tert-amyl propionate, 3-ethoxy-2, ethyl 3-ditert-amylpropionate, 3-ethoxy-3-iso-butyl Ethyl 2-cyclohexylpropionate, 3-ethoxy-2, ethyl 3-dicyclohexylpropionate, ethyl 3-ethoxy-3-iso-butyl-2-cyclopentylpropionate, 3-ethoxy-2, 3-dicyclopentylpropionic acid Ethyl, 3-ethoxy-2, ethyl 3-diphenylpropionate, ethyl 3-methoxy-2,2-diiso-propylpropionate, methyl 3-methoxy-2,2-diiso-propylpropionate, 3-ethoxy -2,2-diiso-propyl ethyl propionate, 3-ethoxy 2-methyl-2-diiso-propylpropionate, 3-ethoxy-2, ethyl 2-diphenylpropionate, 3-ethoxy-2, methyl 2-diphenylpropionate, 3-methoxy-2-iso-propyl- Methyl 2-iso-butylpropionate, ethyl 3-methoxy-2-iso-propyl-2-iso-butylpropionate, ethyl 3-ethoxy-2-iso-propyl-2-iso-butylpropionate, 3-methoxy Methyl 2-iso-propyl-2-tert-butylpropionate, ethyl 3-methoxy-2-iso-propyl-2-tert-butylpropionate, 3-ethoxy-2-iso-propyl-2-tert-butyl Ethyl propionate, 3-methoxy-2-iso-propyl-2-tert-amylpropiate Methyl acetate, ethyl 3-methoxy-2-iso-propyl-2-tert-amylpropionate, ethyl 3-ethoxy-2-iso-propyl-2-tert-amylpropionate, 3-methoxy-2-iso- Methyl propyl-2-cyclopentylpropionate, ethyl 3-methoxy-2-iso-propyl-2-cyclopentylpropionate, ethyl 3-ethoxy-2-iso-propyl-2-cyclopentylpropionate, 3-methoxy-2-iso -Methyl propyl-2-cyclohexylpropionate, ethyl 3-methoxy-2-iso-propyl-2-cyclohexylpropionate, ethyl 3-ethoxy-2-iso-propyl-2-cyclohexylpropionate, 3-methoxy-2- iso-propyl-2-phenylpropio Acid methyl, ethyl 3-methoxy-2-iso-propyl-2-phenylpropionate, ethyl 3-ethoxy-2-iso-propyl-2-phenylpropionate, 3-methoxy-2,2-diiso-butylpropion Acid ethyl, methyl 3-methoxy-2,2-diiso-butylpropionate, ethyl 3-ethoxy-2,2-diiso-butylpropionate, methyl 3-ethoxy-2,2-diiso-butylpropionate Methyl 3-methoxy-2-iso-butyl-2-tert-butylpropionate, ethyl 3-methoxy-2-iso-butyl-2-tert-butylpropionate, 3-ethoxy-2-iso-butyl-2 -Ethyl tert-butylpropionate, 3-methoxy-2-iso-butyl-2-tert-amylpropionic acid Methyl, ethyl 3-methoxy-2-iso-butyl-2-tert-amylpropionate, ethyl 3-ethoxy-2-iso-butyl-2-tert-amylpropionate, 3-methoxy-2-iso-butyl- Methyl 2-cyclopentylpropionate, ethyl 3-methoxy-2-iso-butyl-2-cyclopentylpropionate, ethyl 3-ethoxy-2-iso-butyl-2-cyclopentylpropionate, 3-methoxy-2-iso-butyl Methyl 2-cyclohexylpropionate, ethyl 3-methoxy-2-iso-butyl-2-cyclohexylpropionate, ethyl 3-ethoxy-2-iso-butyl-2-cyclohexylpropionate, 3-methoxy-2-iso- Methyl butyl-2-phenylpropionate, 3-methoxy Ethyl 2-iso-butyl-2-phenylpropionate, ethyl 3-ethoxy-2-iso-butyl-2-phenylpropionate, ethyl 3-methoxy-2,2-di-tert-butylpropionate, 3-methoxy- Methyl 2,2-ditert-butylpropionate, ethyl 3-ethoxy-2,2-ditert-butylpropionate, methyl 3-ethoxy-2,2-ditert-butylpropionate, 3-methoxy-2- methyl tert-butyl-2-methylpropionate, ethyl 3-methoxy-2-tert-butyl-2-methylpropionate, ethyl 3-ethoxy-2-tert-butyl-2-methylpropionate, 3-methoxy-2 -Methyl tert-butyl-2-ethylpropionate, 3-methoxy-2-tert-butyl-2-ethyl Ethyl lupropionate, ethyl 3-ethoxy-2-tert-butyl-2-ethylpropionate, methyl 3-methoxy-2-tert-butyl-2-n-propylpropionate, 3-methoxy-2-tert-butyl Ethyl 2-n-propylpropionate, ethyl 3-ethoxy-2-tert-butyl-2-n-propylpropionate, methyl 3-methoxy-2-tert-butyl-2-n-butylpropionate, 3- Methyl-2-tert-butyl-2-n-butylpropionate, 3-ethoxy-2-tert-butyl-2-n-butylpropionate, 3-methoxy-2-tert-butyl-2-n- Methyl pentylpropionate, ethyl 3-methoxy-2-tert-butyl-2-n-pentylpropionate, 3-eth Ethyl-2-tert-butyl-2-n-pentylpropionate, ethyl 3-ethoxy-2,2-dicyclohexylpropionate, ethyl 3-ethoxy-2,2-dicyclopentylpropionate, 3-ethoxy-2- iso-propylpropionic acid chloride, 3-ethoxy-2-tert-butylpropionic acid chloride, 3-ethoxy-2-tert-amylpropionic acid chloride, 3-ethoxy-2-cyclohexylpropionic acid chloride, 3-ethoxy-2- Cyclopentylpropionic acid chloride, 3-ethoxy-2-adamantylpropionic acid chloride, 3-ethoxy-2-phenylpropionic acid chloride, 3-ethoxy-2- (2,3-dimethyl-2-butyl) propionic acid chloride, 3- Ethoxy-2- (2 3,3-trimethyl-2-butyl) propionic acid chloride, 3-ethoxy-2- (2-methyl-2-hexyl) propionic acid chloride, 3-iso-butoxy-2-iso-propylpropionic acid chloride, 3- iso-butoxy-2-iso-butylpropionic acid chloride, 3-iso-butoxy-2-tert-butylpropionic acid chloride, 3-iso-butoxy-2-tert-amylpropionic acid chloride, 3-iso-butoxy-2 -Cyclohexylpropionic acid chloride, 3-iso-butoxy-2-cyclopentylpropionic acid chloride, 3-iso-butoxy-2-adamantylpropionic acid chloride, 3-iso-butoxy-2-phenylpropionic acid chloride, 3-methoxy-2 -Iso- Pyrpropionic acid chloride, 3-methoxy-2-iso-butylpropionic acid chloride, 3-methoxy-2-tert-butylpropionic acid chloride, 3-methoxy-2-tert-amylpropionic acid chloride, 3-methoxy-2- Cyclohexylpropionic acid chloride, 3-methoxy-2-cyclopentylpropionic acid chloride, 3-methoxy-2-adamantylpropionic acid chloride, 3-methoxy-2-phenylpropionic acid chloride, 3-methoxy-2- (2,3-dimethyl) -2-butyl) propionic acid chloride, 3-methoxy-2- (2,3,3-trimethyl-2-butyl) propionic acid chloride, 3-methoxy-2- (2-methyl-2-hexyl) propionic acid chloride , 3-ethoxy-3-iso- Propyl-2-iso-butylpropionic acid chloride, 3-ethoxy-3-iso-butyl-2-iso-butylpropionic acid chloride, 3-ethoxy-3-iso-butyl-2-tert-butylpropionic acid chloride, 3 -Ethoxy-2,3-di tert-
Butylpropionic acid chloride, 3-ethoxy-3-iso-butyl-2-tert-amylpropionic acid chloride, 3-ethoxy-3-tert-butyl-2-tert-amylpropionic acid chloride, 3-ethoxy-2, 3 Di-tert-amylpropionic acid chloride, 3-ethoxy-3-iso-butyl-2-cyclohexylpropionic acid chloride, 3-ethoxy-2, 3-dicyclohexylpropionic acid chloride, 3-ethoxy-3-iso-butyl-2 -Cyclopentylpropionic acid chloride, 3-ethoxy-2, 3-dicyclopentylpropionic acid chloride, 3-methoxy-2,2-diiso-propylpropionic acid chloride, 3-ethoxy-2,2-diiso-propylpropionic acid Chloride, 3-metoki 2-iso-propyl-2-iso-butylpropionic acid chloride, 3-ethoxy-2-iso-propyl-2-iso-butylpropionic acid chloride, 3-methoxy-2-iso-propyl-2-tert-butyl Propionic acid chloride, 3-ethoxy-2-iso-propyl-2-tert-butylpropionic acid chloride, 3-methoxy-2-iso-propyl-2-tert-amylpropionic acid chloride, 3-ethoxy-2-iso- Propyl-2-tert-amylpropionic acid chloride, 3-methoxy-2-iso-propyl-2-cyclopentylpropionic acid chloride, 3-ethoxy-2-iso-propyl-2-cyclopentylpropionic acid chloride, 3-methoxy-2 -Iso-propyl-2-cycl Hexylpropionic acid chloride, 3-ethoxy-2-iso-propyl-2-cyclohexylpropionic acid chloride, 3-methoxy-2-iso-propyl-2-phenylpropionic acid chloride, 3-ethoxy-2-iso-propyl-2 -Phenylpropionic acid chloride, 3-methoxy-2,2-diiso-butylpropionic acid chloride, 3-ethoxy-2,2-diiso-butylpropionic acid chloride, 3-methoxy-2-iso-butyl-2- tert-Butylpropionic acid chloride, 3-ethoxy-2-iso-butyl-2-tert-butylpropionic acid chloride, 3-methoxy-2-iso-butyl-2-tert-amylpropionic acid chloride, 3-ethoxy-2 -Iso-butyl-2-tert-amyl Propionic acid chloride, 3-methoxy-2-iso-butyl-2-cyclopentylpropionic acid chloride, 3-ethoxy-2-iso-butyl-2-cyclopentylpropionic acid chloride, 3-methoxy-2-iso-butyl-2- Cyclohexylpropionic acid chloride, 3-ethoxy-2-iso-butyl-2-cyclohexylpropionic acid chloride, 3-methoxy-2-iso-butyl-2-phenylpropionic acid chloride, 3-ethoxy-2-iso-butyl-2 -Phenylpropionic acid chloride, 3-methoxy-2,2-ditert-butylpropionic acid chloride, 3-ethoxy-2,2-ditert-butylpropionic acid chloride, 3-methoxy-2-tert-butyl-2- Methyl propionic acid chloride, -Ethoxy-2-tert-butyl-2-methylpropionic acid chloride, 3-methoxy-2-tert-butyl-2-ethylpropionic acid chloride, 3-ethoxy-2-tert-butyl-2-ethylpropionic acid chloride, 3-methoxy-2-tert-butyl-2-n-propylpropionic acid chloride, 3-ethoxy-2-tert-butyl-2-n-propylpropionic acid chloride, 3-methoxy-2-tert-butyl-2- n-butylpropionic acid chloride, 3-ethoxy-2-tert-butyl-2-n-butylpropionic acid chloride, 3-methoxy-2-tert-butyl-2-n-pentylpropionic acid chloride, 3-ethoxy-2 -Tert-butyl-2-n-pentylpropionic acid chloride, 3- Butoxy -2-tert- butyl-2-phenylpropionic acid chloride, 3-ethoxy -2-tert- butyl-2-phenylpropionic acid chloride, 3-ethoxy-2,2-dicyclohexyl-propionic acid chloride, and the like.

Among them, ethyl 3-ethoxy-2-tert-butylpropionate, ethyl 3-ethoxy-2-tert-amylpropionate, ethyl 3-ethoxy-2-cyclohexylpropionate, ethyl 3-ethoxy-2-cyclopentylpropionate, Ethyl 3-ethoxy-2-phenylpropionate, ethyl 3-methoxy-2-phenylpropionate, methyl 3-ethoxy-2-phenylpropionate, methyl 3-methoxy-2-phenylpropionate, 3-ethoxy-2- (2,3-dimethyl-2-butyl) ethyl propionate, ethyl 3-ethoxy-2- (2,3,3-trimethyl-2-butyl) propionate, 3-ethoxy-2- (2-methyl-2 -Hexyl) ethyl propionate, ethyl 3-methoxy-2-tert-butylpropionate Methyl 3-ethoxy-2-tert-butylpropionate, methyl 3-methoxy-2-tert-butylpropionate, ethyl 3-ethoxy-3-iso-butyl-2-tert-butylpropionate, 3-ethoxy- 2,3-diethyl tert-butylpropionate, ethyl 3-ethoxy-3-tert-butyl-2-tert-amylpropionate, methyl 3-methoxy-2-iso-propyl-2-tert-butylpropionate, Ethyl 3-methoxy-2-iso-propyl-2-tert-butylpropionate, ethyl 3-ethoxy-2-iso-propyl-2-tert-butylpropionate, 3-methoxy-2-iso-butyl-2- methyl tert-butylpropionate, 3-methoxy-2-iso-butyl-2-te ethyl t-butylpropionate, ethyl 3-ethoxy-2-iso-butyl-2-tert-butylpropionate, ethyl 3-methoxy-2,2-di-tert-butylpropionate, 3-methoxy-2,2- Methyl ditert-butylpropionate, ethyl 3-ethoxy-2,2-ditert-butylpropionate, methyl 3-ethoxy-2,2-ditert-butylpropionate, 3-methoxy-2-tert-butyl- Methyl 2-methylpropionate, ethyl 3-methoxy-2-tert-butyl-2-methylpropionate, ethyl 3-ethoxy-2-tert-butyl-2-methylpropionate, 3-methoxy-2-tert-butyl Methyl-2-ethylpropionate, 3-methoxy-2-tert-butyl-2-ethylpropionic acid Ethyl, ethyl 3-ethoxy-2-tert-butyl-2-ethylpropionate, methyl 3-methoxy-2-tert-butyl-2-n-propylpropionate, 3-methoxy-2-tert-butyl-2- ethyl n-propylpropionate, ethyl 3-ethoxy-2-tert-butyl-2-n-propylpropionate, methyl 3-methoxy-2-tert-butyl-2-n-butylpropionate, 3-methoxy-2 -Ethyl tert-butyl-2-n-butylpropionate, ethyl 3-ethoxy-2-tert-butyl-2-n-butylpropionate, 3-methoxy-2-tert-butyl-2-n-pentylpropionic acid Methyl, 3-methoxy-2-tert-butyl-2-n-pentylpropionate, 3-ethoxy-2-te ethyl t-butyl-2-n-pentylpropionate, 3-ethoxy-2-tert-butylpropionic acid chloride, 3-ethoxy-2-cyclohexylpropionic acid chloride, 3-ethoxy-2-cyclopentylpropionic acid chloride, 3- Ethoxy-2-phenylpropionic acid chloride, 3-methoxy-2-phenylpropionic acid chloride, 3-ethoxy-2- (2,3-dimethyl-2-butyl) propionic acid chloride, 3-ethoxy-2- (2, 3,3-trimethyl-2-butyl) propionic acid chloride, 3-ethoxy-2- (2-methyl-2-hexyl) propionic acid chloride, 3-methoxy-2-tert-butylpropionic acid chloride, 3-ethoxy- 3-iso-butyl-2-tert-butylpropion Chloride, 3-ethoxy-2, 3-ditert-butylpropionic acid chloride, 3-ethoxy-3-tert-butyl-2-tert-amylpropionic acid chloride, 3-methoxy-2-iso-propyl-2-tert -Butylpropionic acid chloride, 3-ethoxy-2-iso-propyl-2-tert-butylpropionic acid chloride, 3-methoxy-2-iso-butyl-2-tert-butylpropionic acid chloride, 3-ethoxy-2- iso-butyl-2-tert-butylpropionic acid chloride, 3-methoxy-2,2-ditert-butylpropionic acid chloride, 3-ethoxy-2,2-ditert-butylpropionic acid chloride, 3-methoxy-2 -Tert-butyl-2-methylpropionic acid chlori 3-ethoxy-2-tert-butyl-2-methylpropionic acid chloride, 3-methoxy-2-tert-butyl-2-ethylpropionic acid chloride, 3-ethoxy-2-tert-butyl-2-ethylpropionic acid Acid chloride, 3-methoxy-2-tert-butyl-2-n-propylpropionic acid chloride, 3-ethoxy-2-tert-butyl-2-n-propylpropionic acid chloride, 3-methoxy-2-tert-butyl 2-n-butylpropionic acid chloride, 3-ethoxy-2-tert-butyl-2-n-butylpropionic acid chloride, 3-methoxy-2-tert-butyl-2-n-pentylpropionic acid chloride, 3- Ethoxy-2-tert-butyl-2-n-pentylpropionic acid chloride, Preferably, ethyl 3-ethoxy-2-tert-butylpropionate, ethyl 3-ethoxy-2-phenylpropionate, ethyl 3-ethoxy-2- (2,3-dimethyl-2-butyl) propionate, 3-ethoxy Ethyl 2- (2,3,3-trimethyl-2-butyl) propionate, ethyl 3-ethoxy-2- (2-methyl-2-hexyl) propionate, 3-ethoxy-2-tert-butylpropionic acid Chloride, 3-ethoxy-2-phenylpropionic acid chloride, 3-ethoxy-2- (2,3-dimethyl-2-butyl) propionic acid chloride, 3-ethoxy-2- (2,3,3-trimethyl-2) -Butyl) propionic acid chloride, 3-ethoxy-2- (2-methyl-2-hexyl) propionic acid chloride are particularly preferred. There.

  The amount of component (d) to be used is preferably 0.01 ml to 10 ml, more preferably 0.03 ml to 5 ml, still more preferably 0.05 ml to 1 ml per 1 g of component (x). . Component (d) is used at one time or divided into arbitrary multiple times.

<Preparation of solid catalyst component (component (a))>
The preferable solid catalyst component (component (a)) is obtained by bringing the component (x), the component (y) and the component (d) into contact with each other. All of these contact treatments are usually performed in an inert gas atmosphere such as nitrogen or argon.

Specific examples of the contact treatment for obtaining the component (a) include the following:
A method for producing a solid catalyst component by adding component (y) and component (d) to component (x) in any order;
-A method of producing a solid catalyst component by adding a mixture of component (y) and component (d) to component (x)-Adding component (d) to component (x), then adding component (y) A method for producing a solid catalyst component;
A method of producing a solid catalyst component by adding component (d) to component (x) and then adding component (y) and component (d) in any order;
A method of producing a solid catalyst component by adding component (d) to component (x) and then adding a mixture of component (y) and component (d);
A method for producing a solid catalyst component by adding component (x) and component (d) to component (y) in any order;
A method for producing a solid catalyst component by adding a mixture of component (x) and component (d) to component (y);

  The contact treatment can be performed by any known method such as a slurry method or a mechanical pulverization means such as a ball mill that can contact each component. However, when mechanical pulverization is performed, a large amount of fine powder is generated in the solid catalyst component, The particle size distribution may be wide, which is not preferable from an industrial viewpoint. Therefore, it is preferable to contact both in the presence of a diluent. Further, after the contact treatment, the next operation can be performed as it is, but in order to remove surplus, it is preferable to perform a washing treatment with a diluent.

  The diluent is preferably inert to the component to be treated, aliphatic hydrocarbons such as pentane, hexane, heptane, and octane, aromatic hydrocarbons such as benzene, toluene, xylene, cyclohexane, cyclopentane, etc. Halogenated hydrocarbons such as alicyclic hydrocarbons, 1,2-dichloroethane, and monochlorobenzene can be used. The amount of the diluent used in the contact treatment is preferably 0.1 ml to 1000 ml per gram of component (x), more preferably 1 ml to 100 ml per gram, for one stage of contact treatment. In addition, the amount of diluent used in a single washing operation is similar. The number of washing operations in the washing treatment is usually 1 to 5 times per one-step contact treatment.

  The temperature of the contact treatment and / or cleaning treatment is preferably −50 to 150 ° C., more preferably 0 to 140 ° C., and still more preferably 60 to 135 ° C. The time for the contact treatment is not particularly limited, but is preferably 0.5 to 8 hours, and more preferably 1 to 6 hours. The time for the washing operation is not particularly limited, but is preferably 1 to 120 minutes, and more preferably 2 to 60 minutes.

  The amount of component (y) used is preferably 0.5 to 1000 mmol, more preferably 1 to 200 mmol, and still more preferably 2 to 100 mmol, relative to 1 g of component (x). . Moreover, when using a component (y), it is preferable to use a component (d) together. In this case, the amount of the component (d) used relative to 1 mol of the component (y) is preferably 1 to 100 mol, more preferably 1.5 to 75 mol, and still more preferably 2 to 50 mol. It is.

  When the contact treatment is performed using each compound a plurality of times, the amount of each compound described above represents the amount of each compound used once and for each kind of compound.

  The obtained component (a) may be used for polymerization in a slurry state in combination with an inert diluent, or may be used for polymerization as a fluid powder obtained by drying. Examples of the drying method include a method of removing volatile components under reduced pressure conditions, and a method of removing volatile components under the flow of an inert gas such as nitrogen and argon. The temperature at the time of drying is preferably 0 to 200 ° C, more preferably 50 to 100 ° C. The drying time is preferably 0.01 to 20 hours, and more preferably 0.5 to 10 hours.

<Organic aluminum compound (component (b))>
Examples of the component (b) include an organoaluminum compound having at least one Al-carbon bond in the molecule, and preferably a trialkylaluminum, a mixture of a trialkylaluminum and a dialkylaluminum halide, or an alkyl Alumoxane, more preferably triethylaluminum, triisobutylaluminum, a mixture of triethylaluminum and diethylaluminum chloride or tetraethyldialumoxane.

  The amount of component (b) used is preferably a molar ratio of Al atoms in component (b) / Ti atoms in component (a), preferably 1 to 2000, more preferably 5 to 1500. The molar ratio of Al atoms in component (c) / component (b) is preferably 0.02 to 500, and more preferably 0.05 to 50.

<External electron donor (component (c))>
Examples of the component (c) include compounds described in Japanese Patent No. 2950168, Japanese Patent Application Laid-Open No. 2006-96936, Japanese Patent Application Laid-Open No. 2009-173870, and Japanese Patent Application Laid-Open No. 2010-168545. Among these, an oxygen-containing compound or a nitrogen-containing compound is preferable. Examples of the oxygen-containing compound include alkoxy silicon, ether, ester, and ketone. Among them, preferred is alkoxy silicon or ether.

The alkoxysilicon as the component (c) is preferably a compound represented by any of the following formulas (7) to (9).
R ³⁰ _t Si (OR ³¹ ) _4-t (7)
Si (OR ³² ) ₃ (NR ³³ R ³⁴ ) (8)
Si (OR ³² ) ₃ (NR ³⁵ ) (9)
[Wherein, R ³⁰ represents a hydrocarbyl group having 1 to 20 carbon atoms or a hydrogen atom, R ³¹ represents a hydrocarbyl group having 1 to 20 carbon atoms, and t is 0 ≦ t <4. Represents an integer that satisfies. If one or both of R ³⁰ and ^{R 31} there are a plurality, a plurality of ^{R 30} and ^{R 31} may or may not be the same as each other. R ³² represents a hydrocarbyl group having 1 to 6 carbon atoms, R ³³ and R ³⁴ represent a hydrogen atom or a hydrocarbyl group having 1 to 12 carbon atoms, and NR ³⁵ represents a carbon atom having 5 to 20 carbon atoms. Represents a cyclic amino group. ]

Examples of the hydrocarbyl group of R ³⁰ and R ³¹ in the above formula (7) include an alkyl group, an aralkyl group, an aryl group, and an alkenyl group. The alkyl group of R ³⁰ and R ³¹ includes a methyl group, Linear alkyl groups such as ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, and n-octyl; iso-propyl, iso-butyl Groups, tert-butyl, iso-pentyl, neopentyl, and branched alkyl groups such as 2-ethylhexyl; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl A cyclic alkyl group such as, preferably a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. Kill group. Examples of the aralkyl group for R ³⁰ and R ³¹ 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 of R ³⁰ and R ³¹ 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 ³⁰ and R ³¹ include linear alkenyl groups such as vinyl group, allyl group, 3-butenyl group, and 5-hexenyl group; iso-butenyl group, and 5-methyl-3-pentenyl group A branched alkenyl group such as 2-cyclohexenyl group and a cyclic alkenyl group such as 3-cyclohexenyl group, preferably an alkenyl group having 2 to 10 carbon atoms.

  Specific examples of the alkoxysilicon represented by the above formula (7) include cyclohexylmethyldimethoxysilane, cyclohexylethyldimethoxysilane, diiso-propyldimethoxysilane, tert-butylethyldimethoxysilane, tert-butyl-n-propyldimethoxy. Silane, phenyltrimethoxysilane, diphenyldimethoxysilane, dicyclobutyldimethoxysilane, dicyclopentyldimethoxysilane, tetraethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, iso-butyltriethoxysilane, vinyltriethoxysilane, sec- Examples include butyltriethoxysilane, cyclohexyltriethoxysilane, and cyclopentyltriethoxysilane.

Examples of the hydrocarbyl group of R ^{32 in} the above formulas (8) and (9) include an alkyl group and an alkenyl group. Examples of the alkyl group of R ³² include a methyl group, an ethyl group, an n-propyl group, linear alkyl groups such as n-butyl, n-pentyl, and n-hexyl; iso-propyl, iso-butyl, tert-butyl, iso-pentyl, and neopentyl A branched alkyl group; a cyclic alkyl group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group is exemplified, and a linear alkyl group having 1 to 6 carbon atoms is preferred. ^Examples of the alkenyl group for R ³² include linear alkenyl groups such as vinyl group, allyl group, 3-butenyl group, and 5-hexenyl group; branched groups such as iso-butenyl group and 5-methyl-3-pentenyl group. A cyclic alkenyl group such as a 2-cyclohexenyl group and a 3-cyclohexenyl group, preferably a linear alkenyl group having 2 to 6 carbon atoms, particularly preferably a methyl group and an ethyl group It is.

Examples of the hydrocarbyl group of R ³³ and R ³⁴ in the above formula (8) include an alkyl group and an alkenyl group. Examples of the alkyl group of R ³³ and R ³⁴ include a methyl group, an ethyl group, and n-propyl group. Linear alkyl groups such as n-butyl, n-pentyl, and n-hexyl; iso-propyl, iso-butyl, tert-butyl, iso-pentyl, and neopentyl Such branched alkyl groups; cyclic alkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, and cyclohexyl group are exemplified, and a linear alkyl group having 1 to 6 carbon atoms is preferable. Examples of the alkenyl group for R ³³ and R ³⁴ include linear alkenyl groups such as vinyl group, allyl group, 3-butenyl group, and 5-hexenyl group; iso-butenyl group, and 5-methyl-3-pentenyl group A branched alkenyl group such as 2-cyclohexenyl group and a cyclic alkenyl group such as 3-cyclohexenyl group, preferably a linear alkenyl group having 2 to 6 carbon atoms, particularly preferably methyl. Group and ethyl group.

  Specific examples of the alkoxysilicon represented by the above formula (8) include dimethylaminotrimethoxysilane, diethylaminotrimethoxysilane, di-n-propylaminotrimethoxysilane, dimethylaminotriethoxysilane, diethylaminotriethoxysilane, Di-n-propylaminotriethoxysilane, methylethylaminotriethoxysilane, methyl-n-propylaminotriethoxysilane, tert-butylaminotriethoxysilane, diiso-propylaminotriethoxysilane, methyliso-propylaminotri An ethoxysilane is mentioned.

As the cyclic amino group of NR ³⁵ in the above formula (9), a perhydroquinolino group, a perhydroisoquinolino group, a 1,2,3,4-tetrahydroquinolino group, a 1,2,3,4-tetrahydro group Examples thereof include an isoquinolino group and an octamethyleneimino group.

  Specific examples of the alkoxysilicon represented by the above formula (9) include perhydroquinolinotriethoxysilane, perhydroisoquinolinotriethoxysilane, 1,2,3,4-tetrahydroquinolinotriethoxysilane, 1 2,3,4-tetrahydroisoquinolinotriethoxysilane, octamethyleneiminotriethoxysilane.

  The ether of component (c) is preferably a cyclic ether compound. The cyclic ether compound is a heterocyclic compound having at least one —C—O—C— bond in the ring structure, and more preferably at least one —C—O—C—O—C in the ring structure. -A cyclic ether compound having a bond, particularly preferably 1,3-dioxolane or 1,3-dioxane.

  The method of contacting the component (a), the component (b), and the component (c) is not particularly limited as long as the solid catalyst for olefin polymerization is produced. Contact is performed in the presence or absence of a solvent. These contact mixtures may be supplied to the polymerization tank, each component may be separately supplied to the polymerization tank and contacted in the polymerization tank, or any two-component contact mixture and the remaining components may be contacted. You may supply separately to a polymerization tank and you may make these contact in a polymerization tank.

  The polymerization method for producing the propylene polymer of the present invention may be carried out, for example, in a batch system (a type in which raw materials are charged into one reaction tank and reacted), or a continuous system (a plurality of reaction tanks are connected). Then, the reaction may be performed sequentially in each tank). Also, slurry polymerization or solution polymerization with an inert hydrocarbon solvent such as propane, butane, isobutane, pentane, hexane, heptane, octane, bulk polymerization or gas phase polymerization using a liquid olefin as a medium at the polymerization temperature, and Examples thereof include a continuous bulk-gas phase polymerization method.

（３）
（式（３）中、ｐは２以上の整数を表す。） <Compound (component (B))>
The component (B) 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 (3) 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 (2) 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 (2)
(In formula (2), m represents an integer of 3 or more.)

(3)
(In formula (3), 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 (2) (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 (2)

  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.

（２−１） As a preferable alkoxy compound, for example, a compound represented by the formula (2-1) (wherein R ⁴¹ represents an alkyl group having 1 to 12 carbon atoms, preferably 5 to 12 carbon atoms), and the like. Can give.

(2-1)

  Examples of the compound represented by the formula (2-1) 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.

（３） For the compound represented by the following formula (3) (hereinafter sometimes referred to as “compound (S3)”), in formula (3), p represents an integer of 2 or more, preferably 2 to 2. It represents an integer of 6, more preferably 5.

(3)

  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.

  Content of the component (B) in the polypropylene resin composition of this invention is 0.01-0.5 weight part with respect to 100 weight part of component (A), Preferably, it is 0.01-0.25. Parts by weight.

  When the content of the component (B) is less than 0.01 parts by weight with respect to 100 parts by weight of the component (A), 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.

<Compound having a hydroxyphenyl group (component (C))>
Component (C) is a compound having a hydroxyphenyl group as a substituent, for example, 2,6-di-t-butyl-4-methylphenol, tetrakis [methylene-3 (3 ′, 5′-di). -T-butyl-4-hydroxyphenyl) propionate] methane, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 3,9-bis [2- {3- (3- t-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 1,3,5-tris 2 [3 (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl isocyanate, 1,3,5-trimethyl-2,4,6-tris (3,5-di t-butyl-4-hydroxybenzyl) benzene, tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-t-butyl-3-hydroxy-2) , 6-Dimethylbenzyl) isocyanurate, pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], triethylene glycol-N-bis-3- (3-t -Butyl-5-methyl-4-hydroxyphenyl) propionate, 1,6-hexanediol bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,2-thiobis-diethylene Bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,2′-methylene-bis- (4 Methyl-6-tert-butylphenol), 2,2′-methylene-bis- (4-ethyl-6-tert-butylphenol), 2,2′-methylene-bis- (4,6-di-tert-butylphenol) 2,2′-ethylidene-bis- (4,6-di-tert-butylphenol), 2,2′-butylidene-bis- (4-methyl-6-tert-butylphenol), 4,4′-butylidenebis ( 3-methyl-6-t-butylphenol), 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2,4-di-t- Amyl-6- (1- (3,5-di-t-amyl-2-hydroxyphenyl) ethyl) phenyl acrylate, 2,4-di-t-pentyl-6- [1- (3,5-di- t-pentyl-2-hydroxyl Nyl) ethyl] phenyl acrylate and 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 6- [3- (3-t- Butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-t-butyldibenz [d, f] [1,3,2] dioxaphosphine, coferols and the like. It is done. Examples of tocopherols include vitamin E, which is α-tocopherol.

  The component (C) is preferably a compound selected from the group consisting of a compound represented by the following formula (4) and a compound represented by the formula (5).

（４）
（式（４）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)
(In Formula (4), 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 (4) 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 (4) 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 (4) represents a hydrogen atom or a methyl group, and preferably a hydrogen atom.

  Examples of the compound represented by the formula (4) 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 (4), 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 (4) is a commercially available product, or is produced according to a known method (for example, the method described in JP2010-168545A or JP58-84835A). can do.

（５）
（式（５）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（５−１）

（５−１）
（式（５−１）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（５−２）

（５−２）
（式（５−２）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。）

(5)
(In formula (5), 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 (5-1)

(5-1)
(In formula (5-1), 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 (5-2)

(5-2)
(In Formula (5-2), 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 (5), 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 (5-1). Examples of the alkyl group having 1 to 8 carbon atoms represented by R ^p6 in the formula (5-1) 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 (5-1), and more preferably a single bond.

A represents an alkylene group having 2 to 8 carbon atoms or a divalent group represented by the above formula (5-2), preferably an alkylene group having 2 to 8 carbon atoms. 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 (5-2) 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 (5), 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 (5) 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.

  The compound represented by the formula (5) can be produced by, for example, the method described in JP-A-10-273494.

  When a compound selected from the group consisting of the compound represented by the above formula (4) and the compound represented by the formula (5) is used as the component (C), a further compound having a hydroxyphenyl group is combined. Can.

  The compound having another hydroxyphenyl group is preferably a compound represented by the following formula (10) (hereinafter sometimes referred to as “component (C-2)”).

（１０）
［式（１０）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。］

(10)
[In Formula (10), 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 (10) 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 the formula (10) 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 (C-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 (C-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)).

  More preferred component (C-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 (C-2) is pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate].

  Component (C-2) is a commercially available product, or is produced according to a known method (for example, the method described in US Pat. No. 3,30859, US Pat. No. 3,644,482 or JP-A-59-25826). can do.

  Content of the component (C) in the polypropylene resin composition of this invention is 0.01-0.5 weight part with respect to 100 weight part of components (A), Preferably, it is 0.01-0.25. Parts by weight.

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

  When the component (C) is composed of compounds having two different hydroxyphenyl groups, the compounding ratio of the compound having the other hydroxyphenyl group to the compound having one hydroxyphenyl group is 1: 1 to 10 in weight ratio. : 1 can be selected.

  The polypropylene resin composition according to the present invention may be a resin or rubber other than the propylene polymer (component (A)), a compound having a hydroxyphenyl group (component (C)), as long as the object of the present invention is not impaired. ) And other additives and inorganic fillers may be added.

  Examples of the resin other than the propylene polymer (component (A)) include, for example, ethylene-α-olefin random copolymerization (hereinafter sometimes referred to as “component (D)”), 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 (D) 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 (D-1)”) or an ethylene-α-olefin random copolymer (hereinafter referred to as “component (D)” having a melt flow rate of 10 g / 10 min or more. -2) ").
The melt flow rate of component (D-1) is preferably 3 g / 10 min or less, and the melt flow rate of component (D-2) is preferably 12 g / 10 min or more.

Examples of the α-olefin used in the component (D-1) and the component (D-2) include the same α-olefin having 4 to 10 carbon atoms as the α-olefin used in the propylene polymer (component (A)). 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 (D-1) and component (D-2), ethylene-1-butene copolymer, ethylene-1-hexene copolymer, ethylene-1-octene copolymer, ethylene-1- Decene copolymers, ethylene- (3-methyl-1-butene) copolymers, and copolymers of ethylene and α-olefins having a cyclic structure.

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

Further, from the viewpoint of improving the impact resistance of the molded article of the polypropylene resin composition, the densities of the component (D-1) and the component (D-2) are 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 .

Component (D-1) and component (D-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.

  A commercial item may be used for a component (D-1) and a component (D-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 (C) include ultraviolet absorbers, antistatic agents, lubricants, nucleating agents, pressure-sensitive adhesives, antifogging agents, and antiblocking agents.

  As said inorganic filler, a non-fibrous inorganic filler (henceforth "component (E-1)" may be described.), A fibrous inorganic filler (henceforth "component (E-2)"). May be described.).

A component (E-1) means the inorganic filler which has shapes other than fiber shape, such as powder form, flake shape, and granular form. 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.
Component (E-1) may be used as it is, but improves the interfacial adhesion with the propylene polymer (component (A)) and is dispersed in the propylene polymer (component (A)). 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 (E-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 (E-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 (E-2) may be used as it is, but improves the interfacial adhesion with the propylene polymer (component (A)) and is dispersed in the propylene polymer (component (A)). 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 (E-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 melt-kneads each component of a propylene polymer (component (A)), a compound (component (B)), and a compound having a hydroxyphenyl group (component (C)), and further molding. And can be used as a molded body.

  The melt kneading described above can be performed using a conventionally known method and apparatus. For example, a propylene polymer (component (A)), a compound (component (B)), and a compound having a hydroxyphenyl group (component (C)) are mixed in a Henschel mixer, a ribbon blender, a tumble mixer, etc. After mixing using an apparatus, a propylene polymer, an ethylene-α-olefin copolymer, and various additives are continuously supplied at a constant rate using a melt kneading method or a quantitative feeder. Examples of the method include obtaining a homogeneous mixture, and then melt-kneading the mixture using a single-screw or twin-screw extruder, a Banbury mixer, a roll kneader, or the like.

  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 0.1, 0.2, and 0.5 g / dl 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) The weight ratio (F _II ) of the polymer component (II) to the whole component (A) and the content of units derived from the comonomer of the polymer component (II) in the propylene polymer component (A) ( (Cα ') _II )
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, F _II and Cα ′) _II were calculated according to the method described above.

(4) 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

(Synthesis of solid catalyst component (a-1))
After replacing a 2 L flask equipped with a stirrer and a thermometer with nitrogen, 76.63 g of diethoxymagnesium and 613 ml of toluene were added to the flask. The temperature in the flask was adjusted to 0.1 ° C., and 153 ml of titanium tetrachloride was charged into the flask. Thereafter, the temperature in the flask was raised to 80 ° C., and 30.7 ml of ethyl 3-ethoxy-2-tert-butylpropionate was charged into the flask. Thereafter, the temperature in the flask was raised to 110 ° C., and the components charged in the flask were stirred at the same temperature for 1 hour. Next, the stirred mixture was subjected to solid-liquid separation to obtain a solid. The solid was washed three times with 770 ml of toluene at 100 ° C., and 613 ml of toluene was added to the washed solid to form a slurry. 153 ml of titanium tetrachloride was added to the slurry to form a mixture, and the mixture was stirred at 110 ° C. for 1 hour. Thereafter, the stirred mixture was subjected to solid-liquid separation to obtain a solid. The solid was washed 3 times with 770 ml of toluene at 100 ° C., and further washed 3 times with 770 ml of hexane at room temperature. The washed solid was dried under reduced pressure to obtain 75.89 g of a solid catalyst component for olefin polymerization. The solid catalyst component for olefin polymerization contained 1.64% by weight of titanium atoms and 10.5% by weight of ethyl 3-ethoxy-2-tert-butylpropionate.

(Synthesis of solid catalyst component (a-2))
A solid catalyst was synthesized by the method described in Example 1 of JP2009-173870A.

(Production Example 1) Propylene polymer (1)
Using the solid catalyst (a-1), it was produced by the following method.
[Preliminary polymerization]
Into a SUS autoclave with a stirrer of 3 L in volume, 1.5 L of n-hexane, 20 mmol of triethylaluminum, 2.0 mmol of cyclohexylethyldimethoxysilane and 16 g of the above solid catalyst (a-1) sufficiently dehydrated and degassed. Was added and 32 g of propylene was continuously supplied over about 40 minutes while maintaining the temperature in the autoclave at about 5 to 10 ° C., and then prepolymerization was performed, and then the prepolymerized slurry was made of SUS with a stirrer having an internal volume of 200 L It transferred to the autoclave and 132 L of liquid butane was added to make a slurry of the prepolymerized catalyst component.
[Polymerization step (1)]
A slurry of propylene, hydrogen, triethylaluminum, cyclohexylethyldimethoxysilane and a prepolymerized catalyst component is continuously supplied to a vessel type reactor with a stirrer having an internal volume of 40 L, the polymerization temperature is set to 78 ° C., the stirring speed is set to 150 rpm, The amount of liquid in the reactor is maintained at 18 L, the supply amount of propylene is 25 kg / hour, the supply amount of hydrogen is 75 NL / hour, the supply amount of triethylaluminum is 35 mmol / hour, and the supply amount of cyclohexylethyldimethoxysilane. The continuous polymerization was carried out for 0.26 hours at a rate of 5.25 mmol / hour, the amount of the prepolymerized catalyst component slurry supplied was 0.81 g / hour in terms of solid catalyst component. The polymer was discharged at a rate of 2.31 kg / hour.
[Polymerization step (2)]
The slurry discharged from the reactor in the polymerization step (1) is continuously transferred to a vessel type reactor different from the reactor in the polymerization step (1), and propylene and hydrogen are continuously supplied to set the polymerization temperature to 75. , The stirring rate was 150 rpm, the amount of liquid in the reactor was maintained at 44 L, the supply amount of propylene was 15 kg / hour, the supply amount of hydrogen was 30 NL / hour, and continuous polymerization was further performed for 0.44 hours. . The polymer was discharged at a rate of 3.19 kg / hour.
[Polymerization step (3)]
The slurry discharged from the reactor in the polymerization step (2) is continuously transferred to a vessel type reactor different from the reactors in the polymerization steps (1) and (2), the polymerization temperature is set to 70 ° C., and the stirring speed is increased. At 150 rpm, the amount of liquid in the reactor was maintained at 44 L, and continuous polymerization was further performed for 0.48 hours. The polymer was discharged at a rate of 2.63 kg / hour.
[Polymerization step (4)]
The slurry discharged from the reactor in the polymerization step (3) is continuously transferred to a fluidized bed reactor equipped with a stirrer with an internal volume of 1 m ³ , propylene and hydrogen are continuously supplied, the polymerization temperature is set to 80 ° C., and polymerization is performed. The pressure was set to 1.8 MPa, and the concentration ratio of propylene and hydrogen in the reactor gas was 96.0% by volume / 4.0% by volume (propylene concentration / hydrogen concentration), and polymerization was carried out for 1.91 hours. The propylene polymer (1) was discharged at a rate of 7.57 kg / hour. The intrinsic viscosity ([η]) of the obtained propylene polymer (1) was 1.01 dL / g.

Production Example 2 Propylene Polymer (2)
Using the solid catalyst (a-2) described in Production Example 1, the catalyst was produced by the following method.
[Preliminary polymerization]
To an SUS autoclave with a stirrer with an internal volume of 3 L, 1.5 L of fully dehydrated and degassed n-hexane, 20 mmol of triethylaluminum, 2.0 mmol of cyclohexylethyldimethoxysilane and 16 g of the above solid catalyst were added, and the autoclave The preliminary polymerization was carried out by continuously supplying 32 g of propylene over about 40 minutes while maintaining the temperature at about 5 to 10 ° C., and then the prepolymerized slurry was transferred to a 200-liter SUS autoclave with a stirrer, 132 L of liquid butane was added to prepare a slurry of a prepolymerized catalyst component.
[Polymerization step (1)]
A slurry of propylene, hydrogen, triethylaluminum, cyclohexylethyldimethoxysilane and a prepolymerized catalyst component is continuously supplied to a vessel type reactor with a stirrer having an internal volume of 40 L, the polymerization temperature is set to 78 ° C., the stirring speed is set to 150 rpm, The amount of liquid in the reactor is maintained at 18 L, the supply amount of propylene is 25 kg / hour, the supply amount of hydrogen is 175 NL / hour, the supply amount of triethylaluminum is 35 mmol / hour, and the supply amount of cyclohexylethyldimethoxysilane. The continuous polymerization was carried out for 0.27 hours at a rate of 5.25 millimoles / hour, the amount of the prepolymerized catalyst component slurry supplied was 0.54 g / hour in terms of solid catalyst component. The polymer was discharged at a rate of 2.73 kg / hour.
[Polymerization step (2)]
The slurry discharged from the reactor in the polymerization step (1) is continuously transferred to a vessel type reactor different from the reactor in the polymerization step (1), and propylene and hydrogen are continuously supplied to set the polymerization temperature to 75. , The stirring rate was 150 rpm, the amount of liquid in the reactor was maintained at 44 L, the amount of propylene was 15 kg / hour, the amount of hydrogen was 63 NL / hour, and continuous polymerization was further performed for 0.45 hours. . The polymer was discharged at a rate of 3.82 kg / hour.
[Polymerization step (3)]
The slurry discharged from the reactor in the polymerization step (2) is continuously transferred to a vessel type reactor different from the reactors in the polymerization steps (1) and (2), the polymerization temperature is set to 70 ° C., and the stirring speed is increased. The liquid volume in the reactor was maintained at 44 L at 150 rpm, and continuous polymerization was further performed for 0.49 hours. The polymer was discharged at a rate of 3.13 kg / hour.
[Polymerization step (4)]
The slurry discharged from the reactor in the polymerization step (3) is continuously transferred to a fluidized bed reactor equipped with a stirrer with an internal volume of 1 m ³ , propylene and hydrogen are continuously supplied, the polymerization temperature is set to 80 ° C., and polymerization is performed. Polymerization was carried out for 1.82 hours at a pressure of 1.8 MPa and a propylene / hydrogen concentration ratio in the reactor gas of 91.44% by volume / 8.6% by volume (propylene concentration / hydrogen concentration). The propylene polymer (2) was discharged at a rate of 6.82 kg / hour. The intrinsic viscosity ([η]) of the obtained propylene polymer (2) was 1.06 dL / g.

(Production Example 3) Propylene polymer (3)
Using the solid catalyst (a-1) described in Production Example 1, the catalyst was produced by the following method.
[Preliminary polymerization]
To an SUS autoclave with a stirrer with an internal volume of 3 L, 1.5 L of fully dehydrated and degassed n-hexane, 20 mmol of triethylaluminum, 2.0 mmol of cyclohexylethyldimethoxysilane and 16 g of the above solid catalyst were added, and the autoclave The preliminary polymerization was carried out by continuously supplying 32 g of propylene over about 40 minutes while maintaining the temperature at about 5 to 10 ° C., and then the prepolymerized slurry was transferred to a 200-liter SUS autoclave with a stirrer, 132 L of liquid butane was added to prepare a slurry of a prepolymerized catalyst component.
[Polymerization step (1)]
A slurry of propylene, hydrogen, triethylaluminum, cyclohexylethyldimethoxysilane and a prepolymerized catalyst component is continuously supplied to a vessel type reactor with a stirrer having an internal volume of 40 L, the polymerization temperature is set to 78 ° C., the stirring speed is set to 150 rpm, The amount of liquid in the reactor is maintained at 18 L, the supply amount of propylene is 25 kg / hour, the supply amount of hydrogen is 75 NL / hour, the supply amount of triethylaluminum is 35 mmol / hour, and the supply amount of cyclohexylethyldimethoxysilane. The continuous polymerization was carried out for 0.26 hours at a rate of 5.25 mmol / hour, the amount of the prepolymerized catalyst component slurry supplied was 0.79 g / hour in terms of solid catalyst component. The polymer was discharged at a rate of 2.40 kg / hour.
[Polymerization step (2)]
The slurry discharged from the reactor in the polymerization step (1) is continuously transferred to a vessel type reactor different from the reactor in the polymerization step (1), and propylene and hydrogen are continuously supplied to set the polymerization temperature to 75. , The stirring rate was 150 rpm, the amount of liquid in the reactor was maintained at 44 L, the supply amount of propylene was 15 kg / hour, the supply amount of hydrogen was 30 NL / hour, and continuous polymerization was further performed for 0.44 hours. . The polymer was discharged at a rate of 3.35 kg / hour.
[Polymerization step (3)]
The slurry discharged from the reactor in the polymerization step (2) is continuously transferred to a vessel type reactor different from the reactors in the polymerization steps (1) and (2), the polymerization temperature is set to 70 ° C., and the stirring speed is increased. At 150 rpm, the amount of liquid in the reactor was maintained at 44 L, and continuous polymerization was further performed for 0.48 hours. The polymer was discharged at a rate of 2.75 kg / hour.
[Polymerization step (4)]
The slurry discharged from the reactor in the polymerization step (3) is continuously transferred to a fluidized bed reactor equipped with a stirrer with an internal volume of 1 m ³ , propylene and hydrogen are continuously supplied, the polymerization temperature is set to 80 ° C., and polymerization is performed. Polymerization was carried out for 1.86 hours at a pressure of 1.8 MPa and a concentration ratio of propylene and hydrogen in the reactor gas of 95.9% by volume / 4.1% by volume (propylene concentration / hydrogen concentration). The polymer was discharged at a rate of 7.59 kg / hour.
[Polymerization step (5)]
The polymer component (component (I)) discharged from the reactor in the polymerization step (4) was continuously fed to a fluidized bed reactor with a stirrer having an internal volume of 1 m ³ different from the reactor used in the polymerization step (4). Propylene, ethylene, and hydrogen are continuously fed, the polymerization temperature is 70 ° C., the polymerization pressure is 1.4 MPa, and the concentration ratio of propylene, ethylene, and hydrogen in the reactor gas is 73.8 / 24.0% by volume / 2.2% by volume (propylene concentration / ethylene concentration / hydrogen concentration), and oxygen was added as a quenching agent at a molar ratio of 0.0075 to the triethylaluminum supplied in the polymerization step (1). Then, polymerization was carried out for 3.0 hours. The polymer was discharged at a rate of 3.91 kg / hour. The polymer thus obtained is referred to as a propylene polymer (3). The structural analysis results of the resulting propylene polymer (3) are shown in Table 1.

(Production Example 4) Propylene polymer (4)
Using the solid catalyst (a-2) described in Production Example 1, the catalyst was produced by the following method.
[Preliminary polymerization]
To an SUS autoclave with a stirrer with an internal volume of 3 L, 1.5 L of fully dehydrated and degassed n-hexane, 20 mmol of triethylaluminum, 2.0 mmol of cyclohexylethyldimethoxysilane and 16 g of the above solid catalyst were added, and the autoclave The preliminary polymerization was carried out by continuously supplying 32 g of propylene over about 40 minutes while maintaining the temperature at about 5 to 10 ° C., and then the prepolymerized slurry was transferred to a 200-liter SUS autoclave with a stirrer, 132 L of liquid butane was added to prepare a slurry of a prepolymerized catalyst component.
[Polymerization step (1)]
A slurry of propylene, hydrogen, triethylaluminum, cyclohexylethyldimethoxysilane and a prepolymerized catalyst component is continuously supplied to a vessel type reactor with a stirrer having an internal volume of 40 L, the polymerization temperature is set to 78 ° C., the stirring speed is set to 150 rpm, The amount of liquid in the reactor is maintained at 18 L, the supply amount of propylene is 25 kg / hour, the supply amount of hydrogen is 175 NL / hour, the supply amount of triethylaluminum is 35 mmol / hour, and the supply amount of cyclohexylethyldimethoxysilane. The continuous polymerization was carried out for 0.27 hours at a rate of 5.25 millimoles / hour, the amount of the prepolymerized catalyst component slurry supplied was 0.54 g / hour in terms of solid catalyst component. The polymer was discharged at a rate of 2.80 kg / hour.
[Polymerization step (2)]
The slurry discharged from the reactor in the polymerization step (1) is continuously transferred to a vessel type reactor different from the reactor in the polymerization step (1), and propylene and hydrogen are continuously supplied to set the polymerization temperature to 75. , The stirring rate was 150 rpm, the amount of liquid in the reactor was maintained at 44 L, the amount of propylene was 15 kg / hour, the amount of hydrogen was 63 NL / hour, and continuous polymerization was further performed for 0.45 hours. . The polymer was discharged at a rate of 3.90 kg / hour.
[Polymerization step (3)]
The slurry discharged from the reactor in the polymerization step (2) is continuously transferred to a vessel type reactor different from the reactors in the polymerization steps (1) and (2), the polymerization temperature is set to 70 ° C., and the stirring speed is increased. The liquid volume in the reactor was maintained at 44 L at 150 rpm, and continuous polymerization was further performed for 0.50 hours. The polymer was discharged at a rate of 3.30 kg / hour.
[Polymerization step (4)]
The slurry discharged from the reactor in the polymerization step (3) is continuously transferred to a fluidized bed reactor equipped with a stirrer with an internal volume of 1 m ³ , propylene and hydrogen are continuously supplied, the polymerization temperature is set to 80 ° C., and polymerization is performed. Polymerization was carried out for 1.77 hours at a pressure of 1.8 MPa and a propylene / hydrogen concentration ratio in the reactor gas of 91.44% by volume / 8.6% by volume (propylene concentration / hydrogen concentration). The polymer was discharged at a rate of 6.93 kg / hour.
[Polymerization step (5)]
The polymer component (component (I)) discharged from the reactor in the polymerization step (4) was continuously fed to a fluidized bed reactor with a stirrer having an internal volume of 1 m ³ different from the reactor used in the polymerization step (4). Propylene, ethylene, and hydrogen are continuously fed, the polymerization temperature is 70 ° C., the polymerization pressure is 1.4 MPa, and the concentration ratio of propylene, ethylene, and hydrogen in the reactor gas is 68.6 volumes. % / 27.9% by volume / 3.5% by volume (propylene concentration / ethylene concentration / hydrogen concentration), and a molar ratio of 0.0038 to triethylaluminum supplied in the polymerization step (1) as a quenching agent is 0.0038. Was added for polymerization for 2.5 hours. The polymer was discharged at a rate of 3.47 kg / hour. The polymer thus obtained is referred to as a propylene polymer (4). The structural analysis results of the resulting propylene polymer (4) are shown in Table 1.

[Example 1]
2,4-di-t-pentyl-6- [1- (3,5-di-t-pentyl-2-hydroxyphenyl) with respect to 500 g of the polymer powder of the propylene polymer (1) described in Production Example 1 ) Ethyl] Phenyl acrylate (Sumitomo Chemical Co., Ltd .: Sumilizer GS) 0.5 g and Trehalose (Tokyo Chemical Industries, Ltd., D-(+)-trehalose dihydrate) 0.25 g The mixture was melt-kneaded at 210 ° C. and pelletized 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). Table 2 shows the results of a fogging test of the pelletized propylene polymer (1).

[Example 2]
2,4-di-t-pentyl-6- [1- (3,5-di-t-pentyl-2-hydroxyphenyl) with respect to 500 g of the polymer powder of the propylene polymer (1) described in Production Example 1 ) Ethyl] phenyl acrylate (Sumitomo Chemical Co., Ltd .: Sumilizer GS) 0.5 g and trehalose (Tokyo Chemical Industry Co., Ltd., D-(+)-trehalose dihydrate) 0.25 g and penta Erythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate (BASF: Irganox 1010) was mixed in the same manner as in Example 1 except that 0.25 g was mixed. Turned into. Table 2 shows the results of a fogging test of the pelletized propylene polymer (1).

[Example 3]
2,4-di-t-pentyl-6 with respect to 57 g of the propylene polymer (1) described in Production Example 1 and 383 g (total 500 g) of the propylene polymer (3) described in Production Example 3 -[1- (3,5-di-t-pentyl-2-hydroxyphenyl) ethyl] phenyl acrylate (Sumitomo Chemical Co., Ltd .: Sumilizer GS) 0.5 g and trehalose (Tokyo Chemical Industry Co., Ltd.) 0.25 g of D-(+)-trehalose dihydrate), 20 mm single screw extruder (VS20-14 type, manufactured by Tanabe Plastics Machine Co., Ltd., L / D = 12.6 full flight) Using a mold screw) at 210 ° C. and pelletized. Table 2 shows the results of the fogging test of the pellets.

[Comparative Example 1]
2,4-di-t-pentyl-6- [1- (3,5-di-t-pentyl-2-hydroxyphenyl) with respect to 500 g of the polymer powder of the propylene polymer (1) described in Production Example 1 ) Ethyl] Phenyl acrylate (Sumitomo Chemical Co., Ltd .: Sumilizer GS) 0.5 g was mixed, and 20 mm single screw extruder (VS20-14 type, manufactured by Tanabe Plastics Machine Co., Ltd., L / D = 12.6). Melt-kneaded at 210 ° C. using a full flight type screw) and pelletized. Table 2 shows the results of a fogging test of the pelletized propylene polymer (1).

[Comparative Example 2]
Propylene polymer (2) pellets were obtained in the same manner as in Production Example 1 except that 500 g of the propylene polymer (2) described in Production Example 2 was used. The results of the fogging test of this pellet are shown in Table 2.

[Comparative Example 3]
2,4-di-t-pentyl-6 with respect to 57 g of the propylene polymer (1) described in Production Example 1 and 383 g (total 500 g) of the propylene polymer (3) described in Production Example 3 -[1- (3,5-di-t-pentyl-2-hydroxyphenyl) ethyl] phenyl acrylate (Sumitomo Chemical Co., Ltd .: Sumilizer GS) 0.5 g was mixed, and a 20 mm single screw extruder (VS20). -14 type, manufactured by Tanabe Plastics Machine Co., Ltd., with L / D = 12.6 full flight type screw) was melt-kneaded at 210 ° C. and pelletized. Table 2 shows the results of the fogging test of the pellets.

[Comparative Example 4]
The same as the method described in Example 3, except that a mixture of 60 g of the propylene polymer (2) described in Production Example 2 and 440 g (total 500 g) of the propylene polymer (4) described in Production Example 4 was used. In this way, a pellet was obtained. 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, it can be seen that the amount of the volatile organic compound component is small because the amount of decrease in the sample weight by the fogging test is small. On the other hand, it can be seen that Comparative Examples 1, 2, 3, and 4 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 (6)

A propylene polymer (component (A)) produced using the following olefin polymerization catalyst;
0.01 to 0.5 parts by weight of the following compound (component (B)) with respect to 100 parts by weight of the component (A),
A polypropylene resin composition comprising 0.01 to 0.5 parts by weight of a compound having a hydroxyphenyl group (component (C)) with respect to 100 parts by weight of the component (A).

Olefin polymerization catalyst:
Obtained by contacting a solid catalyst component (component (a)) containing a titanium atom, a magnesium atom and a halogen atom, an organoaluminum compound (component (b)), and an external electron donor (component (c)),
The catalyst for olefin polymerization in which the said component (a) contains the compound (component (d)) represented by following formula (1).

(1)
(In the formula, R ¹ represents a hydrocarbyl group having 1 to 20 carbon atoms, and R ² , R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom, a halogen atom, or a C 1-20 carbon atom. And R ⁶ represents a halogen atom or a hydrocarbyloxy group having 1 to 20 carbon atoms.)

Compound (component (B)): 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 (3) 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 (2) 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 (2)
(In formula (2), m represents an integer of 3 or more.)

(3)
(In formula (3), p represents an integer of 2 or more.)   The polypropylene resin composition according to claim 1, wherein the compound (component (B)) is trehalose. 3. The compound having a hydroxyphenyl group (component (C)) is a compound selected from the group consisting of a compound represented by the following formula (4) and a compound represented by the formula (5). The polypropylene resin composition described in 1.

(4)
(In Formula (4), 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.)

(5)
(In formula (5), 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 (5-1)

(5-1)
(In formula (5-1), 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 (5-2)

(5-2)
(In Formula (5-2), 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 compound having a hydroxyphenyl group (component (C)) is 2,4-di-t-pentyl-6- [1- (3,5-di-t-pentyl-2-hydroxyphenyl) ethyl] phenyl acrylate, Or 6- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-t-butyldibenz [d, f] [1,3,2 The polypropylene resin composition according to any one of claims 1 to 3, which is dioxaphosphepine.   Component (a) is a solid component (component (x)) containing a magnesium atom, a titanium atom and a hydrocarbon oxy group, a halogenated compound (component (y)), and a compound represented by formula (1) (component ( The polypropylene resin composition according to any one of claims 1 to 4, which is a component obtained by contacting d)).   The molded object containing the polypropylene resin composition in any one of Claims 1-5.